US20060106045A1 - Spiroindolinepiperidine derivatives - Google Patents

Spiroindolinepiperidine derivatives Download PDF

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Publication number
US20060106045A1
US20060106045A1 US10/517,957 US51795705A US2006106045A1 US 20060106045 A1 US20060106045 A1 US 20060106045A1 US 51795705 A US51795705 A US 51795705A US 2006106045 A1 US2006106045 A1 US 2006106045A1
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alkyl
optionally substituted
alkoxy
halogen
haloalkyl
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US10/517,957
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David John Hughes
Paul Worthington
Charles Russell
Eric Clarke
James Peace
Mark Ashton
Thomas Coulter
Richard Roberts
Louis-Pierre Molleyres
Fredrik Cederbaum
Jerome Cassayre
Peter Maienfisch
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Syngenta Participations AG
Syngenta Ltd
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David John Hughes
Worthington Paul A
Russell Charles A
Clarke Eric D
Peace James E
Ashton Mark R
Coulter Thomas S
Roberts Richard S
Louis-Pierre Molleyres
Fredrik Cederbaum
Jerome Cassayre
Peter Maienfisch
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Application filed by David John Hughes, Worthington Paul A, Russell Charles A, Clarke Eric D, Peace James E, Ashton Mark R, Coulter Thomas S, Roberts Richard S, Louis-Pierre Molleyres, Fredrik Cederbaum, Jerome Cassayre, Peter Maienfisch filed Critical David John Hughes
Publication of US20060106045A1 publication Critical patent/US20060106045A1/en
Assigned to SYNGENTA PARTICIPATIONS AG reassignment SYNGENTA PARTICIPATIONS AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROBERTS, RICHARD SPURRING, CEDERBAUM, FREDRIK, MOLLEYRES, LOUIS-PIERRE, MAIENFISCH, PETER, CASSAYRE, JEROME
Assigned to SYNGENTA LIMITED reassignment SYNGENTA LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HUGHES, DAVID JOHN, CLARKE, ERIC DANIEL, PEACE, JAMES EDWARD, WORTHINGTON, PAUL ANTHONY, RUSSELL, CHARLES ADAM, ASHTON, MARK RICHARD, COULTER, THOMAS STEPHEN
Priority to US14/859,410 priority Critical patent/US9686990B2/en
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P5/00—Drugs for disorders of the endocrine system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/74—Oxygen atoms
    • C07D211/76—Oxygen atoms attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the present invention relates to spiroindoline derivatives, to processes for preparing them, to insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
  • Spiroindoline derivatives with pharmaceutical properties are disclosed in for example WO9825605, WO9429309, WO9828297 and WO9964002. Synthetic routes to selected compounds with pharmaceutical properties are described in Proc. Natl. Acad. Sci. USA (1995), 92, 7001, Tetrahedron (1997), 53, 10983 and Tetrahedron Letters (1997), 38, 1497. It has now surprisingly been found that certain spiroindolines have insecticidal properties.
  • the present invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I): wherein Y is a single bond, C ⁇ O, C ⁇ S or S(O) q where q is 0, 1 or 2; R 1 is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted heterocyclyloxy, cyan
  • the compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • Each alkyl moiety either alone or as part of a larger group is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or neo-pentyl.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, NCS—, C 3-7 cycloalkyl (itself optionally substituted with C 1-6 alkyl or halogen), C 5-7 cycloalkenyl (itself optionally substituted with C 1-6 alkyl or halogen), hydroxy, C 1-10 alkoxy, C 1-10 alkoxy(C 1-10 )alkoxy, tri(C 1-4 )alkylsilyl(C 1-6 )alkoxy, C 1-6 alkoxycarbonyl(C 1-10 )alkoxy, C 1-10 haloalkoxy, aryl(C 1-4 )-alkoxy (where the aryl group is optionally substituted), C 3-7 cycloalkyloxy
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the ( E ) or ( Z )-configuration. Examples are vinyl, allyl and propargyl.
  • the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.
  • acyl is optionally substituted C 1-6 alkylcarbonyl (for example acetyl), optionally substituted C 2-6 alkenylcarbonyl, optionally substituted C 2-6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
  • C 1-6 alkylcarbonyl for example acetyl
  • C 2-6 alkenylcarbonyl optionally substituted C 2-6 alkynylcarbonyl
  • arylcarbonyl for example benzoyl
  • heteroarylcarbonyl for example benzoyl
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 Cl, CF 3 CH 2 or CHF 2 CH 2 .
  • aryl and aromatic ring system refer to ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.
  • heteroaryl refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur.
  • groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-tria
  • heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N.
  • examples of such rings include 1,3-dioxolane, tetrahydrofuran and morpholine.
  • the optional substituents on heterocyclyl include C 1-6 alkyl and C 1-6 haloalkyl as well as those optional substituents given above for an alkyl moiety.
  • Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
  • Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
  • cycloalkyl or cycloalkenyl include C 1-3 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
  • the optional substituents on aryl or heteroaryl are selected independently, from halogen, nitro, cyano, NCS—, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy-(C 1-6 )alkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl (itself optionally substituted with C 1-6 alkyl or halogen), C 5-7 cycloalkenyl (itself optionally substituted with C 1-6 alkyl or halogen), hydroxy, C 1-10 alkoxy, C 1-10 alkoxy(C 1-10 )alkoxy, tri(C 1-4 )alkyl-silyl(C 1-6 )alkoxy, C 1-6 alkoxycarbonyl(C 1-10 )alkoxy, C 1-10 haloalkoxy, aryl(C 1-4 )alkoxy (where the aryl group is optional
  • aryl or heteroaryl include aryl carbonyl amino (where the aryl group is substituted by C 1-6 alkyl or halogen), (C 1-6 )alkyloxycarbonylamino (C 1-6 )alkyloxycarbonyl-N—(C 1-6 )alkylamino, aryloxycarbonylamino (where the aryl group is substituted by C 1-6 alkyl or halogen), aryloxycarbonyl-N—(C 1-6 )alkylamino, (where the aryl group is substituted by C 1-6 alkyl or halogen), arylsulphonylamino (where the aryl group is substituted by C 1-6 alkyl or halogen), arylsulphonyl-N—(C 1-6 )alkylamino (where the aryl group is substituted by C 1-6 alkyl or halogen), aryl-N—(C 1-6 )alkylamino (where the aryl
  • substituents are independently selected from halogen, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-6 alkylthio, C 1-6 haloalkylthio, C 1-6 alkylsulfinyl, C 1-6 haloalkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 haloalkylsulfonyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, nitro, cyano, CO 2 H, C 1-6 alkylcarbonyl, C 1-6 alkoxycarbonyl, R 31 R 32 N or R 33 R 34 NC(O); wherein R 31 R 32 N or R 33 R 34 NC(O); wherein R 31
  • Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms
  • dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (C 1-6 )alkyl groups.
  • heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C 1-6 ) alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO 2 C, C 1-10 alkoxy (itself optionally substituted by C 1-10 alkoxy), aryl(C 1-4 )alkoxy, C 1-10 alkylthio, C 1-10 alkylcarbonyl, C 1-10 alkoxycarbonyl, C 1-6 alkylaminocarbonyl, di(C 1-6 alkyl)aminocarbonyl, (C 1-6 )alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C 3-7 cycloalkyl (itself optionally substituted with (C 1-6 )alkyl or halogen), C 3-7 cycloalkyloxy, C 5-7 cycloalkenyl, C 1-6 alkylsulfonyl, C 1-6 alkyl
  • the optional substituents on alkenyl or alkynyl include one or more of halogen, C 3-7 cycloalkyl and aryl; the aryl group may be optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino.
  • a preferred optional substituent for heterocyclyl is C 1-6 alkyl.
  • the optional substituents for cycloalkyl include halogen, cyano and C 1-3 alkyl.
  • the optional substituents for cycloalkenyl include C 1-3 alkyl, halogen and cyano.
  • R 1 is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted heterocyclyloxy, cyano, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, formyl, optionally substituted heterocyclyl, optionally substituted alkylthio or NR 13 R 14 where R 13 and R 14 are independently hydrogen
  • Another group of preferred compounds are those of formula (IB) which are compounds of formula (I) wherein Y is a single bond, C ⁇ O or S(O) q where q is 0, 1 or 2;
  • R 1 is hydrogen, C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 5-6 cycloalkenyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 3-6 alkenyloxy(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl-(C 1-6 )alkyl, C 2-6 alkynylcarbonyl(C 1-6
  • a further group of preferred compounds are those of formula (IC) which are compounds of formula (I) wherein Y is a single bond, C ⁇ O or S(O) q where q is 0, 1 or 2;
  • R 1 is hydrogen, C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 5-6 cycloalkenyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 3-6 alkenyloxy(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl-(C 1-6 )alkyl, C 2-6 alkynylcarbonyl(C 1-6
  • Another group of preferred compounds are those of formula (ID) which are compounds of formula (I) wherein Y is a single bond or C ⁇ O;
  • R 1 is hydrogen, C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 5-6 cycloalkenyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 3-6 alkenyloxy(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl-(C 1-6 )alkyl, C 2-6 alkynylcarbonyl(C 1-6 )alkyl, C 1-6 alkoxycarbonyl(
  • Yet another group of preferred compounds are those of formula (IE), which are compounds of formula (I) wherein Y, R 1 , R 2 , R 3 , R 4 , R 8 and n are as defined for compounds of formula IC; R 9 and R 10 are independently hydrogen, C 1-2 alkyl or halogen, and preferably all are hydrogen; and salts or N-oxides thereof.
  • formula (IE) are compounds of formula (I) wherein Y, R 1 , R 2 , R 3 , R 4 , R 8 and n are as defined for compounds of formula IC; R 9 and R 10 are independently hydrogen, C 1-2 alkyl or halogen, and preferably all are hydrogen; and salts or N-oxides thereof.
  • a further group of preferred compounds are those of formula (IF), which are compounds of formula (I) wherein Y, R 1 , R 4 , R 8 , R 9 , R 10 and n are as defined for compounds of formula (IE) and R 2 and R 3 are independently hydrogen, halogen, C 1-2 alkyl, C 1-2 haloalkyl, C 1-2 alkoxy, cyano, or R 2 and R 3 together are ⁇ O, or R 2 and R 3 together with the atoms to which they are attached form a 4, 5, 6, or 7 membered carbocylic or heterocyclic ring; and salts or N-oxides thereof.
  • formula (IF) are compounds of formula (I) wherein Y, R 1 , R 4 , R 8 , R 9 , R 10 and n are as defined for compounds of formula (IE) and R 2 and R 3 are independently hydrogen, halogen, C 1-2 alkyl, C 1-2 haloalkyl, C 1-2 alkoxy, cyano, or R
  • IG are compounds of formula () wherein Y, R 1 , R 2 , R 3 , R 8 , R 9 , R 10 and n are as defined for compounds of formula (IF) and each R 4 is independently halogen, nitro, cyano, C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 1-6 alkylaminocarbonyl(C 1-6 )alkyl, di(C 1-6 )alkylaminocarbonyl(C 1-6 )alkyl, phenyl(C 1-6 )alkyl (wherein the phenyl group is optionally substituted by halogen,
  • a further group of preferred compounds are those of formula (IG′), which are compounds of formula (I) wherein Y, R 1 , R 2 , R 3 , R 8 , R 9 , R 10 and n are as defined for compounds of formula (IB) and each R 4 is independently halogen, nitro, cyano, C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 1-6 alkylaminocarbonyl(C 1-6 )alkyl, di(C 1-6 )alkylaminocarbonyl(C 1-6 )alkyl, phenyl(C 1-6 )alkyl (wherein the phenyl group is optionally substituted by
  • R 1 is C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 5-6 cycloalkenyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )-alkyl, C 3-6 alkenyloxy(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl(C 1-6 )alkyl
  • Another group of preferred compounds are those of formula (IH′), which are compounds of formula (I) wherein R 2 , R 3 , R 4 , R 8 , R 9 , R 10 and n are as defined for compounds of formula (IG′) and R 1 is C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 5-6 cycloalkenyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )-alkyl, C 3-6 alkenyloxy(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl(C 1-6 )alkyl, C 2-6 alkynyl
  • a further group of preferred compounds are those of formula (IJ), which are compounds of formula (I) wherein Y, R 1 , R 2 , R 3 , R 4 , R 9 , R 10 and n are as defined for compounds of formula (IH) and R 8 is C 1-10 alkyl optionally substituted by C 1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C 1-4 alkyl or C 1-4 alkoxy), C 2-6 alkenyl optionally substituted by C 1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C 1-4 alkyl or C 1-4 alkoxy) or C 2-6 alkyl optionally substituted by C 1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C 1-4 alkyl or C 1-4 alkoxy); and salts or N-oxides thereof.
  • a further group of preferred compounds are those of formula (IJ′), which are compounds of formula (I) wherein Y, R 1 , R 2 , R 3 , R 4 , R 9 , R 10 and n are as defined for compounds of formula (IH′) and R 8 is C 1-6 alkyl optionally substituted by phenyl or heteroaryl (the phenyl and heteroaryl groups being optionally substituted halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino); or —C(R 51 )( 52 )—[CR 53 ⁇ CR 54 ] z R 55 where z is 1 or 2, R 51 and R 52 are each independently H, halo or C 1-2 alkyl, R 53 and R 54 are each independently H, halogen, C 1-4 alkyl or C 1-4 haloalkyl and R 55 is
  • Still another preferred group of compounds are those of formula (IK), which are compounds of formula (I) wherein Y is a single bond, C ⁇ O or S(O) q where q is 0, 1 or 2; R 1 is C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 3-6 alkenyloxy-(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl(C 1-6 )alkyl, C 2-6 alkynylcarbonyl(C 1-6 )alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alky
  • Still another preferred group of compounds are those of formula (IL), which are compounds of formula (I) wherein Y is a single bond or C ⁇ O;
  • R 1 is C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 3-6 alkenyloxy-(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl(C 1-6 )alkyl, C 2-6 alkynylcarbonyl(C 1-6 )alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alkyl, C 3-6 alkenyloxycarbonyl(
  • An even more preferred group of compounds are those of formula (IM), which are compounds of formula (I) wherein Y is a single bond or C ⁇ O;
  • R 1 is C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 3-6 alkenyloxy-(C 1-6 )-alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl-(C 1-6 )alkyl, C 2-6 alkenylcarbonyl(C 1-6 )alkyl, C 2-6 alkynylcarbonyl(C 1-6 )alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alkyl, C 3-6 alkenyloxycarbon
  • Y is a single bond, C ⁇ O, C ⁇ S or S(O) q where q is 0, 1 or 2.
  • Y is a single bond, C ⁇ O or SO 2 .
  • Y is a single bond or C ⁇ O, especially C ⁇ O.
  • R 1 is preferably hydrogen, C 1-6 alkyl, C 1-6 cyanoalkyl, C 1-6 haloalkyl, C 3-7 cycloalkyl(C 1-4 )alkyl, C 1-6 alkoxy(C 1-6 )alkyl, heteroaryl(C 1-6 )alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-6 alkylsulfonyl, C 1-6 alkylsulfinyl, C 1-6 alkylthio, C 1-6 alkoxycarbonyl, C 1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), ary
  • R 1 is hydrogen, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy(C 1-6 )alkyl, heteroaryl(C 1-6 )alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-6 alkylsulfonyl, C 1-6 alkylsulfinyl, C 1-6 alkylthio, C 1-6 alkoxycarbonyl, C 1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), phenyl(C 1-6 )alkyl (wherein the phenyl group may be optionally substituted by halogen),
  • R 1 is C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy(C 1-6 )alkyl, heteroaryl(C 1-3 )alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 1-6 alkylsulfonyl, C 1-6 alkoxycarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), phenyl(C 1-3 )alkyl (wherein the phenyl group may be optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2
  • R 1 is C 1-6 alkyl, C 1-6 haloalkyl, heteroaryl(C 1-3 )alkyl (wherein the heteroaryl group maybe optionally substituted by halo, cyano, C 1-6 alkyl, C 1-6 haloalkyl) where the heteroaryl group is a pyridine, pyrimidine, pyrazine or pyridazine ring, heteroaryl (optionally substituted by halo, cyano, C 1-6 alkyl, C 1-6 haloalkyl) where the heteroaryl group is a pyridine, pyrimidine, pyrazine or pyridazine ring, C 1-6 alkoxy or heterocyclyl (optionally substituted by halo, cyano, C 1-3 alkyl, C 1-3 haloalkyl, or C 1-3 alkoxy).
  • R 1 is pyridyl (optionally substituted by halo, C 1-3 alkyl or C 1-3 haloalkyl) or C 1-6 alkoxy, especially halo-substituted pyridyl.
  • R 2 and R 3 are independently hydrogen or C 1-4 alkyl.
  • R 2 and R 3 are independently hydrogen or methyl.
  • R 2 is hydrogen and R 3 is hydrogen or methyl
  • R 2 and R 3 are both hydrogen.
  • each R 4 is independently halogen, cyano, C 1-8 alkyl, C 1-8 haloalkyl, C 1-6 cyanoalkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C 5-6 cycloalkenyl(C 1-6 )alkyl, C 3-6 alkenyloxy(C 1-6 )alkyl, C 3-6 alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6 carboxyalkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 2-6 alkenylcarbonyl(C 1-6 )alkyl, C 2-6 alkynylcarbonyl(C 1-6 )-alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alkyl, C 3-6 alkenyloxycarbonyl(C 1-6 )alky
  • each R 4 is independently halogen, cyano, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 cyanoalkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 2-6 alkynyl, trimethylsilyl(C 2-6 )alkynyl, C 1-6 alkoxycarbonyl, C 3-7 cycloalkyl, C 1-3 alkyl (C 3-7 ) cycloalkyl, phenyl (optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heterocyclyl (optionally substituted by halo, nitro, cyano, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy or C 1-6 haloalkoxy), C 1-8 alk
  • each R 4 is independently halogen, cyano, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 cyanoalkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 2-6 alkynyl, heterocyclyl (optionally substituted by C 1-6 alkyl), C 1-8 alkoxy, C 1-6 haloalkoxy, phenoxy (optionally substituted by halo, cyano, C 1-3 alkyl or C 1-3 haloalkyl), heteroaryloxy (optionally substituted by halo, cyano, C 1-3 alkyl or C 1-3 haloalkyl), di(C 1-8 )alkylamino or 2 adjacent groups R 4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4;
  • each R 4 is independently fluoro, chloro, bromo, cyano, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 cyanoalkyl or C 1-3 alkoxy(C 1-3 )alkyl; n is 0, 1 or 2;
  • each R 4 is independently fluoro, chloro, bromo, C 1-4 alkyl or C 1-4 haloalkyl; n is 1 or 2.
  • R 8 is C 1-10 alkyl, C 1-10 haloalkyl, aryl(C 1-6 )alkyl (wherein the aryl group is optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryl(C 1-6 )alkyl (wherein the heteroaryl group is optionally substituted halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), arylcarbonyl-(C 1-6 )alkyl (wherein the aryl group may be optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl,
  • R 8 is more preferably C 1-6 alkyl, C 1-6 haloalkyl, aryl(C 1-4 )alkyl (wherein the aryl group is optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryl(C 1-6 )alkyl (wherein the heteroaryl group is optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), C 2-6 alkenyl, aryl(C 2-6 )alkenyl (wherein the aryl group is optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4
  • R 8 is phenyl(C 1-4 )alkyl (wherein the phenyl group is optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryl(C 1-6 )alkyl (wherein the heteroaryl group is optionally substituted halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), phenyl(C 2-6 )alkenyl (wherein the phenyl group is optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , ary
  • R 8 is phenylCH 2 — (wherein the phenyl group is optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryl CH 2 — (wherein the heteroaryl group is a bicyclic group optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), or —C(R 51 )(R 52 )—[CR 53 ⁇ ]z-R 55 where z is 1 or 2, R 51 and R 52 are each independently H, halo or C 1-2 alkyl, R 53 and R 54 are each independently H, halogen, C 1-4 alkyl or C
  • R 8 is —C(R 51 )(R 52 )—[CR 53 ⁇ CR 54 ]z-R 55 where z is 1 or 2, preferably 1, R 51 and R 52 are each independently H, halo or C 1-2 alkyl, R 53 and R 54 are each independently H, halogen, C 1-4 alkyl or C 1-4 haloalkyl and R 55 is phenyl substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino or heteroaryl substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino
  • R 9 and R 10 are both hydrogen.
  • R 51 and R 52 are preferably hydrogen.
  • R 53 and R 54 are preferably hydrogen or halogen, especially hydrogen.
  • R 55 is preferably phenyl substituted with one to three substituents selected from halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino
  • novel compounds of formula (I) are novel and as such form a further aspect of the invention.
  • novel compounds of formula (IK) as defined above and salts or N-oxides thereof provided that R 8 is not methyl and YR 1 is not SO 2 CH 3 , methyl, ethyl, phenyl or fluoro-substituted phenyl.
  • R 1 is C 1-6 alkyl, C 1-6 haloalkyl, heteroaryl(C 1-3 )alkyl (wherein the heteroaryl group may be optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino and the heteroaryl group is a pyridine, pyrimidine, pyrazine or pyridazine ring), heteroaryl (optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino and where the heteroaryl group is a pyridine, pyridine, pyridine, pyr
  • Table I provides 301 compounds of formula Ia
  • Table II provides 301 compounds of formula Ib wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table III provides 301 compounds of formula Ic wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table IV provides 301 compounds of formula Id wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table V provides 301 compounds of formula Ie wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table VI provides 301 compounds of formula If wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table VII provides 301 compounds of formula Ig wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table VIII provides 301 compounds of formula Ih wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table IX provides 301 compounds of formula Ii wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table X provides 301 compounds of formula Ij wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XI provides 301 compounds of formula Ik wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XII provides 301 compounds of formula Il wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XIV provides 301 compounds of formula In wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XV provides 301 compounds of formula Io wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are give in Table 1
  • Table XVI provides 301 compounds of formula Ip wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XVII provides 301 compounds of formula Iq wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XVIII provides 301 compounds of formula Ir wherein the values of R 8 , R 4a , R 4b , R4 and R 4d are given in Table 1
  • Table XIX provides 301 compounds of formula Is wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XX provides 301 compounds of formula It wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXI provides 301 compounds of formula Iu wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXII provides 301 compounds of formula Iv wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXIII provides 301 compounds of formula Iw wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXIV provides 301 compounds of formula Ix wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXV provides 301 compounds of formula Iy wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXVI provides 301 compounds of formula Iz wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXVII provides 301 compounds of formula Iaa wherein the values of R 8 , R 4a , R 4b , R 4c and R 4d are given in Table 1
  • Table XXVIIl provides 270 compounds of formula Iab
  • Table XXIX provides 214 compounds of formula Iac
  • Table XXX provides 121 compounds of formula Iad (Iad) R 4 n R53 R54 R S n Y R1 XXX-1 6-OCF 3 H H 4-Cl C(O) Me XXX-2 6-OCF 3 H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-3 4-OCF 3 H H 4-Cl C(O) Me XXX-4 6-OCF 2 CHF 2 H H H 4-Cl C(O) Me XXX-5 4-OCF 2 CHF 2 H H H 4-Cl C(O) Me XXX-6 4-OCF 3 H H H 4-Cl C(O) 2-chloropyrid-4-yl XX-7 6-OCF 2 CHF 2 H H H 4-Cl C(O) 2-chloropyrid-4-yl XX-8 4-OCF 2 CHF 2 H H H 4-Cl C(O) 2-chloropyrid-4-yl XX-9 7-O—Ph H H
  • Table XXXI provides 8 compounds of formula Iae (Iae) R 4 n R53 R54 Rt Y R1 XXXI-1 5-Cl H H 5-trifluoromethyl- C(O) 2-chloropyrid- pyrid-2-yl 4-yl XXXI-2 5-F H H 5-chloro- C(O) 2-chloropyrid- thiophen-2-yl 4-yl XXXI-3 5-Cl H H thiophen-2-yl C(O) 2-chloropyrid- 4-yl XXXI-4 5-Cl H H naphtha-2-yl C(O) 2-chloropyrid- 4-yl XXXI-5 5-Cl H H —CH ⁇ CH- C(O) 2-chloropyrid- phenyl 4-yl XXXI-6 5-Cl H H H benzothiophen-2- C(O) 2-chloropyrid- yl 4-yl
  • Table XXXII provides 10 compounds of formula Iaf (Iaf) R 4 n Ru Y R1 XXXII-1 5-Cl 4-F-Ph C(O) 2-chloropyrid-4-yl XXXII-2 5-Cl 4-OCF 3 -Ph C(O) 2-chloropyrid-4-yl XXXII-3 5-Cl 4-Cl-Ph C(O) 2-chloropyrid-4-yl XXXII-4 5-F 6-F-naphth-2-yl C(O) 2-chloropyrid-4-yl XXXII-5 5-Cl —CH(OH)CH 2 O-4-Cl- C(O) 2-chloropyrid-4-yl Ph XXXII-6 5-Cl —C(Me) ⁇ NO-Ph C(O) 2-chloropyrid-4-yl XXII-7 5-Cl 5-Cl-benzoxazol
  • the compounds of the invention may be made in a variety of ways. For example they may be made by the reactions summarised in Scheme I.
  • a compound of formula 1 may be synthesised from compounds of formula 2a or 2b by reaction with an alkylating agent of the formula R8-L, where L is chloride, bromide, iodide or a sulfonate (e.g.
  • mesylate or tosylate or similar leaving group at a temperature of between ambient temperature and 100° C., typically 65° C., in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally catalysed by halide salts such as sodium iodide, potassium iodide or tetrabutylammonium iodide.
  • organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane
  • a tertiary amine base such as triethylamine or diisopropylethylamine
  • halide salts such as sodium iodide, potassium iodide or tetrabutylammonium iodide.
  • a compound of formula 2a or 2b may be reacted with an aldehyde of the formula RCHO at a temperature between ambient temperature and 100° C. in an organic solvent such as tetrahydrofuran or ethanol or mixtures of solvents in the presence of a reducing agent such as borane-pyridine complex, sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or such like, to produce a compound of formula 1 where R8 is CH 2 —R.
  • a reducing agent such as borane-pyridine complex, sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or such like
  • a compound of formula 2a or 2b may be reacted with paraformaldehyde and a boronic acid of the formula R—B(OH) 2 at a temperature between ambient temperature and 1 00° C. in an organic solvent such as ethanol, 1,4dioxane or water to produce a compound of formula 1 where R8 is CH 2 —R.
  • a compound of formula 2a may be obtained from a compound of formula 3 by reaction with an acid such as trifluoroacetic acid at ambient temperature in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane followed by neutralisation of the reaction mixture with an aqueous solution of an inorganic base such as sodium carbonate, sodium bicarbonate or similar compound.
  • an acid such as trifluoroacetic acid at ambient temperature in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane followed by neutralisation of the reaction mixture with an aqueous solution of an inorganic base such as sodium carbonate, sodium bicarbonate or similar compound.
  • a compound of formula 2b may be formed by reaction of a compound of formula 3 with an acid such as trifluoroacetic acid at ambient temperature in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane followed by evaporation of the solvents and trituration with organic solvents such as ether or hexane.
  • an acid such as trifluoroacetic acid
  • organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane
  • Compounds of formula 3 may be obtained from compounds of formula 4 by reaction with a suitable electrophilic species.
  • Compounds of formula 3 where Y is a carbonyl group may be formed by the reaction of compounds of formula 4 with a carboxylic acid derivative of formula R1-C(O)-Z where Z is chloride, hydroxy, alkoxy or acyloxy at a temperature between 0° C. and 150° C.
  • Compounds of formula 3 where Y is a group of formula S(O) q may be formed from compounds of formula 4 by treatment with compounds of formula of R1-S(O) q —Cl under similar conditions.
  • Compounds of formula 3 where Y is a thiocarbonyl group and R1 is an amino substituent of formula R′—NH— may be formed by the reaction of compounds of formula 3 with an isothiocyanate of formula R′—N ⁇ C ⁇ S under similar conditions.
  • compounds of formula 3 where Y is a thiocarbonyl group and R1 is a carbon substituent may be formed by treatment of compounds of formula 3 where Y is a carbonyl group and R1 is a carbon substituent with a suitable thionating agent such as Lawesson's reagent.
  • acid derivatives of the formula R1-C(O)-Z, isocyanates of formula R′—N ⁇ C ⁇ O, isothiocyanates of formula R′—N ⁇ C ⁇ S and sulfur electrophiles of formula R1-S(O) q —Cl are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
  • Compounds of formula 4 may be obtained by reacting compounds of formula 5 with compounds of formula 6 at a temperature of between 0° C. and 100° C. in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of an acid such as hydrochloric acid or trifluoroacetic acid and a co-solvent such as water, methanol or ethanol, or in the presence of a Lewis acidic metal salt such as a zinc(II) dihalide.
  • the intermediates formed (compounds of formula 4a) are subsequently treated with a nucleophile R3-M (where M is a metallic species.
  • R3-M is for example a Grignard reagent) or, when R3 is hydrogen, a reducing agent such as sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or similar at ambient temperature in organic solvent such as ethanol or chloroform.
  • a reducing agent such as sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or similar at ambient temperature in organic solvent such as ethanol or chloroform.
  • Compounds of formula 6 may be obtained from compounds of formula 7 by reaction with a 1-alkoxy substituted phosphonium salt such as methoxymethyl(triphenyl)phosphonium chloride and a base such as potassium tert-butoxide at a temperature of 0° C. to room temperature in tetrahydrofuran.
  • a 1-alkoxy substituted phosphonium salt such as methoxymethyl(triphenyl)phosphonium chloride
  • a base such as potassium tert-butoxide
  • Compounds of formula 5 and 7 are either known compounds or may be obtained from known compounds by known techniques.
  • a compound of formula 1′ may be obtained from a compound of formula 8 by reaction with an acid chloride or chloroformate of the formula R1COCl at a temperature between 0 ° C. and ambient in organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • a compound of formula 1′ may be obtained from a compound of formula 8 by reaction with a carboxylic acid of the formula R1COOH and a standard coupling agent such as 2-chloro-1,3-dimethyl-2-imidazolium hexafluorophosphate, or carbodiimide reagents such as dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at a temperature between 0° C. and ambient in organic solvent such as dichloromethane or tetrahydrofuran in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • a standard coupling agent such as 2-chloro-1,3-dimethyl-2-imidazolium hexafluorophosphate
  • carbodiimide reagents such as dicyclohexylcarbodiimide or 1-(
  • a compound of formula 1′ may alternatively be obtained from a compound of formula 8 by reaction with a isocyanate or isothiocyanate of the formula RNCO or RNCS respectively at a temperature between 0° C. and ambient in organic solvent such as dichloromethane or tetrahydrofuran, optionally in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • a compound of formula 1′ may also be obtained from a compound of formula 8 by reaction with a sulfonyl chloride of the formula R1SO 2 Cl at a temperature between 0° C. and ambient in organic solvent such as dichloromethane or tetrahydrofuran, in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • a compound of formula 1′ may be obtained from a compound of formula 8 by reaction with an aryl or heteroaryl compound of formula Ar-L where L is a leaving group such as halide (especially fluoride), such as a 2-halopyridine, a 2-halopyrimidine, a 4-halopyridine, a 2-halopyrazine or such like at a temperature between 50° C. and 150° C. in a solvent such as dimethylsulfoxide in the presence of a strong base such as sodium hydride.
  • L is a leaving group such as halide (especially fluoride), such as a 2-halopyridine, a 2-halopyrimidine, a 4-halopyridine, a 2-halopyrazine or such like at a temperature between 50° C. and 150° C. in a solvent such as dimethylsulfoxide in the presence of a strong base such as sodium hydride.
  • Compounds of formula 8 may be obtained by reacting compounds of formula 9 with compounds of formula 5 (in scheme I) at a temperature of between ambient and 100° C. in organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of an acid such as trifluoroacetic acid for typically 4 to 12 hours, followed by addition of a reducing agent such as triethylsilane and reaction at a temperature of ambient to 100° C. until the reaction is complete.
  • organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane
  • an acid such as trifluoroacetic acid
  • a reducing agent such as triethylsilane
  • Compounds of formula 8 may be obtained by reacting compounds of formula 9 with compounds of formula 5 at a temperature of between 0° C. and 100° C. in organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of an acid such as hydrochloric acid, or trifluoroacetic acid and a co-solvent of either water or methanol or ethanol, or in the presence of a Lewis acidic metal salt such as zinc(II) dihalide.
  • organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane
  • an acid such as hydrochloric acid, or trifluoroacetic acid
  • a co-solvent of either water or methanol or ethanol or in the presence of a Lewis acidic metal salt such as zinc(II) dihalide.
  • the intermediates formed are subsequently treated with a reducing agent such as sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or such like at ambient temperature in organic solvent such as ethanol or chloroform.
  • a reducing agent such as sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or such like at ambient temperature in organic solvent such as ethanol or chloroform.
  • Compounds of formula 8 may also be obtained by the hydrolysis of compounds of formula 1a (which are also a sub-set of compounds of formula 1) preferably with an aqueous acid, typically 6 N hydrochloric acid at reflux temperature.
  • Compounds of formula 9 may be obtained from compounds of formula 10 by reaction with methoxymethyl(triphenyl)phosphonium chloride or the corresponding bromide salt and a base such as potassium tert-butoxide at a temperature of 0° C. to ambient in tetrahydrofuran.
  • Compounds of formula 10 may be obtained by reacting compounds of formula 11 with an aqueous solution of acid, typically 6 N hydrochloric acid at reflux temperature.
  • Compounds of formula 11 may be obtained from compounds of formula 12 by reaction with an electrophile of the formula R8-L, where L is chloride, bromide, iodide or a sulfonate (e.g. mesylate or tosylate) or similar leaving group at between ambient temperature and 100° C., typically around 60° C.
  • L is chloride, bromide, iodide or a sulfonate (e.g. mesylate or tosylate) or similar leaving group at between ambient temperature and 100° C., typically around 60° C.
  • a tertiary amine base such as triethylamine or diisopropylethylamine and optionally catalysed by halide salts such as sodium iodide, potassium iodide or tetrabutylammonium iodide.
  • Compounds of formula 12 are known compounds or may be obtained from known compounds by known techniques.
  • the compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests.
  • the pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp.
  • the invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest,
  • the compounds of formula (I) are preferably used against insects, acarines or nematodes.
  • plant as used herein includes seedlings, bushes and trees.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting).
  • compositions both solid and liquid formulations
  • the composition is generally used for the control of pests such that a compound of formula (I) is applied at a rate of from 0.1 g to 1 kg per hectare, preferably from 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably 0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.
  • the present invention provides an insecticidal, acaricidal, nematicidal or molluscicidal composition
  • an insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.
  • the composition is preferably an insecticidal, acaricidal, nematicidal or molluscicidal composition.
  • the invention provides a method of combating and controlling pests at a locus which comprises treating the pests or the locus of the pests with an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a composition comprising a compound of formula (I).
  • the compounds of formula (I) are preferably used against insects, acarines or nematodes.
  • compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations.
  • the l0 formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -C 10 fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as cycl
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane).
  • a compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment.
  • a compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • a compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • the preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.
  • Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- and tri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • alkylphenols such as octylphenol, nonyl
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pests
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components.
  • suitable pesticides include the following:
  • pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • acaricidal ovo-larvicides such as clofentezine, flubenzimine, hexythiazox or tetradifon
  • acaricidal motilicides such as dicofol or propargite
  • acaricides such as bromopropylate or chlorobenzilate
  • growth regulators such
  • fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide, ⁇ -[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]- ⁇ -butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N—(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281, zoxamide), N-allyl4,5,-dimethyl-2-
  • the compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
  • synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • An example of a rice selective herbicide which may be included is propanil.
  • An example of a plant growth regulator for use in cotton is PIXTM.
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • Step 1 Preparation of 4-methoxymethylenepiperidine-1-carboxylic acid tert-butyl ester
  • Step 2 Preparation of 5-chlorospiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester
  • Trifluoroacetic acid (12 ml) was added to a stirred solution of 4-methoxymethylene-piperidine-1-carboxylic acid tert-butyl ester (12.5 g), 4-chlorophenylhydrazine hydrochloide (9.75 g) and ethanol (1 ml) in chloroform (1200 ml) at 4° C. under an atmosphere of nitrogen. The mixture was then stirred at 50° C. overnight, turning a dark green colour. The reaction was quenched with concentrated ammonia solution (200 ml) in ice water (500 ml), the organic layer turning orange. The organic layer was separated and the aqueous was further extracted twice with dichloromethane.
  • Step 3 Preparation of 1-acetyl-5-chlorospiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester
  • Trifluoroacetic acid 25 ml was added to a stirred solution of 1-acetyl-5-chlorospiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester (8 g) in anhydrous dichloromethane (250 ml) under an atmosphere of nitrogen. The reaction was left as such for 3 h. The reaction was washed with saturated bicarbonate solution (200 ml) and dried over sodium sulphate and concentrated in vacuo to yield an off white solid.
  • Step 5 Preparation of 1-acetyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Step 1 1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester
  • Step 2 preparation of 1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]trifluoroacetic acid salt
  • Trifluoroacetic acid (30 ml) was added to a solution of solution of 1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester (2.3 g) in anhydrous dichloromethane (50 ml), the solution darkening upon addition. The reaction was left as such for 15 min. The reaction mixture was evaporated in vacuo and the dark residue re-suspended in dry ether (100 ml). The residue was triturated until it became a free-flowing beige precipitate.
  • Step 3 Preparation of 1-(2-chloropyridin-4-yl)carbonyl-1′-[trans-3-phenylallyl]spiro[indoline-3,4′-piperidine]
  • Step 1 Preparation of 5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Step 2 Preparation of 1-(pyridin-4-yl)carbonyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Step 1 Preparation of 8-[trans-3-(4-chlorophenyl)allyl]-1,4-dioxa-8-azaspiror4.5]decane
  • 1,4-Dioxa-8-azaspiro[4.5]decane (0.88 g) was dissolved in chloroform (5 ml) and diisopropylethylamine (2.1 ml) was added. A solution of 4-chlorocinnamyl chloride (1.2 g) dissolved in chloroform (2 ml) was added and mixture was heated to 70° C. overnight. The solvents were evaporated in vacuo and flash chromatography [SiO 2; ethyl acetate-hexane-triethylamine (50:50:2)] yielded 1.38 g (76%) of the desired ketal as a yellow oil.
  • Methoxymethyltriphenylphosphonium chloride (2.4 g) was dissolved in tetrahydrofuran (20 ml) and was cooled to 4° C. Potassium tert-butoxide (0.78 g) was added, turning the solution a bright orange colour. The reaction was left as such for 30 min. A solution of 1-[trans-3-(4-chlorophenyl)allyl]-4-oxopiperidine (0.85 g) dissolved in tetrahydrofuran (10 ml) was added and the mixture was stirred for 10 min. The solvents were evaporated in vacuo and the residue re-suspended in ether. The organics were washed with water and dried over anhydrous magnesium sulfate.
  • Step 4 Preparation of 5-methyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Trifluoroacetic acid (0.75 ml) was added to a stirred solution of 1-[trans-3-(4-chlorophenyl)allyl]-4-methoxymethylenepiperidine-and 4-tolylhydrazine hydrochloride (28 mg) in chloroform (5 ml) and the reaction was heated to 50° C. for 5 h.
  • Triethylsilane (2 ml) was added and the reaction was heated at 50° C. for a further 5 h. The mixture was allowed to cool and was quenched in concentrated ammonia solution/ice chips (20 ml).
