EP0630370A1 - Fungicidal oxazolidinones - Google Patents

Fungicidal oxazolidinones

Info

Publication number
EP0630370A1
EP0630370A1 EP93907384A EP93907384A EP0630370A1 EP 0630370 A1 EP0630370 A1 EP 0630370A1 EP 93907384 A EP93907384 A EP 93907384A EP 93907384 A EP93907384 A EP 93907384A EP 0630370 A1 EP0630370 A1 EP 0630370A1
Authority
EP
European Patent Office
Prior art keywords
optionally substituted
alkyl
phenyl
substituted
pyridyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93907384A
Other languages
German (de)
French (fr)
Inventor
Carlton Lane Campbell
Charlene Marie Gross
Jeffrey Arthur Sternberg
King-Mo Sun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0630370A1 publication Critical patent/EP0630370A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/44—Two oxygen atoms
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/46—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/48—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to substituted oxazolidinone compounds, fungicidal compositions containing such compounds, and method of use of the compounds and compositions as fungicides.
  • New compounds effective for controlling the growth of undesired fungi are in constant demand. In the most common situation, such compounds are sought to
  • WO90/12791 teaches the use of fungicidal compounds of Formula i
  • A is O or NR 4 ;
  • W is O or S.
  • WO90/12791 also relates to processes for the preparation of these compounds and to certain novel compounds.
  • the compounds of WO90/12791 differ from those of the present invention in the nature of R 2 .
  • the above reference does not disclose the compounds of the present invention.
  • the present invention comprises compounds of
  • Formula I including all geometric and stereoisomers, agricultural compositions containing them and use of the compounds and compositions as fungicides.
  • the variation in Formula I occurs primarily in substituent R 2 .
  • Formula I comprises:
  • R 1 is H; C 1 -C 4 alkyl; C 1 -C 4 haloalkyl; C 3 -C 6
  • R 2 is C 7 -C 20 alkyl; C 7 -C 20 haloalkyl; C 4 -C 17 alkyl substituted with C 3 -C 6 cycloalkyl; C 4 -C 17 alkyl substituted with phenyl optionally substituted with R 31 on the phenyl ring; C 3 -C 14 alkyl substituted with phenoxy or phenylthio each optionally substituted with R 31 ; C 1 -C 20 alkyl substituted with R 19 ; C 2 -C 6 alkoxyalkyl substituted with R 21 ; C 7 -C 20 alkoxyalkyl
  • R 21 optionally substituted with R 21 ; C 7 -C 20 alkenyl;
  • R 3 is phenyl, pyridyl, pyrimidinyl or pyridazyl
  • R 4 is H, methyl, or a ⁇ etyl
  • R 5 , R 7 , R 11 , R 14 , R 23 , R 24 , R 3 °, R 39 , R 43 , and R 55 are each independently H or C 1 -C 4 alkyl;
  • R 6 , R 29 , R 34 , R 38 , R 42 , R 44 , and R 56 are each
  • R 8 is C 1 -C 19 alkyl; C 2 -C 19 alkylcarbonyl; C 2 -C 19
  • R 9 is C 1 -C 18 alkyl; or phenyl optionally
  • R 10 , R 27 , and R 45 are each independently 1-2
  • R 12 is H; C 1 -C 8 alkyl optionally substituted with
  • R 11 and R 58 can be taken together as -CH 2 (CH 2 ) 2 CH 2 -, -CH 2 (CH 2 ) 3 CH 2 -, -CH 2 (CH 2 ) 4 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH 2 SCH 2 CH 2 -, -CH 2 CH 2 N(R 5 )CH 2 CH 2 - or
  • R 13 is C 1 -C 6 alkyl; C 3 -C 6 cycloalkyl; phenyl
  • R 15 is C 1 -C 12 alkyl; C 2 -C 12 alkylcarbonyl; benzoyl optionally substituted with R 16 on the phenyl ring; C 2 -C 12 alkoxycarbonyl; C 2 -C 12 alkylaminocarbonyl substituted with R 55 on nitrogen;
  • phenoxycarbonyl optionally substituted with R 46 on the phenyl ring; or phenylaminocarbonyl optionally substituted with R 46 on the phenyl ring and with R 55 on nitrogen;
  • R 16 is 3 halogen; cyano; C 5 -C 8 alkyl; C 2 -C 8
  • R 17 , R 18 , R 32 , R 35 , R 47 , and R 53 are each
  • R 19 is cyano; nitro; C 1 -C 19 alkylthio; C 1 -C 19
  • alkylsulfinyl C 1 -C 19 haloalkoxy; C 5 -C 6
  • phenylsulfonyl phenyl-sulfinyl, pyridyl or pyridyloxy each optionally substituted with R 31 ; thienyl, pyrimidinyl, furanyl,
  • naphthalenyl naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R 38 ;
  • R 20 is cyano; nitro; C 1 -C 17 alkylthio; C 1 -C 17
  • alkylsulfinyl C 1 -C 17 haloalkoxy; C 5 -C 6
  • R 21 is cyano; nitro; C 1 -C 17 alkylthio; C 1 -C 17
  • alkylsulfinyl C 1 -C 17 haloalkoxy; C 5 -C 6
  • alkynyloxy C 1 -C 17 alkylsulfonyl; C 2 -C 17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
  • naphthalenyl naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R 38 ;
  • R 22 is C 1 -C 16 alkyl; phenyl optionally substituted with R 36 ; or pyridyl optionally substituted with R 36 ;
  • R 25 is H; C 1 -C 6 alkyl; or phenyl optionally
  • R 26 is C 1 -C 6 alkyl; C 1 -C 6 alkoxy; phenoxy
  • R 28 is phenyl, pyridyl or pyrimidyl each optionally substituted with R 37 ; or thienyl, furanyl, isoxazolyl, oxazolyl or pyrazolyl each
  • R 31 , R 36 , R 37 , R 41 , R 46 are independently 1-2
  • R 33 is C 1 -C 6 alkyl; or phenyl optionally
  • R 40 is pyridyl or pyrimidyl each optionally
  • R 48 is cyano; nitro; C 1 -C 17 alkylthio; C 1 -C 17
  • alkylsulfinyl C 1 -C 17 haloalkoxy; C 5 -C 6
  • phenylsulfonyl phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R 31 ; thienyl, pyrimidinyl, furanyl,
  • naphthalenyl naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R 38 ;
  • R 49 is C 5 -C 12 alkyl; C 2 -C 12 haloalkyl; C 5 -C 12
  • R 50 is C 1 -C 6 alkyl; C 1 -C 6 haloalkyl; C 1 -C 6 alkoxy;
  • R 51 is phenyl substituted with R 52 ; pyridyl or pyrimidyl each optionally substituted with R 37 ; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazo
  • R 54 is phenyl substituted with R 37 ; pyridyl or
  • R 57 is C 1 -C 12 alkyl; C 3 -C 6 cycloalkyl; C 1 -C 12
  • haloalkyl C 3 -C 12 alkenyl; C 3 -C 12 haloalkenyl; C 3 -C 12 alkynyl; C 3 -C 12 haloalkynyl; phenyl, naphthalenyl or pyridyl each optionally substituted with R 41 ; or furanyl or thienyl each optionally substituted with R 42 ;
  • R 59 is phenyl optionally substituted with R 38 ;
  • A is O, NR 25 , or a direct bond
  • E and V are independently O or S;
  • J is O or N-A-L
  • n 1-4;
  • n 3-4;
  • Q is O, NR 11 , or a direct bond
  • T is phenyl optionally substituted with 1-2
  • W is O, S, or N-Q-R 58 ;
  • R 2 is an optionally substituted phenyl or heterocyclic ring, only H or F can be
  • the phenyl group is not attached to the alkyl carbon attached to the oxazolidinone ring.