  • Step 5 Preparation of 1-(4-cyanobenzoyl)-5-methyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • This step was achieved using a Zymark XP2 synthetic chemistry robot.
  • a solution of 5-methyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (2 ml of a solution derived from dissolving 1.43 g in 100 ml of THF) was added to a robot tube and the solvent was removed in vacuo.
  • 4-Cyanobenzoic acid 28 mg was weighed into a different robot tube.
  • Compounds XXIX-201, I-282, I-232 were prepared according to standard procedures analogous to those described in Example 7.
  • Compound XXV-222 was prepared by treating compound XXIX-201 with potassium carbonate in methanol.
  • Compound I-222 was prepared by re-acylation of compound XXV-222 under standard conditions.
  • Step 1 Preparation of (E)-3-(4-trifluoromethyl-phenyl)-acrylic acid ethyl ester
  • step 1 To a solution of the ester obtained in step 1 (37.1 g) in toluene (310 ml) at 0° C. was added dropwise diisobutylaluminium hydride (1.2M in toluene, 317 ml) and the solution was stirred at 0° C. for 1 h. Water (47.6 ml) was carefully added at 0° C. followed by sodium hydroxide 2M (47.6 ml) and finally water (95.1 ml). The mixture was allowed to stir at room temperature for 1 h.
  • diisobutylaluminium hydride 1.2M in toluene, 317 ml
  • step 2 To a solution of the alcohol obtained in step 2 (10 g) in dimethylacetamide (100 ml) at room temperature were added triphenylphosphine (23 g) and carbon tetrabromide (29 g). The resulting solution was stirred at room temperature for 1 h, poured into water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried over sodium sulfate and filtered over silica gel to give 13 g of the desired product as a white solid (95%) which was characterized by its mass and NMR spectra.
  • Step 4 Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(E)-3-(4-trifluoromethyl-phenyl)allyl]spiro[indolin-3,4′-piperidine]
  • Step 1 Preparation of (Z)-3-(4-chloro-phenyl)-2-fluoro-acrylic acid methyl ester
  • 4-Chlorobenzaldehyde (0.66 g) was added to a suspension of diethylfluorooxalacetate, sodium salt (1 g, prepared from diethyl oxalate, ethylfluoroacetate and sodium hydride according to Alberg et al. J. Am. Chem. Soc. 1992, 3542) in tetrahydrofuran (20 ml) at 0° C., and the resulting: mixture was stirred 1 h at 0° C. then 3 h at 80° C.
  • reaction mixture was concentrated in vacuo, diluted with diethyl ether, washed with aqueous sodium bicarbonate, water and brine, dried over sodium sulfate and concentrated in vacuo to afford a crude residue (1.2 g) which was used diretly in the next step.
  • Step 4 Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-2-fluoro-allyl]spiro[indolin-3,4′-piperidine]
  • Step 2 to 4 were carried out following the procedure described in Example 8, step 2-4 to give 0.17 g of the desired product (41%) which was characterized by its mass and NMR spectra. MS (ES+) 530.
  • Step 3 Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[trans-3-(4-methoxy-phenyl)allyl]spiro[indolin-3,4′-piperidine]
  • Step 1 Preparation of (Z)-3-chloro-3-(4-chloro-phenyl)-acrylic acid methyl ester
  • step 2 (Z)-3-chloro-3-(4-chloro-phenyl)-acrylic acid methyl ester ( 462 mg) was converted into the desired product (391 mg, 96%) which was characterized by its mass and NMR spectra.
  • Step 4 Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-3-chloro-allyl]spiro[indolin-3,4′-piperidine]
  • Step 1 Preparation of (Z)-3-(4-Chloro-phenyl)-3-fluoro-acrylic acid methyl ester
  • Step 4 Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-3-fluoro-allyl]spiro[indolin-3,4′-piperidine]
  • Step 2 to 4 were carried out following the procedure described in Example 11, step 2-4 to give 163 mg of the desired product (42%) which was characterized by its mass and NMR spectra. MS (ES+) 531.
  • Step 1 Preparation of Compound XXX-121. 1-nitroso-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Step 2 Preparation of 1-amino-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Step 3 Preparation of 1-carboxylic acid (4-chloro-phenyl)-amide-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Standard wash will refer to the following washing sequence: dimethylformamide, dichloromethane, dimethylformamide, dichloromethane, methanol, dichloromethane, methanol (X2), tert-butyl methyl ether (X2) and resin swelling protocol will be based on a standard of 10 ml of solvent per gram of resin.
  • Compound identities and purities were determined using High Performance Liquid Chromatography lo coupled Mass Spectrometry (HPLC-MS) and Proton Nuclear Magnetic Resonance (1H NMR) on selected compounds.
  • REM resin was prepared from commercially available (hydroxymethyl)polystyrene resin and acryloyl chloride. The loading of the resins were assumed to be constant at 1.2 mmolg ⁇ 1 throughout the synthesis.
  • Step A Loading of 4-Formylpiperidine dimethyl acetal onto REM resin (Resin A)
  • Step D Preparation of Solid supported 1,2-Dihydro-spiro[3H-indole-3,4′-piperidine] (Resin D)
  • Step E Preparation of Solid supported 1,2-Dihydro-1-(4-nitrobenzoyl)-spiro[3H-indole-3,4′-piperidine] (Resin E)
  • Resin D (0.5 g, 0.6 mmol) was swollen in anhydrous dichloromethane (5 ml). To the mixture was added 4-nitrobenzoyl chloride (0.33 g, 1.8 mmol) and N,N-diisopropylethylamine (0.42 ml, 2.4 mmol). After shaking at room temperature for 18 hours, the resin was filtered, washed according to the standard wash cycle and dried in vacuo to afford 0.53 g of the desired resin E.
  • Step F Quaternization of Solid supported 1,2-Dihydro-1-(4-nitrobenzoyl)-spiro[3H-indole-3,4′-piperidine] (Resin F)
  • Step G Preparation of 1,2-Dihydro-1-(4-nitrobenzoyl)-1′-(3-phenyl-2-propenyl)-spiro[3H-indole-3,4′-piperidine]
  • This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I).
  • Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with 5 L 1 larvae. The samples were checked for mortality, repellent effect, feeding behaviour, and growth regulation 3 days after treatment (DAT).
  • Eggs (0-24 h old) were placed in 24-well microtiter plate on artificial diet and treated with test solutions at an application rate of 200 ppm by pipetting. After an incubation period of 4 days, samples were checked for egg mortality, larval mortality, and growth regulation.
  • MTP microtiter plate
  • Bean leaf discs on agar in 24-well microtiter plates were sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality. The following compounds gave at least 80% control of Tetranychus urticae:
  • Aedes larvae (L2) together with a nutrition mixture are placed in 96-well microtiter plates. Test solutions at an application rate of 2ppm are pipetted into the wells. 2 days later, insects were checked for mortality and growth inhibition. The following compounds gave at least 80% control of Aedes aegypti

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Abstract

Insecticidal, acaricidal, nematicidal or molluscicidal compounds of formula (I) wherein Y is a single bond, C═O, C═S or C═(O)q where q is 0, 1 or 2; and R1, R2, R3, R4, R8, R9 and R10 are as defined in the claims or salts or N-oxides thereof, processes for preparing them and compositions containing them.
Figure US20060106045A1-20060518-C00001

Description

  • The present invention relates to spiroindoline derivatives, to processes for preparing them, to insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
  • Spiroindoline derivatives with pharmaceutical properties are disclosed in for example WO9825605, WO9429309, WO9828297 and WO9964002. Synthetic routes to selected compounds with pharmaceutical properties are described in Proc. Natl. Acad. Sci. USA (1995), 92, 7001, Tetrahedron (1997), 53, 10983 and Tetrahedron Letters (1997), 38, 1497. It has now surprisingly been found that certain spiroindolines have insecticidal properties.
  • The present invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I):
    Figure US20060106045A1-20060518-C00002
    wherein Y is a single bond, C═O, C═S or S(O)q where q is 0, 1 or 2; R1 is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted heterocyclyloxy, cyano, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, formyl, optionally substituted heterocyclyl, optionally substituted alkylthio, NO or NR13R14 where R13 and R14 are independently hydrogen, COR40, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl or R13 and R14 together with the N atom to which they are attached form a group —N═C(R41)—NR42R43; R2 and R3 are independently hydrogen, halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl or C(O)NR15R16 where R15 and R16 are independently hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl, or R2 and R3 together are ═O, or R2 and R3 together with the atoms to which they are attached form a 4, 5, 6, or 7 membered carbocyclic or heterocyclic ring; each R4 is independently halogen, nitro, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted C3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio or R19R20N where R19 and R20 are, independently, hydrogen, C1-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C3-7 cycloalkyl(C1-4)alkyl, C2-6 haloalkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1-6 alkyl groups, or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4; R8 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; R9 and R10 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl or R9 and R10 together form a group —CH2—, CH═CH— or —CH2CH2—; R40 is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy optionally substituted heteroaryl, optionally substituted heteroaryloxy or NR44R45; R41 , R42 and R43 are each independently H or lower alkyl; R44 and R45 are independently optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl or salts or N-oxides thereof
  • The compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • Each alkyl moiety either alone or as part of a larger group (such as alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or neo-pentyl.
  • When present, the optional substituents on an alkyl moiety (alone or as part of a larger group such as alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) include one or more of halogen, nitro, cyano, NCS—, C3-7 cycloalkyl (itself optionally substituted with C1-6 alkyl or halogen), C5-7 cycloalkenyl (itself optionally substituted with C1-6 alkyl or halogen), hydroxy, C1-10 alkoxy, C1-10 alkoxy(C1-10)alkoxy, tri(C1-4)alkylsilyl(C1-6)alkoxy, C1-6 alkoxycarbonyl(C1-10)alkoxy, C1-10 haloalkoxy, aryl(C1-4)-alkoxy (where the aryl group is optionally substituted), C3-7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), C2-10 alkenyloxy, C2-10 alkynyloxy, SH, C1-10 alkylthio, C1-10 haloalkylthio, aryl(C1-4)alkylthio (where the aryl group is optionally substituted), C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), tri(C1-4)alkylsilyl(C1-6)alkylthio, arylthio (where the aryl group is optionally substituted), C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group may be optionally substituted), tri(C1-4)alkylsilyl, aryldi(C1-4)alkylsilyl, (C1-4)alkyldiarylsilyl, triarylsilyl, C1-10 alkylcarbonyl, HO2C, C1-10 alkoxycarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6 alkyl)aminocarbonyl, N—(C1-3 alkyl)-N—(C1-3 alkoxy)aminocarbonyl, C1-6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C1-6)alkylaminocarbonyloxy, oximes such as ═NOalkyl, ═NOhaloalkyl and ═NOaryl (itself optionally substituted), aryl (itself optionally substituted), heteroaryl (itself optionally substituted), heterocyclyl (itself optionally substituted with C1-6 alkyl or halogen), aryloxy (where the aryl group is optionally substituted), heteroaryloxy, (where the heteroaryl group is optionally substituted), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C1-6 alkyl or halogen), amino, C1-6 alkylamino, di(C1-6)alkylamino, C1-6 alkylcarbonylamino, N—(C1-6)alkylcarbonyl-N—(C1-6)alkylamino, C2-6 alkenylcarbonyl, C2-6 alkynylcarbonyl, C3-6 alkenyloxycarbonyl, C3-6 alkynyloxycarbonyl, aryloxycarbonyl (where the aryl group is optionally substituted) and arylcarbonyl (where the aryl group is optionally substituted).
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E) or (Z)-configuration. Examples are vinyl, allyl and propargyl.
  • When present, the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.
  • In the context of this specification acyl is optionally substituted C1-6 alkylcarbonyl (for example acetyl), optionally substituted C2-6 alkenylcarbonyl, optionally substituted C2-6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF3, CF2Cl, CF3CH2 or CHF2CH2.
  • In the context of the present specification the terms “aryl” and “aromatic ring system” refer to ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl. In addition, the terms “heteroaryl”, “heteroaromatic ring” or “heteroaromatic ring system” refer to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur. Examples of such groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl. Preferred examples of heteroaromatic radicals include pyridyl, pyrimidyl, triazinyl, thienyl, furyl, oxazolyl, isoxazolyl, and thiazolyl.
  • The terms heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1,3-dioxolane, tetrahydrofuran and morpholine.
  • When present, the optional substituents on heterocyclyl include C1-6 alkyl and C1-6 haloalkyl as well as those optional substituents given above for an alkyl moiety.
  • Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
  • Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
  • When present, the optional substituents on cycloalkyl or cycloalkenyl include C1-3 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
  • When present, the optional substituents on aryl or heteroaryl are selected independently, from halogen, nitro, cyano, NCS—, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy-(C1-6)alkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl (itself optionally substituted with C1-6 alkyl or halogen), C5-7 cycloalkenyl (itself optionally substituted with C1-6 alkyl or halogen), hydroxy, C1-10 alkoxy, C1-10 alkoxy(C1-10)alkoxy, tri(C1-4)alkyl-silyl(C1-6)alkoxy, C1-6 alkoxycarbonyl(C1-10)alkoxy, C1-10 haloalkoxy, aryl(C1-4)alkoxy (where the aryl group is optionally substituted with halogen or C1-6 alkyl), C3-7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), C2-10 alkenyloxy, C2-10 alkynyloxy, SH, C1-10 alkylthio, C1-10 haloalkylthio, aryl(C1-4)alkylthio C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), tri(C1-4)-alkylsilyl(C1-6)alkylthio, arylthio, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, arylsulfonyl, tri(C1-4)alkylsilyl, aryldi(C1-4)-alkylsilyl, (C1-4)alkyldiarylsilyl, triarylsilyl, C1-10 alkylcarbonyl, HO2C, C1-10 alkoxycarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6 alkyl)-aminocarbonyl, N—(C1-3 alkyl)-N—(C1-3 alkoxy)aminocarbonyl, C1-6 alkylcarbonyloxy, arylcarbonyloxy, di(C1-6)alkylamino-carbonyloxy, aryl (itself optionally substituted with C1-6 alkyl or halogen), heteroaryl (itself optionally substituted with C1-6 alkyl or halogen), heterocyclyl (itself optionally substituted with C1-6 alkyl or halogen), aryloxy (where the aryl group is optionally substituted with C1-6 alkyl or halogen), heteroaryloxy (where the heteroaryl group is optionally substituted with C1-6 alkyl or halogen), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C1-6 alkyl or halogen), amino, C1-6 alkylamino, di(C1-6)alkylamino, C1-6 alkylcarbonylamino, N—(C1-6)alkylcarbonyl-N—(C1-6)alkylamino, arylcarbonyl, (where the aryl group is itself optionally substituted with halogen or C1-6 alkyl) or two adjacent positions on an aryl or heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen or C1-6 alkyl. Further substituents for aryl or heteroaryl include aryl carbonyl amino (where the aryl group is substituted by C1-6 alkyl or halogen), (C1-6)alkyloxycarbonylamino (C1-6)alkyloxycarbonyl-N—(C1-6)alkylamino, aryloxycarbonylamino (where the aryl group is substituted by C1-6 alkyl or halogen), aryloxycarbonyl-N—(C1-6)alkylamino, (where the aryl group is substituted by C1-6 alkyl or halogen), arylsulphonylamino (where the aryl group is substituted by C1-6 alkyl or halogen), arylsulphonyl-N—(C1-6)alkylamino (where the aryl group is substituted by C1-6 alkyl or halogen), aryl-N—(C1-6)alkylamino (where the aryl group is substituted by C1-6 alkyl or halogen), arylamino (where the aryl group is substituted by C1-6 alkyl or halogen), heteroaryl amino (where the heteroaryl group is substituted by C1-6 alkyl or halogen), heterocyclylamino (where the heterocyclyl group is substituted by C1-6 alkyl or halogen), aminocarbonylamino, C1-6 alkylaminocarbonyl amino, di(C1-6)alkylaminocarbonyl amino, arylaminocarbonyl amino where the aryl group is substituted by C1-6 alkyl or halogen), aryl-N—(C1-6)alkylaminocarbonylamino where the aryl group is substituted by C1-6 alkyl or halogen), C1-6 alkylaminocarbonyl-N—(C1-6)alkyl amino, di(C1-6)alkylaminocarbonyl-N—(C1-6)alkyl amino, arylaminocarbonyl-N—(C1-6)alkyl amino (where the aryl group is substituted by C1-6 alkyl or halogen) and aryl-N—(C1-6)alkylaminocarbonyl-N—(C1-6)alkyl amino (where the aryl group is substituted by C1-6 alkyl or halogen).
  • For substituted phenyl moieties, heterocyclyl and heteroaryl groups it is preferred that one or more substituents are independently selected from halogen, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylthio, C1-6 haloalkylthio, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, nitro, cyano, CO2H, C1-6 alkylcarbonyl, C1-6 alkoxycarbonyl, R31R32N or R33R34NC(O); wherein R31, R32, R33 and R34 are, independently, hydrogen or C1-6 alkyl. Further preferred substituents are amino, dialkylamino, aryl and heteroaryl groups.
  • Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms
  • It is to be understood that dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (C1-6)alkyl groups. When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C1-6) alkyl groups.
  • Preferably the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO2C, C1-10 alkoxy (itself optionally substituted by C1-10 alkoxy), aryl(C1-4)alkoxy, C1-10 alkylthio, C1-10 alkylcarbonyl, C1-10 alkoxycarbonyl, C1-6 alkylaminocarbonyl, di(C1-6 alkyl)aminocarbonyl, (C1-6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C3-7 cycloalkyl (itself optionally substituted with (C1-6)alkyl or halogen), C3-7 cycloalkyloxy, C5-7 cycloalkenyl, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, tri(C1-4)alkylsilyl, tri(C1-4)alkylsilyl(C1-6)alkoxy, aryldi(C1-4)alkylsilyl, (C1-4)alkyldiarylsilyl and triarylsilyl.
  • Preferably the optional substituents on alkenyl or alkynyl include one or more of halogen, C3-7 cycloalkyl and aryl; the aryl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino.
  • A preferred optional substituent for heterocyclyl is C1-6 alkyl.
  • Preferably the optional substituents for cycloalkyl include halogen, cyano and C1-3 alkyl.
  • Preferably the optional substituents for cycloalkenyl include C1-3 alkyl, halogen and cyano.
  • One group of preferred compounds are those of formula (IA) which are compounds of formula (I) wherein Y is a single bond, C═O, C═S or S(O)q where q is 0, 1 or 2; R1 is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted heterocyclyloxy, cyano, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, formyl, optionally substituted heterocyclyl, optionally substituted alkylthio or NR13R14 where R13 and R14 are independently hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl; R2 and R3 are independently hydrogen, halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl or C(O)NR15R16 where R15 and R16 are independently hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl, or R2 and R3 together are ═O, or R2 and R3 together with the atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring; each R4 is independently halogen, nitro, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted C3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio or R19R20N where R19 and R20 are, independently, hydrogen, C1-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C3-7 cycloalkyl(C1-4)alkyl, C2-6 haloalkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1-6 alkyl groups, or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4; R8 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; R9 and R10 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl or R9 and R10 together form a group —CH2—, —CH═CH— or —CH2CH2—; or salts or N-oxides thereof.
  • Another group of preferred compounds are those of formula (IB) which are compounds of formula (I) wherein Y is a single bond, C═O or S(O)q where q is 0, 1 or 2; R1 is hydrogen, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C5-6 cycloalkenyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl-(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)-alkyl, C1-6 alkylthio(C1-6)alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)-alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkyl-aminocarbonyl, phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, aryloxy (wherein the aryl group may be optionally substituted with halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryloxy (wherein the heteroaryl group may be optionally substituted with halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), cyano, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, aminocarbonyl-(C2-6)alkenyl, C1-6 alkylaminocarbonyl(C2-6)alkenyl, di(C1-6)alkylaminocarbonyl(C2-6)alkenyl, phenyl(C2-4)alkenyl, (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkynyl, aminocarbonyl(C2-6)-alkynyl, C1-6 alkylaminocarbonyl(C2-6)-alkynyl, di(C1-6)alkylaminocarbonyl(C2-6)alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7, cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl-(C3-7)halocycloalkyl, C5-6 cycloalkenyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkylthio, or R13R14N where R13 and R14 are independently hydrogen, COR40, C1-6 alkyl, aryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl amino or dialkylamino), heteroaryl (optionally substituted by halogen or C1-3 alkyl) or R13 and R14 together with the N atom to which they are attached form a group —N═C(R41)—NR42R43 where R41, R42 and R43 are independently H or C1-4 lower alkyl; R2 and R3 are independently hydrogen, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or cyano; each R4 is independently halogen, nitro, cyano, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-6)alkyl (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, C3-7 cycloalkyl, phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkoxy, C1-8 haloalkoxy, aryloxy (where the aryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (where the heteroaryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); n is 0, 1, 2, 3 or 4; R8 is C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or —C(R51)(R52)—[CR53═CR54]z—R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is aryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamin); R9 and R10 are independently hydrogen, C1-2 alkyl or halogen; R40 is H, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, phenoxy (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C11-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), heteroaryloxy (wherein the heteroaryl group may be optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy) or NR44R45 where R44 and R45 are independently C1-6 alkyl (optionally substituted with halogen, nitro, cyano, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), phenyl (optionally substituted with halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryl (optionally substituted with halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy) and salts or N-oxides thereof.
  • A further group of preferred compounds are those of formula (IC) which are compounds of formula (I) wherein Y is a single bond, C═O or S(O)q where q is 0, 1 or 2; R1 is hydrogen, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C5-6 cycloalkenyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl-(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)-alkyl, C1-6 alkylthio(C1-6)alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)-alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, phenyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, aryloxy (wherein the aryl group may be optionally substituted with halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy),heteroaryloxy (wherein the heteroaryl group may be optionally substituted with halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy),cyano, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, aminocarbonyl-(C2-6)alkenyl, C1-6 alkylaminocarbonyl(C2-6)alkenyl, di(C1-6)alkylaminocarbonyl(C2-6)alkenyl, phenyl(C2-4)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkynyl, aminocarbonyl(C2-6)-alkynyl, C1-6 alkylaminocarbonyl(C2-6)alkenyl, di(C1-6)alkylaminocarbonyl(C2-6)alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl-(C3-7)halocycloalkyl, C5-6 cycloalkenyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkylthio, or R13R14N where R13 and R14 are independently hydrogen, C1-6 alkyl, aryl (optionally substituted by halogen, C1,3 alkyl, nitro, cyano, C1-3 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy) or heteroaryl (optionally substituted by halogen or C1-3 alkyl); R2 and R3 are independently hydrogen, C1-6 alkyl, C1-6haloalkyl, C1-6alkoxy or cyano; each R4is independently halogen, nitro, cyano, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl-(C1-6)alkyl, phenyl(C1-6)alkyl (wherein the phenyl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, C3-7 cycloalkyl, phenyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkoxy, C1-8 haloalkoxy, aryloxy (where the aryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy) or heteroaryloxy (where the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy); n is 0, 1, 2, 3 or 4; R8 is C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy) or C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy); R9 and R10 are independently hydrogen, C1-2 alkyl or halogen; and salts or N-oxides thereof.
  • Another group of preferred compounds are those of formula (ID) which are compounds of formula (I) wherein Y is a single bond or C═O; R1 is hydrogen, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C5-6 cycloalkenyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl-(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)-alkyl, C1-6 alkylthio(C1- 6)alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)-alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group maybe substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, aryloxy (wherein the aryl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino),heteroaryloxy (wherein the heteroaryl group may be optionally substituted with halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy),cyano, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, aminocarbonyl-(C2-6)alkenyl, C1-6 alkylaminocarbonyl(C2-6)alkenyl, di(C1-6)alkylaminocarbonyl(C2-6)alkenyl, phenyl(C2-4)alkenyl, (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkynyl, aminocarbonyl(C2-6)-alkynyl, C1-6 alkylaminocarbonyl(C2-6)alkynyl, di(C1-6)alkylaminocarbonyl(C2-6)alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl-(C3-7)halocycloalkyl, C5-6 cycloalkenyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkylthio, or R13R14N where R13 and R14 are independently hydrogen, COR40, C1-6 alkyl, aryl (optionally substituted by halogen, C1-3 alkyl, nitro, cyano, C1-3 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl (optionally substituted by halogen or C1-3 alkyl); R2 and R3 are independently hydrogen or methyl, preferably both ydrogen; each R4 is independently halogen, nitro, cyano, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-6)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl-(C1-6)alkyl (wherein the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, C2-6 akynyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, C3-7 cycloalkyl, phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkoxy, Cis haloalkoxy, aryloxy (where the aryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (where the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy); n is 0, 1, 2, 3 or 4; R8 is C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), heteroaryl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); or —C(R51)(R52)—[CR53=CR54]z—R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is aryl (optionally substituted by halogen, C1-4alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); R9 and R10 are both hydrogen; R40 is H, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, phenoxy (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) and salts or N-oxides thereof.
  • Yet another group of preferred compounds are those of formula (IE), which are compounds of formula (I) wherein Y, R1, R2, R3, R4, R8 and n are as defined for compounds of formula IC; R9 and R10 are independently hydrogen, C1-2 alkyl or halogen, and preferably all are hydrogen; and salts or N-oxides thereof.
  • A further group of preferred compounds are those of formula (IF), which are compounds of formula (I) wherein Y, R1, R4, R8, R9, R10 and n are as defined for compounds of formula (IE) and R2 and R3 are independently hydrogen, halogen, C1-2 alkyl, C1-2 haloalkyl, C1-2 alkoxy, cyano, or R2 and R3 together are ═O, or R2 and R3 together with the atoms to which they are attached form a 4, 5, 6, or 7 membered carbocylic or heterocyclic ring; and salts or N-oxides thereof.
  • Yet another group of preferred compounds are those of formula (IG), which are compounds of formula () wherein Y, R1, R2, R3, R8, R9, R10 and n are as defined for compounds of formula (IF) and each R4 is independently halogen, nitro, cyano, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-6)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-4 haloalkoxy, CN, or NO2), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkyl-aminocarbonyl, C3-7 cycloalkyl, phenyl (optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-4 haloalkoxy, CN, or NO2), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkoxy, C1-8 haloalkoxy, aryloxy (where the aryl group is optionally substituted by halogen, C1-6 alkyl, C,6 alkoxy, C, haloalkyl, C1-4 haloalkoxy, CN, or NO2) or heteroaryloxy (where the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy); and salts or N-oxides thereof.
  • A further group of preferred compounds are those of formula (IG′), which are compounds of formula (I) wherein Y, R1, R2, R3, R8, R9, R10 and n are as defined for compounds of formula (IB) and each R4 is independently halogen, nitro, cyano, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-6)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkyl-aminocarbonyl, C3-7 cycloalkyl, phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkoxy, C1-8 haloalkoxy, phenoxy (where the phenyl group is optionally substituted by halogen, C1-6 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (where the heteroaryl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy); and salts or N-oxides thereof.
  • Another group of preferred compounds are those of formula (IH), which are compounds of formula (I) wherein R2, R3, R4, R8, R9, R10 and n are as defined for compounds of formula (IG) and Y is a single bond or C═O; R1 is C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C5-6 cycloalkenyl(C1-6)alkyl, C1-6 alkoxy(C1-6)-alkyl, C3-6 alkenyloxy(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)-alkyl, C3-6 alkynyl-oxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-4 haloalkoxy, CN, or NO2), heteroaryl(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)-alkylaminocarbonyl, phenyl (optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-4 haloalkoxy, CN, or NO2), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, aryloxy (where the arylyl group may be optionally substituted halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-4 haloalkoxy, CN, or NO2), cyano, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, aminocarbonyl(C2-6)alkenyl, C1-6 alkylaminocarbonyl(C2-6)-alkenyl, di(C1-6)alkyl-aminocarbonyl(C2-6)alkenyl, phenyl(C2-4)alkenyl, (wherein the phenyl group is optionally substituted halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-4 haloalkoxy, CN, or NO2), C2-6 alkynyl, aminocarbonyl(C2-6)alkynyl, alkylaminocarbonyl(C2-6)alkynyl, di(C1-6)alkylamino-carbonyl(C2-6)alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl(C3-7)halocycloalkyl, C5-6 cycloalkenyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkylthio or R13R14N where R13 and R14 are independently hydrogen, C1-6 alkyl, aryl (optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, C1-4 haloalkoxy, CN, or NO2) or heteroaryl (optionally substituted by halogen or C1-3 alkyl); and salts or N-oxides thereof.
  • Another group of preferred compounds are those of formula (IH′), which are compounds of formula (I) wherein R2, R3, R4, R8, R9, R10 and n are as defined for compounds of formula (IG′) and R1 is C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C5-6 cycloalkenyl(C1-6)alkyl, C1-6 alkoxy(C1-6)-alkyl, C3-6 alkenyloxy(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)-alkyl, C3-6 alkynyl-oxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl-(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)-alkylaminocarbonyl, phenyl (optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, aryloxy (where the aryl group may be optionally substituted with halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), cyano, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, aminocarbonyl(C2-6)alkenyl, C1-6 alkylaminocarbonyl(C2-6)-alkenyl, di(C1-6)alkyl-aminocarbonyl(C2-6)alkenyl, phenyl(C2-4)alkenyl, (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkynyl, aminocarbonyl(C2-6)alkynyl, alkylaminocarbonyl(C2-6)alkynyl, di(C1-6)alkylamino-carbonyl(C2-6)alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl(C3-7)halocycloalkyl, C5-6 cycloalkenyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkylthio or R13R14N where R13 and R14 are independently hydrogen, C1-6 alkyl, COR40, where C1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), amino, C1-6 alkylamino, phenylamino (wherein the phenyl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino)and salts or N-oxides thereof.
  • A further group of preferred compounds are those of formula (IJ), which are compounds of formula (I) wherein Y, R1, R2, R3, R4, R9, R10 and n are as defined for compounds of formula (IH) and R8 is C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy) or C2-6 alkyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy); and salts or N-oxides thereof.
  • A further group of preferred compounds are those of formula (IJ′), which are compounds of formula (I) wherein Y, R1, R2, R3, R4, R9, R10 and n are as defined for compounds of formula (IH′) and R8 is C1-6 alkyl optionally substituted by phenyl or heteroaryl (the phenyl and heteroaryl groups being optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); or —C(R51)(52)—[CR53═CR54]zR55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is aryl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, or heteroaryl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino.
  • Yet another preferred group of compounds are those of formula (IK), which are compounds of formula (I) wherein Y is a single bond, C═O or S(O)q where q is 0, 1 or 2; R1 is C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy-(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)-alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)-alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), phenyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy) or C1-6 alkylthio; R2 and R3 are independently hydrogen or C1-4 alkyl; each R4 is independently halogen, cyano, C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy) or C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy); n is 0, 1, 2, 3 or 4; R8 is C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy) or C2-6 alkyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy); R9 and R10 are both hydrogen; and salts or N-oxides thereof.
  • Yet another preferred group of compounds are those of formula (IL), which are compounds of formula (I) wherein Y is a single bond or C═O; R1 is C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy-(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)-alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)-alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl-(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy) or C1-6 alkylthio, C1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), amino, C1-6 alkylamino, phenylamino (wherein the phenyl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); R2 and R3 are independently hydrogen or C1-4 alkyl; each R4 is independently halogen, cyano, C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); n is 0, 1, 2, 3 or 4; R8 is C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), or —C(R51)(R52)—[CR53═CR54)z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is phenyl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino or heteraryl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl amino or dialkylamino; R40 is H, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, phenoxy (wherein the phenyl group may be optionally substituted with halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); R9 and R10 are both hydrogen or methyl; and salts or N-oxides thereof.
  • An even more preferred group of compounds are those of formula (IM), which are compounds of formula (I) wherein Y is a single bond or C═O; R1 is C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy-(C1-6)-alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl-(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)-alkyl, C3-6 alkynyloxycarbonyl (C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)-alkyl, C1-6 alkylsulfinyl(C1-6)-alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)-alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy) or C1-6 alkylthio, C1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), amino, C1-6 alkylamino, phenylamino (wherein the phenyl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); R2 and R3 are independently hydrogen or methyl, preferably both hydrogen; each R4 is independently halogen, cyano, C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkenyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); n is 0, 1, 2, 3 or 4; R8 is phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-4)alkyl (wherein the heteroaryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), —C(R51)(R52)—[CR53=]z-R55 where z is 1 or 2 and more preferably z is 1, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is phenyl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino or heteraryl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino; R40 is H, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, phenoxy (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (optionally substituted by halogen, C1-14 allyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) and salts or N-oxides thereof.
  • It is preferred that Y is a single bond, C═O, C═S or S(O)q where q is 0, 1 or 2.
  • More preferably Y is a single bond, C═O or SO2.
  • Most preferably Y is a single bond or C═O, especially C═O.
  • R1 is preferably hydrogen, C1-6 alkyl, C1-6 cyanoalkyl, C1-6 haloalkyl, C3-7 cycloalkyl(C1-4)alkyl, C1-6 alkoxy(C1-6)alkyl, heteroaryl(C1-6)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), aryl(C1-6)alkyl (wherein the aryl group may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C1-6 alkylcarbonylamino(C1-6)alkyl, aryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), heteroaryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C1-6 alkoxy, C1-6 haloalkoxy, phenoxy (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryloxy (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocycyloxy (optionally substituted by halo, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), cyano, C2-6 alkenyl, C2-6 alkynyl, C3-6 cycloalkyl, C5-7 cycloalkenyl, heterocyclyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkylthio, C1-6 haloalkylthio or NR13R14 where R13 and R14 are independently hydrogen, C2-6 alkyl, C2-6 haloalkyl, phenyl (which may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino or C1-4 alkoxycarbonyl) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy, C1-4 alkoxycarbonyl C1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), amino, C1-6 alkylamino or phenylamino (wherein the phenyl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino).
  • More preferably R1 is hydrogen, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy(C1-6)alkyl, heteroaryl(C1-6)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), phenyl(C1-6)alkyl (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C1-6 alkylcarbonylamino(C1-6)alkyl, phenyl (which may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), heteroaryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C1-6 alkoxy, C1-6 haloalkoxy, phenoxy (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryloxy (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocycyloxy (optionally substituted by halo, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), cyano, C2-6 alkenyl, C3-6 cycloalkyl, C5-7 cycloalkenyl, heterocyclyl (optionally substituted by halo, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkylthio, C1-6 haloalkylthio, NR13R14 where R13 and R14 are independently hydrogen, COR40, C2-6 alkyl, C2-6 haloalkyl, phenyl (which may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino, C1-4 alkoxycarbonyl) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-4 alkoxycarbonyl); C1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), amino, C1-6 alkylamino, phenylamino (wherein the phenyl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino).
  • Even more preferably R1 is C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy(C1-6)alkyl, heteroaryl(C1-3)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), phenyl(C1-3)alkyl (wherein the phenyl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino, C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), phenyl (which may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino, C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), heteroaryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkoxycarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C1-6 alkoxy, C1-6 haloalkoxy, C2-6 alkenyl, heterocyclyl (optionally substituted by halo, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkylthio, C1-6 haloalkylthio or NR13R14 where R13 and R14 independently hydrogen, C2-6 alkyl or C2-6 haloalkyl, C2-6 alkylcarbonyl or phenylcarbonyl, (where the phenyl is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino).
  • Yet more preferably R1 is C1-6 alkyl, C1-6 haloalkyl, heteroaryl(C1-3)alkyl (wherein the heteroaryl group maybe optionally substituted by halo, cyano, C1-6 alkyl, C1-6 haloalkyl) where the heteroaryl group is a pyridine, pyrimidine, pyrazine or pyridazine ring, heteroaryl (optionally substituted by halo, cyano, C1-6 alkyl, C1-6 haloalkyl) where the heteroaryl group is a pyridine, pyrimidine, pyrazine or pyridazine ring, C1-6 alkoxy or heterocyclyl (optionally substituted by halo, cyano, C1-3 alkyl, C1-3 haloalkyl, or C1-3 alkoxy).
  • Most preferably R1 is pyridyl (optionally substituted by halo, C1-3 alkyl or C1-3 haloalkyl) or C1-6 alkoxy, especially halo-substituted pyridyl.
  • It is preferred that R2 and R3 are independently hydrogen or C1-4 alkyl.
  • More preferably R2 and R3 are independently hydrogen or methyl.
  • Even more preferably R2 is hydrogen and R3 is hydrogen or methyl;
  • Most preferably R2 and R3 are both hydrogen.
  • Preferably each R4 is independently halogen, cyano, C1-8 alkyl, C1-8 haloalkyl, C1-6 cyanoalkyl, C1-6 alkoxy(C1-6)alkyl, C3-7 cycloalkyl(C1-6)alkyl, C5-6 cycloalkenyl(C1-6)alkyl, C3-6 alkenyloxy(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)-alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, aminocarbonyl(C2-6)alkenyl, C1-6 alkylaminocarbonyl(C2-6)alkenyl, di(C1-6)alkylaminocarbonyl(C2-6)alkenyl, phenyl(C2-4)-alkenyl, (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkynyl, trimethylsilyl(C2-6)alkynyl, aminocarbonyl(C2-6)alkynyl, C1-6 alkylaminocarbonyl(C2-6)alkynyl, di(C1-6)alkylaminocarbonyl(C2-6)alkynyl, C1-6 alkoxycarbonyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)-cycloalkyl, C1-3 alkyl(C3-7)halocycloalkyl,phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C1-6 allyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen, C1-8 alkoxy, C1-6 haloalkoxy, phenoxy (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryloxy (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkylthio or R19R20N where R19 and R20 are, independently, hydrogen, C1-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C2-6 haloalkyl, C1-6 alkoxycarbonyl or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1-6 alkyl groups; n is 0, 1, 2, 3 or 4.
  • More preferably each R4 is independently halogen, cyano, C1-8 alkyl, C1-8 haloalkyl, C1-8 cyanoalkyl, C1-6 alkoxy(C1-6)alkyl, C2-6 alkynyl, trimethylsilyl(C2-6)alkynyl, C1-6 alkoxycarbonyl, C3-7 cycloalkyl, C1-3 alkyl (C3-7) cycloalkyl, phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heterocyclyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkoxy, C1-6 haloalkoxy, phenoxy (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryloxy (optionally substituted by halo, nitro, cyano, C1-3 alkyl, C1-3 haloalkyl, C1-3 alkoxy or C1-3 haloalkoxy), di(C1-8)alkylamino, or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4.
  • Even more preferably each R4 is independently halogen, cyano, C1-8 alkyl, C1-8 haloalkyl, C1-8 cyanoalkyl, C1-6 alkoxy(C1-6)alkyl, C2-6 alkynyl, heterocyclyl (optionally substituted by C1-6 alkyl), C1-8 alkoxy, C1-6 haloalkoxy, phenoxy (optionally substituted by halo, cyano, C1-3 alkyl or C1-3 haloalkyl), heteroaryloxy (optionally substituted by halo, cyano, C1-3 alkyl or C1-3 haloalkyl), di(C1-8)alkylamino or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4;
  • Yet more preferably each R4 is independently fluoro, chloro, bromo, cyano, C1-4 alkyl, C1-4 haloalkyl, C1-4 cyanoalkyl or C1-3 alkoxy(C1-3)alkyl; n is 0, 1 or 2;
  • Most preferably each R4 is independently fluoro, chloro, bromo, C1-4 alkyl or C1-4 haloalkyl; n is 1 or 2.
  • Preferably R8 is C1-10 alkyl, C1-10 haloalkyl, aryl(C1-6)alkyl (wherein the aryl group is optionally substituted by halogen, C1-4alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), arylcarbonyl-(C1-6)alkyl (wherein the aryl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino and the alkyl group may be optionally substituted by aryl), C2-8 alkenyl, C2-8 haloalkenyl, aryl(C2-6)-alkenyl (wherein the aryl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, C1-6 alkoxycarbonyl, or two adjacent substituents can cyclise to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring), C2-6 alkynyl, phenyl(C2-6)alkynyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C3-7 cycloalkyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 haloalkylcarbonyl or aryl(C2-6)alkenylcarbonyl (wherein the aryl group may be optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), or —C(R51)(R52)—[CR53═CR54]z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is optionally substituted aryl or optionally substituted heteroaryl.
  • R8 is more preferably C1-6 alkyl, C1-6 haloalkyl, aryl(C1-4)alkyl (wherein the aryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkenyl, aryl(C2-6)alkenyl (wherein the aryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkyl, phenyl(C2-6)alkynyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); or —C(R51)(R52)—[CR53═CR54]z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is optionally substituted aryl or optionally substituted heteraryl
  • Even more preferably R8 is phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), phenyl(C2-6)alkenyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino) or phenyl(C2-6)alkynyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, or —C(R51)(R52)—[CR53═CR54]z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is optionally substituted aryl or optionally substituted heteraryl
  • Even more preferably R8 is phenylCH2— (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl CH2— (wherein the heteroaryl group is a bicyclic group optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), or —C(R51)(R52)—[CR53═]z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is optionally substituted aryl or optionally substituted heteroaryl Yet more preferably R8 is phenyl(C2-4)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C1-3 alkyl, C1-3 haloalkyl, C1-3 alkoxy, C1-3 alkoxycarbonyl or C1-3 haloalkoxy) or phenyl(C2-4)alkynyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C1-3 alkyl, C1-3 haloalkyl, C1-3 alkoxy, C1-3 alkoxycarbonyl or C1-3 haloalkoxy).; or R8 is —C(R51)(R52)—[CR53═CR54]z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4haloalkyl and R55 is phenyl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino or heteroaryl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino.
  • Most preferably R8 is —C(R51)(R52)—[CR53═CR54]z-R55 where z is 1 or 2, preferably 1, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is phenyl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino or heteroaryl substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino
  • It is preferred that R9 and R10 are both hydrogen.
  • R51 and R52 are preferably hydrogen.
  • R53 and R54 are preferably hydrogen or halogen, especially hydrogen.
  • R55 is preferably phenyl substituted with one to three substituents selected from halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino
  • Certain compounds of formula (I) are novel and as such form a further aspect of the invention. For example there are provided novel compounds of formula (IK) as defined above and salts or N-oxides thereof provided that R8 is not methyl and YR1 is not SO2CH3, methyl, ethyl, phenyl or fluoro-substituted phenyl.
  • Further novel compounds are those of formula IN which are compounds of formual I wherein Y is a single bond or C═O; R1 is C1-6 alkyl, C1-6 haloalkyl, heteroaryl(C1-3)alkyl (wherein the heteroaryl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino and the heteroaryl group is a pyridine, pyrimidine, pyrazine or pyridazine ring), heteroaryl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino and where the heteroaryl group is a pyridine, pyrimidine, pyrazine or pyridazine ring), C1-6 alkoxy or heterocyclyl (optionally substituted by halo, cyano, C1-3 alkyl, C1-3 haloalkyl, or C1-3 alkoxy); R4 is independently fluoro, chloro, bromo, cyano, C1-4 alkyl, C1-4 haloalkyl, C1-4 cyanoalkyl or C1-3 alkoxy(C1-3)alkyl; n is 0, 1 or 2; R8 is phenyl(C2-4)alkenyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino or C1-3 alkoxycarbonyl) or phenyl(C2-4)alkynyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino or C1-3 alkoxycarbonyl) and R2 R3 R9 and R10 are all hydrogen.
  • Further novel compounds are those of formula IP which are compounds of formual I wherein Y is C(O); R1 is pyridyl (optionally substituted by halo, C1-3 alkyl or C1-3 haloalkyl) or C1-6 alkoxy, R2, R3, R9 and R10 are all hydrogen; R4 is fluoro, chloro, bromo, C1-4 alkyl or C1-4 haloalkyl; n is 1 or 2 and R8 is phenylCH2— (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl CH2— (wherein the heteroaryl group is a bicyclic group optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), or —C(R51)(R52)—[CR53═CR54]z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is optionally substituted aryl or optionally substituted heteroaryl provided that a) when R4n is 5-fluoro and R1 is 2,6-dichloropyrid-4-yl then R8 is not 4-methylbenzyl, 3-methylbenzyl, 4-trifluormethoxybenzyl, 4-trifluormethybenzyl, 4-cyanobenzyl, 4-methylcarbonylbenzyl or cinnamyl and b) when R4n is 5-fluoro and R1 is 2-chloropyrid-4-yl then R8 is not 3-chlorobenzyl, 3,5-difluorobenzyl, 4-trifluormethoxybenzyl, 4-trifluormethybenzyl, 4-cyanobenzyl or 4-methylcarbonylbenzyl.
  • The compounds in Tables I to XXXII below illustrate the compounds of the invention.
  • Table I provides 301 compounds of formula Ia
    Figure US20060106045A1-20060518-C00003
  • wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
    TABLE 1
    Com-
    pound R8 R4a R4b R4c R4d
    I-1 Cinnamyl H H H H
    I-2 4-chlorocinnamyl H H H H
    I-3 4-fluorocinnamyl H H H H
    I-4 4-nitrocinnamyl H H H H
    I-5 4-methoxycinnamyl H H H H
    I-6 4-methylcinnamyl H H H H
    I-7 4-trifluoromethylcinnamyl H H H H
    I-8 4-cyanocinnamyl H H H H
    I-9 2,4-dichlorocinnamyl H H H H
    I-10 2,4-difluorocinnamyl H H H H
    I-11 cinnamyl Cl H H H
    I-12 4-chlorocinnamyl Cl H H H
    I-13 4-fluorocinnamyl Cl H H H
    I-14 4-nitrocinnamyl Cl H H H
    I-15 4-methoxycinnamyl Cl H H H
    I-16 4-methylcinnamyl Cl H H H
    I-17 4-trifluoromethylcinnamyl Cl H H H
    I-18 4-cyanocinnamyl Cl H H H
    I-19 2,4-dichlorocinnamyl Cl H H H
    I-20 2,4-difluorocinnamyl Cl H H H
    I-21 cinnamyl H Cl H H
    I-22 4-chlorocinnamyl H Cl H H
    I-23 4-fluorocinnamyl H Cl H H
    I-24 4-nitrocinnamyl H Cl H H
    I-25 4-methoxycinnamyl H Cl H H
    I-26 4-methylcinnamyl H Cl H H
    I-27 4-tifluoromethylcinnamyl H Cl H H
    I-28 4-cyanocinnamyl H Cl H H
    I-29 2,4-dichlorocinnamyl H Cl H H
    I-30 2,4-difluorocinnamyl H Cl H H
    I-31 cinnamyl H H Cl H
    I-32 4-chlorocinnamyl H H Cl H
    I-33 4-fluorocinnamyl H H Cl H
    I-34 4-nitrocinnamyl H H Cl H
    I-35 4-methoxycinnamyl H H Cl H
    I-36 4-methylcinnamyl H H Cl H
    I-37 4-trifluoromethylcinnamyl H H Cl H
    I-38 4-cyanocinnamyl H H Cl H
    I-39 2,4-dichlorocinnamyl H H Cl H
    I-40 2,4-difluorocinnamyl H H Cl H
    I-41 cinnamyl H H H Cl
    I-42 4-chlorocinnamyl H H H Cl
    I-43 4-fluorocinnamyl H H H Cl
    I-44 4-nitrocinnamyl H H H Cl
    I-45 4-methoxycinnamyl H H H Cl
    I-46 4-methylcinnamyl H H H Cl
    I-47 4-trifluoromethylcinnamyl H H H Cl
    I-48 4-cyanocinnamyl H H H Cl
    I-49 2,4-dichlorocinnamyl H H H Cl
    I-50 2,4-difluorocinnamyl H H H Cl
    I-51 cinnamyl F H H H
    I-52 4-chlorocinnamyl F H H H
    I-53 4-fluorocinnamyl F H H H
    I-54 4-nitrocinnamyl F H H H
    I-55 4-methoxycinnamyl F H H H
    I-56 4-methylcinnamyl F H H H
    I-57 4-trifluoromethylcinnamyl F H H H
    I-58 4-cyanocinnamyl F H H H
    I-59 2,4-dichlorocinnamyl F H H H
    I-60 2,4-difluorocinnamyl F H H H
    I-61 cinnamyl H F H H
    I-62 4-chlorocinnamyl H F H H
    I-63 4-fluorocinnamyl H F H H
    I-64 4-nitrocinnamyl H F H H
    I-65 4-methoxycinnamyl H F H H
    I-66 4-methylcinnamyl H F H H
    I-67 4-trifluoromethylcinnamyl H F H H
    I-68 4-cyanocinnamyl H F H H
    I-69 2,4-dichlorocinnamyl H F H H
    I-70 2,4-difluorocinnamyl H F H H
    I-71 cinnamyl H H F H
    I-72 4-chlorocinnamyl H H F H
    I-73 4-fluorocinnamyl H H F H
    I-74 4-nitrocinnamyl H H F H
    I-75 4-methoxycinnamyl H H F H
    I-76 4-methylcinnamyl H H F H
    I-77 4-trifluoromethylcinnamyl H H F H
    I-78 4-cyanocinnamyl H H F H
    I-79 2,4-dichlorocinnamyl H H F H
    I-80 2,4-difluorocinnamyl H H F H
    I-81 cinnamyl H H H F
    I-82 4-chlorocinnamyl H H H F
    I-83 4-fluorocinnamyl H H H F
    I-84 4-nitrocinnamyl H H H F
    I-85 4-methoxycinnamyl H H H F
    I-86 4-methylcinnamyl H H H F
    I-87 4-trifluoromethylcinnamyl H H H F
    I-88 4-cyanocinnamyl H H H F
    I-89 2,4-dichlorocinnamyl H H H F
    I-90 2,4-difluorocinnamyl H H H F
    I-91 cinnamyl Br H H H
    I-92 4-chlorocinnamyl Br H H H
    I-93 4-fluorocinnamyl Br H H H
    I-94 4-nitrocinnamyl Br H H H
    I-95 4-methoxycinnamyl Br H H H
    I-96 4-methylcinnamyl Br H H H
    I-97 4-trifluoromethylcinnamyl Br H H H
    I-98 4-cyanocinnamyl Br H H H
    I-99 2,4-dichlorocinnamyl Br H H H
    I-100 2,4-difluorocinnamyl Br H H H
    I-101 cinnamyl H Br H H
    I-102 4-chlorocinnamyl H Br H H
    I-103 4-fluorocinnamyl H Br H H
    I-104 4-nitrocinnamyl H Br H H
    I-105 4-methoxycinnamyl H Br H H
    I-106 4-methylcinnamyl H Br H H
    I-107 4-trifluoromethylcinnamyl H Br H H
    I-108 4-cyanocinnamyl H Br H H
    I-109 2,4-dichlorocinnamyl H Br H H
    I-110 2,4-difluorocinnamyl H Br H H
    I-111 cinnamyl H H Br H
    I-112 4-chlorocinnamyl H H Br H
    I-113 4-fluorocinnamyl H H Br H
    I-114 4-nitrocinnamyl H H Br H
    I-115 4-methoxycinnamyl H H Br H
    I-116 4-methylcinnamyl H H Br H
    I-117 4-trifluoromethylcinnamyl H H Br H
    I-118 4-cyanocinnamyl H H Br H
    I-119 2,4-dichlorocinnamyl H H Br H
    I-120 2,4-difluorocinnamyl H H Br H
    I-121 cinnamyl H H H Br
    I-122 4-chlorocinnamyl H H H Br
    I-123 4-fluorocinnamyl H H H Br
    I-124 4-nitrocinnamyl H H H Br
    I-125 4-methoxycinnamyl H H H Br
    I-126 4-methylcinnamyl H H H Br
    I-127 4-trifluoromethylcinnamyl H H H Br
    I-128 4-cyanocinnamyl H H H Br
    I-129 2,4-dichlorocinnamyl H H H Br
    I-130 2,4-difluorocinnamyl H H H Br
    I-131 cinnamyl H Cl H Cl
    I-132 4-chlorocinnamyl H Cl H Cl
    I-133 4-fluorocinnamyl H Cl H Cl
    I-134 4-nitrocinnamyl H Cl H Cl
    I-135 4-methoxycinnamyl H Cl H Cl
    I-136 4-methylcinnamyl H Cl H Cl
    I-137 4-trifluoromethylcinnamyl H Cl H Cl
    I-138 4-cyanocinnamyl H Cl H Cl
    I-139 2,4-dichlorocinnamyl H Cl H Cl
    I-140 2,4-difluorocinnamyl H Cl H Cl
    I-141 cinnamyl H F H F
    I-142 4-chlorocinnamyl H F H F
    I-143 4-fluorocinnamyl H F H F
    I-144 4-nitrocinnamyl H F H F
    I-145 4-methoxycinnamyl H F H F
    I-146 4-methylcinnamyl H F H F
    I-147 4-trifluoromethylcinnamyl H F H F
    I-148 4-cyanocinnamyl H F H F
    I-149 2,4-dichlorocinnamyl H F H F
    I-150 2,4-difluorocinnamyl H F H F
    I-151 cinnamyl Cl F H H
    I-152 4-chlorocinnamyl Cl F H H
    I-153 4-fluorocinnamyl Cl F H H
    I-154 4-nitrocinnamyl Cl F H H
    I-155 4-methoxycinnamyl Cl F H H
    I-156 4-methylcinnamyl Cl F H H
    I-157 4-trifluoromethylcinnamyl Cl F H H
    I-158 4-cyanocinnamyl Cl F H H
    I-159 2,4-dichlorocinnamyl Cl F H H
    I-160 2,4-difluorocinnamyl Cl F H H
    I-161 cinnamyl H F Cl H
    I-162 4-chlorocinnamyl H F Cl H
    I-163 4-fluorocinnamyl H F Cl H
    I-164 4-nitrocinnamyl H F Cl H
    I-165 4-methoxycinnamyl H F Cl H
    I-166 4-methylcinnamyl H F Cl H
    I-167 4-trifluoromethylcinnamyl H F Cl H
    I-168 4-cyanocinnamyl H F Cl H
    I-169 2,4-dichlorocinnamyl H F Cl H
    I-170 2,4-difluorocinnamyl H F Cl H
    I-171 cinnamyl H Cl Cl H
    I-172 4-chlorocinnamyl H Cl Cl H
    I-173 4-fluorocinnamyl H Cl Cl H
    I-174 4-nitrocinnamyl H Cl Cl H
    I-175 4-methoxycinnamyl H Cl Cl H
    I-176 4-methylcinnamyl H Cl Cl H
    I-177 4-trifluoromethylcinnamyl H Cl Cl H
    I-178 4-cyanocinnamyl H Cl Cl H
    I-179 2,4-dichlorocinnamyl H Cl Cl H
    I-180 2,4-difluorocinnamyl H Cl Cl H
    I-181 cinnamyl H I H H
    I-182 4-chlorocinnamyl H I H H
    I-183 4-fluorocinnamyl H I H H
    I-184 4-nitrocinnamyl H I H H
    I-185 4-methoxycinnamyl H I H H
    I-186 4-methylcinnamyl H I H H
    I-187 4-trifluoromethylcinnamyl H I H H
    I-188 4-cyanocinnamyl H I H H
    I-189 2,4-dichlorocinnamyl H I H H
    I-190 2,4-difluorocinnamyl H I H H
    I-191 cinnamyl H OMe H H
    I-192 4-chlorocinnamyl H OMe H H
    I-193 4-fluorocinnamyl H OMe H H
    I-194 4-nitrocinnamyl H OMe H H
    I-195 4-methoxycinnamyl H OMe H H
    I-196 4-methylcinnamyl H OMe H H
    I-197 4-trifluoromethylcinnamyl H OMe H H
    I-198 4-cyanocinnamyl H OMe H H
    I-199 2,4-dichlorocinnamyl H OMe H H
    I-200 2,4-difluorocinnamyl H OMe H H
    I-201 cinnamyl H Me H H
    I-202 4-chlorocinnamyl H Me H H
    I-203 4-fluorocinnamyl H Me H H
    I-204 4-nitrocinnamyl H Me H H
    I-205 4-methoxycinnamyl H Me H H
    I-206 4-methylcinnamyl H Me H H
    I-207 4-trifluoromethylcinnamyl H Me H H
    I-208 4-cyanocinnamyl H Me H H
    I-209 2,4-dichlorocinnamyl H Me H H
    I-210 2,4-difluorocinnamyl H Me H H
    I-211 cinnamyl H CN H H
    I-212 4-chlorocinnamyl H CN H H
    I-213 4-fluorocinnamyl H CN H H
    I-214 4-nitrocinnamyl H CN H H
    I-215 4-methoxycinnamyl H CN H H
    I-216 4-methylcinnamyl H CN H H
    I-217 4-trifluoromethylcinnamyl H CN H H
    I-218 4-cyanocinnamyl H CN H H
    I-219 2,4-dichlorocinnamyl H CN H H
    I-220 2,4-difluorocinnamyl H CN H H
    I-221 cinnamyl H CCH H H
    I-222 4-chlorocinnamyl H CCH H H
    I-223 4-fluorocinnamyl H CCH H H
    I-224 4-nitrocinnamyl H CCH H H
    I-225 4-methoxycinnamyl H CCH H H
    I-226 4-methylcinnamyl H CCH H H
    I-227 4-trifluoromethylcinnamyl H CCH H H
    I-228 4-cyanocinnamyl H CCH H H
    I-229 2,4-dichlorocinnamyl H CCH H H
    I-230 2,4-difluorocinnamyl H CCH H H
    I-231 cinnamyl H COOMe H H
    I-232 4-chlorocinnamyl H COOMe H H
    I-233 4-fluorocinnamyl H COOMe H H
    I-234 4-nitrocinnamyl H COOMe H H
    I-235 4-methoxycinnamyl H COOMe H H
    I-236 4-methylcinnamyl H COOMe H H
    I-237 4-trifluoromethylcinnamyl H COOMe H H
    I-238 4-cyanocinnamyl H COOMe H H
    I-239 2,4-dichlorocinnamyl H COOMe H H
    I-240 2,4-difluorocinnamyl H COOMe H H
    I-241 cinnamyl H Me Cl H
    I-242 4-chlorocinnamyl H Me Cl H
    I-243 4-fluorocinnamyl H Me Cl H
    I-244 4-nitrocinnamyl H Me Cl H
    I-245 4-methoxycinnamyl H Me Cl H
    I-246 4-methylcinnamyl H Me Cl H
    I-247 4-trifluoromethylcinnamyl H Me Cl H
    I-248 4-cyanocinnamyl H Me Cl H
    I-249 2,4-dichlorocinnamyl H Me Cl H
    I250 2,4difluorocinnamyl H Me Cl H
    I-251 cinnamyl Cl Me H H
    I-252 4-chlorocinnamyl Cl Me H H
    I-253 4-fluorocinnamyl Cl Me H H
    I-254 4-nitrocinnamyl Cl Me H H
    I-255 4-methoxycinnamyl Cl Me H H
    I-256 4-methylcinnamyl Cl Me H H
    I-257 4-trifluoromethylcinnamyl Cl Me H H
    I-258 4-cyanocinnamyl Cl Me H H
    I-259 2,4-dichlorocinnamyl Cl Me H H
    I-260 2,4-difluorocinnamyl Cl Me H H
    I-261 cinnamyl H Cl H Me
    I-262 4-chlorocinnamyl H Cl H Me
    I-263 4-fluorocinnamyl H Cl H Me
    I-264 4-nitrocinnamyl H Cl H Me
    I-265 4-methoxycinnamyl H Cl H Me
    I-266 4-methylcinnamyl H Cl H Me
    I-267 4-trifluoromethylcinnamyl H Cl H Me
    I-268 4-cyanocinnamyl H Cl H Me
    I-269 2,4-dichlorocinnamyl H Cl H Me
    I-270 2,4-difluorocinnamyl H Cl H Me
    I-271 cinnamyl H H 4-Cl-PhO H
    I-272 4-chlorocinnamyl H H 4-Cl-PhO H
    I-273 4-fluorocinnamyl H H 4-Cl-PhO H
    I-274 4-nitrocinnamyl H H 4-Cl-PhO H
    I-275 4-methoxycinnamyl H H 4-Cl-PhO H
    I-276 4-methylcinnamyl H H 4-Cl-PhO H
    I-277 4-trifluoromethylcinnamyl H H 4-Cl-PhO H
    I-278 4-cyanocinnamyl H H 4-Cl-PhO H
    I-279 2,4-dichlorocinnamyl H H 4-Cl-PhO H
    I-280 2,4-difluorocinnamyl H H 4-Cl-PhO H
    I-281 cinnamyl H 4-F-Ph H H
    I-282 4-chlorocinnamyl H 4-F-Ph H H
    I-283 4-fluorocinnamyl H 4-F-Ph H H
    I-284 4-nitrocinnamyl H 4-F-Ph H H
    I-285 4-methoxycinnamyl H 4-F-Ph H H
    I-286 4-methylcinnamyl H 4-F-Ph H H
    I-287 4-trifluoromethylcinnamyl H 4-F-Ph H H
    I-288 4-cyanocinnamyl H 4-F-Ph H H
    I-289 2,4-dichlorocinnamyl H 4-F-Ph H H
    I-290 2,4-difluorocinnamyl H 4-F-Ph H H
    I-291 cinnamyl H CF3O H H
    I-292 4-chlorocinnamyl H CF3O H H
    I-293 4-fluorocinnamyl H CF3O H H
    I-294 4-nitrocinnamyl H CF3O H H
    I-295 4-methoxycinnamyl H CF3O H H
    I-296 4-methylcinnamyl H CF3O H H
    I-297 4-trifluoromethylcinnamyl H CF3O H H
    I-298 4-cyanocinnamyl H CF3O H H
    I-299 2,4-dichlorocinnamyl H CF3O H H
    I-300 2,4-difluorocinnamyl H CF3O H H
    I-301 C(O)CH═CH-4- H 4-CF3-Ph H H
    chlorophenyl
  • Table II provides 301 compounds of formula Ib
    Figure US20060106045A1-20060518-C00004
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table III provides 301 compounds of formula Ic
    Figure US20060106045A1-20060518-C00005
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table IV provides 301 compounds of formula Id
    Figure US20060106045A1-20060518-C00006
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table V provides 301 compounds of formula Ie
    Figure US20060106045A1-20060518-C00007
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table VI provides 301 compounds of formula If
    Figure US20060106045A1-20060518-C00008
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table VII provides 301 compounds of formula Ig
    Figure US20060106045A1-20060518-C00009
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table VIII provides 301 compounds of formula Ih
    Figure US20060106045A1-20060518-C00010
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table IX provides 301 compounds of formula Ii
    Figure US20060106045A1-20060518-C00011
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table X provides 301 compounds of formula Ij
    Figure US20060106045A1-20060518-C00012
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XI provides 301 compounds of formula Ik
    Figure US20060106045A1-20060518-C00013
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XII provides 301 compounds of formula Il
    Figure US20060106045A1-20060518-C00014
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XIII provides 301 compounds of formula Im
    Figure US20060106045A1-20060518-C00015
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XIV provides 301 compounds of formula In
    Figure US20060106045A1-20060518-C00016
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XV provides 301 compounds of formula Io
    Figure US20060106045A1-20060518-C00017
    wherein the values of R8, R4a, R4b, R4c and R4d are give in Table 1
  • Table XVI provides 301 compounds of formula Ip
    Figure US20060106045A1-20060518-C00018
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XVII provides 301 compounds of formula Iq
    Figure US20060106045A1-20060518-C00019
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XVIII provides 301 compounds of formula Ir
    Figure US20060106045A1-20060518-C00020
    wherein the values of R8, R4a, R4b, R4 and R4d are given in Table 1
  • Table XIX provides 301 compounds of formula Is
    Figure US20060106045A1-20060518-C00021
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XX provides 301 compounds of formula It
    Figure US20060106045A1-20060518-C00022
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXI provides 301 compounds of formula Iu
    Figure US20060106045A1-20060518-C00023
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXII provides 301 compounds of formula Iv
    Figure US20060106045A1-20060518-C00024
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXIII provides 301 compounds of formula Iw
    Figure US20060106045A1-20060518-C00025
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXIV provides 301 compounds of formula Ix
    Figure US20060106045A1-20060518-C00026
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXV provides 301 compounds of formula Iy
    Figure US20060106045A1-20060518-C00027
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXVI provides 301 compounds of formula Iz
    Figure US20060106045A1-20060518-C00028
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXVII provides 301 compounds of formula Iaa
    Figure US20060106045A1-20060518-C00029
    wherein the values of R8, R4a, R4b, R4c and R4d are given in Table 1
  • Table XXVIIl provides 270 compounds of formula Iab
    Figure US20060106045A1-20060518-C00030
  • wherein the values of R8, R4a, R4b, R4c,R4d and (Ra)n are given in Table 2
    TABLE 2
    Compound R8 R4a R4b R4c R4d (Ra)n
    XXVIII-1 cinnamyl H H H H 4-SMe
    XXVIII-2 4-chlorocinnamyl H H H H 4-SMe
    XXVIII-3 4-fluorocinnamyl H H H H 4-SMe
    XXVIII-4 4-trifluoromethylcinnamyl H H H H 4-SMe
    XXVIII-5 4-cyanocinnamyl H H H H 4-SMe
    XXVIII-6 cinnamyl H Cl H H 4-SMe
    XXVIII-7 4-chlorocinnamyl H Cl H H 4-SMe
    XXVIII-8 4-fluorocinnamyl H Cl H H 4-SMe
    XXVIII-9 4-trifluoromethylcinnamyl H Cl H H 4-SMe
    XXVIII-10 4-cyanocinnamyl H Cl H H 4-SMe
    XXVIII-11 cinnamyl H F H H 4-SMe
    XXVIII-12 4-chlorocinnamyl H F H H 4-SMe
    XXVIII-13 4-fluorocinnamyl H F H H 4-SMe
    XXVIII-14 4-trifluoromethylcinnamyl H F H H 4-SMe
    XXVIII-15 4-cyanocinnamyl H F H H 4-SMe
    XXVIII-16 cinnamyl H H F H 4-SMe
    XXVIII-17 4-chlorocinnamyl H H F H 4-SMe
    XXVIII-18 4-fluorocinnamyl H H F H 4-SMe
    XXVIII-19 4-trifluoromethylcinnamyl H H F H 4-SMe
    XXVIII-20 4-cyanocinnamyl H H F H 4-SMe
    XXVIII-21 cinnamyl H F H F 4-SMe
    XXVIII-22 4-chlorocinnamyl H F H F 4-SMe
    XXVIII-23 4-fluorocinnamyl H F H F 4-SMe
    XXVIII-24 4-trifluoromethylcinnamyl H F H F 4-SMe
    XXVIII-25 4-cyanocinnamyl H F H F 4-SMe
    XXVIII-26 cinnamyl H OMe H H 4-SMe
    XXVIII-27 4-chlorocinnamyl H OMe H H 4-SMe
    XXVIII-28 4-fluorocinnamyl H OMe H H 4-SMe
    XXVIII-29 4-trifluoromethylcinnamyl H OMe H H 4-SMe
    XXVIII-30 4-cyanocinnamyl H OMe H H 4-SMe
    XXVIII-31 cinnamyl H H H H 4-C(O)Ph
    XXVIII-32 4-chlorocinnamyl H H H H 4-C(O)Ph
    XXVIII-33 4-fluorocinnamyl H H H H 4-C(O)Ph
    XXVIII-34 4-trifluoromethylcinnamyl H H H H 4-C(O)Ph
    XXVIII-35 4-cyanocinnamyl H H H H 4-C(O)Ph
    XXVIII-36 cinnamyl H Cl H H 4-C(O)Ph
    XXVIII-37 4-chlorocinnamyl H Cl H H 4-C(O)Ph
    XXVIII-38 4-fluorocinnamyl H Cl H H 4-C(O)Ph
    XXVIII-39 4-trifluoromethylcinnamyl H Cl H H 4-C(O)Ph
    XXVIII-40 4-cyanocinnamyl H Cl H H 4-C(O)Ph
    XXVIII-41 cinnamyl H F H H 4-C(O)Ph
    XXVIII-42 4-chlorocinnamyl H F H H 4-C(O)Ph
    XXVIII-43 4-fluorocinnamyl H F H H 4-C(O)Ph
    XXVIII-44 4-trifluoromethylcinnamyl H F H H 4-C(O)Ph
    XXVIII-45 4-cyanocinnamyl H F H H 4-C(O)Ph
    XXVIII-46 cinnamyl H H F H 4-C(O)Ph
    XXVIII-47 4-chlorocinnamyl H H F H 4-C(O)Ph
    XXVIII-48 4-fluorocinnamyl H H F H 4-C(O)Ph
    XXVIII-49 4-trifluoromethylcinnamyl H H F H 4-C(O)Ph
    XXVIII-50 4-cyanocinnamyl H H F H 4-C(O)Ph
    XXVIII-51 cinnamyl H F H F 4-C(O)Ph
    XXVIII-52 4-chlorocinnamyl H F H F 4-C(O)Ph
    XXVIII-53 4-fluorocinnamyl H F H F 4-C(O)Ph
    XXVIII-54 4-trifluoromethylcinnamyl H F H F 4-C(O)Ph
    XXVIII-55 4-cyanocinnamyl H F H F 4-C(O)Ph
    XXVIII-56 cinnamyl H OMe H H 4-C(O)Ph
    XXVIII-57 4-chlorocinnamyl H OMe H H 4-C(O)Ph
    XXVIII-58 4-fluorocinnamyl H OMe H H 4-C(O)Ph
    XXVIII-59 4-trifluoromethylcinnamyl H OMe H H 4-C(O)Ph
    XXVIII-60 4-cyanocinnamyl H OMe H H 4-C(O)Ph
    XXVIII-61 cinnamyl H H H H 4-F
    XXVIII-62 4-chlorocinnamyl H H H H 4-F
    XXVIII-63 4-fluorocinnamyl H H H H 4-F
    XXVIII-64 4-trifluoromethylcinnamyl H H H H 4-F
    XXVIII-65 4-cyanocinnamyl H H H H 4-F
    XXVIII-66 cinnamyl H Cl H H 4-F
    XXVIII-67 4-chlorocinnamyl H Cl H H 4-F
    XXVIII-68 4-fluorocinnamyl H Cl H H 4-F
    XXVIII-69 4-trifluoromethylcinnamyl H Cl H H 4-F
    XXVIII-70 4-cyanocinnamyl H Cl H H 4-F
    XXVIII-71 cinnamyl H F H H 4-F
    XXVIII-72 4-chlorocinnamyl H F H H 4-F
    XXVIII-73 4-fluorocinnamyl H F H H 4-F
    XXVIII-74 4-trifluoromethylcinnamyl H F H H 4-F
    XXVIII-75 4-cyanocinnamyl H F H H 4-F
    XXVIII-76 cinnamyl H H F H 4-F
    XXVIII-77 4-chlorocinnamyl H H F H 4-F
    XXVIII-78 4-fluorocinnamyl H H F H 4-F
    XXVIII-79 4-trifluoromethylcinnamyl H H F H 4-F
    XXVIII-80 4-cyanocinnamyl H H F H 4-F
    XXVIII-81 cinnamyl H F H F 4-F
    XXVIII-82 4-chlorocinnamyl H F H F 4-F
    XXVIII-83 4-luorocinnamyl H F H F 4-F
    XXVIII-84 4-trifluoromethylcinnamyl H F H F 4-F
    XXVIII-85 4-cyanocinnamyl H F H F 4-F
    XXVIII-86 cinnamyl H OMe H H 4-F
    XXVIII-87 4-chlorocinnamyl H OMe H H 4-F
    XXVIII-88 4-fluorocinnamyl H OMe H H 4-F
    XXVIII-89 4-trifluoromethylcinnamyl H OMe H H 4-F
    XXVIII-90 4-cyanocinnamyl H OMe H H 4-F
    XXVIII-91 cinnamyl H H H H 3-CN
    XXVIII-92 4-chlorocinnamyl H H H H 3-CN
    XXVIII-93 4-fluorocinnamyl H H H H 3-CN
    XXVIII-94 4-trifluoromethylcinnamyl H H H H 3-CN
    XXVIII-95 4-cyanocinnamyl H H H H 3-CN
    XXVIII-96 cinnamyl H Cl H H 3-CN
    XXVIII-97 4-chlorocinnamyl H Cl H H 3-CN
    XXVIII-98 4-fluorocinnamyl H Cl H H 3-CN
    XXVIII-99 4-trifluoromethylcinnamyl H Cl H H 3-CN
    XXVIII-100 4-cyanocinnamyl H Cl H H 3-CN
    XXVIII-101 cinnamyl H F H H 3-CN
    XXVIII-102 4-chlorocinnamyl H F H H 3-CN
    XXVIII-103 4-fluorocinnamyl H F H H 3-CN
    XXVIII-104 4-trifluoromethylcinnamyl H F H H 3-CN
    XXVIII-105 4-cyanocinnamyl H F H H 3-CN
    XXVIII-106 cinnamyl H H F H 3-CN
    XXVIII-107 4-chlorocinnamyl H H F H 3-CN
    XXVIII-108 4-fluorocinnamyl H H F H 3-CN
    XXVIII-109 4-trifluoromethylcinnamyl H H F H 3-CN
    XXVIII-110 4-cyanocinnamyl H H F H 3-CN
    XXVIII-111 cinnamyl H F H F 3-CN
    XXVIII-112 4-chlorocinnamyl H F H F 3-CN
    XXVIII-113 4-fluorocinnamyl H F H F 3-CN
    XXVIII-114 4-trifluoromethylcinnamyl H F H F 3-CN
    XXVIII-115 4-cyanocinnamyl H F H F 3-CN
    XXVIII-116 cinnamyl H OMe H H 3-CN
    XXVIII-117 4-chlorocinnamyl H OMe H H 3-CN
    XXVIII-118 4-fluorocinnamyl H OMe H H 3-CN
    XXVIII-119 4-trifluoromethylcinnamyl H OMe H H 3-CN
    XXVIII-120 4-cyanocinnamyl H OMe H H 3-CN
    XXVIII-121 cinnamyl H H H H 4-n-Pr
    XXVIII-122 4-chlorocinnamyl H H H H 4-n-Pr
    XXVIII-123 4-fluorocinnamyl H H H H 4-n-Pr
    XXVIII-124 4-trifluoromethylcinnamyl H H H H 4-n-Pr
    XXVIII-125 4-cyanocinnamyl H H H H 4-n-Pr
    XXVIII-126 cinnamyl H Cl H H 4-n-Pr
    XXVIII-127 4-chlorocinnamyl H Cl H H 4-n-Pr
    XXVIII-128 4-fluorocinnamyl H Cl H H 4-n-Pr
    XXVIII-129 4-trifluoromethylcinnamyl H Cl H H 4-n-Pr
    XXVIII-130 4-cyanocinnamyl H Cl H H 4-n-Pr
    XXVIII-131 cinnamyl H F H H 4-n-Pr
    XXVIII-132 4-chlorocinnamyl H F H H 4-n-Pr
    XXVIII-133 4-fluorocinnamyl H F H H 4-n-Pr
    XXVIII-134 4-trifluoromethylcinnamyl H F H H 4-n-Pr
    XXVIII-135 4-cyanocinnamyl H F H H 4-n-Pr
    XXVIII-136 cinnamyl H H F H 4-n-Pr
    XXVIII-137 4-chlorocinnamyl H H F H 4-n-Pr
    XXVIII-138 4-fluorocinnamyl H H F H 4-n-Pr
    XXVIII-139 4-trifluoromethylcinnamyl H H F H 4-n-Pr
    XXVIII-140 4-cyanocinnamyl H H F H 4-n-Pr
    XXVIII-141 cinnamyl H F H F 4-n-Pr
    XXVIII-142 4-chlorocinnamyl H F H F 4-n-Pr
    XXVIII-143 4-fluorocinnamyl H F H F 4-n-Pr
    XXVIII-144 4-trifluoromethylcinnamyl H F H F 4-n-Pr
    XXVIII-145 4-cyanocinnamyl H F H F 4-n-Pr