  • This invention further comprises a fungicidal composition
  • a fungicidal composition comprising an effective amount of a compound of Formula I as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.
  • the invention further comprises a method of
  • controlling fungal diseases in plants comprising treating the locus to be protected with an effective amount of a compound of Formula I, as defined above.
  • a compound of Formula I as defined above.
  • the preferred compounds for use in the method of the present invention are defined as below for the
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” denotes straight chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, etc. isomers.
  • Me denotes methyl.
  • Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkyloxy denotes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • Cycloalkenyl denotes groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl.
  • Alkenyl denotes straight chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl , pentenyl, hexenyl, etc.
  • Alkenyl also denotes polyenes such as
  • Alkynyl denotes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl, hexynyl, etc. isomers.
  • Alkynyl can also denote moieties comprised of multiple triple bonds; e.g., 2,7-octadiyne and
  • Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy, hexyloxy, etc. isomers.
  • alkoxyalkoxyalkoxy examples include
  • Alkynyloxy denotes straight or branched
  • alkynyloxy moieties examples include HC ⁇ CCH 2 O,
  • Alkylthio denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl denotes both enantiomers of an alkylsulfinyl group. For example, CH 3 SO, CH 3 CH 2 SO, CH 3 CH 2 CH 2 SO, (CH 3 ) 2 CHSO and the different butylsulfinyl, pentylsulfinyl and hexylsufinyl isomers.
  • alkylsulfonyl examples include CH 3 SO 2 ,
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CF 2 .
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CCl 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, CF 2 HCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCT 3 S, CF 3 S,
  • haloalkylsulfonyl examples include CF 3 SO 2 , CCl 3 SO 2 , CF 3 CH 2 SO 2 and
  • haloalkoxyalkoxy include CF 3 OCH 2 O, ClCH 2 CH 2 OCH 2 CH 2 O, Cl 3 CCH 2 OCH 2 O as well as branched alkyl derivatives.
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 20. For example, C 1 -C 3
  • alkylsulfonyl designates methylsulfonyl
  • C 2 alkoxyalkoxy designates CH 3 OCH 2 O
  • C 3 alkoxyalkoxy designates, for example, CH 3 OCH 2 CH 2 O or CH 3 CH 2 OCH 2 O
  • C 4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 O, and CH 3 CH 2 OCH 2 CH 2 O.
  • alkoxyalkyl include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Formula I is comprised of one or more pyridyl
  • Preferred for greatest fungicidal activity and/or ease of synthesis are the compounds of Preferred 1 that are the compounds of Formula I wherein: Preferred 1 :
  • R 1 is H; C 1 -C 2 alkyl; or vinyl;
  • R 2 is C 7 -C 20 alkyl; C 7 -C 20 haloalkyl; C 3 -C 8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R 31 ; C 1 -C 16 alkyl substituted with R 19 ; C 2 -C 6 alkoxyalkyl substituted with R 21 ; C 7 -C 16 alkoxyalkyl optionally substituted with R 21 ; C 7 -C 20 alkenyl; C 2 -C 16 alkenyl substituted with R 20 ; pyridyl substituted with one substituent selected from R 49 , or one group from R 50 and one from R 18 ; or -T-Z;
  • R 3 is phenyl optionally substituted with C 1 -C 2
  • R 4 is H or methyl
  • R 12 is C 1 -C 8 alkyl; phenylmethyl; or phenyl;
  • R 28 is phenyl or pyridyl each optionally
  • R 40 is pyridyl or pyrimidyl each optionally
  • R 37 substituted with R 37 ; or thienyl or furanyl each optionally substituted with R 38 ; 2-tetrahydropyranyl; or 2-tetrahydrofuranyl;
  • R 51 is phenyl substituted with R 52 ; pyridyl
  • R 57 is C 1 -C 12 alkyl; C 3 -C 6 cycloalkyl; C 1 -C 12
  • haloalkyl phenyl, naphthalenyl or pyridyl each optionally substituted with R 41 ; or furanyl or thienyl each optionally substituted with R 42 ;
  • R 58 is R 12 ;
  • A is O or NR 25 ;
  • G is -OR 51 or -SR 51 ;
  • L is H; C 1 -C 8 alkyl; phenylmethyl optionally
  • Q is OH, NH, or a direct bond
  • Y is -OR 28 or -SR 28 ;
  • R 1 is methyl
  • R 2 is C 7 -C 20 alkyl; C 7 -C 20 haloalkyl; C 3 -C 8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R 31 ; C 1 -C 16 alkyl substituted with R 19 ; C 2 -C 6 alkoxyalkyl substituted with R 21 ; C 7 -C 16 alkoxyalkyl optionally substituted with R 21 ; C 7 -C 20 alkenyl; C 2 -C 16 alkenyl substituted with R 20 ; pyridyl substituted with one substituent selected from R 49 , or one group from R 50 and one from R 18 ; or -T-Z;
  • R 3 is phenyl optionally substituted with F, Cl, or methyl
  • R 4 is H
  • R 16 is 3 halogen; C 5 -C 8 alkyl; C 2 -C 8 haloalkyl;
  • R 22 is C 1 -C 16 alkyl; or phenyl optionally
  • R 28 is phenyl or pyridyl each optionally
  • R 29 , R 38 , R 42 , and R 44 are independently 1-2 halogen selected from the group consisting of F and
  • R 31 , R 36 , R 37 , and R 41 are independently trifluoromethyl; 1-2 halogen; cyano; C 1 -C 4 alkyl; C 1 -C 4 alkoxy; or phenoxy substituted with R 44 ;
  • R 40 is pyridyl substituted with R 37 ; or thienyl
  • R 49 is C 5 -C 8 alkyl; C2-C 8 haloalkyl; C 5 -C 8 alkoxy;
  • R 50 is C 1 -C 6 alkyl; C 1 -C 6 haloalkyl; C 1 -C 6 alkoxy;
  • R 57 is C 1 -C 12 alkyl; phenyl or pyridyl optionally substituted with R4 1 ; or thienyl optionally substituted with R 42 ;
  • A is O or NH
  • L is C 1 -C 8 alkyl; phenylmethyl; or phenyl;