    XXVIII-146 cinnamyl H OMe H H 4-n-Pr
    XXVIII-147 4-chlorocinnamyl H OMe H H 4-n-Pr
    XXVIII-148 4-fluorocinnamyl H OMe H H 4-n-Pr
    XXVIII-149 4-trifluoromethylcinnamyl H OMe H H 4-n-Pr
    XXVIII-150 4-cyanocinnamyl H OMe H H 4-n-Pr
    XXVIII-151 cinnamyl H H H H 2-OMe-4-SMe
    XXVIII-152 4-chlorocinnamyl H H H H 2-OMe-4-SMe
    XXVIII-153 4-fluorocinnamyl H H H H 2-OMe-4-SMe
    XXVIII-154 4-trifluoromethylcinnamyl H H H H 2-OMe-4-SMe
    XXVIII-155 4-cyanocinnamyl H H H H 2-OMe-4-SMe
    XXVIII-156 cinnamyl H Cl H H 2-OMe-4-SMe
    XXVIII-157 4-chlorocinnamyl H Cl H H 2-OMe-4-SMe
    XXVIII-158 4-fluorocinnamyl H Cl H H 2-OMe-4-SMe
    XXVIII-159 4-trifluoromethylcinnamyl H Cl H H 2-OMe-4-SMe
    XXVIII-160 4-cyanocinnamyl H Cl H H 2-OMe-4-SMe
    XXVIII-161 cinnamyl H F H H 2-OMe-4-SMe
    XXVIII-162 4-chlorocinnamyl H F H H 2-OMe-4-SMe
    XXVIII-163 4-fluorocinamyl H F H H 2-OMe-4-SMe
    XXVIII-164 4-trifluoromethylcinnamyl H F H H 2-OMe-4-SMe
    XXVIII-165 4-cyanocinnamyl H F H H 2-OMe-4-SMe
    XXVIII-166 cinnamyl H H F H 2-OMe-4-SMe
    XXVIII-167 4-chlorocinnamyl H H F H 2-OMe-4-SMe
    XXVIII-168 4-fluorocinnamyl H H F H 2-OMe-4-SMe
    XXVIII-169 4-trifluoromethylcinnamyl H H F H 2-OMe-4-SMe
    XXVIII-170 4-cyanocinnamyl H H F H 2-OMe-4-SMe
    XXVIII-171 cinnamyl H F H F 2-OMe-4-SMe
    XXVIII-172 4-chlorocinnamyl H F H F 2-OMe-4-SMe
    XXVIII-173 4-fluorocinnamyl H F H F 2-OMe-4-SMe
    XXVIII-174 4-trifluoromethylcinnamyl H F H F 2-OMe-4-SMe
    XXVIII-175 4-cyanocinnamyl H F H F 2-OMe-4-SMe
    XXVIII-176 cinnamyl H OMe H H 2-OMe-4-SMe
    XXVIII-177 4-chlorocinnamyl H OMe H H 2-OMe-4-SMe
    XXVIII-178 4-fluorocinnamyl H OMe H H 2-OMe-4-SMe
    XXVIII-179 4-trifluoromethylcinnamyl H OMe H H 2-OMe-4-SMe
    XXVIII-180 4-cyanocinnamyl H OMe H H 2-OMe-4-SMe
    XXVIII-181 cinnamyl H H H H 2-Cl-4-SO2Me
    XXVIII-182 4-chlorocinnamyl H H H H 2-Cl-4-SO2Me
    XXVIII-183 4-fluorocinnamyl H H H H 2-Cl-4-SO2Me
    XXVIII-184 4-trifluoromethylcinnamyl H H H H 2-Cl-4-SO2Me
    XXVIII-185 4-cyanocinnamyl H H H H 2-Cl-4-SO2Me
    XXVIII-186 cinnamyl H Cl H H 2-Cl-4-SO2Me
    XXVIII-187 4-chlorocinnamyl H Cl H H 2-Cl-4-SO2Me
    XXVIII-188 4-fluorocinnamyl H Cl H H 2-Cl-4-SO2Me
    XXVIII-189 4-trifluoromethylcinnamyl H Cl H H 2-Cl-4-SO2Me
    XXVIII-190 4-cyanocinnamyl H Cl H H 2-Cl-4-SO2Me
    XXVIII-191 cinnamyl H F H H 2-Cl-4-SO2Me
    XXVIII-192 4-chlorocinnamyl H F H H 2-Cl-4-SO2Me
    XXVIII-193 4-fluorocinnamyl H F H H 2-Cl-4-SO2Me
    XXVIII-194 4-trifluoromethylcinnamyl H F H H 2-Cl-4-SO2Me
    XXVIII-195 4-cyanocinnamyl H F H H 2-Cl-4-SO2Me
    XXVIII-196 cinnamyl H H F H 2-Cl-4-SO2Me
    XXVIII-197 4-chlorocinnamyl H H F H 2-Cl-4-SO2Me
    XXVIII-198 4-fluorocinnamyl H H F H 2-Cl-4-SO2Me
    XXVIII-199 4-trifluoromethylcinnamyl H H F H 2-Cl-4-SO2Me
    XXVIII-200 4-cyanocinnamyl H H F H 2-Cl-4-SO2Me
    XXVIII-201 cinnamyl H F H F 2-Cl-4-SO2Me
    XXVIII-202 4-chlorocinnamyl H F H F 2-Cl-4-SO2Me
    XXVIII-203 4-fluorocinnamyl H F H F 2-Cl-4-SO2Me
    XXVIII-204 4-trifluoromethylcinnamyl H F H F 2-Cl-4-SO2Me
    XXVIII-205 4-cyanocinnamyl H F H F 2-Cl-4-SO2Me
    XXVIII-206 cinnamyl H OMe H H 2-Cl-4-SO2Me
    XXVIII-207 4-chlorocinnamyl H OMe H H 2-Cl-4-SO2Me
    XXVIII-208 4-fluorocinnamyl H OMe H H 2-Cl-4-SO2Me
    XXVIII-209 4-trifluoromethylcinnamyl H OMe H H 2-Cl-4-SO2Me
    XXVIII-210 4-cyanocinnamyl H OMe H H 2-Cl-4-SO2Me
    XXVIII-211 cinnamyl H H H H 4-n-PrO
    XXVIII-212 4-chlorocinnamyl H H H H 4-n-PrO
    XXVIII-213 4-fluorocinnamyl H H H H 4-n-PrO
    XXVIII-214 4-trifluoromethylcinnamyl H H H H 4-n-PrO
    XXVIII-215 4-cyanocinnamyl H H H H 4-n-PrO
    XXVIII-216 cinnamyl H Cl H H 4-n-PrO
    XXVIII-217 4-chlorocinnamyl H Cl H H 4-n-PrO
    XXVIII-218 4-fluorocinnamyl H Cl H H 4-n-PrO
    XXVIII-219 4-trifluoromethylcinnamyl H Cl H H 4-n-PrO
    XXVIII-220 4-cyanocinnamyl H Cl H H 4-n-PrO
    XXVIII-221 cinnamyl H F H H 4-n-PrO
    XXVIII-222 4-chlorocinnamyl H F H H 4-n-PrO
    XXVIII-223 4-fluorocinnamyl H F H H 4-n-PrO
    XXVIII-224 4-trifluoromethylcinnamyl H F H H 4-n-PrO
    XXVIII-225 4-cyanocinnamyl H F H H 4-n-PrO
    XXVIII-226 cinnamyl H H F H 4-n-PrO
    XXVIII-227 4-chlorocinnamyl H H F H 4-n-PrO
    XXVIII-228 4-fluorocinnamyl H H F H 4-n-PrO
    XXVIII-229 4-trifluoromethylcinnamyl H H F H 4-n-PrO
    XXVIII-230 4-cyanocinnamyl H H F H 4-n-PrO
    XXVIII-231 cinnamyl H F H F 4-n-PrO
    XXVIII-232 4-chlorocinnamyl H F H F 4-n-PrO
    XXVIII-233 4-fuorocinnamyl H F H F 4-n-PrO
    XXVIII-234 4-trifluoromethylcinnamyl H F H F 4-n-PrO
    XXVIII-235 4-cyanocinnamyl H F H F 4-n-PrO
    XXVIII-236 cinnamyl H OMe H H 4-n-PrO
    XXVIII-237 4-chlorocinnamyl H OMe H H 4-n-PrO
    XXVIII-238 4-fluorocinnamyl H OMe H H 4-n-PrO
    XXVIII-239 4-trifluoromethylcinnamyl H OMe H H 4-n-PrO
    XXVIII-240 4-cyanocinnamyl H OMe H H 4-n-PrO
    XXVIII-241 cinnamyl H H H H 2-Me
    XXVIII-242 4-chlorocinnamyl H H H H 2-Me
    XXVIII-243 4-fluorocinnamyl H H H H 2-Me
    XXVIII-244 4-trifluoromethylcinnamyl H H H H 2-Me
    XXVIII-245 4-cyanocinnamyl H H H H 2-Me
    XXVIII-246 cinnamyl H Cl H H 2-Me
    XXVIII-247 4-chlorocinnamyl H Cl H H 2-Me
    XXVIII-248 4-fluorocinnamyl H Cl H H 2-Me
    XXVIII-249 4-trifluoromethylcinnamyl H Cl H H 2-Me
    XXVIII-250 4-cyanocinnamyl H Cl H H 2-Me
    XXVIII-251 cinnamyl H F H H 2-Me
    XXVIII-252 4-chlorocinnamyl H F H H 2-Me
    XXVIII-253 4-fluorocinnamyl H F H H 2-Me
    XXVIII-254 4-trifluoromethylcinnamyl H F H H 2-Me
    XXVIII-255 4-cyanocinnamyl H F H H 2-Me
    XXVIII-256 cinnamyl H H F H 2-Me
    XXVIII-257 4-chlorocinnamyl H H F H 2-Me
    XXVIII-258 4-fluorocinnamyl H H F H 2-Me
    XXVIII-259 4-trifluoromethylcinnamyl H H F H 2-Me
    XXVIII-260 4-cyanocinnamyl H H F H 2-Me
    XXVIII-261 cinnamyl H F H F 2-Me
    XXVIII-262 4-chlorocinnamyl H F H F 2-Me
    XXVIII-263 4-fluorocinnamyl H F H F 2-Me
    XXVIII-264 4-trifluoromethylcinnamyl H F H F 2-Me
    XXVIII-265 4-cyanocinnamyl H F H F 2-Me
    XXVIII-266 cinnamyl H OMe H H 2-Me
    XXVIII-267 4-chlorocinnamyl H OMe H H 2-Me
    XXVIII-268 4-fluorocinnamyl H OMe H H 2-Me
    XXVIII-269 4-trifluoromethylcinnamyl H OMe H H 2-Me
    XXVIII-270 4-cyanocinnamyl H OMe H H 2-Me
  • Table XXIX provides 214 compounds of formula Iac
    Figure US20060106045A1-20060518-C00031
  • wherein the values of R8, R4a, R4b, Y and R1 are given in Table 3
    TABLE 3
    R8 R4a R4b Y R1
    XXIX-1 2- H Cl C(O) 2-chloropyrid-4-yl
    (benzoxazolyl)methyl
    XXIX-2 2- H F C(O) 2-chloropyrid-4-yl
    (benzoxazolyl)methyl
    XXIX-3 2- H Cl bond carbomethoxy
    (benzoxazolyl)methyl
    XXIX-4 2- H F bond carbomethoxy
    (benzoxazolyl)methyl
    XXIX-5 2- H Cl bond acetyl
    (benzoxazolyl)methyl
    XXIX-6 2- H F bond acetyl
    (benzoxazolyl)methyl
    XXIX-7 2-methyl-3-(3′,4′- H Cl C(O) 2-chloropyrid-4-yl
    methylenedioxyphenyl)
    prop-2-enyl
    XXIX-8 2-methyl-3-(3′,4′- H F C(O) 2-chloropyrid-4-yl
    methylenedioxyphenyl)
    prop-2-enyl
    XXIX-9 2-methyl-3-(3′,4′- H Cl bond Carbomethoxy
    methylenedioxyphenyl)
    prop-2-enyl
    XXIX-10 2-methyl-3-(3′,4′- H F bond carbomethoxy
    methylenedioxyphenyl)
    prop-2-enyl
    XXIX-11 2-methyl-3-(3′,4′- H Cl bond acetyl
    methylenedioxyphenyl)
    prop-2-enyl
    XXIX-12 2-methyl-3-(3′,4′- H F bond acetyl
    methylenedioxyphenyl)
    prop-2-enyl
    XXIX-13 3-phenylprop-2-ynyl H Cl C(O) 2-chloropyrid-4-yl
    XXIX-14 3-phenylprop-2-ynyl H F C(O) 2-chloropyrid-4-yl
    XXIX-15 3-phenylprop-2-ynyl H Cl bond carbomethoxy
    XXIX-16 3-phenylprop-2-ynyl H F bond carbomethoxy
    XXIX-17 3-phenylprop-2-ynyl H Cl bond acetyl
    XXIX-18 3-phenylprop-2-ynyl H F bond acetyl
    XXIX-19 trifluoroacetamido H Cl C(O) 2-chloropyrid-4-yl
    XXIX-20 trifluoroacetamido H F C(O) 2-chloropyrid-4-yl
    XXIX-21 trifluoroacetamido H Cl bond carbomethoxy
    XXIX-22 trifluoroacetamido H F bond carbomethoxy
    XXIX-23 trifluoroacetamido H Cl bond acetyl
    XXIX-24 trifluoroacetamido H F bond acetyl
    XXIX-25 4-chlorocinnamate H Cl C(O) 2-chloropyrid-4-yl
    XXIX-26 4-chlorocinnamate H F C(O) 2-chloropyrid-4-yl
    XXIX-27 4-chlorocinnamate H Cl bond carbomethoxy
    XXIX-28 4-chlorocinnamate H F bond carbomethoxy
    XXIX-29 4-chlorocinnamate H Cl bond acetyl
    XXIX-30 4-chlorocinnamate H F bond acetyl
    XXIX-31 2-oxo-2-(2′-chloro- H Cl C(O) 2-chloropyrid-4-yl
    4′-
    methylphenyl)ethyl
    XXIX-32 2-oxo-2-2′-chloro- H F C(O) 2-chloropyrid-4-yl
    4′-
    methylphenyl)ethyl
    XXIX-33 2-oxo-2-(2′-chloro- H Cl bond carbomethoxy
    4′-
    methylphenyl)ethyl
    XXIX-34 2-oxo-2-(2′-chloro- H F bond carbomethoxy
    4′-
    methylphenyl)ethyl
    XXIX-35 2-oxo-2-(2′-chloro- H Cl bond acetyl
    4′-
    methylphenyl)ethyl
    XXIX-36 2-oxo-2-(2′-chloro- H F bond acetyl
    4′-
    methylphenyl)ethyl
    XXIX-37 2-oxo-1,2- H Cl C(O) 2-chloropyrid-4-yl
    diphenylethyl
    XXIX-38 2-oxo-1,2- H F C(O) 2-chloropyrid-4-yl
    diphenylethyl
    XXIX-39 2-oxo-1,2- H Cl bond carbomethoxy
    diphenylethyl
    XXIX-40 2-oxo-1,2- H F bond carbomethoxy
    diphenylethyl
    XXIX-41 2-oxo-1,2- H Cl bond acetyl
    diphenylethyl
    XXIX-42 2-oxo-1,2- H F bond acetyl
    diphenylethyl
    XXIX-43 3,3-dichloroallyl H Cl C(O) 2-chloropyrid-4-yl
    XXIX-44 3,3-dichloroallyl H F C(O) 2-chloropyrid-4-yl
    XXIX-45 3,3-dichloroallyl H Cl bond carbomethoxy
    XXIX-46 3,3-dichloroallyl H F bond carbomethoxy
    XXIX-47 3,3-dichloroallyl H Cl bond acetyl
    XXIX-48 3,3-dichloroallyl H F bond acetyl
    XXIX-49 t-butyloxycarbonyl H F bond H
    XXIX-50 t-butyloxycarbonyl H Cl bond H
    XXIX-51 t-butyloxycarbonyl H Cl C(O) 2-chloropyrid-4-yl
    XXIX-52 t-butyloxycarbonyl H F C(O) 2-chloropyrid-4-yl
    XXIX-53 t-butyloxycarbonyl H Cl bond carbomethoxy
    XXIX-54 t-butyloxycarbonyl H F bond carbomethoxy
    XXIX-55 t-butyloxycarbonyl H Cl bond acetyl
    XXIX-56 t-butyloxycarbonyl H F bond acetyl
    XXIX-57 4-chlorocinnamyl H Cl bond 5-trifluoromethylpyrid-2-
    yl
    XXIX-58 4-chlorocinnamyl H F bond 5-trifluoromethylpyrid-2-
    yl
    XXIX-59 4-chlorocinnamyl Br H bond 5-trifluoromethylpyrid-2-
    yl
    XXIX-60 4-fluorocinnamyl H Cl bond 5-trifluoromethylpyrid-2-
    yl
    XXIX-61 4-fluorocinnamyl H F bond 5-trifluoromethylpyrid-2-
    yl
    XXIX-62 4-fluorocinnamyl Br H bond 5-trifluoromethylpyrid-2-
    yl
    XXIX-63 4-chlorocinnamyl H Cl bond pyrimidin-2-yl
    XXIX-64 4-chlorocinnamyl H F bond pyrimidin-2-yl
    XXIX-65 4-chlorocinnamyl Br H bond pyrimidin-2-yl
    XXIX-66 4-fluorocinnamyl H Cl bond pyrimidin-2-yl
    XXIX-67 4-fluorocinnamyl H F bond pyrimidin-2-yl
    XXIX-68 4-fluorocinnamyl Br H bond pyrimidin-2-yl
    XXIX-69 4-chlorocinnamyl H Cl C(O) pyrazinyl
    XXIX-70 4-chlorocinnamyl H F C(O) pyrazinyl
    XXIX-71 4-chlorocinnamyl Br H C(O) pyrazinyl
    XXIX-72 4-fluorocinnamyl H Cl C(O) pyrazinyl
    XXIX-73 4-fluorocinnamyl H F C(O) pyrazinyl
    XXIX-74 4-fluorocinnamyl Br H C(O) pyrazinyl
    XXIX-75 4-chlorocinnamyl H Cl C(O) 2-chloropyrid-5-yl
    XXIX-76 4-chlorocinnamyl H F C(O) 2-chloropyrid-5-yl
    XXIX-77 4-chlorocinnamyl Br H C(O) 2-chloropyrid-5-yl
    XXIX-78 4-fluorocinnamyl H Cl C(O) 2-chloropyrid-5-yl
    XXIX-79 4-fluorocinnamyl H F C(O) 2-chloropyrid-5-yl
    XXIX-80 4-fluorocinnamyl Br H C(O) 2-chloropyrid-5-yl
    XXIX-81 4-chlorocinnamyl H Cl C(O) 1,2,3-thiadiazol-4-yl
    XXIX-82 4-chlorocinnamyl H F C(O) 1,2,3-thiadiazol-4-yl
    XXIX-83 4-chlorocinnamyl Br H C(O) 1,2,3-thiadiazol-4-yl
    XXIX-84 4-fluorocinnamyl H Cl C(O) 1,2,3-thiadiazol-4-yl
    XXIX-85 4-fluorocinnamyl H F C(O) 1,2,3-thiadiazol-4-yl
    XXIX-86 4-fluorocinnamyl Br H C(O) 1,2,3-thiadiazol-4-yl
    XXIX-87 4-chlorocinnamyl H Cl C(O) 1-methyl-5-nitro-[1H]-
    pyrazol-4-yl
    XXIX-88 4-chlorocinnamyl H F C(O) 1-methyl-5-nitro-[1H]-
    pyrazol-4-yl
    XXIX-89 4-chlorocinnamyl Br H C(O) 1-methyl-5-nitro-[1H]-
    pyrazol-4-yl
    XXIX-90 4-fluorocinnamyl H Cl C(O) 1-methyl-5-nitro-[1H]-
    pyrazol-4-yl
    XXIX-91 4-fluorocinnamyl H F C(O) 1-methyl-5-nitro-[1H]-
    pyrazol-4-yl
    XXIX-92 4-fluorocinnamyl Br H C(O) 1-methyl-5-nitro-[1H]-
    pyrazol-4-yl
    XXIX-93 4-chlorocinnamyl H Cl C(O) 5-carbomethoxypyrid-2-
    yl
    XXIX-94 4-chlorocinnamyl H F C(O) 5-carbomethoxypyrid-2-
    yl
    XXIX-95 4-chlorocinnamyl Br H C(O) 5-carbomethoxypyrid-2-
    yl
    XXIX-96 4-fluorocinnamyl H Cl C(O) 5-carbomethoxypyrid-2-
    yl
    XXIX-97 4-fluorocinnamyl H F C(O) 5-carbomethoxypyrid-2-
    yl
    XXIX-98 4-fluorocinnamyl Br H C(O) 5-carbomethoxypyrid-2-
    yl
    XXIX-99 4-chlorocinnamyl H Cl C(O) 4-chloropyrid-2-yl
    XXIX-100 4-chlorocinnamyl H F C(O) 4-chloropyrid-2-yl
    XXIX-101 4-chlorocinnamyl Br H C(O) 4-chloropyrid-2-yl
    XXIX-102 4-fluorocinnamyl H Cl C(O) 4-chloropyrid-2-yl
    XXIX-103 4-fluorocinnamyl H F C(O) 4-chloropyrid-2-yl
    XXIX-104 4-fluorocinnamyl Br H C(O) 4-chloropyrid-2-yl
    XXIX-105 4-chlorocinnamyl H Cl C(O) 2-methyl-6-
    trifluoromethylpyrid-3-yl
    XXIX-106 4-chlorocinnamyl H F C(O) 2-methyl-6-
    trifluoromethylpyrid-3-yl
    XXIX-107 4-chlorocinnamyl Br H C(O) 2-methyl-6-
    trifluoromethylpyrid-3-yl
    XXIX-108 4-fluorocinnamyl H Cl C(O) 2-methyl-6-
    trifluoromethylpyrid-3-yl
    XXIX-109 4-fluorocinnamyl H F C(O) 2-methyl-6-
    trifluoromethylpyrid-3-yl
    XXIX-110 4-fluorocinnamyl Br H C(O) 2-methyl-6-
    trifluoromethylpyrid-3-yl
    XXIX-111 4-chlorocinnamyl H Cl C(O) 5-methylisoxazol-3-yl
    XXIX-112 4-chlorocinnamyl H F C(O) 5-methylisoxazol-3-yl
    XXIX-113 4-chlorocinnamyl Br H C(O) 5-methylisoxazol-3-yl
    XXIX-114 4-fluorocinnamyl H Cl C(O) 5-methylisoxazol-3-yl
    XXIX-115 4-fluorocinnamyl H F C(O) 5-methylisoxazol-3-yl
    XXIX-116 4-fluorocinnamyl Br H C(O) 5-methylisoxazol-3-yl
    XXIX-117 4-chlorocinnamyl H Cl C(O) (pyrid-4-yl)methyl
    XXIX-118 4-chlorocinnamyl H F C(O) (pyrid-4-yl)methyl
    XXIX-119 4-chlorocinnamyl Br H C(O) (pyrid-4-yl)methyl
    XXIX-120 4-fluorocinnamyl H Cl C(O) (pyrid-4-yl)methyl
    XXIX-121 4-fluorocinnamyl H F C(O) (pyrid-4-yl)methyl
    XXIX-122 4-fluorocinnamyl Br H C(O) (pyrid-4-yl)methyl
    XXIX-123 4-chlorocinnamyl H Cl C(O) (thiophen-2-yl)methyl
    XXIX-124 4-chlorocinnamyl H F C(O) (thiophen-2-yl)methyl
    XXIX-125 4-chlorocinnamyl Br H C(O) (thiophen-2-yl)methyl
    XXIX-126 4-fluorocinnamyl H Cl C(O) (thiophen-2-yl)methyl
    XXIX-127 4-fluorocinnamyl H F C(O) (thiophen-2-yl)methyl
    XXIX-128 4-fluorocinnamyl Br H C(O) (thiophen-2-yl)methyl
    XXIX-129 4-chlorocinnamyl H Cl C(O) cyclopentyl
    XXIX-130 4-chlorocinnamyl H F C(O) cyclopentyl
    XXIX-131 4-chlorocinnamyl Br H C(O) cyclopentyl
    XXIX-132 4-fluorocinnamyl H Cl C(O) cyclopentyl
    XXIX-133 4-fluorocinnamyl H F C(O) cyclopentyl
    XXIX-134 4-fluorocinnamyl Br H C(O) cyclopentyl
    XXIX-135 4-chlorocinnamyl H Cl C(O) acetylaminomethyl
    XXIX-136 4-chlorocinnamyl H F C(O) acetylaminomethyl
    XXIX-137 4-chlorocinnamyl Br H C(O) acetylaminomethyl
    XXIX-138 4-fluorocinnamyl H Cl C(O) acetylaminomethyl
    XXIX-139 4-fluorocinnamyl H F C(O) acetylaminomethyl
    XXIX-140 4-fluorocinnamyl Br H C(O) acetylaminomethyl
    XXIX-141 4-chlorocinnamyl H Cl SO2 4-acetylaminophenyl
    XXIX-142 4-chlorocinnamyl H F SO2 4-acetylaminophenyl
    XXIX-143 4-chlorocinnamyl Br H SO2 4-acetylaminophenyl
    XXIX-144 4-fluorocinnamyl H Cl SO2 4-acetylaminophenyl
    XXIX-145 4-fluorocinnamyl H F SO2 4-acetylaminophenyl
    XXIX-146 4-fluorocinnamyl Br H SO2 4-acetylaminophenyl
    XXIX-147 4-chlorocinnamyl H Cl SO2 3,5-dimethylisoxazol-4-
    yl
    XXIX-148 4-chlorocinnamyl H F SO2 3,5-dimethylisoxazol-4-
    yl
    XXIX-149 4-chlorocinnamyl Br H SO2 3,5-dimethylisoxazol-4-
    yl
    XXIX-150 4-fluorocinnamyl H Cl SO2 3,5-dimethylisoxazol-4-
    yl
    XXIX-151 4-fluorocinnamyl H F SO2 3,5-dimethylisoxazol-4-
    yl
    XXIX-152 4-fluorocinnamyl Br H SO2 3,5-dimethylisoxazol-4-
    yl
    XXIX-153 4-chlorocinnamyl H Cl C(O) (2-methoxyphenyl)amino
    XXIX-154 4-chlorocinnamyl H F C(O) (2-methoxyphenyl)amino
    XXIX-155 4-chlorocinnamyl Br H C(O) (2-methoxyphenyl)amino
    XXIX-156 4-fluorocinnamyl H Cl C(O) (2-methoxyphenyl)amino
    XXIX-157 4-fluorocinnamyl H F C(O) (2-methoxyphenyl)amino
    XXIX-158 4-fluorocinnamyl Br H C(O) (2-methoxyphenyl)amino
    XXIX-159 4-chlorocinnamyl H F C(O) cyclohexen-1-yl
    XXIX-160 4-chlorocinnamyl H Cl C(O) cyclohexen-1-yl
    XXIX-161 4-chlorocinnamyl Br H C(O) cyclohexen-1-yl
    XXIX-162 4-fluorocinnamyl H Cl C(O) cyclohexen-1-yl
    XXIX-163 4-fluorocinnamyl H F C(O) cyclohexen-1-yl
    XXIX-164 4-fluorocinnamyl Br H C(O) cyclohexen-1-yl
    XXIX-165 4-chlorocinnamyl H F C(O) quinolin-3-yl
    XXIX-166 4-chlorocinnamyl H Cl C(O) quinolin-3-yl
    XXIX-167 4-chlorocinnamyl Br H C(O) quinolin-3-yl
    XXIX-168 4-fluorocinnamyl H Cl C(O) quinolin-3-yl
    XXIX-169 4-fluorocinnamyl H F C(O) quinolin-3-yl
    XXIX-170 4-fluorocinnamyl Br H C(O) quinolin-3-yl
    XXIX-171 4-chlorocinnamyl H F C(O) benzothiophen-2-yl
    XXIX-172 4-chlorocinnamyl H Cl C(O) benzothiophen-2-yl
    XXIX-173 4-chlorocinnamyl Br H C(O) benzothiophen-2-yl
    XXIX-174 4-fluorocinnamyl H Cl C(O) benzothiophen-2-yl
    XXIX-175 4-fluorocinnamyl H F C(O) benzothiophen-2-yl
    XXIX-176 4-fluorocinnamyl Br H C(O) benzothiophen-2-yl
    XXIX-177 4-chlorocinnamyl H F C(O) 5-nitro-[1H]-pyrazol-3-yl
    XXIX-178 4-chlorocinnamyl H Cl C(O) 5-nitro-[1H]-pyrazol-3-yl
    XXIX-179 4-chlorocinnamyl Br H C(O) 5-nitro-[1H]-pyrazol-3-yl
    XXIX-180 4-fluorocinnamyl H Cl C(O) 5-nitro-[1H]-pyrazol-3-yl
    XXIX-181 4-fluorocinnamyl H F C(O) 5-nitro-[1H]-pyrazol-3-yl
    XXIX-182 4-fluorocinnamyl Br H C(O) 5-nitro-[1H]-pyrazol-3-yl
    XXIX-183 4-chlorocinnamyl H F C(O) ([1H]-tetrazol-1-
    yl)methyl
    XXIX-184 4-chlorocinnamyl H Cl C(O) ([1H]-tetrazol-1-
    yl)methyl
    XXIX-185 4-chlorocinnamyl Br H C(O) ([1H]-tetrazol-1-
    yl)methyl
    XXIX-186 4-fluorocinnamyl H Cl C(O) ([1H]-tetrazol-1-
    yl)methyl
    XXIX-187 4-fluorocinnamyl H F C(O) ([1H]-tetrazol-1-
    yl)methyl
    XXIX-188 4-fluorocinnamyl Br H C(O) ([1H]-tetrazol-1-
    yl)methyl
    XXIX-189 4-chlorocinnamyl H Cl bond benzyl
    XXIX-190 4-chlorocinnamyl H F bond benzyl
    XXIX-191 4-chlorocinnamyl Br H bond benzyl
    XXIX-192 4-fluorocinnamyl H Cl bond benzyl
    XXIX-193 4-fluorocinnamyl H F bond benzyl
    XXIX-194 4-fluorocinnamyl Br H bond benzyl
    XXIX-195 4-chlorocinnamyl H F C(O) (4-cyanophenyl)amino
    XXIX-196 4-chlorocinnamyl H Cl C(O) (4-cyanophenyl)amino
    XXIX-197 4-chlorocinnamyl Br H C(O) (4-cyanophenyl)amino
    XXIX-198 4-fluorocinnamyl H Cl C(O) (4-cyanophenyl)amino
    XXIX-199 4-fluorocinnamyl H F C(O) (4-cyanophenyl)amino
    XXIX-200 4-fluorocinnamyl Br H C(O) (4-cyanophenyl)amino
    XXIX-201 4-chlorocinnamyl H Me3Si C(O) 2-chloropyrid-4-yl
    CC
    XXIX-202 4-fluorocinnamyl H Me3Si C(O) 2-chloropyrid-4-yl
    CC
    XXIX-203 4-chlorocinnamyl H Me3Si bond carbomethoxy
    CC
    XXIX-204 4-fluorocinnamyl H Me3Si bond carbomethoxy
    CC
    XXIX-205 4-chlorocinnamyl H Me3Si bond acetyl
    CC
    XXIX-206 4-fluorocinnamyl H Me3Si bond acetyl
    CC
    XXIX-207 4-chlorocinnamyl H OMe SO2 n-butyl
    XXIX-208 4-chlorocinnamyl H F SO2 n-butyl
    XXIX-209 4-chlorocinnamyl H Cl SO2 n-butyl
    XXIX-210 4-chlorocinnamyl Br H SO2 n-butyl
    XXIX-211 4-fluorocinnamyl H OMe SO2 n-butyl
    XXIX-212 4-fluorocinnamyl H Cl SO2 n-butyl
    XXIX-213 4-fluorocinnamyl H F SO2 n-butyl
    XXIX-214 4-fluorocinnamyl Br H SO2 n-butyl
  • Table XXX provides 121 compounds of formula Iad
    (Iad)
    Figure US20060106045A1-20060518-C00032
    R4n R53 R54 RSn Y R1
    XXX-1 6-OCF3 H H 4-Cl C(O) Me
    XXX-2 6-OCF3 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-3 4-OCF3 H H 4-Cl C(O) Me
    XXX-4 6-OCF2CHF2 H H 4-Cl C(O) Me
    XXX-5 4-OCF2CHF2 H H 4-Cl C(O) Me
    XXX-6 4-OCF3 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-7 6-OCF2CHF2 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-8 4-OCF2CHF2 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-9 7-O—Ph H H 4-Cl C(O) Me
    XXX-10 7-O—Ph H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-11 5-OCH2CH3 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-12 6-OCF3 H H 4-Cl C(O) 2,6-dibromopyrid-
    4-yl
    XXX-13 6-OCF3 H H 4-Cl C(O) 2,6-dichloropyrid-
    4-yl
    XXX-14 6-OCF3 H H 4-Cl C(O) pyrid-3-yl
    XXX-15 4-OCF2CHF2 H H 4-Cl C(O) 2,6-dibromopyrid-
    4-yl
    XXX-16 4-OCF2CHF2 H H 4-Cl C(O) 2,6-dichloropyrid-
    4-yl
    XXX-17 4-OCF2CHF2 H H 4-Cl C(O) pyrid-3-yl
    XXX-18 4-OCF3 H H 4-Cl C(O) 2,6-dibromopyrid-
    4-yl
    XXX-19 4-OCF3 H H 4-Cl C(O) 2,6-dichloropyrid-
    4-yl
    XXX-20 4-OCF3 H H 4-Cl C(O) pyrid-3-yl
    XXX-21 6-OCF2CHF2 H H 4-Cl C(O) 2,6-dibromopyrid-
    4-yl
    XXX-22 6-OCF2CHF2 H H 4-Cl C(O) 3,5-dichloropyrid-
    4-yl
    XXX-23 4-OCF3 H H 4-Cl C(O) 4,6-dimethoxy-
    pyrimidin-2-yl
    XXX-24 4-OCF2CHF2 H H 4-Cl C(O) 4,6-dimethoxy-
    pyrimidin-2-yl
    XXX-25 6-OCF3 H H 4-Cl C(O) 2-chloropyrid-3-yl
    XXX-26 7-OCF3 H H 4-Cl C(O) 2-chloropyrid-3-yl
    XXX-27 6-OCF2CHF2 H H 4-Cl C(O) 2-chloropyrid-3-yl
    XXX-28 4-OCF2CHF2 H H 4-Cl C(O) 2-chloropyrid-3-yl
    XXX-29 5-O-(4- H H 4-Cl C(O) 2-chloropyrid-4-yl
    trifluoromethyl-
    phenyl)
    XXX-30 5-OCF3 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-31 5-F H H 4-F C(O) 2-chloropyrid-4-yl
    XXX-32 5-Cl H H 2,4-Cl2 C(O) 2-chloropyrid-4-yl
    XXX-33 5,7-Cl2 H H 4-Cl C(O) Me
    XXX-34 7-Cl H H 4-Cl C(O) Me
    XXX-35 7-Cl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-36 5,7-dimethyl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-37 4,7-dimethyl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-38 6-CF3 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-39 4,6-Cl2 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-40 4,6-Cl2 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-41 5-isopropyl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-42 5-Br H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-43 6,7-dimethyl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-44 5,6-Cl2 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-45 4-CF3 H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-46 7-CH2Cl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-47 7-Br H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-48 5-tert-butyl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-49 4,6-dimethyl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-50 4-CF3-7-Cl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-51 5-Cl H H 4-CF3 C(O) 2-chloropyrid-4-yl
    XXX-52 5-Cl H H 4- C(O) 2-chloropyrid-4-yl
    CH═CH2
    XXX-53 5-Cl H H 4-CF3 C(O) 2-chloropyrid-4-yl
    XXX-54 5-Cl H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-55 5-Cl H H 4-NO2 C(O) 2-chloropyrid-4-yl
    XXX-56 5-Cl H H 3,5-(CF3)2 C(O) 2-chloropyrid-4-yl
    XXX-57 5-Cl H H 3-Br C(O) 2-chloropyrid-4-yl
    XXX-58 5-Cl H H 3-ethoxy C(O) 2-chloropyrid-4-yl
    XXX-59 5-Cl H H 2-Me C(O) 2-chloropyrid-4-yl
    XXX-60 5-Cl H H 4-Me C(O) 2-chloropyrid-4-yl
    XXX-61 5-Cl H H 3-Cl,4-F C(O) 2-chloropyrid-4-yl
    XXX-62 5-Cl H H 3,5-Cl2 C(O) 2-chloropyrid-4-yl
    XXX-63 5-Cl H H 4-N3 C(O) 2-chloropyrid-4-yl
    XXX-64 5-Cl H H 2-Br C(O) 2-chloropyrid-4-yl
    XXX-65 5-Cl H H 2,6- C(O) 2-chloropyrid-4-yl
    dimethoxy
    XXX-66 5-Cl H H 4-ethoxy C(O) 2-chloropyrid-4-yl
    XXX-67 5-Cl H H 3-Cl C(O) 2-chloropyrid-4-yl
    XXX-68 5-Cl H H 3-Me,4- C(O) 2-chloropyrid-4-yl
    OMe,5-Cl
    XXX-69 5-Cl H H 4-OPh C(O) 2-chloropyrid-4-yl
    XXX-70 5-Cl H H 4-CN C(O) 2-chloropyrid-4-yl
    XXX-71 5-Cl H H 3-F,4-Ph C(O) 2-chloropyrid-4-yl
    XXX-72 5-Cl H H 4-SMe C(O) 2-chloropyrid-4-yl
    XXX-73 5-Cl H H 3-Br C(O) 2-chloropyrid-4-yl
    XXX-74 5-Cl H H 4-F C(O) 2-chloropyrid-4-yl
    XXX-75 5-Cl H H 4-Br C(O) 2-chloropyrid-4-yl
    XXX-76 5-Cl H H 2,4-Cl2 C(O) 2-chloropyrid-4-yl
    XXX-77 5-Cl H H 2,4-F2 C(O) 2-chloropyrid-4-yl
    XXX-78 5-Cl H H 3-CF3 C(O) 2-chloropyrid-4-yl
    XXX-79 5-Cl H H 3,4- C(O) 2-chloropyrid-4-yl
    diethoxy
    XXX-80 5-Cl H H 3-Me,4-F C(O) 2-chloropyrid-4-yl
    XXX-81 5-Cl H H 4-Ph C(O) 2-chloropyrid-4-yl
    XXX-82 5-Cl H Me 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-83 5-Cl H Me 4-Cl C(O) Me
    XXX-84 5-Cl H Me 4-F C(O) 2-chloropyrid-4-yl
    XXX-85 5-Cl H Me 4-F C(O) Me
    XXX-86 5-Cl H H 4-OCF3 C(O) 2-chloropyrid-4-yl
    XXX-87 5-Cl H H 4-OCF3 C(O) Me
    XXX-88 5-Cl H F H C(O) 2-chloropyrid-4-yl
    XXX-89 5-Cl H F 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-90 5-Cl H F 4-Cl C(O) Me
    XXX-91 5-Cl H CF3 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-92 5-Cl H CF3 4-Cl C(O) Me
    XXX-93 5-F H H 4-Cl C(O) imidazol-1-yl
    XXX-94 5-F H H 4-Cl Bond NH2
    XXX-95 5-F H H 4-Cl Bond —NHCO-
    2-chloropyrid-4-yl
    XXX-96 5-Cl H H 4-NO2 C(O) Me
    XXX-97 5-Cl H H 4-Cl Bond NHCO-4-
    trifluoromethoxy-
    phenyl
    XXX-98 5-Cl H H 4-Cl Bond —NHCO-
    pyrid-4-yl
    XXX-99 5-Cl H H 4-Cl Bond —NHCO-
    3-chloropyrid-4-yl
    XXX-100 5-F H H 4-Cl Bond —NHCONH-4-
    trifluoromethoxy-
    phenyl
    XXX-101 5-F H H 4-Cl Bond —NHCONH-3-
    chlorophenyl
    XXX-102 5-Cl H H 4-Cl Bond —N═C(Me)NMe2
    XXX-103 5-Cl H H 4-Cl Bond —NHCONH-4-
    trifluoromethyl-
    phenyl
    XXX-104 5-F H H 4-Cl C(O) —NH-isopropyl
    XXX-105 5-F H H 4-Cl C(O) —NH(CH2)2OMe
    XXX-106 5-F H H 4-Cl C(O) —NHCH2-pyrid-3-yl
    XXX-107 5-F H H 4-Cl C(O) —NH(CH2)2OH
    XXX-108 5-F H H 4-Cl C(O) —NH(CH2)2-
    morpholinyl
    XXX-109 5-F H H 4-Cl C(O) —NHCH2-pyrid-4-yl
    XXX-110 5-F H H 4-Cl C(O) —NH-ethyl
    XXX-111 5-F H H 4-Cl C(O) —NH-methyl
    XXX-112 5-F H H 4-Cl C(O) —NH-benzyl
    XXX-113 5-Cl F H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-114 5-Cl F H 4-CF3 C(O) 2-chloropyrid-4-yl
    XXX-115 5-Cl H Cl 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-116 5 + 6 -O—CF2—O— H H 4-Cl C(O) Me
    XXX-117 5 + 6 -O—CF2—O— H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-118 5 + 6 -O—CH2—O— H H 4-Cl C(O) 2-chloropyrid-4-yl
    XXX-119 5-F H H 4-Cl Bond —NHCONH-4-
    chlorophenyl
    XXX-120 5-F H H 4-Cl Bond Ethyl
    XXX-121 5-Cl H H 4-Cl Bond NO
  • Table XXXI provides 8 compounds of formula Iae
    (Iae)
    Figure US20060106045A1-20060518-C00033
    R4n R53 R54 Rt Y R1
    XXXI-1 5-Cl H H 5-trifluoromethyl- C(O) 2-chloropyrid-
    pyrid-2-yl 4-yl
    XXXI-2 5-F H H 5-chloro- C(O) 2-chloropyrid-
    thiophen-2-yl 4-yl
    XXXI-3 5-Cl H H thiophen-2-yl C(O) 2-chloropyrid-
    4-yl
    XXXI-4 5-Cl H H naphtha-2-yl C(O) 2-chloropyrid-
    4-yl
    XXXI-5 5-Cl H H —CH═CH- C(O) 2-chloropyrid-
    phenyl 4-yl
    XXXI-6 5-Cl H H benzothiophen-2- C(O) 2-chloropyrid-
    yl 4-yl
    XXXI-7 5-Cl H H —CH═CH- C(O) 2-chloropyrid-
    4-chlorophenyl 4-yl
    XXXI-8 5-Cl H H Br C(O) 2-chloropyrid-
    4-yl
  • Table XXXII provides 10 compounds of formula Iaf
    (Iaf)
    Figure US20060106045A1-20060518-C00034
    R4n Ru Y R1
    XXXII-1 5-Cl 4-F-Ph C(O) 2-chloropyrid-4-yl
    XXXII-2 5-Cl 4-OCF3-Ph C(O) 2-chloropyrid-4-yl
    XXXII-3 5-Cl 4-Cl-Ph C(O) 2-chloropyrid-4-yl
    XXXII-4 5-F 6-F-naphth-2-yl C(O) 2-chloropyrid-4-yl
    XXXII-5 5-Cl —CH(OH)CH2O-4-Cl- C(O) 2-chloropyrid-4-yl
    Ph
    XXXII-6 5-Cl —C(Me)═NO-Ph C(O) 2-chloropyrid-4-yl
    XXXII-7 5-Cl 5-Cl-benzoxazol-2-yl C(O) 2-chloropyrid-4-yl
    XXXII-8 5-Cl 4-NHCOOCH(Me)2-Ph C(O) 2-chloropyrid-4-yl
    XXXII-9 5-Cl 4-NHCOOCH(Me)2-Ph C(O) 2-chloropyrid-4-yl
    XXXII-10 5-Cl (2-ethyl-terazol-5-yl)- C(O) 2-chloropyrid-4-yl
    4--Ph
  • Mass spectra data were obtained for selected compounds of Tables I to XXIX on Micromass Platform 2 machines. The data are shown in Table 3.
    TABLE 3
    Compound No MS data
    I-1 444 (95%),
    446 (100%)
    I-2 478 (100%),
    480 (70%),
    482 (15%)
    I-3 462 (100%),
    464 (95%)
    I-4 489 (100%),
    491 (70%)
    I-5 147 (100%),
    474 (30%),
    476 (80%)
    I-12 512 (95%),
    514 (100%),
    516 (35%),
    518 (5%)
    I-21 478 (100%),
    480 (70%),
    482 (15%)
    I-22 512 (100%),
    514 (98%),
    516 (35%),
    518 (5%)
    I-23 496 (100%),
    498 (75%),
    500 (15%)
    I-32 512 (90%),
    514 (100%),
    516 (35%),
    518 (5%)
    I-52 496 (100%),
    498 (70%),
    500 (15%)
    I-61 462 (100%),
    464 (30%)
    I-62 496 (100%),
    498 (80%),
    500 (20%)
    I-72 496 (100%),
    498 (70%),
    500 (15%)
    I-82 496 (100%),
    498 (75%),
    500 (15%)
    I-92 556 (55%),
    558 (100%),
    560 (40%),
    562 (8%)
    I-112 556 (55%),
    558 (100%),
    560 (40%),
    562 (8%)
    I-132 546 (75%),
    548 (100%),
    550 (40%),
    552 (10%)
    I-142 514 (100%),
    516 (70%),
    518 (15%)
    I-152 530 (97%),
    532 (100%),
    534 (40%),
    536 (5%)
    I-162 530 (100%),
    532 (97%),
    534 (40%),
    536 (5%)
    I-171 512 (98%),
    514 (100%),
    516 (35%),
    518 (5%)
    I-182 604 (100%),
    606 (70%),
    608 (15%)
    I-192 508 (100%),
    510 (80%),
    512 (20%)
    I-202 492 (100%),
    494 (70%),
    496 (15%)
    I-212 503 (100%),
    505 (70%),
    507 (15%)
    I-222 502 (100%),
    504 (70%),
    506 (15%)
    I-232 536 (100%),
    538 (70%),
    540 (15%)
    I-242 526 (100%),
    528 (99%),
    530 (35%),
    532 (5%)
    I-252 526 (100%),
    528 (90%),
    530 (35%),
    532 (5%)
    I-262 526 (95%),
    528 (100%),
    530 (35%),
    532 (5%)
    I-282 572 (100%),
    574 (80%),
    576 (20%)
    I-292 562 (100%),
    564 (70%),
    566 (15%)
    II-22 431 (100%),
    433 (60%),
    435 (15%)
    II-62 415 (100%),
    417 (35%)
    V-21 381 (100%),
    383 (35%)
    V-22 415 (100%),
    417 (70%),
    419 (15%)
    V-62 399 (100%),
    401 (40%)
    V-192 411 (100%),
    413 (60%)
    V-202 395 (100%),
    397 (80%)
    VI-1 410 (100%)
    VI-22 478 (100%),
    480 (70%),
    482 (15%)
    VI-62 462 (100%),
    464 (30%)
    VI-101 488 (100%),
    490 (100%)
    VI-202 458 (100%),
    460 (30%)
    IX-62 435 (100%),
    437 (40%)
    X-22 459 (100%),
    461 (75%),
    463 (15%)
    X-62 443 (100%),
    445 (40%)
    XI-62 467 (100%),
    469 (40%)
    XII-22 478 (100%),
    480 (75%),
    482 (35%),
    484 (5%)
    XIII-22 471 (100%),
    473 (70%),
    475 (15%)
    XIII-62 455 (100%),
    457 (35%)
    XIV-22 451 (100%),
    453 (70%),
    455 (15%)
    XV-22 528 (100%),
    530 (70%),
    532 (10%)
    XVII-62 533 (100%),
    535 (40%)
    XVIII-22 555 (100%),
    557 (80%),
    559 (20%)
    XVIII-202 535 (100%),
    537 (40%)
    XIX-22 502 (100%),
    504 (70%),
    506 (10%)
    XIX-202 482 (100%),
    484 (40%)
    XX-22 521 (100%),
    523 (75%),
    525 (15%)
    XX-62 505 (100%),
    507 (40%)
    XXI-22 557 (100%),
    559 (70%),
    561 (15%)
    XXI-62 541 (100%),
    543 (40%)
    XXII-22 526 (100%),
    528 (97%),
    530 (30%),
    532 (5%)
    XXV-62 357 (100%),
    359 (55%)
    XXV-222 363 (100%),
    365 (30%)
    XXVI-1 460 (100%),
    462 (100%)
    XXVI-2 494 (100%),
    496 (100%),
    498 (20%)
    XXVI-22 528 (100%),
    530 (97%),
    532 (30%),
    534 (5%)
    XXVIII-7 523 (100%),
    525 (80%),
    527 (20%)
    XXVIII-27 519 (100%),
    521 (40%)
    XXVIII-42 565 (100%),
    567 (40%)
    XXVIII-67 495 (100%),
    497 (70%),
    499 (10%)
    XXVIII-97 502 (100%),
    504 (70%),
    506 (10%)
    XXVIII-132 503 (100%),
    505 (40%)
    XXVIII-162 537 (100%),
    539 (40%)
    XXVIII-187 589 (95%),
    591 (100%),
    593 (40%),
    595 (5%)
    XXVIII-217 535 (100%),
    537 (70%),
    539 (10%)
    XXVIII-252 475 (100%),
    477 (40%)
    XXIX-1 492 (100%),
    494 (70%),
    496 (15%)
    XXIX-7 536 (100%),
    538 (70%),
    540 (15%)
    XXIX-13 476 (100%),
    478 (80%),
    480 (20%)
    XXIX-19 458 (100%),
    460 (85%),
    462 (15%)
    XXIX-31 528 (100%),
    530 (97%),
    532 (30%),
    534 (5%)
    XXIX-37 556 (100%),
    558 (70%),
    560 (15%)
    XXIX-43 470 (100%),
    472 (100%),
    474 (100%),
    476 (30%)
    XXIX-49 251 (100%),
    307 (70%)
    XXIX-69 479 (100%),
    481 (70%),
    483 (15%)
    XXIX-75 512 (95%),
    514 (100%),
    516 (40%),
    518 (5%)
    XXIX-81 485 (100%),
    487 (75%),
    489 (20%)
    XXIX-87 526 (100%),
    528 (70%),
    530 (10%)
    XXIX-93 536 (100%),
    538 (70%),
    540 (15%)
    XXIX-99 512 (95%),
    514 (100%),
    516 (30%),
    518 (5%)
    XXIX-105 560 (100%),
    562 (70%),
    564 (15%)
    XXIX-111 482 (100%),
    484 (70%),
    486 (15%)
    XXIX-117 373 (100%),
    375 (70%),
    377 (15%)
    492 (20%),
    494 (15%)
    XXIX-123 497 (100%),
    499 (75%),
    501 (15%)
    XXIX-129 469 (100%),
    471 (75%),
    473 (15%)
    XXIX-135 472 (100%),
    474 (70%),
    476 (15%)
    XXIX-141 570 (100%),
    572 (75%),
    574 (15%)
    XXIX-147 532 (100%),
    534 (80%),
    536 (20%)
    XXIX-153 522 (100%),
    524 (75%),
    526 (15%)
    XXIX-159 465 (100%),
    467 (40%)
    XXIX-165 512 (100%),
    514 (40%)
    XXIX-171 517 (100%),
    519 (40%)
    XXIX-177 427 (100%),
    496 (80%),
    498 (30%)
    XXIX-183 467 (100%),
    469 (35%)
    XXIX-189 463 (100%),
    465 (55%),
    467 (15%)
    XXIX-195 501 (100%),
    503 (40%)
    XXIX-196 517 (100%),
    519 (70%),
    521 (15%)
    XXIX-201 574 (100%),
    576 (80%),
    578 (20%)
    XXIX-207 489 (100%),
    491 (40%)
  • Mass spectra data were obtained for selected compounds of Tables XXX to XXXII using LCMS: LC5: 254 nm—gradient 10% A to 100% B A=H2O+0.01% HCOOH B=CH3CN/CH3OH+0.010% HCOOH positive electrospray 150-1000 m/z
  • The data are shown in Table 4.
    TABLE 4
    LCMS
    (Ret. Time, LCMS
    Compound mp (° C.) min) (M + H)
    XXX-1 2′27 465
    XXX-2 2′55 562
    XXX-3 2′26 465
    XXX-4 2′30 497
    XXX-5 2′30 497
    XXX-6 2′48 562
    XXX-7 2′48 594
    XXX-8 2′51 594
    XXX-9 2′28 473
    XXX-10 2′43 570
    XXX-11 2′26 522
    XXX-12 2′57 686
    XXX-13 2′56 596
    XXX-14 2′09 528
    XXX-15 2′60 718
    XXX-16 2′71 630
    XXX-17 2′22 560
    XXX-18 2′66 686
    XXX-19 2′64 596
    XXX-20 2′29 528
    XXX-21 2′68 718
    XXX-22 2′68 630
    XXX-23 2′43 589
    XXX-24 2′53 621
    XXX-25 2′30 562
    XXX-26 2′33 562
    XXX-27 2′35 594
    XXX-28 2′42 594
    XXX-29 2′60 638
    XXX-30 562
    XXX-31 480
    XXX-32 546
    XXX-33 171-172 2′27 449
    XXX-34 59-61 2′01 415
    XXX-35 182-184 2′33 512
    XXX-36 158-160 2′43 506
    XXX-37 199-201 2′42 506
    XXX-38 2′48 546
    XXX-39 157-159 2′52 546
    XXX-40 2′46 546
    XXX-41 2′47 520
    XXX-42 140-142 2′37 556
    XXX-43 106-110 2′39 506
    XXX-44 2′53 546
    XXX-45 170-172 2′39 546
    XXX-46 146-148 2′36 506
    XXX-47 196-198 2′31 556
    XXX-48 149-151 2′49 534
    XXX-49 194-196 2′33 506
    XXX-50 165-167 2′48 580
    XXX-51 546
    XXX-52 504
    XXX-53 546
    XXX-54 513
    XXX-55 523
    XXX-56 614
    XXX-57 557
    XXX-58 522
    XXX-59 492
    XXX-60 492
    XXX-61 531
    XXX-62 547
    XXX-63 533
    XXX-64 557
    XXX-65 538
    XXX-66 522
    XXX-67 513
    XXX-68 557
    XXX-69 571
    XXX-70 503
    XXX-71 573
    XXX-72 525
    XXX-73 557
    XXX-74 496
    XXX-75 557
    XXX-76 547
    XXX-77 514
    XXX-78 546
    XXX-79 538
    XXX-80 510
    XXX-81 555
    XXX-82 2′45 528
    XXX-83 2′22 429
    XXX-84 2′30 510
    XXX-85 2′05 413
    XXX-86 70 2′40 562
    XXX-87 2′27 465
    XXX-88 2′22 497
    XXX-89 2′44 530
    XXX-90 2′15 433
    XXX-91
    XXX-92 2′53 483
    XXX-93 1′93 451
    XXX-94 1′74 372
    XXX-95 2′08 511
    XXX-96 1′93 426
    XXX-97 2′57 576
    XXX-98 1′99 493
    XXX-99 2′20 527
    XXX-100 2′55 575
    XXX-101 2′46 525
    XXX-102 1′45 457
    XXX-103 2′60 575
    XXX-104 2′13 442
    XXX-105 1′96 458
    XXX-106 1′67 491
    XXX-107 1′86 444
    XXX-108 1′41 513
    XXX-109 1′55 491
    XXX-110 2′00 428
    XXX-111 1′90 414
    XXX-112 2′31 490
    XXX-113 2′74 530
    XXX-114 2′44 520
    XXX-115 2′53 548
    XXX-116 2′20 461
    XXX-117 2′47 558
    XXX-118 2′17 522
    XXX-120 399
    XXX-121 2′05 427
    XXX1-1 547
    XXXI-2 147-148
    XXXI-3 484
    XXX1-4 528
    XXXI-5 504
    XXXI-6 535
    XXXI-7 539
    XXXI-8 1′86 482
    XXXII-1 470
    XXXII-2 536
    XXXII-3 486
    XXXII-4 504
    XXXII-5 546
    XXXII-6 509
    XXXII-7 527
    XXXII-8 2′27
    XXXII-9 1′96
    XXXII-10 2′21
  • The compounds of the invention may be made in a variety of ways. For example they may be made by the reactions summarised in Scheme I.
    Figure US20060106045A1-20060518-C00035
    Figure US20060106045A1-20060518-C00036
  • Thus a compound of formula 1 may be synthesised from compounds of formula 2a or 2b by reaction with an alkylating agent of the formula R8-L, where L is chloride, bromide, iodide or a sulfonate (e.g. mesylate or tosylate) or similar leaving group at a temperature of between ambient temperature and 100° C., typically 65° C., in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally catalysed by halide salts such as sodium iodide, potassium iodide or tetrabutylammonium iodide.
  • Alternatively, a compound of formula 2a or 2b may be reacted with an aldehyde of the formula RCHO at a temperature between ambient temperature and 100° C. in an organic solvent such as tetrahydrofuran or ethanol or mixtures of solvents in the presence of a reducing agent such as borane-pyridine complex, sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or such like, to produce a compound of formula 1 where R8 is CH2—R.
  • Alternatively, a compound of formula 2a or 2b may be reacted with paraformaldehyde and a boronic acid of the formula R—B(OH)2 at a temperature between ambient temperature and 1 00° C. in an organic solvent such as ethanol, 1,4dioxane or water to produce a compound of formula 1 where R8 is CH2—R.
  • A compound of formula 2a may be obtained from a compound of formula 3 by reaction with an acid such as trifluoroacetic acid at ambient temperature in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane followed by neutralisation of the reaction mixture with an aqueous solution of an inorganic base such as sodium carbonate, sodium bicarbonate or similar compound.
  • Similarly a compound of formula 2b may be formed by reaction of a compound of formula 3 with an acid such as trifluoroacetic acid at ambient temperature in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane followed by evaporation of the solvents and trituration with organic solvents such as ether or hexane.
  • Compounds of formula 3 may be obtained from compounds of formula 4 by reaction with a suitable electrophilic species. Compounds of formula 3 where Y is a carbonyl group may be formed by the reaction of compounds of formula 4 with a carboxylic acid derivative of formula R1-C(O)-Z where Z is chloride, hydroxy, alkoxy or acyloxy at a temperature between 0° C. and 150° C. optionally in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane, optionally in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally in the presence of a coupling agent such as dicyclohexylcarbodiimide. Compounds of formula 3 where Y is a carbonyl group and R1 is an amino substituent of formula R′—NH— may be formed by the reaction of compounds of formula 4 with an isocyanate of formula R′—N═C═O under similar conditions. Compounds of formula 3 where Y is a group of formula S(O)q may be formed from compounds of formula 4 by treatment with compounds of formula of R1-S(O)q—Cl under similar conditions. Compounds of formula 3 where Y is a thiocarbonyl group and R1 is an amino substituent of formula R′—NH— may be formed by the reaction of compounds of formula 3 with an isothiocyanate of formula R′—N═C═S under similar conditions. Alternatively compounds of formula 3 where Y is a thiocarbonyl group and R1 is a carbon substituent may be formed by treatment of compounds of formula 3 where Y is a carbonyl group and R1 is a carbon substituent with a suitable thionating agent such as Lawesson's reagent.
  • In the above procedures, acid derivatives of the formula R1-C(O)-Z, isocyanates of formula R′—N═C═O, isothiocyanates of formula R′—N═C═S and sulfur electrophiles of formula R1-S(O)q—Cl are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
  • Compounds of formula 4 may be obtained by reacting compounds of formula 5 with compounds of formula 6 at a temperature of between 0° C. and 100° C. in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of an acid such as hydrochloric acid or trifluoroacetic acid and a co-solvent such as water, methanol or ethanol, or in the presence of a Lewis acidic metal salt such as a zinc(II) dihalide. The intermediates formed (compounds of formula 4a) are subsequently treated with a nucleophile R3-M (where M is a metallic species. R3-M is for example a Grignard reagent) or, when R3 is hydrogen, a reducing agent such as sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or similar at ambient temperature in organic solvent such as ethanol or chloroform. The basic procedure is described in Tetrahedron (1997), 53, 10983-10992.
  • Compounds of formula 6 may be obtained from compounds of formula 7 by reaction with a 1-alkoxy substituted phosphonium salt such as methoxymethyl(triphenyl)phosphonium chloride and a base such as potassium tert-butoxide at a temperature of 0° C. to room temperature in tetrahydrofuran.
  • Compounds of formula 5 and 7 are either known compounds or may be obtained from known compounds by known techniques.
  • Certain compounds of formula 2, 3, 4, 4a and 6 are novel and as such form a further aspect of the invention.
  • Further procedures for making compounds of formula 1′ (compounds of formula I where R2, R3, R9 and R10 are all hydrogen) are illustrated in scheme II below
    Figure US20060106045A1-20060518-C00037
  • Thus a compound of formula 1′ may be obtained from a compound of formula 8 by reaction with an acid chloride or chloroformate of the formula R1COCl at a temperature between 0 ° C. and ambient in organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • Alternatively, a compound of formula 1′ may be obtained from a compound of formula 8 by reaction with a carboxylic acid of the formula R1COOH and a standard coupling agent such as 2-chloro-1,3-dimethyl-2-imidazolium hexafluorophosphate, or carbodiimide reagents such as dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at a temperature between 0° C. and ambient in organic solvent such as dichloromethane or tetrahydrofuran in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • A compound of formula 1′ may alternatively be obtained from a compound of formula 8 by reaction with a isocyanate or isothiocyanate of the formula RNCO or RNCS respectively at a temperature between 0° C. and ambient in organic solvent such as dichloromethane or tetrahydrofuran, optionally in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • A compound of formula 1′ may also be obtained from a compound of formula 8 by reaction with a sulfonyl chloride of the formula R1SO2Cl at a temperature between 0° C. and ambient in organic solvent such as dichloromethane or tetrahydrofuran, in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine.
  • Alternatively, a compound of formula 1′ may be obtained from a compound of formula 8 by reaction with an aryl or heteroaryl compound of formula Ar-L where L is a leaving group such as halide (especially fluoride), such as a 2-halopyridine, a 2-halopyrimidine, a 4-halopyridine, a 2-halopyrazine or such like at a temperature between 50° C. and 150° C. in a solvent such as dimethylsulfoxide in the presence of a strong base such as sodium hydride.
  • Compounds of formula 8 may be obtained by reacting compounds of formula 9 with compounds of formula 5 (in scheme I) at a temperature of between ambient and 100° C. in organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of an acid such as trifluoroacetic acid for typically 4 to 12 hours, followed by addition of a reducing agent such as triethylsilane and reaction at a temperature of ambient to 100° C. until the reaction is complete.
  • Alternatively, Compounds of formula 8 may be obtained by reacting compounds of formula 9 with compounds of formula 5 at a temperature of between 0° C. and 100° C. in organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of an acid such as hydrochloric acid, or trifluoroacetic acid and a co-solvent of either water or methanol or ethanol, or in the presence of a Lewis acidic metal salt such as zinc(II) dihalide. The intermediates formed (compounds of formula (9a)) are subsequently treated with a reducing agent such as sodium borohydride, sodium (triacetoxy)borohydride, sodium cyanoborohydride or such like at ambient temperature in organic solvent such as ethanol or chloroform.
  • Compounds of formula 8 may also be obtained by the hydrolysis of compounds of formula 1a (which are also a sub-set of compounds of formula 1) preferably with an aqueous acid, typically 6 N hydrochloric acid at reflux temperature.
  • Compounds of formula 9 may be obtained from compounds of formula 10 by reaction with methoxymethyl(triphenyl)phosphonium chloride or the corresponding bromide salt and a base such as potassium tert-butoxide at a temperature of 0° C. to ambient in tetrahydrofuran.
  • Compounds of formula 10 may be obtained by reacting compounds of formula 11 with an aqueous solution of acid, typically 6 N hydrochloric acid at reflux temperature.
  • Compounds of formula 11 may be obtained from compounds of formula 12 by reaction with an electrophile of the formula R8-L, where L is chloride, bromide, iodide or a sulfonate (e.g. mesylate or tosylate) or similar leaving group at between ambient temperature and 100° C., typically around 60° C. in an organic solvent such as dichloromethane, chloroform or 1,2-dichloroethane in the presence of an excess of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally catalysed by halide salts such as sodium iodide, potassium iodide or tetrabutylammonium iodide.
  • Compounds of formula 12 are known compounds or may be obtained from known compounds by known techniques.
  • Certain compounds of formula 8, 9, 9a, 10 and 11 are novel and as such form a further aspect of the invention.
  • The skilled person will readily recognise that it is possible to interconvert one compound of formula I to other compounds of formula I and examples of such procedures are given in schemes III, IV, V, Va and VI below.
    Figure US20060106045A1-20060518-C00038
    Figure US20060106045A1-20060518-C00039
    Figure US20060106045A1-20060518-C00040
    Figure US20060106045A1-20060518-C00041
  • Compounds of formula I where R8 is optionally substituted cinnamyl may be prepared by the reactions in scheme VII below where R4, R53, R54 and RS are as defined above. The scheme is illustrated in Examples 8-12.
    Figure US20060106045A1-20060518-C00042
  • Compounds of formula (I) in which R2 and R3 together are an oxo group and R1, R4 and R8 are as defined above may be made by the methods of WO 0145707 as set out in scheme VIII below.
    Figure US20060106045A1-20060518-C00043
  • Compounds of formula (I) in which R2 and R3 together are an oxo group and and R8 are as defined above may be made from compounds of formula 4a by the methods of scheme IX below.
    Figure US20060106045A1-20060518-C00044
  • The compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • Examples of pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafrniner), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp.(citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
  • The invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, The compounds of formula (I) are preferably used against insects, acarines or nematodes.
  • The term “plant” as used herein includes seedlings, bushes and trees.
  • In order to apply a compound of formula (I) as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of pests such that a compound of formula (I) is applied at a rate of from 0.1 g to 1 kg per hectare, preferably from 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg per hectare.
  • When used in a seed dressing, a compound of formula (I) is used at a rate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably 0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.
  • In another aspect the present invention provides an insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal, acaricidal, nematicidal or molluscicidal composition.
  • In a still further aspect the invention provides a method of combating and controlling pests at a locus which comprises treating the pests or the locus of the pests with an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a composition comprising a compound of formula (I). The compounds of formula (I) are preferably used against insects, acarines or nematodes.
  • The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The l0 formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
  • Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
  • Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
  • Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-C10 fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- and tri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • A compound of formula (I) may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following:
    • a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate;
    • b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;
    • c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl;
    • d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron;
    • e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin;
    • f) Pyrazoles, such as tebufenpyrad and fenpyroximate;
    • g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin;
    • h) Hormones or pheromones;
    • i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin;
    • j) Amidines, such as chlordimeform or amitraz;
    • k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam;
    • l) Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam;
    • m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide;
    • n) Diphenyl ethers, such as diofenolan or pyriproxifen;
    • o) Indoxacarb;
    • p) Chlorfenapyr; or
    • q) Pymetrozine.
  • In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N—(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281, zoxamide), N-allyl4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON65500), N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1,1′-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl(Z)-N—benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulifuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-A1, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quatemary ammnonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb and ziram.
  • The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
  • Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PIX™.
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
  • The invention is illustrated by the following Examples:
    • EXAMPLE 1
  • This Example illustrates the preparation of compound V-22, 1-Acetyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4+-piperidine]
    Figure US20060106045A1-20060518-C00045
    • Step 1: Preparation of 4-methoxymethylenepiperidine-1-carboxylic acid tert-butyl ester
  • Potassium tert-butoxide (21.3 g) was added in portions to a stirred solution of methoxymethyltriphenylphosphonium chloride (65.3 g) in anhydrous THF (500 ml) under an atmosphere of nitrogen at 4° C. A vivid orange colour was noted and the reaction was left as such for 1 h. 4-Oxopiperidine-1-carboxylic acid tert-butyl ester 1 (25 g) was added slowly not letting the temperature rise above 10° C. and the mixture was then allowed to warn to room temperature overnight.
  • The reaction mixture was poured onto water (150 ml), extracted three times with ethyl acetate (100 ml) and the combined organics were washed with brine (300 ml), dried over anhydrous sodium sulphate and concentrated in vacuo to yield a brown oil (50 g). Flash chromatography [SiO2; hexane, then ethyl acetate-hexane (10:90)] yielded 26.4 g (77%) of the desired enol ether. 1H NMR (400 MHz, CDCl3) 1.5 (9H, m), 2.0-2.2 (m, 4H), 3.4 (m, 4H), 3.5 (s, 3H), 5.9 (s, 1H). MS (ES+) 228 (M+H+), 172 (M-ibutene+H+)
    • Step 2: Preparation of 5-chlorospiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester
  • Trifluoroacetic acid (12 ml) was added to a stirred solution of 4-methoxymethylene-piperidine-1-carboxylic acid tert-butyl ester (12.5 g), 4-chlorophenylhydrazine hydrochloide (9.75 g) and ethanol (1 ml) in chloroform (1200 ml) at 4° C. under an atmosphere of nitrogen. The mixture was then stirred at 50° C. overnight, turning a dark green colour. The reaction was quenched with concentrated ammonia solution (200 ml) in ice water (500 ml), the organic layer turning orange. The organic layer was separated and the aqueous was further extracted twice with dichloromethane. The combined organics were washed with brine (300 ml), dried over anhydrous sodium sulphate and concentrated in vacuo to yield 13 g of the crude imine 5-chlorospiro[3H-indole-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester (purity approximately 80% by NMR). 1H NMR (400 MHz, CDCl3) 1.5 (9H, m), 1.70 (m, 2H), 1.85 (m, 2H), 3.50 (m, 2H), 4.05 (m, 2H), 7.35 (m, 2H), 7.60 (s, 1H), 8.35 (s, 1H). MS (ES+) 321/323 (M+H+), 265/267 (M-ibutene+H+), 221/223 (M-Boc+H+).
  • Sodium borohydride (6.0 g) was added to a stirred solution of crude imine (12 g) in absolute ethanol (500 ml) under an atmosphere of nitrogen. The reaction was stirred for 15 min and left to stand overnight. The mixture was concentrated in vacuo and the residue re-dissolved in dichloromethane (100 ml). The organics were washed with water (100 ml) and brine (100 ml), dried over anhydrous sodium sulphate and concentrated in vacuo to yield a brown solid. Flash chromatography [SiO2: ethyl acetate-hexane-triethylamine (25:75:1)) yielded 9.8 g (56%, over both steps) of the desired indoline. M.p. 165-166° C. 1H NMR (400 MHz, CDCl3) 1.5 (9H, s), 1.70 (m, 4H), 2.9 (m, 2H), 3.50 (s, 2H), 3.75 (br s, 1H), 4.05 (m, 2H), 6.55 (d, J=6 Hz, 1H), 7.00 (m, 2H). MS (ES+) 323/325 (M+H+), 267/269 (M-ibutene+H+), 223/225 (M-Boc+H+).
    • Step 3: Preparation of 1-acetyl-5-chlorospiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester
  • Acetyl chloride (2.8 ml) was added dropwise to a stirred solution of 5-chlorospiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester (9.8 g) and triethylamine (15 ml) in anhydrous dichloromethane (400 ml) under an atmosphere of nitrogen. The reaction was stirred for 1 h and was then quenched with saturated sodium bicarbonate solution (200 ml). The organic layer was dried over anhydrous sodium sulphate and concentrated in vacuo to yield 9.8 g (87%) of the desired amide as an off-white solid. M.p. 64-66° C. 1H NMR (400 MHz, CDCl3) a 6:1 mixture of rotamers. Major rotamer 1.5 (9H, s), 1.70 (m, 2H), 1.85 (m, 2H), 2.25 (s, 3H), 2.85 (m, 2H), 3.90 (s, 2H), 4.2 (m, 2H), 6.97 (d, J=1 Hz, 1H), 7.20 (dd, J=7 & 1 Hz, 1H), 8.15 (d, J=7 Hz, 1H). Minor rotamer 1.5 (9H, s), 1.70 (m, 2H), 1.85 (m, 2H), 2.45 (s, 3H), 2.85 (m, 2H), 4.05 (s, 2H), 4.2 (m, 2H), 7.2 (d, J=1 Hz, 1H), 7.25 (dd, J=7 & 1 Hz, 1H), 7.48 (d, J=7 Hz, 1H).
    • Step 4: Preparation of 1-acetyl-5-chlorospiro[indoline-3,4′-piperidine]
  • Trifluoroacetic acid (25 ml) was added to a stirred solution of 1-acetyl-5-chlorospiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester (8 g) in anhydrous dichloromethane (250 ml) under an atmosphere of nitrogen. The reaction was left as such for 3 h. The reaction was washed with saturated bicarbonate solution (200 ml) and dried over sodium sulphate and concentrated in vacuo to yield an off white solid. Flash chromatography [SiO2: methanol-dichloromethane-triethylamine (90:5:5)] yielded 5.6 g (61%) of the desired 1-Acetyl-5-chlorospiro[indoline-3,4′-piperidine]. 1H NMR (400 MHz, CDCl3) a 6:1 mixture of rotamers. Major rotamer 1.70 (m, 2H), 1.80 (m, 2H), 2.27 (s, 3H), 2.75 (t, J=12 Hz, 2H), 3.15 (m, 2H), 3.90 (s, 2H), 7.12 (d, J=1 Hz, 1H), 7.18 (dd, J=7& 1 Hz, 1H), 8.15 (d, J=7 Hz, 1H). Minor rotamer (partial data) 2.44 (s, 3H), 2.86 (m, 2H), 3.10 (m, 2H), 4.05 (s, 2H). MS (ES+) 265/267 (M+H+).
    • Step 5: Preparation of 1-acetyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • A solution of 4-chlorocinnamyl chloride (4.0 g) in chloroform (120 ml) was added slowly to a stirred mixture of 1-acetyl-5-chlorospiro[indoline-3,4′-piperidine] (5.3 g) and diisopropylethylamine (6.7 ml) in chloroform (120 ml) under an atmosphere of nitrogen at room. The reaction was heated to 50° C. for 30 h. The reaction mixture was concentrated in vacuo to yield a red oil. Flash chromatography [SiO2; ethyl acetate-hexane-triethylamine (50:50:1)] yielded 5.1 g (68%) of the desired compound. 1H NMR (400 MHz, CDCl3) a 5:1 mixture of rotamers. Major rotamer 1.70 (d, J=12 Hz, 2H), 2.0 (td, J=12 & 2 Hz), 2.08 (t, J=12 Hz, 2H), 2.25 (s, 3H), 3.03 (d, J=12 Hz, 2H), 3.20 (d, J=7 Hz, 2H), 3.96 (s, 2H), 6.28 (dt, J=12 & 5 Hz, 1H), 6.50 (d, J=12 Hz, 1H), 7.13 (d, J=1 Hz, 1H), 7.18 (dd, J=7 & 1 Hz, 1H), 7.3 (m, 4H), 8.15 (d, J=7 Hz, 1H). Minor rotamer (partial data) 2.42 (s, 3H), 4.00 (s, 2H). MS (ES+) 415/417/419 (M+H+).
  • Compounds II-301, V-21, XXIX-49, V-192, V-62, V-202 XXX-1, XXX-11, XXX1-1, XXX-118, XXX-12, XXX-13, XXX-14, XXX-15, XXX-16, XXX-17, XXX-18, XXX-19, XXX-2, XXX-20, XXX-21, XXX-22, XXX-23, XXX-24, XXX-25, XXX-26, XXX-27, XXX-28, XXX-29, XXX-3, XXX-4, XXX-5, XXX-6, XXX-7, XXXII-7, XXX-8, XXXI-2, XXXI-8, XXXII-1, XXXII-10, XXXII-2, XXXII-3, XXXII-4, XXXII-5, XXXII-6, XXXII-8 and XXXII-9 were prepared according to procedures analogous to those described in Example 1.
    • EXAMPLE 2
  • This Example illustrates the preparation of compound I-1, 1-(2-Chloropyridin-4-1′-[trans-3-phenylallyl]spiro[indoline-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00046
    Spiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester was prepared according to a procedure analogous to that described in steps 1 and 2 of Example 1.
    • Step 1: 1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester
  • Thionyl chloride (20 ml) was added to 2-chloroisonicotinic acid (1.2 g) at room temperature. DMF (2 drops) was added and the mixture was heated to reflux for 1 hour. The excess thionyl chloride was evaporated and the residue was dissolved in dichloromethane (50 ml). Triethylamine (2 ml) was added followed by dropwise addition of a solution of spiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester (1.7 g) dissolved in dichloromethane (20 ml). The mixture was stirred for 48 hours. The reaction mixture was washed with pH 9.4 buffer (100 ml) and the aqueous layer was extracted with dichloromethane. The combined organic layers were dried (magnesium sulfate), filtered and evaporated. The crude product was purified by chromatography [SiO2; ethyl acetate-hexane-triethylamine (50:50:1), increasing polarity to (100:0:1)] to give 2.4 g (94%) of the desired amide. M.p. 212° C; 1H NMR (400 MHz, d6-DMSO) 1.50 (s, 9H), 1.6-1.8 (m, 4H), 2.8 (br s, 2H), 3.9 (br s, 2H), 4.08 (d, 2H), 7.0-7.2 (m, 3H), 7.30 (d, J=6 Hz, 1H), 8.43 (d, J=6 Hz, 1H), 7.40 (s, 1H), 8.0-8.2 (br m, 1H); MS (ES+) 428/430 (M+H+), 372/374 (M+H+-isobutene).
    • Step 2: preparation of 1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]trifluoroacetic acid salt
  • Trifluoroacetic acid (30 ml) was added to a solution of solution of 1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]-1′-carboxylic acid tert-butyl ester (2.3 g) in anhydrous dichloromethane (50 ml), the solution darkening upon addition. The reaction was left as such for 15 min. The reaction mixture was evaporated in vacuo and the dark residue re-suspended in dry ether (100 ml). The residue was triturated until it became a free-flowing beige precipitate. The precipitate was collected by filtration and dried in a stream of nitrogen to give 2.28 g (96%) of the desired amine salt. M.p. 245° C. (decomposition). 1H NMR (400 MHz, d6-DMSO) 1.8 (m, 2H), 1.9 (m, 2H), 2.9 (m, 2H), 3.25 (m, 2H), 3.98 (s, 2H), 7.15-7.3 (m, 2H), 7.24 (d, J=8 Hz, 1H), 7.56 (d, J=7 Hz, 1H), 7.62 (s, 1H), 8.1 (br s, 1H), 8.56 (d, J=7 HZ, 1H), 8.8 (br s, 2H). MS (ES+) 328/330 (M+H+).
    • Step 3: Preparation of 1-(2-chloropyridin-4-yl)carbonyl-1′-[trans-3-phenylallyl]spiro[indoline-3,4′-piperidine]
  • 1-(2-Chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine] trifluoroacetic acid salt (0.44 g) and trans-cinnamaldehyde (0.29 g) were suspended in tetrahydrofuran (8 ml) and ethanol (6 ml). Borane-pyridine complex (0.26 ml) was added and the reaction stirred vigorously overnight at room temperature. The mixture was evaporated and partitioned between dichloromethane and water. The organics were dried over anhydrous magnesium sulfate and evaporated in vacuo. Flash chromatography [SiO2; ethyl acetate-hexane-triethylamine (25:75:1), increasing polarity to (50:50:1)] yielded 0.42 g (94%) of the desired product.
  • 1H NMR (400 MHz, CDCl3) a 3:1 mixture of rotamers. Major rotamer 1.70 (m, 2H), 1.8-2.1 (m, 4H), 3.0 (m, 2H), 3.20 (m, 2H), 3.75 (m, 2H), 6.3 (m, 1H), 6.52 (d, J=12 Hz, 1H), 7.1-7.4 (m, 9H), 7.46 (d, J=2 Hz, 1H), 8.2 (br m, 1H), 8.6 (m, 1H). MS (ES+) 444/446 (M+H+).
  • Compounds I-5, I-4, XXIX-7, XXIX-13, I-182, I-142, I-132, XXII-22, VI-1, VI-101, I-22, XXX-96, XXIX-31 (with an alkylation as the final step), XXIX-37 (with an alkylation as the final step), XXIX-43 (with an alkylation as the final step), XXVII-1 (followed by treatment with HCl in ether), XXVII-2 (followed by treatment with HCl in ether), XXVII-22 (followed by treatment with HCl in ether), XXVI-1 (followed by treatment with hydrogen peroxide in methanol) and XXIX-25 (with an acylation as the final step) were prepared according to procedures analogous to those described in Example 2.
    • EXAMPLE 3
  • This Example illustrates the preparation of compound VI-22, 1-(Pyridin-4-yl)-carbonyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00047
    1-Acetyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] was prepared according to the procedures described in Example 1.
    • Step 1: Preparation of 5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • 1-Acetyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (5.0 g) was dissolved in 6 N hydrochloric acid (100 ml) and heated to reflux for 3 hours. The mixture was cooled and the aqueous layer was basified with solid NaOH pellets (CARE! Exotherm) to pH 12 and triethylamine (20 ml) was added. The mixture was extracted three times with chloroform. The organic layers were dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to give a crude brown oil which was purified by column chromatography (SiO2, ethyl acetate:hexane: triethylamine, 1:1:0.01) to give 3.94 g (88%) of the desired indoline. MS (ES+) 373/375/377 (M+H+).
    • Step 2: Preparation of 1-(pyridin-4-yl)carbonyl-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Isonicotinic acid (0.022 g) and DMF (1 drop) were dissolved in thionyl chloride (2 ml) and the mixture was heated to reflux for 1 hour. The mixture was allowed to cool and the excess thionyl chloride was evaporated in vacuo. The residue was dissolved in chloroform (4 ml) and triethylamine (0.1 ml) was added. A solution of 5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (0.055 g) in chloroform (1 ml) was added and the reaction was allowed to stir at room temperature for 18 hours. Aqueous sodium carbonate solution (1M, 20 ml) was added and the mixture was extracted into chloroform (3×20 ml). The combined organic layers were dried (magnesium sulfate), filtered and evaporated in vacuo to give a crude brown oil which was purified by chromatography (SiO2, ethyl acetate:hexane:triethylamine 0:1:0.01 to 1:0:0.01) to give 0.034 g (49%) of the desired amide. MS (ES+) 478/480/482 (M+H+).