  • T is phenyl optionally substituted with 1-2
  • halogen selected from the group consisting of
  • W is O or S
  • Z is phenoxy optionally substituted with R 16 ;
  • R 2 is C 7 -C 12 alkyl; C 7 -C 12 haloalkyl comprised of fewer than 7 halogens from the group
  • R 18 is F, Cl, Br, or methoxy
  • R 19 is C 1 -C 12 alkylthio; C 5 -C 6 cycloalkyloxy;
  • R 20 is C 1 -C 12 alkylthio; C 5 -C 6 cycloalkyloxy; C 1 -C 12 alkoxy; 1-3 halogen; phenyl or phenoxy each optionally substituted with R 31 ;
  • R 31 , R 37 , and R 41 are 1-2 halogen selected from the group consisting of F and Cl; cyano, C 1 -C 4 alkyl, or C 1 -C 4 alkoxy; or phenoxy;
  • R 38 is 1-2 halogen selected from the group
  • R 49 is C 5 -C 8 alkyl; C 2 -C 8 haloalkyl; C 5 -C 8 alkoxy; or C 2 -C 8 alkylthio;
  • R 50 is C j ⁇ -Cg alkyl; C 1 -C 6 haloalkyl; C ⁇ Cg alkoxy;
  • L is C 1 -C 8 alkyl or phenylmethyl when A is O;
  • T is phenyl optionally substituted with fluorine or methyl
  • compounds of Preferred 4 that are the compounds of Preferred 3 wherein:
  • R 2 is C 7 -C 12 alkyl; C 7 -C 12 haloalkyl; C 4 -C 6 alkyl substituted with phenoxy optionally
  • R 31 substituted with R 31 ; C 1 -C 12 alkyl substituted with R 19 ; C 7 -C 12 alkoxyalkyl; C 7 -C 12 alkenyl; pyridyl substituted with one group from R 50 and one halogen from the group consisting of F and Cl; or -T-Z;
  • R 19 is C 1 -C 19 alkylthio; C 5 -C 6 cycloalkyloxy; or
  • R 50 is C 1 -C 6 alkyl; trifluoromethyl; C 1 -C 6 alkoxy; or phenoxy optionally substituted with R 37 ; and R 57 is C 1 -C 8 alkyl; or phenyl optionally
  • 2-Thioxo-4-oxazolidinones la can be prepared by one or both of the Methods illustrated in Equation 1.
  • Z C 1 -C 4 alkyl, C 3 -C 4 alkenyl, C 3 -C 12 cycloalkyl, C 6 -C 7 cycloalkylalkyl, C 2 -C 4 alkoxyalkyl, PhCH 2
  • Formula 4 can be alkyl (C 1 -C 4 ), alkenyl (C 3 -C 4 ),
  • cycloalkyl (C 3 -C 12 ), cycloalkylalkyl (C 6 -C 7 ),
  • esters in which Z is C 1 -C 4 alkyl are preferred for ease of synthesis and lower expense.
  • the 2-hydroxycarboxylic acid esters of Formula 4 can be prepared by a number of methods known in the literature.
  • 2-hydroxycarboxylic acids by esterification as is well known in the literature.
  • the 2-hydroxycarboxylic acids can be prepared from ketones or aldehydes by formation of cyanohydrins, then hydrolysis, as is also known.
  • Org. Syntheses . Coll. Vol. 4, 58 (1968) teaches the preparation of atrolactic acid from
  • esters can also be synthesized from aldehyde and ketone cyanohydrins by treatment with alcohols in the presence of HC1 to afford the iminoether
  • a third method known for preparing 2-hydroxycarboxylic acids and esters involves treating 2-ketoacids or 2-keto-esters with nucleophilic-organometallic reagents such as Grignard reagents, and alkyl- and aryl-lithium reagents.
  • nucleophilic-organometallic reagents such as Grignard reagents, and alkyl- and aryl-lithium reagents.
  • R. G. Salomon et al. teach the preparation of some esters of Formula 4 by the addition of aryl-Grignard reagents to pyruvate esters ( J. Org. Chem . 1982, 47, 4692).
  • Carbonyl compounds known to undergo this reaction include pyruvate esters and acids, glyoxylate esters and acids, and diesters of oxomalonates.
  • the acids used in the acylation reaction can either be protic in nature, for example, a mixture of acetic and sulfuric acid, or a Lewis acid such as aluminum chloride, tin tetrachloride, titanium tetrachloride, or other Lewis acid known to effect Friedel-Crafts-type reactions.
  • the acid can be used either catalytically or in excess. In some cases, the acid may react destructively with the carbonyl substrate and excess carbonyl compound must be used.
  • the acylation can be conducted neat or in a solvent known by one skilled in the art to be suitable for Friedel-Crafts reactions, for example, methylene chloride, carbon disulfide, and nitrobenzene.
  • the reaction may be conducted from -50°C to 100°C.
  • the specific choice of acid, solvent, temperature, and reaction time will depend on the carbonyl and aromatic substrates to be reacted.
  • WO 90/12791 discloses the preparation of Ib by treating 2b with a substituted hydrazine 3 as illustrated in Equation 1. The preparation of the starting dioxazinediones 2b is also described therein.
  • WO 90/12791 also describes the desulfurization of
  • desulfurizing agents include aqueous OXONE ® (KHSO 5 ) and aqueous silver nitrate. Equation 2
  • compounds of Formula Ib can be prepared by the methods outlined in Equation 3. These procedures involve treatment of a 2-hydroxycarboxylic acid ester 4 with a carbonylating agent 6 to produce compounds of Formula 5, followed by conversion of 5 to Ib by treatment with a substituted hydrazine 3.
  • Equation 3 U can be chlorine, 1-imidazolyl, or other suitable leaving group, and the ester group containing Z is as described above for the 2-hydroxycarboxylic esters 4 in Equation 2.
  • the compounds of Formula 5 can be prepared by the method illustrated in Step 1, Equation 3.
  • the alcohols of Formula 4 are dissolved in an inert solvent such as methylene chloride or 1-chlorobutane, and treated with a tertiary-amine base such as
  • 1-imidazolyl can be prepared using 1,1'-carbonyldiimidazole (CDI, 6b) as described below.
  • the alcohols of Formula 4 are dissolved in an inert solvent in which the CDI has sufficient solubility at the reaction temperature.
  • Methylene chloride, 1-chlorobutane and toluene are three of many suitable inert solvents.