  • Compounds XXV-62, I-192, I-202, XXIX-189, VI-202 and VI-62 were prepared according to procedures analogous to those described in Example 3.
    • EXAMPLE 4
  • This Example illustrates the preparation of compound XIX-202, 1-(4-cyanobenzoyl)-5-methyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00048
    • Step 1: Preparation of 8-[trans-3-(4-chlorophenyl)allyl]-1,4-dioxa-8-azaspiror4.5]decane
  • 1,4-Dioxa-8-azaspiro[4.5]decane (0.88 g) was dissolved in chloroform (5 ml) and diisopropylethylamine (2.1 ml) was added. A solution of 4-chlorocinnamyl chloride (1.2 g) dissolved in chloroform (2 ml) was added and mixture was heated to 70° C. overnight. The solvents were evaporated in vacuo and flash chromatography [SiO2; ethyl acetate-hexane-triethylamine (50:50:2)] yielded 1.38 g (76%) of the desired ketal as a yellow oil. 1H NMR (400 MHz, CDCl3) 1.78 (t, J=4 Hz, 4H), 2.60 (br s, 4H), 3.18 (d, J=5 Hz, 2H), 3.96 (s, 4H), 6.27 (dt, J=12 & 5 Hz, 1H) 6.47 (d, J=12 Hz, 2H), 7.28, m, 4H). MS (ES+) 294/296 M+H+.
    • Step 2: Preparation of 1-[trans-3-(4-chlorophenyl)allyl]-4-oxopiperidine
  • 8-[trans-3-(4-Chlorophenyl)allyl]-1,4-dioxa-8-azaspiro[4.5]decane (1.38 g) was dissolved in methanol (40 ml) and 6 N hydrochloric acid (120 ml) was added. The mixture was heated to reflux for 4 h. The mixture cooled and was basified to pH 14 with solid sodium hydroxide pellets (CARE! Exotherm), the solution becoming opaque. The aqueous was extracted three times with ether. The organics were washed with brine, dried over anhydrous MgSO4 and evaporated to give 1.17g (100%) of the desired ketone 1H NMR (400 MHz, CDCl3) 2.38 (m, 4H), 2.70 (m, 4H), 3.15 (d, J=5 Hz, 2H), 3.96 (s, 4H), 6.17 (dt, J=12 & 5 Hz, 1H), 6.40 (d, J=12 Hz, 1H), 7.20 (m, 4H). MS (ES+) 250/252 M+H+.
    • Step 3: Preparation of 1-[trans-3-(4-chlorophenyl)allyl]-4-methoxymethylenepiperidine
  • Methoxymethyltriphenylphosphonium chloride (2.4 g) was dissolved in tetrahydrofuran (20 ml) and was cooled to 4° C. Potassium tert-butoxide (0.78 g) was added, turning the solution a bright orange colour. The reaction was left as such for 30 min. A solution of 1-[trans-3-(4-chlorophenyl)allyl]-4-oxopiperidine (0.85 g) dissolved in tetrahydrofuran (10 ml) was added and the mixture was stirred for 10 min. The solvents were evaporated in vacuo and the residue re-suspended in ether. The organics were washed with water and dried over anhydrous magnesium sulfate. Flash chromatography [SiO2; ethyl acetate-hexane-triethylamine (50:50:2)] gave 0.85 g (89%) of the desired enol ether. 1H NMR (400 MHz, CDCl3) 2.10 (t, J=6 Hz, 2H), 2.35 (t, J=6 Hz, 2H), 2.4 (m, 4H), 3.13 (d, J=5 Hz, 2H), 3.55 (s, 3H), 5.80 (s, 1H), 6.30 (dt, J=11 & 5 Hz, 1H), 6.45 (d, J=11 Hz, 1H), 7.28 (m, 4H). MS (ES+) 278/280 (M+H+).
    • Step 4: Preparation of 5-methyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • Trifluoroacetic acid (0.75 ml) was added to a stirred solution of 1-[trans-3-(4-chlorophenyl)allyl]-4-methoxymethylenepiperidine-and 4-tolylhydrazine hydrochloride (28 mg) in chloroform (5 ml) and the reaction was heated to 50° C. for 5 h. Triethylsilane (2 ml) was added and the reaction was heated at 50° C. for a further 5 h. The mixture was allowed to cool and was quenched in concentrated ammonia solution/ice chips (20 ml). The aqueous phase was extracted twice with chloroform and the combined organics were dried over anhydrous magnesium sulphate and concentrated in vacuo to yield 0.04 g (63%) of the desired indoline. 1H NMR (400 MHz, CDCl3) 1.75 (d, J=9 Hz, 2H), 1.96 (td, J=8 & 2, 2H), 2.13 (t, J=9 Hz, 2H), 2.25 (s, 3H), 2.95 (d, J=10 Hz, 2H), 3.19 (d, J=5 Hz, 2H), 3.42 (s, 2H), 6.30 (dt, J=11 & 5 Hz, 1H), 6.48 (d, J=11 Hz, 1H), 6.58 (d, J=7 Hz, 1H), 6.85 (d, J=7 Hz, 1H), 6.9 (s, 1H), 7.30 (m, 4H). MS (ES+) 353/355 (M+H+), 203 (M-4-chlorocinnamyl+H+).
    • Step 5: Preparation of 1-(4-cyanobenzoyl)-5-methyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • This step was achieved using a Zymark XP2 synthetic chemistry robot. A solution of 5-methyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (2 ml of a solution derived from dissolving 1.43 g in 100 ml of THF) was added to a robot tube and the solvent was removed in vacuo. 4-Cyanobenzoic acid (28 mg) was weighed into a different robot tube. A solution of 2-chloro-1,3-dimethyl-2-imidazolinium hexafluorophosphate (2 ml of a solution derived from dissolving 4.80 g in 180 ml of chloroform) and a solution of triethylamine (2 ml of a solution derived from dissolving 8.68 ml in 250 ml of chloroform) were added to the acid and the tube was agitated and allowed to stand for 30 minutes. A 2 ml aliquot of the acid solution was added to the tube containing the dry amine. This tube was agitated and allowed to stand overnight. The reaction mixture was washed with 1M aqueous sodium carbonate solution and the solvents were evaporated. The crude mixture was purified by MS directed liquid chromatography to give the desired amide, 2.9 mg. MS (ES+) 482/484 (M+H+).
  • Compounds I-61, I-171, XXVIII-97, XIX-22, XXVIII-67, XXVIII-7, XX-22, XXIX-69, XXIX-75, XVIII-22, XXVIII-217, XXIX-81, XXIX-87, XV-22, XXIX-93, XXIX-99, XXVIII-187, XXI-22, XXIX-105, XXIX-111, XXIX-117, XXIX-123, XIII-22, XXIX-129, X-22, XXIX-135, XXIX-141, XXIX-147, XXIX-153, XII-22, XXIX-196, II-22, XXIX-159, XXVIII-252, XXVIII-27, XXVIII-42, XVIII-202, XX-62, XXIX-165, XXVIII-162, XXVIII-132, XXIX-171, XXIX-177, XXI-62, XVII-62, XIII-62, X-62, XXIX-183, XI-62, IX-62, XXIX-207, XXIX-195, II-62, I-92, 1-112, I-12, I-32, I-52, I-72, I-152, I-162, I-82, I-252, I-242, I-262, I-292, I-62 XXX-10, XXX-116, XXX-117, XXX-30, XXX-33, XXX-34, XXX-35, XXX-36, XXX-37, XXX-38, XXX-39, XXX-40, XXX-41, XXX-42, XXX-43, XXX-44, XXX-45, XXX-46, XXX-47, XXX-48, XXX-49, XXX-50, XXX-9 and XXX-93 were prepared according to procedures analogous to those described in Example 4.
    • EXAMPLE5
  • This example illustrates the preparation of compound XIV-22, 1-(2-Pyrazinyl)-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00049
  • 5-Chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] was prepared according to the procedures described in Example 3.
  • Sodium hydride (50 mg) was added to a stirred solution of 5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (35 mg) and 2-chloropyrazine (43 mg) in anhydrous DMSO (5 ml) under an atmosphere of nitrogen. The reaction was heated to 60° C. overnight. The reaction mixture was diluted with brine (20 ml) and extracted four times with dichloromethane (20 ml). The combined organics were dried over magnesium sulphate and concentrated in vacuo (1 mmHg) to yield a brown oil. Flash chromatography [SiO2, ethyl acetate-hexane-triethylamine gradient (0:98:2) to (98:0:2)] yielded 25 mg (55%) of the desired product. 1H NMR (400 MHz, CDCl3) 1.75 (m, 2H), 2.05 (td, J=8 & 2, 2H), 2.18 (t, J=9 Hz, 2H), 3.05 (d, J=9 Hz, 2H), 3.22 (d, J=5 Hz, 2H), 3.94 (s, 2H), 6.30 (dt, J=11 & 5 Hz, 1H), 6.51 (d, J=11 Hz, 1H), 7.18 (m, 2H), 7.30 (m, 4H), 8.05 (d, J=1Hz, 1H), 8.17 (d, J=6 Hz, 1H), 8.25 (m, 2H). MS (ES+) 451/453/455 M+H+.
  • Compounds XXIX-57 and XXIX-63 were prepared according to procedures analogous to those described in Example 5.
    • EXAMPLE 6
  • This Example illustrates the preparation of compound XXII-3, 1-(2-Chloropyridin-4-yl)carbonyl-1′-[trans-3-(4fluorophenyl)allyl]spiro[indoline-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00050
  • 1-(2-Chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]trifluoroacetic acid salt was prepared according to the procedures described in Example 2.
  • 1-(2-Chloropyridin-4-yl)carbonylspiro[indoline-3,4′-piperidine]trifluoroacetic acid salt (0.25 g) was suspended in dioxane (2 ml) and paraformaldehyde (0.08 g) was added. The mixture was stirred and heated to 90° C. for 20 minutes. 2-(4-fluorophenyl)vinylboronic acid (0.10 g) was dissolved in dioxane (2 ml) and the resulting solution was added to the salt/paraformaldehyde mixture and the resulting mixture was heated to 90° C. for 24 hours. The mixture was allowed to cool and evaporated to dryness in vacuo. The residue was partitioned between dichloromethane and water, and the organic layer was washed with aqueous sodium carbonate solution (1M) and evaporated. The crude product was purified by column chormatography (SiO2, first column in dichloromethane:triethylamine 95:5, then a second column starting with neat dichloromethane, then a gradient from ethyl acetate:hexane: triethylamine 25:75:1 to 95:0:5) to give 0.20 g (76%) of the desired product. MS (ES+) 462/464 M+H+.
  • Compounds I-23, XXIX-1, I-21, I-2, XXVI-2 (followed by treatment with hydrogen peroxide in methanol) and XXVI-22 (followed by treatment with hydrogen peroxide in methanol), were prepared according to procedures analogous to those described in Example 6.
    • EXAMPLE 7
  • This Example illustrates the preparation of compound I-212, 5-Cyano-1-(2-chloropyridin-4-yl)carbonyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00051
  • 5-Iodo-1-(2-chloropyridin-4-yl)carbonyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] was prepared by procedures analogous to those described in Example 2.
  • 5-Iodo-1-(2-chloropyridin-4-yl)carbonyl-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (0.05 g) was dissolved in anhydrous THF (5 ml) under an atmosphere of dry nitrogen. Potassium cyanide (0.011 g) and copper (I) iodide (0.016 g) were added and the mixture was degassed for 15 minutes. Tetrakis(triphenylphosphine) palladium (0.005 g) was added and the mixture was heated to reflux for 28 hours. The reaction mixture was diluted with dichloromethane (50 ml) and washed with water (30 ml). The aqueous layer was extracted with dichloromethane (2×40 ml) and the combined organic layers were dried (magnesium sulfate), filtered and evaporated in vacuo to give a colourless oil that was purified by prep. TLC (SiO2, EtOAc:Hexane:Et3N 1:1:0.01) to give 0.041 g (95%) of the desired product. MS (ES+) 503/505/507 M+H+.
  • Compounds XXIX-201, I-282, I-232 were prepared according to standard procedures analogous to those described in Example 7. Compound XXV-222 was prepared by treating compound XXIX-201 with potassium carbonate in methanol. Compound I-222 was prepared by re-acylation of compound XXV-222 under standard conditions.
    • EXAMPLE 8
  • This example illustrates the preparation of compound XXX-51 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(E)-3-(4-trifluoromethyl-phenyl) allyl]spiro[indolin-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00052
    • Step 1: Preparation of (E)-3-(4-trifluoromethyl-phenyl)-acrylic acid ethyl ester
  • Ethyl diethylphosphonoacetate (84 g) in 1,2-dimethoxyethane (100 ml) was added dropwise to a suspension of sodium hydride (55% in oil, 15 g) in 1,2-dimethoxyethane (500 ml) at room temperature. 4-Trifluorobenzaldehyde (43.5 g) dissolved in 1,2-dimethoxyethane (100 ml) was then added and the resulting mixture was stirred at room temperature for 4 h. The reaction was quenched by addition of water (400 ml), diluted with diethyl ether (700 ml), the organic phase was separated, washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude product was recrystallised from hexane to give 37 g of the desired product (61%) which was characterized by its mass and NMR spectra.
    • Step 2: Preparation of (E)-3-(4-trifluoromethyl-phenyl)-prop-2-en-1-ol
  • To a solution of the ester obtained in step 1 (37.1 g) in toluene (310 ml) at 0° C. was added dropwise diisobutylaluminium hydride (1.2M in toluene, 317 ml) and the solution was stirred at 0° C. for 1 h. Water (47.6 ml) was carefully added at 0° C. followed by sodium hydroxide 2M (47.6 ml) and finally water (95.1 ml). The mixture was allowed to stir at room temperature for 1 h. After filtration, the solution was washed with hydrochloric acid 2N, water and brine, dried over sodium sulfate and concentrated in vacuo to give 29.5 g of the desired alcohol as a solid (96%) which was characterized by its mass and NMR spectra.
    • Step 3: Preparation of 1-((E)-3-bromo-propenyl)-4-trifluoromethyl-benzene
  • To a solution of the alcohol obtained in step 2 (10 g) in dimethylacetamide (100 ml) at room temperature were added triphenylphosphine (23 g) and carbon tetrabromide (29 g). The resulting solution was stirred at room temperature for 1 h, poured into water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried over sodium sulfate and filtered over silica gel to give 13 g of the desired product as a white solid (95%) which was characterized by its mass and NMR spectra.
    • Step 4: Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(E)-3-(4-trifluoromethyl-phenyl)allyl]spiro[indolin-3,4′-piperidine]
  • To a stirred suspension of -(2-chloropyridin-4-yl)carbonyl-5-chloro-spiro[indolin-3,4′-piperidine] (20 g) and diisopropylethylamine (18.2 ml) in acetonitrile (200 ml) was added the allylic bromide obtained in step 3 (11.6 g) and the reaction mixture was stirred overnight at room temperature. The solution was diluted with ethyl acetate (200 ml), washed with brine (3×100 ml), dried over sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate:hexane:triethylamine 95:5:0.1 to ethyl acetate:methanol:triethylamine 95:5:0.1) to give 18.9 g of the desired product (82%). Mp=130° C.
  • Compounds XXX-82, XXX-83, XXX-84, XXX-85, XXX-86, XXX-87, XXX-91 and XXX-92 were prepared according to standard procedures analogous to those described in Example 8.
    • EXAMPLE 9
  • This example illustrates the preparation of compound XXX-113
  • 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-2-fluoro-allyl]spiro[indolin-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00053
    • Step 1: Preparation of (Z)-3-(4-chloro-phenyl)-2-fluoro-acrylic acid methyl ester
  • By analogy with: Cousseau, J. et al. Tetrahedron Lett. 1993, 43, 6903
  • 4-Chlorobenzaldehyde (0.66 g) was added to a suspension of diethylfluorooxalacetate, sodium salt (1 g, prepared from diethyl oxalate, ethylfluoroacetate and sodium hydride according to Alberg et al. J. Am. Chem. Soc. 1992, 3542) in tetrahydrofuran (20 ml) at 0° C., and the resulting: mixture was stirred 1 h at 0° C. then 3 h at 80° C. The reaction mixture was concentrated in vacuo, diluted with diethyl ether, washed with aqueous sodium bicarbonate, water and brine, dried over sodium sulfate and concentrated in vacuo to afford a crude residue (1.2 g) which was used diretly in the next step.
    • Step 2: Preparation of (Z)-3-(4-chloro-phenyl)-2-fluoro-prop-2-en-1-ol Step 3: Preparation of 1-((Z)-3-bromo-2-fluoro-propenyl)-4-chloro-benzene Step 4: Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-2-fluoro-allyl]spiro[indolin-3,4′-piperidine]
  • Step 2 to 4 were carried out following the procedure described in Example 8, step 2-4 to give 0.17 g of the desired product (41%) which was characterized by its mass and NMR spectra. MS (ES+) 530.
  • Compound XXX-114 was prepared according to standard procedures analogous to those described in Example 9.
    • EXAMPLE 10
  • This example illustrates the preparation of I-25
  • 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[trans-3-(4-methoxyphenyl) allyl]spiro[indolin-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00054
    • Step 1: Preparation of 1-(4-Methoxy-phenyl)-prop-2-en-1-ol
  • To a solution of p-anisaldehyde (1.54 ml) in tetrahydrofuran (20 ml) at −10° C. under argon was added dropwise vinyl magnesium bromide (1M in THF, 12.5 ml). The solution was stirred overnight at room temperature and quenched by addition of saturated aqueous ammonium chloride (20 ml). The organic phase was separated, dried over sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate:cyclohexan 7:3) to give 1.05 g of the desired product as a colorless oil (51%) which was characterized by its mass and NMR spectra.
    • Step 2: Preparation of 1-((E)-3-Chloro-propenyl)-4-methoxy-benzene
  • To a solution of the allylic alcohol obtained in step 1 (200 mg) in diethyl ether (3 ml) was added thionyl chloride (0.087 ml) and the solution was stirred at room temperature for 1 h. The solution was concentrated in vacuo to give 221 mg of the desired product (100%) as a colorless solid. Mp=70° C.
    • Step 3: Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[trans-3-(4-methoxy-phenyl)allyl]spiro[indolin-3,4′-piperidine]
  • Alkylation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-spiro[indolin-3,4′-piperidine] (0.43 g) with 1-((E)-3-chloro-propenyl)-4-methoxy-benzene obtained in step 2 (0.22 g) was carried out following the procedure described in example 101, step 4 to afford 0.36 g of the title compound (59%) which was characterized by its mass and NMR spectra. MS (ES+) 509. Mp=83-85° C.
    • EXAMPLE 11
  • This example illustrates the preparation of XXX-115
  • 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-3-chloro-allyl]spiro[indolin-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00055
    • Step 1: Preparation of (Z)-3-chloro-3-(4-chloro-phenyl)-acrylic acid methyl ester
  • By analogy with: Tanaka, M. et al. J. Am. Chem. Soc. 1998, 120, 12365 To a solution of 4-chlorophenylacetylene (100 mg) and Rh(CO)(PPh3)2Cl (5 mg) in toluene (3 ml) was added methyl chloroformate (0.17 ml) and the mixture was stirred in a sealed tube at 110° C. for 10 h. The reaction mixture was concentrated in vacuo and subjected to column chromatography (SiO2, ethyl acetate:cyclohexan 1:9) to give 104 mg of the desired product as a brown solid (61%) which was characterized by its mass and NMR spectra. Mp=40° C.
    • Step 2: Preparation of (Z)-3-chloro-3-(4-chloro-phenyl)-prop-2-en-1-ol
  • Following the procedure described in Example 8, step 2, (Z)-3-chloro-3-(4-chloro-phenyl)-acrylic acid methyl ester ( 462 mg) was converted into the desired product (391 mg, 96%) which was characterized by its mass and NMR spectra.
    • Step 3: Preparation of 1-chloro-4-((Z)-1,3-dichloro-propenyl)-benzene
  • To a solution of (Z)-3-chloro-3-(4-chloro-phenyl)-prop-2-en-1-ol (101 mg) in toluene (3 ml) was added thionyl chloride (0.11 ml) and one drop of dimethylformamide. After 1 h, the solution was concentrated in vacuo to afford 120 mg of the desired allylic chloride (100%) as a colorless oil.
    • Step 4: Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-3-chloro-allyl]spiro[indolin-3,4′-piperidine]
  • Alkylation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-spiro[indolin-3,4′-piperidine] (0.18 g) with 1-chloro-4-((Z)-1,3-dichloro-propenyl)-benzene obtained in step 3 (0.11 g) was carried out following the procedure described in example 101, step 4 to afford 0.17 g of the title compound (64%) as a foam which was characterized by its mass and NMR spectra. MS (ES+) 548.
    • EXAMPLE 12
  • This example illustrates the preparation of XXX-90
  • 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-3-fluoro-allyl]spiro[indolin-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00056
    • Step 1: Preparation of (Z)-3-(4-Chloro-phenyl)-3-fluoro-acrylic acid methyl ester
  • By analogy with: Cousseau, J. J. Chem. Soc. Chem. Commun. 1989, 1493
  • To a solution of (4-chloro-phenyl)-propynoic acid methyl ester (5.36 g) in dimethylformamide (60 ml) was added cesium fluoride (11.4 g) and potassium hydrogen fluoride (2.73 g) in water (5.4 ml) and the mixture was stirred at 80° C. for 8 h. The reaction mixture was cooled to room temperature, diluted with ethyl acetate (50 ml), the organic phase washed with water (3×50 ml) and brine (3×20 ml), dried over sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate:cyclohexan 1:9) to give 1.06 g of the desired product (20%) which was characterized by its mass and NMR spectra.
    • Step 2: Preparation of (Z)-3-(4-chloro-phenyl)-3-fluoro-prop-2-en-1-ol Step 3: Preparation of 1-Chloro-4-((Z)-3-chloro-1-fluoro-propenyl)-benzene Step 4: Preparation of 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-chlorophenyl)-3-fluoro-allyl]spiro[indolin-3,4′-piperidine]
  • Step 2 to 4 were carried out following the procedure described in Example 11, step 2-4 to give 163 mg of the desired product (42%) which was characterized by its mass and NMR spectra. MS (ES+) 531.
  • Compounds XXX-88 and XXX-90 were prepared according to standard procedures analogous to those described in Example 12.
    • EXAMPLE 13
  • This example illustrates the preparation of compound XXX-121 and XXX-94, 1-carboxylic acid (4-chloro-phenyl)-amide-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine].
    Figure US20060106045A1-20060518-C00057
  • 5-Fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] was prepared according to a procedure analogous to that described in steps 1 to 4 of Example 4.
    • Step 1: Preparation of Compound XXX-121. 1-nitroso-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • A solution of 5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (5 g) in dichloromethane (15 ml) was added to a suspension of wet silica gel (50% w/w in water, 2.9 g) and zinc chloride (5.73 g) in dichloromethane (15 ml) and the resulting mixture was stirred for 3.5 hours at room temperature. The reaction mixture was diluted with ethyl acetate and the insoluble residues were removed by filtration. The filtrate was washed with saturated aqueous sodium bicarbonate solution, water and brine, dried over sodium sulfate and the solvents were evaporated in vacuo to afford 5.13 g (95%) of the desired nitroso-amine as a solid. MS (ES+) 386.
    • Step 2: Preparation of 1-amino-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • A solution of 1-nitroso-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (5 g) in tetrahydrofuran (60 ml) was added dropwise to a suspension of lithium aluminium hydride (1.47 g) in tetrahydrofuran (60 ml) at 0° C. and the resulting mixture was stirred at room temperature for 2.5 hours. Water (4.8 ml) was carefully added, followed by 15 % aqueous sodium hydroxide (4.8 ml), and finally water (14.4 ml). The mixture was stirred for 0.5 hours, diluted with ethyl acetate, dried over sodium sulfate, and filtered. The solvents were evaporated in vacuo to afford 5.1 g (100%) of the desired amino-indoline as a solid. MS (ES+) 372.
    • Step 3: Preparation of 1-carboxylic acid (4-chloro-phenyl)-amide-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]
  • 2-Chloroisonicotinoyl chloride (1.2 g) was added to a stirred solution of 1-amino-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (0.2 g) and triethylamine (0.3 ml) in dichloromethane (4 ml) at room temperature. The mixture was stirred for 2 hours.
  • The reaction mixture was washed with water and the aqueous layer was extracted with dichloromethane. The combined organic layers were dried (sodium sulfate), filtered and evaporated. The crude product was purified by chromatography [SiO2; ethyl acetate-methanol (96:4) to give 0.13 g (48%) of the desired product. MS (ES+) 511.
  • Compounds XXX-95, XXX-97, XXX-98 and XXX-99 were prepared according to standard procedures analogous to those described in Example 13
    • EXAMPLE 14
  • This example illustrates the preparation of compound XXX-119, 1-(4-chloro-phenyl)-urea-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine].
    Figure US20060106045A1-20060518-C00058
  • To a solution of 1-amino-5-fluoro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (0.2 g) in tetrahydrofuran (2 ml) was added 4-chlorophenyl isocyanate (70 mg) and the mixture was stirred at room temperature for 10 min. The solvent was evaporated in vacuo and the residue purified by preparative HPLC to afford the title compound (49%) as a solid. MS (ES+) 525.
  • Compounds XXX-100, XXX-101, XXX-102 and XXX-103 were prepared according to standard procedures analogous to those described in Example 14.
    • EXAMPLE 15
  • This example illustrates the preparation of compound XXX-102 N′-[5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine]-1-yl]-N,N-dimethylacetamidine
    Figure US20060106045A1-20060518-C00059
  • To a solution of 1-amino-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (0.15 g) in tetrahydrofuran (2 ml) was added N,N-dimethylacetamide dimethyl acetal (0.2 g) and the mixture was stirred at 70° C. for 24 hours. The solvent was evaporated in vacuo and the residue purified by chromatography [SiO2; ethyl acetate-methanol (9:1) to give 35 mg (20%) of the desired product. MS (ES+) 457.
    • EXAMPLE 16
  • This example illustrates the preparation of compound XXX-105 1-[carboxylic acid (2-methoxy-ethyl)-amide]-5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine].
    Figure US20060106045A1-20060518-C00060
  • 5-Chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4′-piperidine] (2.5 g) was added to a suspension of sodium bicarbonate (1.7 g) in acetonitrile (45 ml) and the resulting mixture cooled to 0° C. 4-Nitrophenyl chloroformate (2.54 g) was then added dropwise and the resulting solution stirred at 0° C. for 2 hours. 3 ml of the solution was added to a solution of 2-methoxy-ethylamine (315 mg) and triethylamine (0.3 ml) in dimethylformamide (10 ml) and the resulting mixture was stirred at 50° C. for 3 hours. The solution was cooled to room temperature, poured into water, extracted three times with ethyl acetate. The organic phase was dried over sodium sulfate, filtered, and the solvents were removed in vacuo. The residue was purified by reverse-phase HPLC to afford the desired product (57% yield). MS (ES+) 458.
  • Compounds XXX-104, XXX-106, XXX-107, XXX-108, XXX-109, XXX-110, XXX-111 and XXX-112 were prepared according to standard procedures analogous to those described in Example 16.
    • EXAMPLE 17
  • Preparation of compound XXVI-1 —1,2-Dihydro-1-(4-nitrobenzoyl)-1′-(3-phenyl-2-propenyl)-spiro[3H-indole-3-4′-piperidine]
    Figure US20060106045A1-20060518-C00061
    Figure US20060106045A1-20060518-C00062
  • In the experimental details to follow, standard wash will refer to the following washing sequence: dimethylformamide, dichloromethane, dimethylformamide, dichloromethane, methanol, dichloromethane, methanol (X2), tert-butyl methyl ether (X2) and resin swelling protocol will be based on a standard of 10 ml of solvent per gram of resin. Compound identities and purities were determined using High Performance Liquid Chromatography lo coupled Mass Spectrometry (HPLC-MS) and Proton Nuclear Magnetic Resonance (1H NMR) on selected compounds. REM resin was prepared from commercially available (hydroxymethyl)polystyrene resin and acryloyl chloride. The loading of the resins were assumed to be constant at 1.2 mmolg−1 throughout the synthesis.
    • Step A: Loading of 4-Formylpiperidine dimethyl acetal onto REM resin (Resin A)
  • REM resin (10 g, 12 mmol) was swollen in dimethylformamide (100 ml). A solution of 4-formylpiperidine dimethyl acetal (2.86 g, 18 mmol) in dimethylformamide (10 ml) was then added. The reaction was left to shake at room temperature for 18 hours. The resulting resin was then filtered, washed according to the standard procedure and dried in vacuo to afford 11.83 g (96% yield) of the desired resin A.
    • Step B: Preparation of Solid supported 4-Formylpiperidine (Resin B)
  • A 100 ml solution of trifluoroacetic acid/dichloromethane/water (49:49:2) was added to resin A (10 g, 12 mmol) and the mixture was then shaken at room temperature for 2 hours. The resulting resin was then filtered, washed using dichloromethane (×3), methanol, dichloromethane, methanol, tert-butyl methyl ether (×2) and dried in vacuo to afford 9.48 g of the desired resin B, which was stored at −50° C. under nitrogen.
    • Step C: Preparation of Solid supported Spiro[3H-indole-3,4′-piperidine) (Resin C)
  • To resin B (1 g, 1.2 mmol) was added a solution of 5% trifluoroacetic acid in dichloromethane (10 ml) followed by addition of anisole (0.0026 g, 0.024 mmol). The mixture was degassed with nitrogen for 10 minutes, and phenylhydrazine (0.39 g, 3.6 mmol) was added. The reaction mixture was stirred under nitrogen and heated to reflux for 36 hours. The mixture was then filtered, washed according to the standard wash cycle and dried in vacuo to afford 1.09 g of the desired resin C, which was used immediately in Step D.
    • Step D: Preparation of Solid supported 1,2-Dihydro-spiro[3H-indole-3,4′-piperidine] (Resin D)
  • To resin C (1 g, 1.2 mmol), swollen in anhydrous dichloromethane (10 ml) was added sodium triacetoxyborohydride (0.51 g, 2.4 mmol) as a solid. The reaction mixture was stirred at room temperature under nitrogen for 2 hours. The resin was then filtered, washed according to the standard wash cycle and dried in vacuo to afford 0.95 g of the desired resin D, which was stored at −50° C. under nitrogen.
    • Step E: Preparation of Solid supported 1,2-Dihydro-1-(4-nitrobenzoyl)-spiro[3H-indole-3,4′-piperidine] (Resin E)
  • Resin D (0.5 g, 0.6 mmol) was swollen in anhydrous dichloromethane (5 ml). To the mixture was added 4-nitrobenzoyl chloride (0.33 g, 1.8 mmol) and N,N-diisopropylethylamine (0.42 ml, 2.4 mmol). After shaking at room temperature for 18 hours, the resin was filtered, washed according to the standard wash cycle and dried in vacuo to afford 0.53 g of the desired resin E.
    • Step F: Quaternization of Solid supported 1,2-Dihydro-1-(4-nitrobenzoyl)-spiro[3H-indole-3,4′-piperidine] (Resin F)
  • To resin E (0.1 g, 0.12 mmol) in anhydrous dimethylformamide (1 ml) was added cinnamyl bromide (0.12 g, 0.6 mmol). The reaction mixture was shaken at room temperature for 48 hours. The resulting resin was then washed according to the standard wash cycle to afford 0.11 g of the desired resin F, which was used immediately in Step G.
    • Step G: Preparation of 1,2-Dihydro-1-(4-nitrobenzoyl)-1′-(3-phenyl-2-propenyl)-spiro[3H-indole-3,4′-piperidine]
  • To resin F (0.11 g, 0.132 mmol) in anhydrous dimethylformamide (1.1 ml) was added Amberlite IRA-93 (previously washed with 10% N,N-diisopropylethylamine/dimethylformamide) (0.11 g). The mixture was shaken at room temperature for 36 hours. The dimethylformamide filtrate was then collected and concentrated under reduced pressure. The resin was further washed with dichloromethane and methanol. All filtrates were then combined and concentrated in vacuo to afford 0.052 g (88% yield) of the desired compound as a pale yellow oil.
  • By an analogous procedure other compounds were prepared including compound XVI-21, 5-Chloro-1,2-dihydro-1-(4-nitrobenzoyl)-1′-(3-phenyl-2-propenyl)-spiro[3H-indole-3-4′-piperidine]
    • EXAMPLE 18
  • This example illustrates the preparation of compound XXX-72, 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(Z)-3-(4-methylthiophenyl) allyl]spiro[indolin-3,4′-piperidine]
    Figure US20060106045A1-20060518-C00063
  • To 13.1 mg 4-thiomethylboronic acid in a “Zisser-block” were added 14.5 mg 1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1′-[(E/Z)-3-bromo-allyl]spiro[indolin-3,4′-piperidine] in 0.05ml dimethoxyethane, 8 mg sodium bicarbonate in 0.3 ml H2O and 2 mg bis-(triphenylphosphin)palladium(II) dichloride. The mixture was stirred at 75° C. for 13 hours.
  • The organic layer was separated and evaporated in vacuo and the residue purified by chromatography (H2O-acetonitrile gradient) to yield the desired product MS (ES+) 525.
  • By an analogous procedure other compounds were prepared including compounds XXX1-4, XXX-51, XXX-52, XXX-53, XXX-54, XXX-55, XXX-56, XXX-57, XXX-58, XXX-59, XXX-60, XXX-61, XXX-62, XXX-63, XXX-64, XXX-65, XXX-66, XXX-67, XXX-68, XXX-69, XXX-70, XXX-71, XXX-73, XXX-74, XXX-75, XXX-76, XXX-77, XXX-78, XXX-79, XXX-80, XXX-81, XXXI-3, XXXI-5, XXXI-6 and XXXI-7.
    • EXAMPLE 19
  • This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I).
  • Test against were performed as follows:
  • Spodoptera littoralis (Egyptian Cotton Leafworm)
  • Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with 5 L1 larvae. The samples were checked for mortality, repellent effect, feeding behaviour, and growth regulation 3 days after treatment (DAT). The following compounds gave at least 80% control of Spodoptera littoralis: I-2, I-12, I-21, I-22, I-23, I-32, I-52, I-61, I-62, I-72, I-82, I-92, I-112, I-132, I-142, I-152, I-162, I-182, I-192, I-202, I-212, I-222, I-232, I-242, I-252, I-262, I-282, II-62, V-22, VI-22, VI-62, VI-202, X-22, X-62, XI-62, XII-22, XIII-62, XIV-22, XV-22, XVII-62, XVIII-22, XIX-22, XIX-202, XX-22, XX-62, XXI-22, XXI-62, XXII-22, XXVI-2, XXVI-22, XXVII-2, XXVII-22, XXIX-43, XXIX-93, XXIX-195, XXIX-196, XXIX-201, XXX-10, XXX-106, XXX-107, XXX-118, XXX-15, XXX-16, XXX-18, XXX-24, XXX-26, XXX-28, XXX-3, XXX-36, XXX-43, XXX-48, XXX-49, XXX-52, XXX-55, XXX-57, XXX-60, XXX-67, XXX-83, XXX-84, XXX-87, XXX-88, XXX-99, XXXI-8, XXXII4, XXX-104, XXX-105, XXX-109, XXX-112, XXX-113, XXX-114, XXX-117, XXX-12, XXX-13, XXX1-4, XXX-19, XXX-2, XXX-20, XXX-30, XXX-38, XXX-39, XXX-40, XXX-41, XXX-42, XXX-44, XXX-45, XXX-50, XXX-53, XXX-59, XXX-6, XXX-61, XXX-62, XXX-65, XXX-7, XXX-70, XX-8, XXX-82, XXX-89, XXX-95, XXXI-2, XXXI-7, XXX-11, XXX1-1, XXX-110, XXX-111, XXX-31, XXX-51, XXX-66, XXX-86, XXX-93 and XXXI-5.
  • Heliothis virescens (Tobacco Budworm):
  • Eggs (0-24 h old) were placed in 24-well microtiter plate on artificial diet and treated with test solutions at an application rate of 200 ppm by pipetting. After an incubation period of 4 days, samples were checked for egg mortality, larval mortality, and growth regulation. The following compounds gave at least 80% control of Heliothis virescen: I-1, I-2, I-3, I-4, I-5, I-12, I-21, I-22, I-23, I-32, I-52, I-61, I-62, I-72, I-82, I-92, I-112, I-132, I-142, I-152, I-162, I-171, I-182, I-192, I-202, I-212, I-222, I-232, I-242, I-252, I-262, I-282, I-292, II-301, II-22, II-62, V-21, V-22, V-62, V-192, V-202, VI-1, VI-22, VI-62, VI-101, VI-202, IX-62, X-22, X-62, XI-62, XII-22, XIII-22, XIII-62, XIV-22, XV-22, XVII-62, XVIII-22, XVIII-202, XIX-22, XIX-202, XX-22, XX-62, XXI-22, XXI-62, XXII-22, XXV-222, XXVI-2, XXVI-22, XXVII-2, XXVII-22, XXVIII-7, XXVIII-27, XXVIII-42, XXVIII-67, XXVIII-97, XXVIII-132, XXVIII-187, XXVIII-217, XXVIII-252, XXIX-1, XXIX-7, XXIX-13, XXIX-57, XXIX-63, XXIX-75, XXIX-81, XXIX-87, XXIX-93, XXIX-111, XXIX-117, XXIX-123, XXIX-129, XXIX-141, XXIX-147, XXIX-153, XXIX-159, XXIX-165, XXIX-171,XXIX-183,XXIX-195,XXIX-196, XXIX-201,XXX-100, XXX-107, XXX-108, XXX-109, XXX-116, XXX-14, XXX-15, XXX-17, XXX-23, XXX-32, XXX-35, XXX-4, XXX-43, XXX-46, XXX-55, XXX-56, XXX-63, XXX-64, XXX-7, XXX-71, XXX-72, XXX-73, XXX-76, XXX-77, XXX-78, XXX-79, XXX-80, XXX-81, XXX-85, XXX-88, XXX-92, XXX-94, XXX-98, XXXII-1, XXXII-2, XXXII-3, XXXII-5, XXXII-8, XXXII-9, XXX-1, XXX-10, XXX-105, XXX-106, XXX-112, XXX-115, XXX-118, XXX-12, XXX-16, XXX-18, XXX-19, XXX-21, XXX-22, XXX-24, XXX-26, XXX-28, XXX-29, XXX-33, XXX-34, XXX-37, XXX-50, XXX-54, XXX-58, XXX-60, XXX-65, XXX-67, XXX-68, XXX-74, XXX-75, XXX-83, XXX-87, XXX-9, XXX-91, XXX-93, XXX-96, XXX-99, XXXI-3, XXXI-6, XXXII-10, XXXII-4, XXXII-6, XXX1-1, XXX-110, XXX-111, XXX-113, XXX-114, XXX-117, XXX-13, XXX1-4, XXX-2, XXX-20, XXX-3, XXX-30, XXX-31, XXX-36, XXX-38, XXX-40, XXX-41, XXX-44, XXX-45, XXX-48, XXX-49, XXX-5, XXX-53, XXX-57, XXX-59, XXX-6, XXX-61, XXX-62, XXX-7, XXX-8, XXX-82, XXX-89, XXX90, XXXI-2, XXX-120 and XXXI-7.
  • Plutella xylostella (Diamond Back Moth):
  • 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 18.2 ppm by pipetting. After drying, the MTP's were infested with larvae (L2)(10-15 per well). After an incubation period of 5 days, samples were checked for larval mortality, antifeedant and growth regulation. The following compounds gave at least 80% control of Plutella xylostella:
  • I-1, I-2, I-3, I-4, I-5, I-12, I-21, I-22, I-23, I-32, I-52, I-61, I-72, I-82, I-92, I-112, I-132, I-142, I-152, I-162, I-171, I-192, I-202, I-212, I-222, I-242, I-252, I-262, I-282, I-292, II-22, II-62, V-22, V-62, V-202, VI-22, VI-62, IX-62, X-22, X-62, XI-62, XII-22, XIII-62, XIV-22, XV-22, XVII-62, XX-22, XXI-62, XXII-22, XXV-62, XXVI-2, XXVI-22, XXVII-1, XXVII-2, XXVII-22, XXVIII-97, XXVIII-187, XXIX-129, XXIX-135, XXIX-159, XXIX-177, XXIX-189, XXIX-195, XXIX-196, XXX-10, XXX-100, XXX-109, XXX-112, XXX-117, XXX-16, XXX-18, XXX-19, XXX-21, XXX-28, XXX-34, XXX-36, XXX-43, XXX-48, XXX-5, XXX-50, XXX-54, XXX-59, XXX-60, XXX-66, XXX-68, XXX-69, XXX-75, XXX-83, XXX-90, XXX-91, XXX-98, XXXI-2, XXXI-7, XXXII-4, XXXII-8, XXXII-9, XXX-101,XXX-104,XXX-107,XXX-110,XXX-111,XXX-118,XXX-12,XXX-13, XXXI-4, XXX-22, XXX-3, XXX-30, XXX-37, XXX-39, XXX-40, XXX-41, XXX-42, XXX-44, XXX-49, XXX-57, XXX-61, XXX-7, XXX-89, XXX-105, XXX-106, XXX1-1, XXX-113, XXX-114, XXX-31, XXX-35, XXX-38, XXX-45, XXX-46, XXX-47, XXX-53, XXX-62, XXX-67, XXX-70, XXX-8, XXX-86, XXXI-5, XXX-2, XXX-120 and XXX-51
  • Myzus persicae (Green Peach Aphid):
  • Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 6 DAT, samples were checked for mortality. The following compounds gave at least 80% control of Myzus persicae:
  • I-2,1-21, II-62, XI-62, XXVII-2, XXVIII-162, XXIX-49 XXX-111, XXX-13, XXX-29, XXX-34 and XXX-47.
  • Tetranychus urticae (Two-Spotted Spider Mite):
  • Bean leaf discs on agar in 24-well microtiter plates wer sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality. The following compounds gave at least 80% control of Tetranychus urticae:
  • I-202, XIII-22, XIX-202, XXVI-1, XXVIII-162, XXIX-207, XXX-57 and XXXI-2.
  • Aedes aegypti (Yellow Fever Mosquito):
  • 10-15 Aedes larvae (L2) together with a nutrition mixture are placed in 96-well microtiter plates. Test solutions at an application rate of 2ppm are pipetted into the wells. 2 days later, insects were checked for mortality and growth inhibition. The following compounds gave at least 80% control of Aedes aegypti
  • I-4, I-5, I-12, I-21, I-22, I-23, I-32, I-52, I-61, I-62, 1-72, I-82, I-92, I-112, I-132, I-142, I-152, I-162, I-202, I-212, I-222, I-232, I-242, I-252, I-262, I-292, II-22, I-62, V-22, VI-22, VI-62, VI-202, XIV-22, XV-22, XVII-62, XVIII-22, XIX-22, XX-22, XXI-22, XXI-62, XXII-22, XXVI-2, XXVI-22, XXVII-22, XXVIII-7, XXVIII-27, XXVIII-67, XXVIII-97, XXVIII-187, XXIX-13, XXIX-19, XXIX-25, XXIX-31, XXIX-37, XXIX-69, XXIX-75, XXIX-93, XXIX-99, XXIX-105, XXIX-117,XXIX-123, XXIX-129, XXIX-135, XXIX-159, XXIX-183, XXX-102, XXX-105, XXX-11, XXX-110, XXX-117, XXX-24, XXX-28, XXX-31, XXX-34, XXX-4, XXX-48, XXX-49, XXX-52, XXX-57, XXX-59, XXX-60, XXX-61, XXX-67, XXX-68, XXX-7, XXX-70, XXX-75, XXX-78, XXX-79, XXX-82, XXX-83, XXX-84, XXX-87, XXX-88, XXX90, XXX-93, XXX-94, XXX-97, XXXI-2, XXXI-7, XXXI-8, XXXII-10, XXXII-4, XXX-104, XXX-106, XXX1-1, XXX-111, XXX-113, XXX-114, XXX-118, XXX-12, XXX-13, XXX1-4, XXX-16, XXX-17, XXX-18, XXX-19, XXX-2, XXX-20, XXX-22, XXX-26, XXX-3, XXX-30, XXX-35, XXX-38, XXX-39, XXX-44, XXX-46, XXX-47, XXX-5, XXX-50, XXX-53, XXX-62, XXX-86, XXX-98, XXXI-5, XXX-109, XXX-45, XXX-51, XXX-6, XXX-66 XXX-121 and XXX-8.

Claims (10)

1. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I):
Figure US20060106045A1-20060518-C00064
wherein Y is a single bond, C═O, C═S or S(O)q where q is 0, 1 or 2; R1 is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted heterocyclyloxy, cyano, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, formyl, optionally substituted heterocyclyl, optionally substituted alkylthio, NO or NR13R14 where R13 and R14 are independently hydrogen, COR40, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl or R13 and R14 together with the N atom to which they are attached form a group —N═C(R41)—NR42R43; R2and R3 are independently hydrogen, halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl or C(O)NR15R16 where R15 and R16 are independently hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl, or R2 and R3 together are ═O, or R2 and R3 together with the atoms to which they are attached form a 4, 5, 6,or 7 membered carbocyclic or heterocyclic ring; each R4 is independently halogen, nitro, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6alkenyl, optionally substituted C2-6alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted C3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio or R19R20N where R19 and R20 are, independently, hydrogen, C1-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C3-7 cycloalkyl(C1-4)alkyl, C2-6 haloalkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1-6 alkyl groups, or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4; R8 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; R9 and R10 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl or R9 and R10 together form a group —CH2—, —CH═CH— or —CH2CH2—; R40 is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy optionally substituted heteroaryl, optionally substituted heteroaryloxy or NR44R45; R41, R42 and R43 are each independently H or lower alkyl; R44 and R45 are independently optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl or salts or N-oxides thereof.
2. A method according to claim 1 wherein Y is a bond or is C═O.
3. A method according to claim 1 wherein R1 is hydrogen, C1-6 alkyl, C1-6 cyanoalkyl, C1-6 haloalkyl, C3-7 cycloalkyl(C1-4)alkyl, C1-6 alkoxy(C1-6)alkyl, heteroaryl(C1-6)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), aryl(C1-6)alkyl (wherein the aryl group may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C1-6 alkylcarbonylamino(C1-6)alkyl, aryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), heteroaryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 alkylsulfinyl, C1-6 alkylthio, C1-6 alkoxycarbonyl, C1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C1-6 alkoxy, C1-6 haloalkoxy, phenoxy (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryloxy (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocycyloxy (optionally substituted by halo, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), cyano, C2-6 alkenyl, C2-6 alkynyl, C3-6 cycloalkyl, C5-7 cycloalkenyl, heterocyclyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkylthio, C1-6 haloalkylthio or NR13R14 where R13 and R14 are independently hydrogen, C2-6 alkyl, C2-6 haloalkyl, phenyl (which may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino or C1-4 alkoxycarbonyl) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy, C1-4 alkoxycarbonyl C1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), amino, C1-6 alkylamino or phenylamino (wherein the phenyl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino).
4. A method according to claim 1, wherin R2 and R3 are are independently hydrogen or C1-4 alkyl.
5. A method according to claim 1, wherein each R4 is independently halogen, cyano, C1-8 alkyl, C1-8 haloalkyl, C1-6 cyanoalkyl, C1-6 alkoxy(C1-6)alkyl, C3-7 cycloalkyl(C1-6)alkyl, C5-6 cycloalkenyl(C1-6)alkyl, C3-6 alkenyloxy(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, aminocarbonyl(C2-6)alkenyl, C1-6 alkylaminocarbonyl(C2-6)-alkenyl, di(C1-6)alkylaminocarbonyl(C2-6)alkenyl, phenyl(C2-4)alkenyl, (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkynyl, trimethylsilyl(C2-6)alkynyl, aminocarbonyl(C2-6)alkynyl, C1-6 alkylaminocarbonyl(C2-6)alkynyl, di(C1-6)alkylaminocarbonyl(C2-6)alkynyl, C1-6 alkoxycarbonyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)-cycloalkyl, C1-3 alkyl(C3-7)halocycloalkyl,phenyl (optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen, C1-8 alkoxy, C1-6 haloalkoxy, phenoxy (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryloxy (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-8 alkylthio or R19R20N where R19 and R20 are, independently, hydrogen, C1-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C2-6 haloalkyl, alkoxycarbonyl or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1-6 alkyl groups; n is 0, 1, 2, 3 or 4.
6. A method according to claim 1, wherin R8 is C1-10 alkyl, C1-10 haloalkyl, aryl(C1-6)alkyl (wherein the aryl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), arylcarbonyl-(C1-6)alkyl (wherein the aryl group may be optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino and the alkyl group may be optionally substituted by aryl), C2-8 alkenyl, C2-8 haloalkenyl, aryl(C2-6)alkenyl (wherein the aryl group is optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, C1-6 alkoxycarbonyl, or two adjacent substituents can cyclise to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring), C2-6 alkynyl, phenyl(C2-6)alkynyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C3-7 cycloalkyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 haloalkylcarbonyl or aryl(C2-6)alkenylcarbonyl (wherein the aryl group may be optionally substituted halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), or —C(R51)(R52)—[CR53═CR54]z-R55 where z is 1 or 2, R51 and R52 are each independently H, halo or C1-2 alkyl, R53 and R54 are each independently H, halogen, C1-4 alkyl or C1-4 haloalkyl and R55 is optionally substituted aryl or optionally substituted heteroaryl.
7. A method according to claim 1, wherein R9 and R10 are both hydrogen.
8. A compound of formula IK
Figure US20060106045A1-20060518-C00065
wherein Y is a single bond, C═O or S(O)q where is 0, 1 or 2; R1 is C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C3-7 cycloalkyl(C1-6)alkyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy-(C1-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, C1-6 carboxyalkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)-alkyl, C3-6 alkynyloxycarbonyl(C1-6)alkyl, aryloxycarbonyl(C1-6)alkyl, C1-6 alkylthio(C1-6)-alkyl, C1-6 alkylsulfinyl(C1-6)alkyl, C1-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6)alkyl, C1-6 alkylaminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl(C1-4)alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), phenyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), C1-6 alkoxy, C1-6 haloalkoxy, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 cyanoalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy) or C1-6 alkylthio; R2 and R3 are independently hydrogen or C1-4 alkyl; each R4 is independently halogen, cyano, C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), C2-6alkenyl optionally substituted by C1-6alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy) or C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy); n is 0, 1, 2, 3 or 4; R8 is C1-10 alkyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy), C2-6 alkenyl optionally substituted by C1-6alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy) or C2-6 alkynyl optionally substituted by C1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C1-4 alkyl or C1-4 alkoxy); R9 and R10 are both hydrogen; and salts or N-oxides thereof provided that R8 is not methyl and YR1 is not SO2CH3, methyl, ethyl, phenyl or fluoro-substituted phenyl.
9. A compound of formula (11)
Figure US20060106045A1-20060518-C00066
where R8 is phenyl(C2-4)alkenyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, provided the substituent is not para-fluoro); or a compound of formula (10)
Figure US20060106045A1-20060518-C00067
where R8 is phenyl(C2-4)alkenyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino, provided the substituent is not a para-fluoro); or a compound of formula (9)
Figure US20060106045A1-20060518-C00068
where R2 is as defined for formula (I) in claim 1 and R8 is phenyl(C2-4)alkenyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino); or a compound of formula (9A)
Figure US20060106045A1-20060518-C00069
where R2 and where (R4)n are as defined for formula (I) in claim 1 and R8 is phenyl(C2-4)alkenyl (wherein the phenyl group is optionally substituted by halogen, C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkyl, C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino).
10. An insecticidal acaricidal and nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula I as defined in claim 1.
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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050288317A1 (en) * 2004-06-24 2005-12-29 Wenqing Yao Amido compounds and their use as pharmaceuticals
US20050288338A1 (en) * 2004-06-24 2005-12-29 Wenqing Yao Amido compounds and their use as pharmaceuticals
US20050288329A1 (en) * 2004-06-24 2005-12-29 Wenqing Yao 2-Methylprop anamides and their use as pharmaceuticals
US20060004049A1 (en) * 2004-06-24 2006-01-05 Wenqing Yao N-substituted piperidines and their use as pharrmaceuticals
US20060009491A1 (en) * 2004-06-24 2006-01-12 Incyte Corporation Amido compounds and their use as pharmaceuticals
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US20060116382A1 (en) * 2004-11-10 2006-06-01 Wenqing Yao Lactam compounds and their use as pharmaceuticals
US20060122197A1 (en) * 2004-08-10 2006-06-08 Wenqing Yao Amido compounds and their use as pharmaceuticals
US20060122210A1 (en) * 2004-11-18 2006-06-08 Wenqing Yao Inhibitors of 11-beta hydroxyl steroid dehydrogenase type I and methods of using the same
US20060270653A1 (en) * 2004-11-29 2006-11-30 Ioana Drutu Modulators of muscarinic receptors
US20070066584A1 (en) * 2005-09-21 2007-03-22 Wenqing Yao Amido compounds and their use as pharmaceuticals
US20070129345A1 (en) * 2005-12-05 2007-06-07 Jincong Zhuo Lactam compounds and methods of using the same
US20070197530A1 (en) * 2006-01-31 2007-08-23 Yun-Long Li Amido compounds and their use as pharmaceuticals
US20070197506A1 (en) * 2006-01-12 2007-08-23 Wenqing Yao Modulators of 11-beta hydroxyl steroid dehydrogenase type 1, pharmaceutical compositions thereof, and methods of using the same
US20070208001A1 (en) * 2006-03-03 2007-09-06 Jincong Zhuo Modulators of 11- beta hydroxyl steroid dehydrogenase type 1, pharmaceutical compositions thereof, and methods of using the same
US20070213315A1 (en) * 2006-02-22 2007-09-13 Robert Davies Modulators of muscarinic receptors
US20070213311A1 (en) * 2006-03-02 2007-09-13 Yun-Long Li Modulators of 11-beta hydroxyl steroid dehydrogenase type 1, pharmaceutical compositions thereof, and methods of using the same
US20070270424A1 (en) * 2006-05-17 2007-11-22 Yun-Long Li Heterocyclic inhibitors of 11-beta hydroxyl steroid dehydrogenase type 1 and methods of using the same
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US20080015179A1 (en) * 2005-12-22 2008-01-17 Makings Lewis R Modulators of muscarinic receptors
US20080047479A1 (en) * 1997-10-27 2008-02-28 Correct Craft, Inc. Water Sport Towing Apparatus and Method
US20080318991A1 (en) * 2007-06-21 2008-12-25 Incyte Corporation Spirocycles as inhibitors of 11-beta hydroxyl steroid dehydrogenase type 1
US20090099222A1 (en) * 2007-10-03 2009-04-16 Davies Robert J Modulators of muscarinic receptors
US20090291946A1 (en) * 2004-11-10 2009-11-26 Incyte Corporation Lactam compounds and their use as pharmaceuticals
US7786107B2 (en) 2006-08-18 2010-08-31 Vertex Pharmaceuticals Incorporated Modulators of muscarinic receptors
US7786141B2 (en) 2004-08-19 2010-08-31 Vertex Pharmaceuticals Incorporated Dihydrospiroindene modulators of muscarinic receptors
US20100311720A1 (en) * 2004-08-19 2010-12-09 Vertex Pharmaceuticals Incorporated Spiroindoline Modulators of Muscarinic Receptors

Families Citing this family (359)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0213715D0 (en) * 2002-06-14 2002-07-24 Syngenta Ltd Chemical compounds
GB0328905D0 (en) * 2003-12-12 2004-01-14 Syngenta Participations Ag Chemical compounds
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JP2007516298A (en) 2003-12-23 2007-06-21 アリーナ ファーマシューティカルズ， インコーポレイテッド Novel spiroindoline or spiroisoquinoline compounds, methods of use and compositions thereof
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GB0601402D0 (en) 2006-01-24 2006-03-08 Syngenta Participations Ag Chemical Compounds
CA2651681A1 (en) * 2006-05-18 2007-11-29 Merck & Co., Inc. Aryl-fused spirocyclic compounds
ATE545416T1 (en) 2006-10-12 2012-03-15 Xenon Pharmaceuticals Inc USE OF SPIRO-OXINDOLE COMPOUNDS AS THERAPEUTICS
CA2741029A1 (en) 2008-10-17 2010-04-22 Xenon Pharmaceuticals Inc. Spiro-oxindole compounds and their use as therapeutic agents
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AR077252A1 (en) 2009-06-29 2011-08-10 Xenon Pharmaceuticals Inc ESPIROOXINDOL COMPOUND ENANTIOMERS AND THEIR USES AS THERAPEUTIC AGENTS
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WO2011095581A1 (en) 2010-02-05 2011-08-11 Intervet International B.V. S piroindoline compounds for use as anthelminthi cs
EP2538919B1 (en) 2010-02-26 2017-07-12 Xenon Pharmaceuticals Inc. Pharmaceutical compositions of spiro-oxindole compound for topical administration and their use as therapeutic agents
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AU2011334989A1 (en) 2010-12-01 2013-06-13 Bayer Intellectual Property Gmbh Use of fluopyram for controlling nematodes in crops and for increasing yield
TWI667347B (en) 2010-12-15 2019-08-01 瑞士商先正達合夥公司 Soybean event syht0h2 and compositions and methods for detection thereof
EP2471363A1 (en) 2010-12-30 2012-07-04 Bayer CropScience AG Use of aryl-, heteroaryl- and benzylsulfonamide carboxylic acids, -carboxylic acid esters, -carboxylic acid amides and -carbonitriles and/or its salts for increasing stress tolerance in plants
EP2675789A1 (en) 2011-02-17 2013-12-25 Bayer Intellectual Property GmbH Substituted 3-(biphenyl-3-yl)-8,8-difluoro-hydroxy-1-azaspiro[4.5]dec-3-en-2-ones for therapy and halogen-substituted spirocyclic ketoenols
CA2827304C (en) 2011-02-17 2018-11-13 Bayer Intellectual Property Gmbh Use of sdhi fungicides on conventionally bred asr-tolerant, stem canker resistant and/or frog-eye leaf spot resistant soybean varieties
CA2828639C (en) 2011-03-01 2019-02-12 Bayer Intellectual Property Gmbh 2-acyloxypyrrolin-4-ones
AR085509A1 (en) 2011-03-09 2013-10-09 Bayer Cropscience Ag INDOL- AND BENCIMIDAZOLCARBOXAMIDS AS INSECTICIDES AND ACARICIDES
US20130345058A1 (en) 2011-03-10 2013-12-26 Wolfram Andersch Use of lipochito-oligosaccharide compounds for safeguarding seed safety of treated seeds
KR101834362B1 (en) 2011-03-18 2018-03-05 바이엘 인텔렉쳐 프로퍼티 게엠베하 N-(3-carbamoylphenyl)-1h-pyrazole-5-carboxamide derivatives and the use thereof for controlling animal pests
AR085568A1 (en) 2011-04-15 2013-10-09 Bayer Cropscience Ag 5- (BICYCLE [4.1.0] HEPT-3-EN-2-IL) -PENTA-2,4-DIENOS AND 5- (BICYCLE [4.1.0] HEPT-3-EN-2-IL) -PENT- 2-IN-4-INOS REPLACED AS ACTIVE PRINCIPLES AGAINST ABIOTIC STRESS OF PLANTS
AR085585A1 (en) 2011-04-15 2013-10-09 Bayer Cropscience Ag VINIL- AND ALQUINILCICLOHEXANOLES SUBSTITUTED AS ACTIVE PRINCIPLES AGAINST STRIPS ABIOTIQUE OF PLANTS
AR090010A1 (en) 2011-04-15 2014-10-15 Bayer Cropscience Ag 5- (CICLOHEX-2-EN-1-IL) -PENTA-2,4-DIENOS AND 5- (CICLOHEX-2-EN-1-IL) -PENT-2-EN-4-INOS REPLACED AS ACTIVE PRINCIPLES AGAINST THE ABIOTIC STRESS OF PLANTS, USES AND TREATMENT METHODS
CN102246775B (en) * 2011-05-17 2013-05-29 德强生物股份有限公司 Insecticidal synergistic composition
EP2535334A1 (en) 2011-06-17 2012-12-19 Bayer CropScience AG Crystalline modifications of penflufen
EP2540163A1 (en) 2011-06-30 2013-01-02 Bayer CropScience AG Nematocide N-cyclopropyl-sulfonylamide derivatives
JP2014520776A (en) 2011-07-04 2014-08-25 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー Use of substituted isoquinolinones, isoquinoline diones, isoquinoline triones and dihydroisoquinolinones or their salts in each case as active agents against abiotic stresses in plants
DK2736327T3 (en) 2011-07-26 2018-04-23 Clariant Int Ltd Etherized lactate esters, processes for their preparation and their use in improving the action of plant protection products
UA115128C2 (en) 2011-07-27 2017-09-25 Байєр Інтеллектуал Проперті Гмбх Seed dressing for controlling phytopathogenic fungi
US9096599B2 (en) 2011-08-04 2015-08-04 Intervet Inc. Spiroindoline compounds
EP2561759A1 (en) 2011-08-26 2013-02-27 Bayer Cropscience AG Fluoroalkyl-substituted 2-amidobenzimidazoles and their effect on plant growth
JP6138797B2 (en) 2011-09-16 2017-05-31 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ Use of acylsulfonamides to improve plant yield
CA2848625A1 (en) 2011-09-16 2013-03-21 Bayer Intellectual Property Gmbh Use of mefenpyr-diethyl in combination with prothioconazole and tebuconazole for improving plant yield
EP2755484A1 (en) 2011-09-16 2014-07-23 Bayer Intellectual Property GmbH Use of 5-phenyl- or 5-benzyl-2 isoxazoline-3 carboxylates for improving plant yield
JP2013082632A (en) 2011-10-05 2013-05-09 Bayer Cropscience Ag Agrochemical formulation and manufacturing method of the same
EP2604118A1 (en) 2011-12-15 2013-06-19 Bayer CropScience AG Active ingredient combinations having insecticidal and acaricidal properties
AU2012357896B9 (en) 2011-12-19 2016-12-15 Bayer Cropscience Ag Use of anthranilic acid diamide derivatives for pest control in transgenic crops
CN104011026B (en) 2011-12-20 2016-07-20 拜耳知识产权股份有限公司 Parasite killing virtue amide
EP2606726A1 (en) 2011-12-21 2013-06-26 Bayer CropScience AG N-Arylamidine-substituted trifluoroethylsulfide derivatives as acaricides and insecticides
BR112014017552A8 (en) 2012-01-21 2017-07-04 Bayer Ip Gmbh use of host defense inducers to control harmful basterian organisms in useful plants
JP2015515454A (en) 2012-03-14 2015-05-28 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ Pesticide arylpyrrolidines
BR112014028367A2 (en) 2012-05-16 2017-07-18 Bayer Cropscience Ag oil-in-water insecticide formulation (o / w).
ES2780356T3 (en) 2012-05-16 2020-08-25 Bayer Cropscience Ag Insecticidal formulation of water in oil (AG / AC)
AR091104A1 (en) 2012-05-22 2015-01-14 Bayer Cropscience Ag COMBINATIONS OF ACTIVE COMPOUNDS THAT INCLUDE A LIPO-CHYTOOLIGOSACARIDE DERIVATIVE AND A NEMATICIDE, INSECTICIDE OR FUNGICIDE COMPOUND
IN2014DN09927A (en) 2012-05-30 2015-08-14 Clariant Int Ltd
JP6285423B2 (en) 2012-05-30 2018-02-28 バイエル・クロップサイエンス・アクチェンゲゼルシャフト Composition comprising a biopesticide and an insecticide
WO2013178662A1 (en) 2012-05-30 2013-12-05 Bayer Cropscience Ag Compositions comprising a biological control agent and an insecticide
US10864275B2 (en) 2012-05-30 2020-12-15 Clariant International Ltd. N-methyl-N-acylglucamine-containing composition
WO2014005982A1 (en) 2012-07-05 2014-01-09 Bayer Cropscience Ag Insecticide and fungicide active ingredient combinations
CN104602520A (en) 2012-07-31 2015-05-06 拜尔农作物科学股份公司 Compositions comprising a pesticidal terpene mixture and an insecticide
CA2881995A1 (en) 2012-08-17 2014-02-20 Bayer Cropscience Ag Azaindole carboxylic acid amides and azaindole thiocarboxylic acid amides for use as insecticides and acaricides
AU2013311826A1 (en) 2012-09-05 2015-03-26 Bayer Cropscience Ag Use of substituted 2-amidobenzimidazoles, 2-amidobenzoxazoles and 2-amidobenzothiazoles or salts thereof as active substances against abiotic plant stress
CN113243374B (en) 2012-10-02 2022-04-26 拜耳农作物科学股份公司 Heterocyclic compounds as pesticides
WO2014060381A1 (en) 2012-10-18 2014-04-24 Bayer Cropscience Ag Heterocyclic compounds as pesticides
US20150284380A1 (en) 2012-10-31 2015-10-08 Bayer Cropscience Ag Novel heterocyclic compounds as pest control agents
DE102012021647A1 (en) 2012-11-03 2014-05-08 Clariant International Ltd. Aqueous adjuvant compositions
UA117816C2 (en) 2012-11-06 2018-10-10 Байєр Кропсайєнс Акцієнгезелльшафт Herbicidal combinations for tolerant soybean cultures
EP2925137A1 (en) 2012-11-30 2015-10-07 Bayer CropScience AG Binary fungicidal or pesticidal mixture
CA3082683A1 (en) 2012-11-30 2014-06-05 Bayer Cropscience Ag Binary fungicidal mixtures
WO2014086753A2 (en) 2012-12-03 2014-06-12 Bayer Cropscience Ag Composition comprising biological control agents
US20150289518A1 (en) 2012-12-03 2015-10-15 Bayer Cropscience Ag Composition comprising a biological control agent and an insecticide
CA2893083A1 (en) 2012-12-03 2014-06-12 Bayer Cropscience Ag Composition comprising a biological control agent and an insecticide
EP2925145A2 (en) 2012-12-03 2015-10-07 Bayer CropScience AG Composition comprising biological control agents
US9867377B2 (en) 2012-12-03 2018-01-16 Bayer Cropscience Ag Composition comprising a biological control agent and an insecticide
JP2016500368A (en) 2012-12-05 2016-01-12 バイエル・クロップサイエンス・アクチェンゲゼルシャフト As substituted 1- (arylethynyl)-, 1- (heteroarylethynyl)-, 1- (heterocyclic ethynyl)-and 1- (cycloalkenylethynyl) -cyclohexanol as active agents against abiotic plant stress use
WO2014090765A1 (en) 2012-12-12 2014-06-19 Bayer Cropscience Ag Use of 1-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenyl]-5-amino-3-trifluoromethyl)-1 h-1,2,4 tfia zole for controlling nematodes in nematode-resistant crops
AR093996A1 (en) 2012-12-18 2015-07-01 Bayer Cropscience Ag BACTERICIDAL COMBINATIONS AND BINARY FUNGICIDES
PT2953942T (en) 2013-02-06 2018-01-17 Bayer Cropscience Ag Halogen-substituted pyrazole derivatives as pesticides
US20150366199A1 (en) 2013-02-11 2015-12-24 Bayer Cropscience Lp Compositions comprising gougerotin and an insecticide
BR112015018676A2 (en) 2013-02-11 2017-07-18 Bayer Cropscience Lp compositions comprising gougerotine and a biological control agent
CN105208865A (en) 2013-03-12 2015-12-30 拜耳作物科学股份公司 Use of dithiine-tetracarboximides for controlling bacterial harmful organisms in useful plants
AR095785A1 (en) * 2013-04-09 2015-11-11 Bayer Pharma AG DERIVATIVES OF SPIROINDOLINE AND PHARMACEUTICAL COMPOSITIONS OF THE SAME
EP2986117A1 (en) 2013-04-19 2016-02-24 Bayer CropScience Aktiengesellschaft Binary insecticidal or pesticidal mixture
EP2986121A1 (en) 2013-04-19 2016-02-24 Bayer CropScience Aktiengesellschaft Active compound combinations having insecticidal properties
BR112015031291A2 (en) 2013-06-20 2017-07-25 Bayer Cropscience Ag aryl sulfide derivatives and arylalkyl sulfoxide derivatives as acaricides and insecticides
CN105722830B (en) 2013-06-20 2019-06-04 拜耳作物科学股份公司 Aryl thioethers derivative and aryl sulfoxid es derivative as acaricide and insecticide
TW201542532A (en) 2013-07-08 2015-11-16 Bayer Cropscience Ag Six-membered C-N-bonded aryl sulphide and aryl sulphoxide derivatives as pesticides
WO2015055554A1 (en) 2013-10-14 2015-04-23 Bayer Cropscience Ag Active substance for treating seed and soil
UY35772A (en) 2013-10-14 2015-05-29 Bayer Cropscience Ag NEW PESTICIDED COMPOUNDS
WO2015059088A1 (en) 2013-10-23 2015-04-30 Bayer Cropscience Ag Substituted quinoxaline derivatives as pest control agent
CA2932163A1 (en) * 2013-12-24 2015-07-02 Zoetis Services Llc Spiroindoline antiparasitic derivatives
CR20160311A (en) 2014-01-03 2016-08-16 Bayer Animal Health Gmbh NEW PIRAZOLIL-HETEROARILAMIDAS AS PLAGUICIDE AGENTS
TW201612161A (en) 2014-01-20 2016-04-01 Bayer Cropscience Ag Quinoline derivatives as insecticides and acaricides
DE202014008418U1 (en) 2014-02-19 2014-11-14 Clariant International Ltd. Low foaming agrochemical compositions
DE202014008415U1 (en) 2014-02-19 2014-11-25 Clariant International Ltd. Aqueous adjuvant composition for increasing the effectiveness of electrolyte active substances
WO2015150300A1 (en) 2014-04-02 2015-10-08 Bayer Cropscience Ag N-(1-(hetero)aryl-1h-pyrazol-4-yl)-(hetero)arylamide derivatives and use thereof as pesticides
WO2015160618A1 (en) 2014-04-16 2015-10-22 Bayer Cropscience Lp Compositions comprising ningnanmycin and a biological control agent
WO2015160620A1 (en) 2014-04-16 2015-10-22 Bayer Cropscience Lp Compositions comprising ningnanmycin and an insecticide
DE102014005771A1 (en) 2014-04-23 2015-10-29 Clariant International Ltd. Use of aqueous drift-reducing compositions
CN106661022B (en) 2014-05-08 2018-05-04 拜耳作物科学股份公司 Pyrazolopyridine sulfonamide as nematicide
ES2747810T3 (en) 2014-06-05 2020-03-11 Bayer Cropscience Ag Bicyclic compounds as agents to combat parasites
WO2016001119A1 (en) 2014-07-01 2016-01-07 Bayer Cropscience Aktiengesellschaft Insecticide and fungicide active ingredient combinations
AU2015289246B2 (en) 2014-07-15 2019-07-25 Bayer Animal Health Gmbh Aryl-triazolyl pyridines as pest control agents
DE102014012022A1 (en) 2014-08-13 2016-02-18 Clariant International Ltd. Organic ammonium salts of anionic pesticides
WO2016055096A1 (en) 2014-10-07 2016-04-14 Bayer Cropscience Ag Method for treating rice seed
AR102942A1 (en) 2014-12-11 2017-04-05 Bayer Cropscience Ag DERIVATIVES OF ARILSULFIDE AND ARILSULPHOXIDE OF FIVE C-N-CONNECTED MEMBERS, AS PESTICIDES
DE102014018274A1 (en) 2014-12-12 2015-07-30 Clariant International Ltd. Sugar surfactants and their use in agrochemical compositions
BR112017012978B1 (en) 2014-12-19 2021-06-08 Clariant International Ltd aqueous adjuvant composition comprising polyalkylene glycol ether sulfate, composition comprising alkylglucamides and the uses thereof
CN107105674B (en) 2014-12-22 2020-10-02 拜耳作物科学有限合伙公司 Methods of treating or preventing pineapple disease using bacillus subtilis or bacillus pumilus strains
EP3081085A1 (en) 2015-04-14 2016-10-19 Bayer CropScience AG Method for improving earliness in cotton
TW201636017A (en) 2015-02-05 2016-10-16 梯瓦製藥國際有限責任公司 Methods of treating postherpetic neuralgia with a topical formulation of a spiro-oxindole compound
UY36547A (en) 2015-02-05 2016-06-01 Bayer Cropscience Ag BICYCLIC CONDENSED HETEROCYCLIC DERIVATIVES REPLACED BY 2- (HET) ARILO AS PESTICIDES
UY36548A (en) 2015-02-05 2016-06-01 Bayer Cropscience Ag BICYCLIC CONDENSED HETEROCYCLIC DERIVATIVES REPLACED BY 2- (HET) ARILO AS PESTICIDES
TWI702212B (en) 2015-02-09 2020-08-21 德商拜耳作物科學股份有限公司 Substituted 2-thioimidazolylcarboxamides as pesticides
EP3268353B1 (en) 2015-03-10 2020-09-09 Bayer Animal Health GmbH Pyrazolyl derivatives as pest control agents
BR112017021408B1 (en) 2015-04-08 2022-05-17 Bayer Cropscience Aktiengesellschaft Condensed bicyclic heterocycle derivatives, method for controlling animal pests, and agrochemical formulation
WO2016174049A1 (en) 2015-04-30 2016-11-03 Bayer Animal Health Gmbh Anti-parasitic combinations including halogen-substituted compounds
EP2910126A1 (en) 2015-05-05 2015-08-26 Bayer CropScience AG Active compound combinations having insecticidal properties
WO2016180802A1 (en) 2015-05-13 2016-11-17 Bayer Cropscience Aktiengesellschaft Insecticidal arylpyrrolidines, method for synthesizing same, and use thereof as agents for controlling animal pests
CN107846888B (en) 2015-07-06 2021-02-26 拜耳作物科学股份公司 Heterocyclic compounds as pesticides
US10667517B2 (en) 2015-08-07 2020-06-02 Bayer Cropscience Aktiengesellschaft 2-(Het)aryl-substituted fused heterocycle derivatives as pesticides
DE202015008045U1 (en) 2015-10-09 2015-12-09 Clariant International Ltd. Universal pigment dispersions based on N-alkylglucamines
DE102015219651A1 (en) 2015-10-09 2017-04-13 Clariant International Ltd. Compositions containing sugar amine and fatty acid
BR112018008440B1 (en) 2015-10-26 2021-12-21 Bayer Cropscience Aktiengesellschaft FUSIONED BICYCLIC HETEROCYCLE DERIVATIVES AS PESTICIDES
WO2017093180A1 (en) 2015-12-01 2017-06-08 Bayer Cropscience Aktiengesellschaft Condensed bicyclic heterocycle derivatives as pest control agents
RU2018123928A (en) 2015-12-03 2020-01-13 Байер Кропсайенс Акциенгезельшафт MESOION HALOGENED 3- (ACETYL) -1 - [(1,3-THIAZOL-5-IL) METHYL] -1H-IMIDAZO [1,2-A] PYRIDIN-4-IUM-2-OLATE DERIVATIVES AND RELATED COMPOUNDS AS INSECTICIDES
US10647699B2 (en) 2016-02-11 2020-05-12 Bayer Cropscience Aktiengesellschaft Substituted 2-oxyimidazolylcarboxamides as pesticides
EP3414236A1 (en) 2016-02-11 2018-12-19 Bayer CropScience Aktiengesellschaft Substituierted 2-(het)aryl-imidazolyl-carboxyamides as pest control agents
WO2017144341A1 (en) 2016-02-23 2017-08-31 Bayer Cropscience Aktiengesellschaft Condensed bicyclic heterocycle derivatives as pest control agents
EP3210468A1 (en) 2016-02-26 2017-08-30 Bayer CropScience Aktiengesellschaft Solvent-free formulations of low-melting point agents
WO2017157735A1 (en) 2016-03-15 2017-09-21 Bayer Cropscience Aktiengesellschaft Substituted sulfonyl amides for controlling animal pests
JP2019513700A (en) 2016-03-16 2019-05-30 バイエル・クロップサイエンス・アクチェンゲゼルシャフト N- (Cyanobenzyl) -6- (cyclopropyl-carbonylamino) -4- (phenyl) -pyridine-2-carboxamide derivative as a pesticide and plant protection agent and related compounds
WO2017174414A1 (en) 2016-04-05 2017-10-12 Bayer Cropscience Aktiengesellschaft Naphthaline-derivatives as pest control agents
US10604525B2 (en) 2016-04-15 2020-03-31 Bayal Animal Health Gmbh Pyrazolopyrimidine derivatives
CN109068649A (en) 2016-04-24 2018-12-21 拜耳农作物科学股份公司 Fluopyram and/or bacillus subtilis are used to prevent and treat the purposes of the wilt disease of Musaceae plant
AU2017256505B2 (en) 2016-04-25 2021-02-18 Bayer Cropscience Aktiengesellschaft Substituted 2-alkylimidazolyl-carboxamides as pest control agents
EP3241830A1 (en) 2016-05-04 2017-11-08 Bayer CropScience Aktiengesellschaft Condensed bicyclic heterocyclic derivatives as pesticides
DE202016003070U1 (en) 2016-05-09 2016-06-07 Clariant International Ltd. Stabilizers for silicate paints
EP3245865A1 (en) 2016-05-17 2017-11-22 Bayer CropScience Aktiengesellschaft Method for increasing yield in brassicaceae
WO2017198450A1 (en) 2016-05-15 2017-11-23 Bayer Cropscience Nv Method for increasing yield in maize
WO2017198449A1 (en) 2016-05-15 2017-11-23 Bayer Cropscience Nv Method for increasing yield in brassicaceae
WO2017198453A1 (en) 2016-05-16 2017-11-23 Bayer Cropscience Nv Method for increasing yield in potato, tomato or alfalfa
WO2017198452A1 (en) 2016-05-16 2017-11-23 Bayer Cropscience Nv Method for increasing yield in soybean
WO2017198454A1 (en) 2016-05-17 2017-11-23 Bayer Cropscience Nv Method for increasing yield in cotton
WO2017198455A2 (en) 2016-05-17 2017-11-23 Bayer Cropscience Nv Method for increasing yield in beta spp. plants
WO2017198451A1 (en) 2016-05-17 2017-11-23 Bayer Cropscience Nv Method for increasing yield in small grain cereals such as wheat and rice
US10653136B2 (en) 2016-07-11 2020-05-19 Covestro Llc Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds
US10653135B2 (en) 2016-07-11 2020-05-19 Covestro Llc Methods for treating seeds with an aqueous composition and seeds treated therewith
US10750750B2 (en) 2016-07-11 2020-08-25 Covestro Llc Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds
MX2019000512A (en) 2016-07-12 2019-05-02 Bayer Cropscience Ag Bicyclic compounds as pest control agents.