  • the CDI is added as a solid or as a solution in an inert solvent at temperatures from 0°C to 100°C.
  • the resulting mixture is poured into a water-immiscible solvent and washed successively with dilute mineral acid, water, and brine. The organic liquid phase of this mixture is separated, dried, and evaporated to isolate the product.
  • isolation of compounds of Formula 5 is not necessary.
  • the compounds can be treated in situ with a hydrazine of Formula 3 as described below for Step 2.
  • CDI can be first prepared, for example by treatment of a solution of imidazole in an inert solvent with phosgene as described by Staab and Wendel (Org. Syntheses. Coll. Vol. 5, 201, (1973)), and then treated in situ with alcohols 4 to afford 5b.
  • compounds of Formula 5 can be dissolved in an inert solvent such as methylene chloride, 1-chlorobutane, or THF and treated with a hydrazine of Formula 3 at a temperature from 0°C to 80°C.
  • an inert solvent such as methylene chloride, 1-chlorobutane, or THF
  • a hydrazine of Formula 3 at a temperature from 0°C to 80°C.
  • a tertiary-amine base such as triethylamine, N, N-diethylaniline, N, N-diisopropylethylamine, or a second equivalent of a hydrazine 3
  • Suitable carboxylic acids include acetic acid, pivalic acid, and benzoic acid.
  • the product of Formula Ib can be isolated by evaporation of the aforementioned inert solvent, and purified by dissolving the residue in a water-immiscible solvent such as ether or methylene chloride, washing with mineral acid, aqueous base, and water, drying, and evaporating the extraction solvent. Crystallization or chromatography can be utilized for additional
  • Acid salts of the hydrazine, hydroxylamine or amine such as dimethylhydrazine hydrochloride and hydroxylamine hydrochloride may also be used, and in these cases an equivalent of additional base is
  • Triethylamine, N, N-diisopropylethylamine and other tertiary amine bases are preferred.
  • the products lc can be isolated by evaporation of the solvent and dissolving the residue in a water- immiscible solvent such as ether. This solution may then be washed with mineral acid, water, and brine, and dried. Evaporation of the solvent followed by
  • hydroxylamines like 7 can also be accomplished by methods known in the art. See, for example, Castellino, A. J., et al. J. Org. Chem . 1984, 49, 1348; Murray, R. W., et al. Synthetic Comm . 1989, 19, 3509 and references cited therein; and
  • the group X in the compounds of Formula 8 may be a halogen, acetate, or other moiety known to be a leaving group in acylation reactions.
  • Chlorine is the most commonly used leaving group X.
  • the compound of Formula 8 is an acid chloride, chloroformate, or carbamoyl chloride
  • the iminooxazolidinones of Formula Ie are dissolved in an inert solvent such as methylene chloride,
  • THF tetrahydrofuran
  • benzene and treated with 8 and a base at a temperature from 0°C to 100°C.
  • Triethylamine, N, N-diisopropylethylamine, and other tertiary amine bases are preferred.
  • the products of Formula Id can be isolated by evaporation of the solvent and dissolving the residue in a water-immiscible solvent such as ether. This solution may be washed with a dilute aqueous mineral acid, water, and brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the purified products.
  • Oxazolidinones of Formula If can be synthesized by reacting a compound of Formula Ie with an isocyanate as described in Equation 6 below.
  • the iminooxazolidinones of Formula Ie are dissolved in an inert solvent such as toluene, THF, acetonitrile, or 1,2-dichloroethane and treated with an isocyanate at temperatures from 0°C to 50°C.
  • the products of Formula If can be isolated by evaporation of the solvent, and dissolving the residue in a water-immiscible solvent such as methylene chloride. This solution may be washed with dilute aqueous mineral acid, water, brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the products of Formula If.
  • alkyl, alkenyl, and alkynyl radicals are the normal isomers.
  • reaction solution was stirred at room temperature overnight and was then added to water (20 mL).
  • the aqueous layer was extracted with EtOAc (3 ⁇ 50 mL). The combined organic layers were washed with water
  • R 1 -R 59 and A, E, V, G, J, L, m, n, Q, T, W, Y, and Z are as defined in Formula I in the Summary of the Invention. Additional variables are used in the compounds and Tables and are:
  • R 60 which is a structural component of some R 19 groups, is R 22 , R 22 O, or R 22 R 43 N;
  • R 52 or R 37 is R 52 or R 37 ;
  • p which designates the size of a portion of some substituted R 2 alkyl groups, is 1-18;
  • q which designates the size of a portion of other substituted R 2 alkyl groups, is 1-19; and r and t designate the length of some alkoxyalkyl R 2 groups. The sum of r and t is 2-20.
  • R 61 R 62 Z 5-F 3-NO 2 (2-CF 3 - - - - 2-F 2-Cl-3, 5-diF-PhO Ph) CH 2 OCH 2 O - - - 3-Cl 2,3,5-triF-PhO - - - 2-F cyclohexyloxy - - - 2-F 2-CN-PhO 3-Br 2-F (Z)-PhCH-CH - - - 2-F 4-CN-PhO - - - 2-F (4-F-Ph)CH CH - - - 3-MeO 2-(1-bromoethyl)PhO

Abstract

La présente invention se rapporte à de nouveaux composés de la formule (I) comprenant des compositions géométriques et stéréo-isomères, s'appliquant à l'agriculture, et à leur utilisation comme fongicides; formule dans laquelle W représente O, S ou N-Q-R58, et R1, R2, R3 et R4 représentent des groupes variés.The present invention relates to new compounds of formula (I) comprising geometric and stereoisomeric compositions, applicable to agriculture, and to their use as fungicides; formula in which W represents O, S or N-Q-R58, and R1, R2, R3 and R4 represent various groups.

Description

TITLE
FUNGICIDAL OXAZOLIDINONES FIELD OF THE INVENTION
The present invention relates to substituted oxazolidinone compounds, fungicidal compositions containing such compounds, and method of use of the compounds and compositions as fungicides.
BACKGROUND OF THE INVENTION
New compounds effective for controlling the growth of undesired fungi are in constant demand. In the most common situation, such compounds are sought to
selectively control the growth of fungi in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked fungus growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. There are many products commercially available for these purposes, but the need continues for products which are more
effective, less costly and environmentally safe.
WO90/12791 teaches the use of fungicidal compounds of Formula i
wherein:
A is O or NR4; and
W is O or S.
WO90/12791 also relates to processes for the preparation of these compounds and to certain novel compounds. The compounds of WO90/12791 differ from those of the present invention in the nature of R2. The above reference does not disclose the compounds of the present invention.
The compounds of the prior art, although useful as fungicides, tend to have drawbacks including poor efficacy, toxicity to non-target organisms and/or unacceptable environmental effects. A need therefore exists for fungicidal products and methods of
application which address the limitations of the prior art.
SUMMARY OF THE INVENTION
The present invention comprises compounds of
Formula I including all geometric and stereoisomers, agricultural compositions containing them and use of the compounds and compositions as fungicides. The variation in Formula I occurs primarily in substituent R2. Formula I comprises:
wherein:
R1 is H; C1-C4 alkyl; C1-C4 haloalkyl; C3-C6
cycloalkyl; C2-C4 alkenyl; C2-C4
alkoxycarbonyl; or phenylmethyl optionally substituted on the phenyl ring with R6 and on the benzylic carbon with R7;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C4-C17 alkyl substituted with C3-C6 cycloalkyl; C4-C17 alkyl substituted with phenyl optionally substituted with R31 on the phenyl ring; C3-C14 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C20 alkyl substituted with R19; C2-C6 alkoxyalkyl substituted with R21; C7-C20 alkoxyalkyl
optionally substituted with R21; C7-C20 alkenyl;
C2-C20 alkenyl substituted with R20; C7-C20 alkynyl; C2-C20 alkynyl substituted with R48; C5-C7 cycloalkenyl; (CH2CH2OCH2CH2) CH-;
(CH2CH2N (R15) CH2CH2) CH-; (CH2CH2SCH2CH2) CH-;
(CH2CH2SO2CH2CH2)CH-; pyrimidyl, pyrazinyl, pyridazinyl, oxazolyl, isoxazolyl, isothiazolyl or thiazolyl each optionally substituted with R26 and R18; furanyl substituted with one substituent selected from R26 and one from R18; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl, pyridyl, pyrimidinyl or pyridazyl
each optionally substituted with R10; or phenylmethy1;
R4 is H, methyl, or aσetyl;
R5, R7, R11, R14, R23, R24, R3°, R39, R43, and R55 are each independently H or C1-C4 alkyl;
R6, R29, R34, R38, R42, R44, and R56 are each
independently 1-2 halogen; C1-C4 alkyl; C1-C4 alkoxy; trifluoromethyl; methylthio; or nitro; R8 is C1-C19 alkyl; C2-C19 alkylcarbonyl; C2-C19
alkoxycarbonyl; (R9R14N)C=O; phenyl optionally substituted with R27; or phenoxycarbonyl optionally substituted with R17;
R9 is C1-C18 alkyl; or phenyl optionally
substituted with R17;
R10, R27, and R45 are each independently 1-2
substituents selected from the group
consisting of trifluoromethyl,
trifluoromethoxy, nitro, CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano;
R12 is H; C1-C8 alkyl optionally substituted with
C2-C7 alkoxycarbonyl; C3-C8 alkenyl; phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5; phenyl optionally substituted with R34; or pyridyl optionally substituted with R34; or
R11 and R58 can be taken together as -CH2 (CH2) 2CH2-, -CH2 (CH2) 3CH2-, -CH2 (CH2) 4CH2-, -CH2CH2OCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2N(R5)CH2CH2- or
-CH2CH2N(R5)CH2CH2CH2- along with the nitrogen to which they are attached to form a ring;
R13 is C1-C6 alkyl; C3-C6 cycloalkyl; phenyl
optionally substituted with R45; or
phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5;
R15 is C1-C12 alkyl; C2-C12 alkylcarbonyl; benzoyl optionally substituted with R16 on the phenyl ring; C2-C12 alkoxycarbonyl; C2-C12 alkylaminocarbonyl substituted with R55 on nitrogen;
phenoxycarbonyl optionally substituted with R46 on the phenyl ring; or phenylaminocarbonyl optionally substituted with R46 on the phenyl ring and with R55 on nitrogen;
R16 is 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy;
C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8 alkoxyalkoxy; C2-C8 alkylthio; C2-C8 alkenyl; C2-C8 haloalkenyl; C2-C8 alkynyl;
hydroxycarbonyl; C2-C8 alkoxy-carbonyl; or phenoxy substituted with R29;
R17, R18, R32, R35, R47, and R53 are each
independently 1-2 halogen; C1-C2 alkyl;
trifluoromethyl; or C1-C2 alkoxy;
R19 is cyano; nitro; C1-C19 alkylthio; C1-C19
alkylsulfinyl; C1-C19 haloalkoxy; C5-C6
cycloalkyloxy; C3-C19 alkenyloxy; C3-C19 alkynyloxy; C1-C19 alkylsulfonyl; C2-C19 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O)O; R8R43N; (C1-C4 alkoxy) 2P (=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenyl-sulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy; or
C(=J)R24;
R20 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17 haloalkynyl; C3-C17 alkynyloxy; C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; R8R43N; (C1-C4 alkoxy) 2P (=E)O; R33SO3; R43R14R23N+; phenyl-sulfonyl,
phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl, naphthalenyl,
pyrimidinyloxy, naphthalenyloxy each
optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C1-C17 alkoxy; 1-3 halogen; C2-C17 alkoxyalkoxy; C3-C17 alkynyl; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R21 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C2-C17 haloalkenyl; C3-C17 alkenyloxy; C3-C17 haloalkynyl; C3-C17
alkynyloxy; C1-C17 alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)(O R22OC(=O)O; R22R43NC (=O) O; R8R43N; (C1-C4 alkoxy) 2P (=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with
R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C1-C17 alkoxy; C2-C17 alkoxyalkoxy; C3-C17 alkynyl; C3-C6 cycloalkyl; phenyl or phenoxy each optionally substituted with R31; or C2-C17 haloalkoxyalkoxy;
R22 is C1-C16 alkyl; phenyl optionally substituted with R36; or pyridyl optionally substituted with R36;
R25 is H; C1-C6 alkyl; or phenyl optionally
substituted with R35;
R26 is C1-C6 alkyl; C1-C6 alkoxy; phenoxy
substituted with R53, or benzyloxy substituted on the phenyl ring with R53;
R28 is phenyl, pyridyl or pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl or pyrazolyl each
optionally substituted with R38;
R31, R36, R37, R41, R46 are independently 1-2
substituents selected from the group
consisting of trifluoromethyl,
trifluoromethoxy, nitro, CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano; or phenoxy substituted with R44;
R33 is C1-C6 alkyl; or phenyl optionally
substituted with R32;
R40 is pyridyl or pyrimidyl each optionally
substituted with R37; or thienyl, furanyl, pyrazolyl, naphthalenyl, isothiazolyl,
thiazolyl, imidazolyl, oxazolyl, or isoxazolyl each optionally substituted with R38; 2-tetrahydropyranyl; or 2-tetrahydrofuranyl;
R48 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17 alkynyloxy; C1-C17 alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O) O; R8R43N; (C1-C4 alkoxy) 2P (=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C1-C17 alkoxy; 1-3 halogen; C2-C17