KR102435080B1 (en) 2016-07-19 2022-08-22 바이엘 크롭사이언스 악티엔게젤샤프트 Condensed Bicyclic Heterocycle Derivatives as Pest Control Agents
BR112019001764A2 (en) 2016-07-29 2019-05-07 Bayer Cropscience Ag combinations of active compounds and methods for plant propagation material protection
UA127919C2 (en) 2016-07-29 2024-02-14 Баєр Кропсаєнс Акціенгезельшафт Formulation comprising a beneficial p. bilaii strain and talc for use in seed treatment
AU2017309725A1 (en) 2016-08-10 2019-02-21 Bayer Cropscience Aktiengesellschaft Substituted 2-heterocyclyl imidazolyl-carboxamides as pest control agents
RU2019107162A (en) 2016-08-15 2020-09-15 Байер Кропсайенс Акциенгезельшафт CONDENSED BICYCLIC HETEROCYCLIC DERIVATIVES AS ANTI-PEST AGENTS
AU2017328614B2 (en) 2016-09-19 2022-01-13 Bayer Aktiengesellschaft Pyrazolo [1,5-a]pyridine derivatives and their use as pesticides
KR102477315B1 (en) 2016-10-06 2022-12-13 바이엘 크롭사이언스 악티엔게젤샤프트 2-(het)aryl-substituted fused bicyclic heterocycle derivatives as pest control agents
WO2018065288A1 (en) 2016-10-07 2018-04-12 Bayer Cropscience Aktiengesellschaft 2-[2-phenyl-1-(sulfonyl-methyl)-vinyl]-imidazo-[4,5-b] pyridine derivatives and related compounds as pesticides in plant protection
US11155517B2 (en) 2016-10-14 2021-10-26 Pi Industries Ltd. 4-substituted phenylamine derivatives and their use to protect crops by fighting undesired phytopathogenic micoorganisms
JP2019532107A (en) 2016-10-14 2019-11-07 ピーアイ インダストリーズ リミテッドＰｉ Ｉｎｄｕｓｔｒｉｅｓ Ｌｔｄ 4-Amino-substituted phenylamidine derivatives and their use for protecting crops by combating undesired phytopathogenic microorganisms
TW201822637A (en) 2016-11-07 2018-07-01 德商拜耳廠股份有限公司 Substituted sulfonamides for controlling animal pests
MX2019005569A (en) 2016-11-11 2019-09-05 Bayer Animal Health Gmbh New anthelmintic quinoline-3-carboxamide derivatives.
BR112019010511A2 (en) 2016-11-23 2019-09-17 Bayer Ag fused bicyclic heterocycle derivatives as pesticides
EP3400801A1 (en) 2017-05-10 2018-11-14 Bayer CropScience Aktiengesellschaft Plant health effect of purpureocillium lilacinum
BR112019012269A2 (en) 2016-12-16 2019-12-03 Bayer Ag heterocyclic compounds as pesticides
JP2020502110A (en) 2016-12-16 2020-01-23 バイエル・アクチエンゲゼルシヤフト Mesoionic imidazopyridines for use as insecticides
WO2018116072A1 (en) 2016-12-20 2018-06-28 Pi Industries Ltd. Heterocyclic compounds
WO2018130443A1 (en) 2017-01-10 2018-07-19 Bayer Aktiengesellschaft Heterocyclene derivatives as pest control agents
AU2018207776B2 (en) 2017-01-10 2021-06-17 Bayer Aktiengesellschaft Heterocyclene derivatives as pest control agents
WO2018138050A1 (en) 2017-01-26 2018-08-02 Bayer Aktiengesellschaft Condensed bicyclic heterocyclene derivatives as pest control agents
TW201833107A (en) 2017-02-06 2018-09-16 德商拜耳廠股份有限公司 2-(het)aryl-substituted fused heterocycle derivatives as pesticides
EP3369320A1 (en) 2017-03-02 2018-09-05 Bayer CropScience Aktiengesellschaft Agent for controlling bugs
EP4298908A3 (en) 2017-03-31 2024-03-20 Bayer Animal Health GmbH Tricyclic carboxamides for the control of arthropods
WO2018177993A1 (en) 2017-03-31 2018-10-04 Bayer Cropscience Aktiengesellschaft Pyrazoles for controlling arthropods
CN110691781A (en) 2017-04-12 2020-01-14 拜耳公司 Mesoionic imidazopyridines as pesticides
TW201838965A (en) 2017-04-20 2018-11-01 印度商Ｐｉ工業公司 Novel phenylamine compounds
EP3612530A1 (en) 2017-04-21 2020-02-26 Bayer Aktiengesellschaft Mesoionic imidazopyridines as insecticides
JP7119001B2 (en) 2017-04-24 2022-08-16 バイエル・アクチエンゲゼルシヤフト Fused Bicyclic Heterocyclic Compound Derivatives as Pesticides
TWI782983B (en) 2017-04-27 2022-11-11 德商拜耳廠股份有限公司 Heteroarylphenylaminoquinolines and analogues
KR102596307B1 (en) 2017-04-27 2023-10-30 바이엘 애니멀 헬스 게엠베하 New bicyclic pyrazole derivatives
WO2018202494A1 (en) 2017-05-02 2018-11-08 Bayer Aktiengesellschaft 2-(het)aryl-substituted condensed bicyclic heterocyclic derivatives as pest control agents
KR20200003045A (en) 2017-05-02 2020-01-08 바이엘 악티엔게젤샤프트 2- (het) aryl-substituted condensed bicyclic heterocyclic derivatives as pest control agents
JP2020518589A (en) 2017-05-03 2020-06-25 バイエル・アクチエンゲゼルシヤフト Tri-substituted silylbenzylbenzimidazoles and analogs
US20200275656A1 (en) 2017-05-03 2020-09-03 Bayer Aktiengesellschaft Trisubstitutedsilylmethylphenoxyquinolines and analogues
WO2018202706A1 (en) 2017-05-03 2018-11-08 Bayer Aktiengesellschaft Trisubstitutedsilylheteroaryloxyquinolines and analogues
ES2919280T3 (en) 2017-05-04 2022-07-22 Bayer Cropscience Ag 2-{[2-(phenyloxymethyl)pyridin-5-yl]oxy}-ethanamine derivatives and related compounds as pesticides, eg for plant protection
WO2018202525A1 (en) 2017-05-04 2018-11-08 Bayer Cropscience Aktiengesellschaft Phenoxyethanamine derivatives for controlling pests
CN110770227B (en) 2017-06-30 2024-03-01 拜耳动物保健有限责任公司 Novel azaquinoline derivatives
WO2019007887A1 (en) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Insecticide and fungicide active ingredient combinations
WO2019007888A1 (en) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Insecticidal active ingredient combinations
WO2019007891A1 (en) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Insecticidal active ingredient combinations
EP3284739A1 (en) 2017-07-19 2018-02-21 Bayer CropScience Aktiengesellschaft Substituted (het) aryl compounds as pesticides
AU2018311019B2 (en) 2017-08-04 2022-05-26 Bayer Animal Health Gmbh Quinoline derivatives for treating infections with helminths
WO2019035881A1 (en) 2017-08-17 2019-02-21 Bayer Cropscience Lp Liquid fertilizer-dispersible compositions and methods thereof
BR112020003481B1 (en) 2017-08-22 2023-12-05 Bayer Aktiengesellschaft Heterocyclene derivatives, their uses, agrochemical formulation, and methods for controlling animal pests and for protecting seeds or a germinating plant from pests
CN111132549B (en) 2017-09-20 2022-04-12 三井化学Agro株式会社 Long-acting control agent for ectoparasites of animals
EP3692045A1 (en) 2017-10-04 2020-08-12 Bayer Aktiengesellschaft Derivatives of heterocyclic compounds as pest control agents
EP3473103A1 (en) 2017-10-17 2019-04-24 Bayer AG Aqueous suspension concentrates based on 2- [(2,4-dichlorophenyl) -methyl] -4,4 '-dimethyl-3-isoxazolidinone
AR113444A1 (en) 2017-10-18 2020-05-06 Bayer Ag COMBINATIONS OF ACTIVE COMPOUNDS WITH INSECTICIDE / ACARICIDAL PROPERTIES
BR112020007544B1 (en) 2017-10-18 2023-12-05 Bayer Aktiengesellschaft SYNERGIC ACTIVE COMPOUND COMBINATIONS, THEIR USES, METHOD FOR CONTROLLING ANIMAL OR MICROBIAL PESTS, AND PROCESS FOR PREPARING A CROP PROTECTION AGENT
SI3697217T1 (en) 2017-10-18 2021-11-30 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
TWI784067B (en) 2017-10-18 2022-11-21 德商拜耳廠股份有限公司 Active compound combinations having insecticidal/acaricidal properties
EP3473100A1 (en) 2017-10-18 2019-04-24 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
AU2018350611B2 (en) 2017-10-18 2023-12-14 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
WO2019092086A1 (en) 2017-11-13 2019-05-16 Bayer Aktiengesellschaft Tetrazolylpropyl derivatives and their use as fungicides
CN111601802A (en) 2017-11-28 2020-08-28 拜耳股份有限公司 Heterocyclic compounds as pesticides
AU2018376146A1 (en) 2017-11-29 2020-05-28 Bayer Aktiengesellschaft Nitrogenous heterocycles as a pesticide
KR20200112816A (en) 2017-12-20 2020-10-05 피아이 인더스트리스 엘티디. Preparation and use of fluorine alkyl compounds
TW201927768A (en) 2017-12-21 2019-07-16 德商拜耳廠股份有限公司 Trisubstitutedsilylmethylheteroaryloxyquinolines and analogues
EP3305786A3 (en) 2018-01-22 2018-07-25 Bayer CropScience Aktiengesellschaft Condensed bicyclic heterocycle derivatives as pesticides
WO2019150311A1 (en) 2018-02-02 2019-08-08 Pi Industries Ltd. 1-3 dithiol compounds and their use for the protection of crops from phytopathogenic microorganisms
EP3752492B1 (en) 2018-02-12 2022-12-21 Bayer Aktiengesellschaft Fungicidal oxadiazoles
WO2019162174A1 (en) 2018-02-21 2019-08-29 Bayer Aktiengesellschaft Condensed bicyclic heterocyclic derivatives as pest control agents
WO2019162228A1 (en) 2018-02-21 2019-08-29 Bayer Aktiengesellschaft 1-(5-substituted imidazol-1-yl)but-3-en derivatives and their use as fungicides
JP2021516238A (en) 2018-03-08 2021-07-01 バイエル・アクチエンゲゼルシヤフト Use of heteroaryl-triazole compounds and heteroaryl-tetrazole compounds as pesticides in plant protection
BR112020017624A2 (en) 2018-03-12 2020-12-22 Bayer Aktiengesellschaft CONDENSED BICYCLIC HETEROCYCLIC DERIVATIVES AS PEST CONTROL AGENTS
WO2019197371A1 (en) 2018-04-10 2019-10-17 Bayer Aktiengesellschaft Oxadiazoline derivatives
AU2019250361B2 (en) 2018-04-12 2023-03-23 Bayer Aktiengesellschaft Heteroaryl-triazole compounds as pesticides
BR112020019390A2 (en) 2018-04-13 2021-01-05 Bayer Aktiengesellschaft COMBINATIONS OF ACTIVE INGREDIENTS WITH INSECTICID, NEMATICIDE AND ACARICIDE PROPERTIES
WO2019197615A1 (en) 2018-04-13 2019-10-17 Bayer Aktiengesellschaft Active ingredient combinations with fungicides, insecticides and acaricidal properties
UY38184A (en) 2018-04-17 2019-10-31 Bayer Ag HETEROARYL-TRIAZOLE AND HETEROARYL-TETRAZOLE COMPOUNDS NOVELTY AS PESTICIDES
WO2019202077A1 (en) 2018-04-20 2019-10-24 Bayer Aktiengesellschaft Heteroaryl-triazole and heteroaryl-tetrazole compounds as pesticides
WO2019201921A1 (en) 2018-04-20 2019-10-24 Bayer Aktiengesellschaft Heterocyclene derivatives as pest control agents
MX2020011275A (en) 2018-04-25 2020-11-13 Bayer Ag Novel heteroaryl-triazole and heteroaryl-tetrazole compounds as pesticides.
EP3790874B1 (en) 2018-05-09 2023-03-15 Bayer Animal Health GmbH Anthelmintic quinoline derivatives
WO2019224143A1 (en) 2018-05-24 2019-11-28 Bayer Aktiengesellschaft Active ingredient combinations with insecticidal, nematicidal and acaricidal properties
CA3104880A1 (en) 2018-06-25 2020-01-02 Bayer Cropscience Lp Seed treatment method
WO2020002189A1 (en) 2018-06-27 2020-01-02 Bayer Aktiengesellschaft Active substance combinations
EP3586630A1 (en) 2018-06-28 2020-01-01 Bayer AG Active compound combinations having insecticidal/acaricidal properties
CA3105410A1 (en) 2018-07-05 2020-01-09 Bayer Aktiengesellschaft Substituted thiophenecarboxamides and analogues as antibacterials agents
WO2020020813A1 (en) 2018-07-25 2020-01-30 Bayer Aktiengesellschaft Fungicidal active compound combinations
WO2020020816A1 (en) 2018-07-26 2020-01-30 Bayer Aktiengesellschaft Novel triazole derivatives
CA3107207A1 (en) 2018-07-27 2020-01-30 Bayer Aktiengesellschaft Controlled release formulations for agrochemicals
AU2019313545A1 (en) 2018-07-31 2021-02-25 Bayer Aktiengesellschaft Controlled release formulations with lignin for agrochemicals
WO2020035826A1 (en) 2018-08-17 2020-02-20 Pi Industries Ltd. 1,2-dithiolone compounds and use thereof
WO2020043650A1 (en) 2018-08-29 2020-03-05 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
JP2022500412A (en) 2018-09-13 2022-01-04 バイエル・アクチエンゲゼルシヤフト Heterocyclic derivative as a pest control agent
AU2019343273A1 (en) 2018-09-17 2021-05-13 Bayer Aktiengesellschaft Use of the fungicide Isoflucypram for controlling Claviceps purpurea and reducing sclerotia in cereals
WO2020070050A1 (en) 2018-10-01 2020-04-09 Bayer Aktiengesellschaft Fungicidal 5-substituted imidazol-1-yl carbinol derivatives
EP3636644A1 (en) 2018-10-11 2020-04-15 Bayer Aktiengesellschaft Mesoionic imidazopyridines as insecticides
WO2020078839A1 (en) 2018-10-16 2020-04-23 Bayer Aktiengesellschaft Active substance combinations
WO2020079167A1 (en) 2018-10-18 2020-04-23 Bayer Aktiengesellschaft Heteroarylaminoquinolines and analogues
EP3867241A1 (en) 2018-10-18 2021-08-25 Bayer Aktiengesellschaft Pyridylphenylaminoquinolines and analogues
TW202028193A (en) 2018-10-20 2020-08-01 德商拜耳廠股份有限公司 Oxetanylphenoxyquinolines and analogues
EP3643711A1 (en) 2018-10-24 2020-04-29 Bayer Animal Health GmbH New anthelmintic compounds
AR117169A1 (en) 2018-11-28 2021-07-14 Bayer Ag (TIO) PYRIDAZINE AMIDES AS FUNGICIDE COMPOUNDS
CN111269237B (en) * 2018-12-04 2022-05-24 南开大学 Gem-difluorinated spiro-gamma-lactam indoline compound, preparation method thereof and application thereof in preventing and treating plant diseases and insect pests
CA3122156A1 (en) 2018-12-07 2020-06-11 Bayer Aktiengesellschaft Herbicidal compositions
AU2019393950A1 (en) 2018-12-07 2021-06-24 Bayer Aktiengesellschaft Herbicide compositions
EP3620052A1 (en) 2018-12-12 2020-03-11 Bayer Aktiengesellschaft Use of phenoxypyridinyl-substituted (1h-1,2,4-triazol-1-yl)alcohols for controlling fungicidal diseases in maize
US20220061323A1 (en) 2018-12-18 2022-03-03 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
BR112021010152A2 (en) 2018-12-20 2021-11-09 Bayer Ag Heterocyclyl pyridazine as fungicidal compounds
EP3669652A1 (en) 2018-12-21 2020-06-24 Bayer AG Active compound combination
CA3124324A1 (en) 2018-12-21 2020-06-25 Bayer Aktiengesellschaft 1,3,4-oxadiazoles and their derivatives as new antifungal agents
EP3679791A1 (en) 2019-01-08 2020-07-15 Bayer AG Active compound combinations
EP3679789A1 (en) 2019-01-08 2020-07-15 Bayer AG Active compound combinations
EP3679790A1 (en) 2019-01-08 2020-07-15 Bayer AG Active compound combinations
EP3679793A1 (en) 2019-01-08 2020-07-15 Bayer AG Active compound combinations
EP3679792A1 (en) 2019-01-08 2020-07-15 Bayer AG Active compound combinations
EP3545764A1 (en) 2019-02-12 2019-10-02 Bayer AG Crystal form of 2-({2-fluoro-4-methyl-5-[(r)-(2,2,2-trifluoroethyl)sulfinyl]phenyl}imino)-3-(2,2,2- trifluoroethyl)-1,3-thiazolidin-4-one
EP3931193A1 (en) 2019-02-26 2022-01-05 Bayer Aktiengesellschaft Fused bicyclic heterocycle derivatives as pesticides
KR20210133984A (en) 2019-02-26 2021-11-08 바이엘 악티엔게젤샤프트 Condensed Bicyclic Heterocyclic Derivatives as Pest Control Agents
WO2020178067A1 (en) 2019-03-01 2020-09-10 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
WO2020178307A1 (en) 2019-03-05 2020-09-10 Bayer Aktiengesellschaft Active compound combination
WO2020182929A1 (en) 2019-03-13 2020-09-17 Bayer Aktiengesellschaft Substituted ureas and derivatives as new antifungal agents
WO2020187656A1 (en) 2019-03-15 2020-09-24 Bayer Aktiengesellschaft Active compound combinations having insecticidal/acaricidal properties
EP3564225A1 (en) 2019-03-21 2019-11-06 Bayer Aktiengesellschaft Crystalline form of spiromesifen
EP3725788A1 (en) 2019-04-15 2020-10-21 Bayer AG Novel heteroaryl-substituted aminoalkyl azole compounds as pesticides
JP2022532087A (en) 2019-05-08 2022-07-13 バイエル・アクチエンゲゼルシヤフト Highly malleable ULV formulation for pesticide compound II
MX2021013613A (en) 2019-05-08 2021-12-10 Bayer Ag Active compound combination.
CA3139524A1 (en) 2019-05-10 2020-11-19 Bayer Cropscience Lp Active compound combinations
WO2020229398A1 (en) 2019-05-14 2020-11-19 Bayer Aktiengesellschaft (1-alkenyl)-substituted pyrazoles and triazoles as pest control agents
EP3750888A1 (en) 2019-06-12 2020-12-16 Bayer Aktiengesellschaft Crystalline form a of 1,4-dimethyl-2-[2-(pyridin-3-yl)-2h-indazol-5-yl]-1,2,4-triazolidine-3,5-dione
WO2020254488A1 (en) 2019-06-21 2020-12-24 Bayer Aktiengesellschaft Hydroxyisoxazolines and use thereof as fungicides
EP3986888A1 (en) 2019-06-21 2022-04-27 Bayer Aktiengesellschaft Thienylhydroxyisoxazolines and derivatives thereof
WO2020254492A1 (en) 2019-06-21 2020-12-24 Bayer Aktiengesellschaft Hydroxyisoxazolines and derivatives thereof
WO2020254487A1 (en) 2019-06-21 2020-12-24 Bayer Aktiengesellschaft Hydroxyisoxazolines and derivatives thereof
WO2020254490A1 (en) 2019-06-21 2020-12-24 Bayer Aktiengesellschaft Phenoxyphenyl hydroxyisoxazolines and analogues as new antifungal agents
WO2020254489A1 (en) 2019-06-21 2020-12-24 Bayer Aktiengesellschaft Benzylphenyl hydroxyisoxazolines and analogues as new antifungal agents
WO2020254494A1 (en) 2019-06-21 2020-12-24 Bayer Aktiengesellschaft Fungicidal oxadiazoles
WO2020254486A1 (en) 2019-06-21 2020-12-24 Bayer Aktiengesellschaft Hydroxyisoxazolines and derivatives thereof
AR119228A1 (en) 2019-06-24 2021-12-01 Bayer Cropscience Lp A STRAIN OF BACILLUS AND METHODS FOR ITS USE IN PROMOTING PLANT GROWTH
EP3608311A1 (en) 2019-06-28 2020-02-12 Bayer AG Crystalline form a of n-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-4-methylsulfonyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazole-3-carboxamide
US20220274945A1 (en) 2019-07-03 2022-09-01 Bayer Aktiengesellschaft Substituted thiophene carboxamides and derivatives thereof as microbicides
WO2021001273A1 (en) 2019-07-04 2021-01-07 Bayer Aktiengesellschaft Herbicidal compositions
EP3771714A1 (en) 2019-07-30 2021-02-03 Bayer AG Nitrogen-containing heterocycles as pesticides
TW202120490A (en) 2019-07-30 2021-06-01 德商拜耳動物保健有限公司 New isoquinoline derivatives
EP3701796A1 (en) 2019-08-08 2020-09-02 Bayer AG Active compound combinations
RU2713902C1 (en) * 2019-08-27 2020-02-10 Владимир Георгиевич Григулецкий Organic growth substance
US20220304305A1 (en) 2019-09-11 2022-09-29 Bayer Aktiengesellschaft Highly effective formulations on the basis of 2-[(2,4-dichlorphenyl)-methyl]-4,4'-dimethyl-3-isoxazolidinones and preemergence herbicides
US20220403410A1 (en) 2019-09-26 2022-12-22 Bayer Aktiengesellschaft Rnai-mediated pest control
TW202128650A (en) 2019-10-11 2021-08-01 德商拜耳動物保健有限公司 Novel heteroaryl-substituted pyrazine derivatives as pesticides
JP2023501978A (en) 2019-11-07 2023-01-20 バイエル・アクチエンゲゼルシヤフト Substituted Sulfonylamides for Animal Pest Control
WO2021097162A1 (en) 2019-11-13 2021-05-20 Bayer Cropscience Lp Beneficial combinations with paenibacillus
WO2021122986A1 (en) 2019-12-20 2021-06-24 Bayer Aktiengesellschaft Thienyloxazolones and analogues
CA3165267A1 (en) 2019-12-20 2021-06-24 Bayer Aktiengesellschaft Substituted thiophene carboxamides, thiophene carboxylic acids and derivatives thereof
EP3845304A1 (en) 2019-12-30 2021-07-07 Bayer AG Capsule suspension concentrates based on polyisocyanates and biodegradable amine based cross-linker
MX2022010059A (en) 2020-02-18 2022-08-25 Bayer Ag Heteroaryl-triazole compounds as pesticides.
EP3868207A1 (en) 2020-02-24 2021-08-25 Bayer Aktiengesellschaft Encapsulated pyrethroids with improved activity in soil and leaf applications
EP3708565A1 (en) 2020-03-04 2020-09-16 Bayer AG Pyrimidinyloxyphenylamidines and the use thereof as fungicides
JP2023521342A (en) 2020-04-09 2023-05-24 バイエル・アニマル・ヘルス・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Substituted condensed azines as anthelmintic compounds
WO2021209366A1 (en) 2020-04-16 2021-10-21 Bayer Aktiengesellschaft Active compound combinations and fungicide compositions comprising those
WO2021209368A1 (en) 2020-04-16 2021-10-21 Bayer Aktiengesellschaft Active compound combinations and fungicide compositions comprising those
AU2021256654A1 (en) 2020-04-16 2022-11-10 Bayer Aktiengesellschaft Active compound combinations and fungicide compositions comprising those
BR112022020792A2 (en) 2020-04-16 2022-11-29 Bayer Ag COMBINATIONS OF ACTIVE COMPOUNDS AND FUNGICIDIAL COMPOSITIONS, INCLUDING THEM
WO2021209490A1 (en) 2020-04-16 2021-10-21 Bayer Aktiengesellschaft Cyclaminephenylaminoquinolines as fungicides
AR121829A1 (en) 2020-04-16 2022-07-13 Bayer Ag COMBINATIONS OF ACTIVE COMPOUNDS AND FUNGICIDE COMPOSITIONS THAT COMPRISE THEM
CN115915941A (en) 2020-05-06 2023-04-04 拜耳公司 Pyridine (thio) amides as fungicidal compounds
BR112022023012A2 (en) 2020-05-12 2022-12-20 Bayer Ag (THIO)AMIDES OF TRIAZINE AND PYRMIDINE AS FUNGICIDAL COMPOUNDS
JP2023529294A (en) 2020-05-19 2023-07-10 バイエル、アクチエンゲゼルシャフト、（ディビジョン、クロップサイエンス） Azabicyclic (thio)amides as fungicidal compounds
EP4161906A1 (en) 2020-06-04 2023-04-12 Bayer Aktiengesellschaft Heterocyclyl pyrimidines and triazines as novel fungicides
JP2023529475A (en) 2020-06-10 2023-07-10 バイエル、アクチエンゲゼルシャフト Azabicyclyl-substituted heterocycles as novel fungicides
BR112022025941A2 (en) 2020-06-18 2023-01-10 Bayer Ag 3-(PYRIDAZIN-4-IL)-5,6-DIHYDRO-4H-1,2,4-OXADIAZINE DERIVATIVES AS FUNGICIDES FOR CROP PROTECTION
BR112022025710A2 (en) 2020-06-19 2023-03-07 Bayer Ag 1,3,4-OXADIAZOLE PYRIMIDINES AND 1,3,4-OXADIAZOLE PYRIDINES AS FUNGICIDES
UY39276A (en) 2020-06-19 2022-01-31 Bayer Ag USE OF 1,3,4-OXADIAZOL-2-ILPYRIMIDINE COMPOUNDS TO CONTROL PHYTOPATHOGENIC MICROORGANISMS, METHODS OF USE AND COMPOSITIONS.
UY39275A (en) 2020-06-19 2022-01-31 Bayer Ag 1,3,4-OXADIAZOLE PYRIMIDINES AS FUNGICIDES, PROCESSES AND INTERMEDIARIES FOR THEIR PREPARATION, METHODS OF USE AND USES OF THE SAME
WO2021255091A1 (en) 2020-06-19 2021-12-23 Bayer Aktiengesellschaft 1,3,4-oxadiazoles and their derivatives as fungicides
CN115989255A (en) 2020-06-26 2023-04-18 拜耳公司 Aqueous capsule suspension concentrate containing biodegradable ester groups
WO2022058327A1 (en) 2020-09-15 2022-03-24 Bayer Aktiengesellschaft Substituted ureas and derivatives as new antifungal agents
EP3915371A1 (en) 2020-11-04 2021-12-01 Bayer AG Active compound combinations and fungicide compositions comprising those
EP3994995A1 (en) 2020-11-08 2022-05-11 Bayer Aktiengesellschaft Low drift, rainfastness, high spreading, high uptake and ulv tank mix adjuvant formulation
EP3994991A1 (en) 2020-11-08 2022-05-11 Bayer Aktiengesellschaft Agrochemical composition with improved drift, spreading, uptake and rainfastness properties
EP3994989A1 (en) 2020-11-08 2022-05-11 Bayer AG Agrochemical composition with improved drift, rainfastness and uptake properties
EP3994986A1 (en) 2020-11-08 2022-05-11 Bayer Aktiengesellschaft Agrochemical composition with improved drift and spreading properties
EP3994988A1 (en) 2020-11-08 2022-05-11 Bayer AG Agrochemical composition with improved drift, spreading and rainfastness properties
EP3994992A1 (en) 2020-11-08 2022-05-11 Bayer AG Low drift, rainfastness, high uptake and ulv tank mix adjuvant formulation
EP3994993A1 (en) 2020-11-08 2022-05-11 Bayer Aktiengesellschaft Low drift, rainfastness, high spreading and ulv tank mix adjuvant formulation
EP3994985A1 (en) 2020-11-08 2022-05-11 Bayer Aktiengesellschaft Agrochemical composition with improved drift properties
EP3994987A1 (en) 2020-11-08 2022-05-11 Bayer AG Agrochemical composition with improved drift and uptake properties
EP3994994A1 (en) 2020-11-08 2022-05-11 Bayer Aktiengesellschaft Low drift, rainfastness, high spreading, high uptake and ulv tank mix adjuvant formulation
EP3994990A1 (en) 2020-11-08 2022-05-11 Bayer AG Agrochemical composition with improved drift, spreading and uptake properties
EP3915971A1 (en) 2020-12-16 2021-12-01 Bayer Aktiengesellschaft Phenyl-s(o)n-phenylamidines and the use thereof as fungicides
WO2022129188A1 (en) 2020-12-18 2022-06-23 Bayer Aktiengesellschaft 1,2,4-oxadiazol-3-yl pyrimidines as fungicides
WO2022129196A1 (en) 2020-12-18 2022-06-23 Bayer Aktiengesellschaft Heterobicycle substituted 1,2,4-oxadiazoles as fungicides
WO2022129190A1 (en) 2020-12-18 2022-06-23 Bayer Aktiengesellschaft (hetero)aryl substituted 1,2,4-oxadiazoles as fungicides
WO2022152728A1 (en) 2021-01-15 2022-07-21 Bayer Aktiengesellschaft Herbicidal compositions
KR20230137956A (en) 2021-01-28 2023-10-05 스페셜티 오퍼레이션스 프랑스 Rice seed treatment method that improves pesticide, micronutrient and colorant retention
BR112023022046A2 (en) 2021-05-10 2023-12-26 Bayer Ag HERBICIDE/PROTECTOR COMBINATION BASED ON SUBSTITUTED [(1,5-DIPHENYL-1H-1,2,4-TRIAZOL-3-YL)OXY]ACETIC ACID CLASS PROTECTORS AND THEIR SALTS
EP4148052A1 (en) 2021-09-09 2023-03-15 Bayer Animal Health GmbH New quinoline derivatives
WO2023078915A1 (en) 2021-11-03 2023-05-11 Bayer Aktiengesellschaft Bis(hetero)aryl thioether (thio)amides as fungicidal compounds
WO2023092050A1 (en) 2021-11-20 2023-05-25 Bayer Cropscience Lp Beneficial combinations with recombinant bacillus cells expressing a serine protease
WO2023099445A1 (en) 2021-11-30 2023-06-08 Bayer Aktiengesellschaft Bis(hetero)aryl thioether oxadiazines as fungicidal compounds
WO2023110656A1 (en) 2021-12-15 2023-06-22 Bayer Aktiengesellschaft Spectroscopic solution for non-destructive quantification of one or more chemical substances in a matrix comprising coating and bulk material in a sample, such as coated seeds, using multivariate data analysis
WO2023205602A1 (en) 2022-04-18 2023-10-26 Basf Corporation High-load agricultural formulations and methods of making same
EP4265110A1 (en) 2022-04-20 2023-10-25 Bayer AG Water dispersible granules with low melting active ingredients prepared by extrusion
WO2023217619A1 (en) 2022-05-07 2023-11-16 Bayer Aktiengesellschaft Low drift aqueous liquid formulations for low, medium, and high spray volume application
WO2024013016A1 (en) 2022-07-11 2024-01-18 Bayer Aktiengesellschaft Herbicidal compositions
WO2024013015A1 (en) 2022-07-11 2024-01-18 Bayer Aktiengesellschaft Herbicidal compositions
WO2024068473A1 (en) 2022-09-27 2024-04-04 Bayer Aktiengesellschaft Herbicide/safener combination based on safeners from the class of substituted [(1,5-diphenyl-1h-1,2,4-triazol-3-yl)oxy]acetic acids and their salts
EP4353082A1 (en) 2022-10-14 2024-04-17 Bayer Aktiengesellschaft Herbicidal compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959475A (en) * 1973-12-12 1976-05-25 American Hoechst Corporation Substituted 1,3-dihydrospiro(isobenzofuran)s
US4233307A (en) * 1978-02-13 1980-11-11 Sumitomo Chemical Company, Limited Spiro-4'-piperidine compounds and their pharmaceutical compositions
US4307235A (en) * 1978-08-23 1981-12-22 American Hoechst Corporation Spiro[indoline-3,4'-piperidine]s

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209625A (en) 1977-04-21 1980-06-24 American Hoechst Corporation Spiro[indoline-3,4'-piperidine]s
ES468860A1 (en) 1977-04-21 1979-09-16 Hoechst Ag Spiro(indoline-3,4'-piperidine)s and related compounds
GB1575800A (en) 1978-05-16 1980-10-01 Sumitomo Chemical Co Spiro amines their production and compositions containing them
JPH0720647B2 (en) 1987-11-24 1995-03-08 松下電工株式会社 Mold sprue bushing
US5536716A (en) * 1992-12-11 1996-07-16 Merck & Co., Inc. Spiro piperidines and homologs which promote release of growth hormone
JPH08511522A (en) 1993-06-07 1996-12-03 メルク エンド カンパニー インコーポレーテッド Spiro-Substituted Aza Rings as Neurokinin Antagonists
AU7186494A (en) * 1993-07-02 1995-01-24 Bayer Aktiengesellschaft Substituted spiroheterocyclic 1h-3-arylpyrrolidine-2,4-dione derivatives, methods of preparing them and their use as pest-control agents
JPH0720647A (en) 1993-07-02 1995-01-24 Mitsubishi Paper Mills Ltd Electrophotographic photoreceptor
EP0813414A4 (en) 1993-10-19 1999-07-21 Merck & Co Inc Combination of bisphosphonates and growth hormone secretagogues
GB9417956D0 (en) 1994-09-02 1994-10-26 Merck Sharp & Dohme Therapeutic agents
WO1998025605A1 (en) 1996-12-13 1998-06-18 Merck & Co., Inc. Spiro-substituted azacycles as modulators of chemokine receptor activity
US5962462A (en) * 1996-12-13 1999-10-05 Merck & Co., Inc. Spiro-substituted azacycles as modulators of chemokine receptor activity
US5783579A (en) 1996-12-20 1998-07-21 Schering Corporation Spiro-substituted azacyclic-substituted piperazino derivatives as neurokinin antagonists
CA2334551A1 (en) 1998-06-11 1999-12-16 Merck & Co., Inc. Spiropiperidine derivatives as melanocortin receptor agonists
US20020128208A1 (en) 2000-12-15 2002-09-12 Snyder James P. Nonpeptide agonists and antagonists of vasopressin receptors
MXPA03009353A (en) 2001-04-12 2004-02-12 Pharmacopeia Inc Aryl and biaryl piperidines used as mch antagonists.
GB0213715D0 (en) * 2002-06-14 2002-07-24 Syngenta Ltd Chemical compounds
GB0328908D0 (en) * 2003-12-12 2004-01-14 Syngenta Participations Ag Chemical compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959475A (en) * 1973-12-12 1976-05-25 American Hoechst Corporation Substituted 1,3-dihydrospiro(isobenzofuran)s
US4233307A (en) * 1978-02-13 1980-11-11 Sumitomo Chemical Company, Limited Spiro-4'-piperidine compounds and their pharmaceutical compositions
US4307235A (en) * 1978-08-23 1981-12-22 American Hoechst Corporation Spiro[indoline-3,4'-piperidine]s

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080047479A1 (en) * 1997-10-27 2008-02-28 Correct Craft, Inc. Water Sport Towing Apparatus and Method
US8071624B2 (en) 2004-06-24 2011-12-06 Incyte Corporation N-substituted piperidines and their use as pharmaceuticals
US20050288317A1 (en) * 2004-06-24 2005-12-29 Wenqing Yao Amido compounds and their use as pharmaceuticals
US20060004049A1 (en) * 2004-06-24 2006-01-05 Wenqing Yao N-substituted piperidines and their use as pharrmaceuticals
US20060009491A1 (en) * 2004-06-24 2006-01-12 Incyte Corporation Amido compounds and their use as pharmaceuticals
US20060009471A1 (en) * 2004-06-24 2006-01-12 Wenqing Yao Amido compounds and their use as pharmaceuticals
US20050288338A1 (en) * 2004-06-24 2005-12-29 Wenqing Yao Amido compounds and their use as pharmaceuticals
US8288417B2 (en) 2004-06-24 2012-10-16 Incyte Corporation N-substituted piperidines and their use as pharmaceuticals
US7687665B2 (en) 2004-06-24 2010-03-30 Incyte Corporation 2-methylprop anamides and their use as pharmaceuticals
US20050288329A1 (en) * 2004-06-24 2005-12-29 Wenqing Yao 2-Methylprop anamides and their use as pharmaceuticals
US20060122197A1 (en) * 2004-08-10 2006-06-08 Wenqing Yao Amido compounds and their use as pharmaceuticals
US8258148B2 (en) 2004-08-19 2012-09-04 Vertex Pharmaceutical Incorporated Spiroindoline modulators of muscarinic receptors
US20100311720A1 (en) * 2004-08-19 2010-12-09 Vertex Pharmaceuticals Incorporated Spiroindoline Modulators of Muscarinic Receptors
US20100311746A1 (en) * 2004-08-19 2010-12-09 Vertex Pharmaceuticals Incorporated Modulators of muscarinic receptors
US7786141B2 (en) 2004-08-19 2010-08-31 Vertex Pharmaceuticals Incorporated Dihydrospiroindene modulators of muscarinic receptors
US8497295B2 (en) 2004-08-19 2013-07-30 Vertex Pharmaceuticals Incorporated Spiroindoline modulators of muscarinic receptors
US7879834B2 (en) 2004-08-19 2011-02-01 Vertex Pharmaceuticals Incorporated Spiroindoline modulators of muscarinic receptors
US8367691B2 (en) 2004-08-19 2013-02-05 Vertex Pharmaceutical Incorporated Modulators of muscarinic receptors
US20090291946A1 (en) * 2004-11-10 2009-11-26 Incyte Corporation Lactam compounds and their use as pharmaceuticals
US20060116382A1 (en) * 2004-11-10 2006-06-01 Wenqing Yao Lactam compounds and their use as pharmaceuticals
US8110581B2 (en) 2004-11-10 2012-02-07 Incyte Corporation Lactam compounds and their use as pharmaceuticals
US8563570B2 (en) 2004-11-10 2013-10-22 Incyte Corporation Lactam compounds and their use as pharmaceuticals
US20060122210A1 (en) * 2004-11-18 2006-06-08 Wenqing Yao Inhibitors of 11-beta hydroxyl steroid dehydrogenase type I and methods of using the same
US20060270653A1 (en) * 2004-11-29 2006-11-30 Ioana Drutu Modulators of muscarinic receptors
US7863449B2 (en) 2004-11-29 2011-01-04 Vertex Pharmaceuticals Incorporated Modulators of muscarinic receptors
US20070066584A1 (en) * 2005-09-21 2007-03-22 Wenqing Yao Amido compounds and their use as pharmaceuticals
US8193207B2 (en) 2005-12-05 2012-06-05 Incyte Corporation Lactam compounds and methods of using the same
US20070129345A1 (en) * 2005-12-05 2007-06-07 Jincong Zhuo Lactam compounds and methods of using the same
US20080015179A1 (en) * 2005-12-22 2008-01-17 Makings Lewis R Modulators of muscarinic receptors
US7858635B2 (en) 2005-12-22 2010-12-28 Vertex Pharmaceuticals Incorporated Spiro compounds as modulators of muscarinic receptors
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