alkoxyalkoxy; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31; R49 is C5-C12 alkyl; C2-C12 haloalkyl; C5-C12
alkoxy; C1-C12 haloalkoxy; C2-C12 alkylthio;
C1-C12 haloalkylthio; C2-C12 alkenyl; C2-C12 haloalkenyl; C3-C12 alkynyl; C2-C12
haloalkynyl; C3-C12 alkenyloxy; C3-C12
haloalkenyloxy; C3-C12 alkynyloxy; C2-C12 alkylsulfonyl; C1-C12 haloalkylsulfonyl; C2-C12 alkoxyalkyl; C2-C12 alkoxyalkoxy; C2-C12 alkoxycarbonyl; N(CH3)2; or G;
R50 is C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy;
C1-C6 haloalkoxy; C1-C6 alkylthio; C1-C6 haloalkylthio; C2-C6 alkenyl; C2-C6
haloalkenyl; C3-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 cycloalkyl; C3-C6 cycloalkyloxy; C1-C6 alkylsulfonyl; C1-C6 haloalkylsulfonyl; C2-C6 alkoxyalkyl; C2-C6 alkoxyalkoxy; C2-C6 alkoxycarbonyl; N(CH3)2; or Y; R51 is phenyl substituted with R52; pyridyl or pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazolyl each optionally substituted with R38; R52 is 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy;
C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8 alkoxyalkoxy; C2-C8 alkylthio; C5-C6 cycloalkyl; C5-C6 cycloalkyloxy; C2-C8 alkenyl;
C2-C8 haloalkenyl; C2-C8 alkynyl; hydroxycarbonyl; C2-C8 alkoxycarbonyl; or phenoxy optionally substituted with R29;
R54 is phenyl substituted with R37; pyridyl or
pyrimidyl each optionally substituted with R377 or thienyl, furanyl, isoxazolyl, -oxazolyl, or pyrazolyl each optionally substituted with R38; R57 is C1-C12 alkyl; C3-C6 cycloalkyl; C1-C12
haloalkyl; C3-C12 alkenyl; C3-C12 haloalkenyl; C3-C12 alkynyl; C3-C12 haloalkynyl; phenyl, naphthalenyl or pyridyl each optionally substituted with R41; or furanyl or thienyl each optionally substituted with R42;
R58 is R12, C(=O)R13, C(=O)OR13 or C (=O)NR13R30;
R59 is phenyl optionally substituted with R38;
A is O, NR25, or a direct bond;
E and V are independently O or S;
G is -OR51; -SR51; -NHR28; -N(CH3)R28; -CH=CHR28
(cis or trans); -C(=V)OR28; -OC(=V)R28;
R28NR39C(=V)O-; -OC(=V)OR28; -C (=V)NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -(CH2)mR59; or phenyl optionally substituted with R38;
J is O or N-A-L;
L is H; C1-C8 alkyl, C3-C8 alkenyl; phenylmethyl optionally substituted with R47 on the phenyl ring and R55 on the benzylic carbon; phenyl optionally substituted with R47; pyridyl optionally substituted with R47; C(=O)R22;
C(=O)OR22; or C(=O)NR22R7;
m is 1-4;
n is 3-4;
Q is O, NR11, or a direct bond;
T is phenyl optionally substituted with 1-2
halogen; C1-C4 alkyl; C1-C4 alkoxy; trifluoromethyl; methylthio; or nitro;
W is O, S, or N-Q-R58;
Y is -OR28; -SR28; -NHR28; -N(CH3)R28; -CH=CHR28 (cis or trans); -C(=V)OR28; -OC(=V)R28; R28NR39C(=V)O-; -OC(=V)OR28; -C (=V) NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -(CH2)mR59; or phenyl optionally substituted with R38; and
Z is phenoxy substituted with R16; C3-C12 alkoxyalkoxyalkoxy; benzyloxymethoxy optionally substituted on the phenyl ring with R56; C5-C6 cycloalkyloxy; styryl optionally substituted on the phenyl ring with R41; -C(=V)OR57; -OC(=V)R57; -OC(=V)NR39R57; -PO(=V)OR57;
-C(=V)NR39R57; -(CH2)nR59; -(CH2)nOR59; -O(CH2)nR59; or -OR40; and the agriculturally suitable salts thereof;
provided that:
i) when W is N-Q-R58, Z is other than phenoxy
substituted with R16, C5-C6 cycloalkyloxy, or -C(=O) (C1-C5 alkoxy);
ii) when R2 is an optionally substituted phenyl or heterocyclic ring, only H or F can be
substituted on the carbon atom(s) of the phenyl or heterocyclic ring adjacent to the carbon bearing the oxazolidinone ring;
iii) when two substituents are selected from the
alkyl and alkoxy groups in R10, R27, R31, R36, R37, R41, R45 or R46, then at least one of said substituents contains only one carbon atom; and iv) when R2 is alkyl substituted with optionally
substituted phenyl, then the phenyl group is not attached to the alkyl carbon attached to the oxazolidinone ring.
This invention further comprises a fungicidal composition comprising an effective amount of a compound of Formula I as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.
The invention further comprises a method of
controlling fungal diseases in plants, comprising treating the locus to be protected with an effective amount of a compound of Formula I, as defined above. The preferred compounds for use in the method of the present invention are defined as below for the
compounds of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" denotes straight chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, etc. isomers. The designation "Me" denotes methyl.
"Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkyloxy" denotes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
"Cycloalkenyl" denotes groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl.
"Alkenyl" denotes straight chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl , pentenyl, hexenyl, etc.
isomers. Alkenyl also denotes polyenes such as
1,3-hexadiene and 2,4,6-heptatriene. "Alkynyl" denotes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl, hexynyl, etc. isomers. "Alkynyl" can also denote moieties comprised of multiple triple bonds; e.g., 2,7-octadiyne and
2,5,8-decatriyne.
"Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy, hexyloxy, etc. isomers.
Examples of "alkoxyalkoxyalkoxy" include
CH3OCH2CH2OCH2O, CH3CH2OCH2CH2OCH2O, and
(CH3) 2CHOCH2CH2OCH2O.
"Alkenyloxy" denotes straight chain or branched alkenyloxy moieties. Examples of alkenyloxy include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3) CH=CHCH2O,
(CH3)CH=C(CH3)CH2O and CH2=CHCH2CH2O.
"Alkynyloxy" denotes straight or branched
alkynyloxy moieties. Examples include HC≡CCH2O,
CH3C≡CCH2O and CH3C≡CCH2CH2O.
"Alkylthio" denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
"Alkylsulfinyl" denotes both enantiomers of an alkylsulfinyl group. For example, CH3SO, CH3CH2SO, CH3CH2CH2SO, (CH3)2CHSO and the different butylsulfinyl, pentylsulfinyl and hexylsufinyl isomers.
Examples of "alkylsulfonyl" include CH3SO2,
CH3CH2SO2, CH3CH2CH2SO2, (CH3)2CHSO2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F3C, ClCH2, CF3CH2 and CF3CF2. Examples of "haloalkenyl" include (Cl)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C, CCl3C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, CF2HCH2CH2O and CF3CH2O.
Examples of "haloalkylthio" include CCT3S, CF3S,
CCl3CH2S and CH2ClCH2CH2S. Examples of "haloalkylsulfonyl" include CF3SO2, CCl3SO2, CF3CH2SO2 and
CF3CF2SO2. Examples of "haloalkoxyalkoxy" include CF3OCH2O, ClCH2CH2OCH2CH2O, Cl3CCH2OCH2O as well as branched alkyl derivatives.
The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 20. For example, C1-C3
alkylsulfonyl designates methylsulfonyl through
propylsulfonyl; C2 alkoxyalkoxy designates CH3OCH2O; C3 alkoxyalkoxy designates, for example, CH3OCH2CH2O or CH3CH2OCH2O; and C4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH3CH2CH2OCH2O, and CH3CH2OCH2CH2O. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2.
Examples of "alkoxycarbonyl" include CH3OC(=O),
CH3CH2OC (=O), CH3CH2CH2OC (=O), (CH3) 2CHOC (=O) and the different butoxy-, pentoxy- and hexyloxycarbonyl isomers.
In the above recitations, when a compound of
Formula I is comprised of one or more pyridyl,
pyrimidinyl, pyridazyl, pyrazinyl, oxazolinyl,
isoxazolinyl, isothiazolyl, or thiazolyl rings, all bonds to these heterocycles are made through the carbon atom(s) of the heterocyclic ring.
Preferred for greatest fungicidal activity and/or ease of synthesis are the compounds of Preferred 1 that are the compounds of Formula I wherein: Preferred 1 :
R1 is H; C1-C2 alkyl; or vinyl;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C3-C8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C16 alkyl substituted with R19; C2-C6 alkoxyalkyl substituted with R21; C7-C16 alkoxyalkyl optionally substituted with R21; C7-C20 alkenyl; C2-C16 alkenyl substituted with R20; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl optionally substituted with C1-C2
alkyl or halogen;
R4 is H or methyl;
R12 is C1-C8 alkyl; phenylmethyl; or phenyl;
R19 is C1-C19 alkylthio; C1-C19 haloalkoxy; C5-C6 cycloalkyloxy; C3-C19 alkenyloxy; C1-C19 alkylsulfonyl; C2-C19 alkoxycarbonyl; hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC (=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl each optionally substituted with R38; 2-tetrahydropyranyloxy; or CH(=N-A-L);
R20 is C 1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C1-C17 alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxycarbonyl; R22C(=O)O; R22OC (=O)O; R22R43NC (=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl optionally substituted with R38; 2-tetrahydropyranyloxy; C1-C17 alkoxy; 1-3 halogen; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31; R21 is C1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxycarbonyl; R22C(=O)O; R22OC(=O)O; R22R43NC (=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl each optionally substituted with R38; 2-tetrahydropyranyloxy; C1-C17 alkoxy; C2-C17 alkoxyalkoxy; or phenyl or phenoxy each
optionally substituted with R31;
R28 is phenyl or pyridyl each optionally
substituted with R37; or thienyl or furanyl each optionally substituted with R38;
R40 is pyridyl or pyrimidyl each optionally
substituted with R37; or thienyl or furanyl each optionally substituted with R38; 2-tetrahydropyranyl; or 2-tetrahydrofuranyl;
R51 is phenyl substituted with R52; pyridyl
optionally substituted with R37; or thienyl or furanyl each optionally substituted with R38;
R57 is C1-C12 alkyl; C3-C6 cycloalkyl; C1-C12
haloalkyl; phenyl, naphthalenyl or pyridyl each optionally substituted with R41; or furanyl or thienyl each optionally substituted with R42;
R58 is R12;
A is O or NR25;
G is -OR51 or -SR51;
L is H; C1-C8 alkyl; phenylmethyl optionally
substituted with R47 on the phenyl ring; phenyl optionally substituted with R47; or C(=O)R22;
Q is OH, NH, or a direct bond;
Y is -OR28 or -SR28; and
Z is phenoxy substituted with R16; -C(=O)OR57;
-OC(=O)R57; -OR40; or -OC(=O)NHR57. provided that the total number of carbons in R2 is less than or equal to 20;
More preferred are the compounds of Preferred 2 that are the compounds of Preferred 1 wherein:
Preferred 2 :
R1 is methyl;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C3-C8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C16 alkyl substituted with R19; C2-C6 alkoxyalkyl substituted with R21; C7-C16 alkoxyalkyl optionally substituted with R21; C7-C20 alkenyl; C2-C16 alkenyl substituted with R20; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl optionally substituted with F, Cl, or methyl;
R4 is H;
R16 is 3 halogen; C5-C8 alkyl; C2-C8 haloalkyl;
C5-C8 alkoxy; C1-C8 haloalkoxy; C2-C8 alkylthio; C2-C8 alkenyl; or phenoxy substituted with R29;
R19 is C1-C19 alkylthio; C1-C19 haloalkoxy; C5-C6 cycloalkyloxy; C3-C19 alkenyloxy; C2-C19 alkoxycarbonyl; R22C(=O)O; R22OC(=O)O; R22R43NC (=O)O; pyridyl optionally substituted with R31; or CH(=N-A-L);
R20 is C1-C17 alkylthio; C-t-C^ haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C2-C17 alkoxycarbonyl; R22C(=O)O; R22OC(=O)O; R22R43NC(=O)O; C1-C17 alkoxy; 1-3 halogen; or phenyl or phenoxy each optionally substituted with R31;
R21 is C1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C2-C17 alkoxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; C1-C17 alkoxy; C2-C17
alkoxyalkoxy; or phenyl or phenoxy each optionally substituted with R31;
R22 is C1-C16 alkyl; or phenyl optionally
substituted with R36;
R28 is phenyl or pyridyl each optionally
substituted with R37; or thienyl optionally substituted with R38;
R29, R38, R42, and R44 are independently 1-2 halogen selected from the group consisting of F and
Cl; C1-C4 alkyl; or C1-C4 alkoxy;
R31, R36, R37, and R41 are independently trifluoromethyl; 1-2 halogen; cyano; C1-C4 alkyl; C1-C4 alkoxy; or phenoxy substituted with R44;
R40 is pyridyl substituted with R37; or thienyl
optionally substituted with R38;
R49 is C5-C8 alkyl; C2-C8 haloalkyl; C5-C8 alkoxy;
C2-C8 alkylthio; or thienyloxy optionally substituted with R38;
R50 is C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy;
C1-C6 haloalkoxy; C1-C6 alkylthio; C2-C6 alkenyl; C3-C6 alkenyloxy; C3-C6 cycloalkyloxy;
C2-C6 alkoxycarbonyl; or -OR28;
R57 is C1-C12 alkyl; phenyl or pyridyl optionally substituted with R41; or thienyl optionally substituted with R42;
A is O or NH;
L is C1-C8 alkyl; phenylmethyl; or phenyl;
T is phenyl optionally substituted with 1-2
halogen selected from the group consisting of
F and Cl, or C1-C2 alkyl;
W is O or S; and
Z is phenoxy optionally substituted with R16;
-C(=O)OR57; -OC(=O)R57; -OR40; or -OC(=O)NHR57. Even more preferred are the compounds of Preferred 3 that are the compounds of Preferred 2 wherein:
Preferred 3 :
R2 is C7-C12 alkyl; C7-C12 haloalkyl comprised of fewer than 7 halogens from the group
consisting of F and Cl; C3-C8 alkyl substituted with phenoxy optionally substituted with R31; C1-C12 alkyl substituted with R19; C7-C12 alkoxyalkyl; C7-C12 alkenyl; C2-C12 alkenyl substituted with R20; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R18 is F, Cl, Br, or methoxy;
R19 is C1-C12 alkylthio; C5-C6 cycloalkyloxy;
pyridyloxy optionally substituted with R31; or
CH (=N-A-L);
R20 is C1-C12 alkylthio; C5-C6 cycloalkyloxy; C1-C12 alkoxy; 1-3 halogen; phenyl or phenoxy each optionally substituted with R31;
R31, R37, and R41 are 1-2 halogen selected from the group consisting of F and Cl; cyano, C1-C4 alkyl, or C1-C4 alkoxy; or phenoxy;
R38 is 1-2 halogen selected from the group
consisting of F and Cl; methyl; or methoxy; R49 is C5-C8 alkyl; C2-C8 haloalkyl; C5-C8 alkoxy; or C2-C8 alkylthio;
R50 is Cj^-Cg alkyl; C1-C6 haloalkyl; C^Cg alkoxy;
C^Cg alkylthio; C3-C6 cycloalkyloxy; or phenoxy optionally substituted with R37; R57 is C1-C8 alkyl; or phenyl optionally
substituted with R41;
L is C1-C8 alkyl or phenylmethyl when A is O; or
C1-C8 alkyl or phenyl when A is NH;
T is phenyl optionally substituted with fluorine or methyl; and
Z is -OC(=O)R57 or -OR40. Especially preferred are the compounds of Preferred 4 that are the compounds of Preferred 3 wherein:
Preferred 4 :
R2 is C7-C12 alkyl; C7-C12 haloalkyl; C4-C6 alkyl substituted with phenoxy optionally
substituted with R31; C1-C12 alkyl substituted with R19; C7-C12 alkoxyalkyl; C7-C12 alkenyl; pyridyl substituted with one group from R50 and one halogen from the group consisting of F and Cl; or -T-Z;
R19 is C1-C19 alkylthio; C5-C6 cycloalkyloxy; or
pyridyloxy optionally substituted with R31;
R50 is C1-C6 alkyl; trifluoromethyl; C1-C6 alkoxy; or phenoxy optionally substituted with R37; and R57 is C1-C8 alkyl; or phenyl optionally
substituted with R41.
Specifically preferred for greatest fungicidal activity and/or ease of synthesis are:
5-methyl-5-octyl-3-(phenylamino)-2,4-oxazolidinedione and the (S)-enantiomer thereof;
5-(2-fluoro-6-phenoxy-3-pyridinyl)-5-methyl-3- (phenylamino)-2,4-oxazolidinedione and the (S)-enantiomer thereof;
5-methyl-5-(3-phenoxypropyl)-3-(phenylamino)- 2,4-oxazolidinedione and the (S)-enantiomer thereof;
4-[5-methyl-2,4-dioxo-3-(phenylamino)-5- oxazolidinyl]phenyl 3-chlorobenzoate and the (S)-enantiomer thereof; and
4-[5-methy1-2,4-dioxo-3-(phenylamino)-5- oxazolidinyl]phenyl 4-cyanobenzoate and the (S)-enantiomer thereof.
When R1 and R2 of the compounds of Formula I are different, the compounds of Formula I possess a chiral center. This invention therefore, comprises racemic mixtures, enriched mixtures, and pure enantiomers. Compounds of Formula I can also exist as a mixture of (E)- and (Z)-imine isomers when W = N-Q-R58. This invention, therefore, also comprises mixtures of geometric isomers as well as the individual isomers.
It is recognized that some reagents and reaction conditions described below for preparing compounds of Formula I may not be compatible with some
functionalities claimed for W, R1, R2, R3, and R4. In these cases, the incorporation of protection/deprotection sequences into the syntheses may be necessary in order to obtain the desired products. The cases in which protecting groups are necessary, and which protecting groups to use, will be apparent to one skilled in chemical synthesis.
The compounds of Formula I can be prepared as described below in the following Equations. Compounds denoted la through If are subsets of Formula I.
2-Thioxo-4-oxazolidinones la can be prepared by one or both of the Methods illustrated in Equation 1.
These Methods are described in detail in the
literature. Geffken, D.; Z. Naturforsch, 1983, 38b, 1008; Geffken, D.; Arch . Pharm ., 1982, 315, 802; and U.S. Patent 4,957,933 teach the procedures for the reactions described in Method 1 as well as the
preparation of the starting thioxodioxazinones 2a.
International Application (PCT) WO 90/12791 teaches the preparation of compounds of Formula la described in Method 2.
Equation 1
Method 1
Method 2
Z = C1-C4 alkyl, C3-C4 alkenyl, C3-C12 cycloalkyl, C6-C7 cycloalkylalkyl, C2-C4 alkoxyalkyl, PhCH2
The preparation of substituted hydrazines of Formula 3 can be accomplished by literature methods (J.
Timberlake; J. Stowell; The Chemistry of the Hydrazo, Azo, and Azoxy Groups (S. Patai, Ed.) John Wiley and Sons, Ltd., London (1975), p 69; Demers, J. P.;
Klaubert, D. J.; Tetrahedron Lett. 1987, 4933).
The ester group containing Z in compounds of
Formula 4 can be alkyl (C1-C4), alkenyl (C3-C4),
cycloalkyl (C3-C12), cycloalkylalkyl (C6-C7),
alkoxyalkyl (C2-C4), and phenylmethyl. Preferred for ease of synthesis and lower expense are esters in which Z is C1-C4 alkyl. The 2-hydroxycarboxylic acid esters of Formula 4 can be prepared by a number of methods known in the literature.
(1) They can be formed from the corresponding
2-hydroxycarboxylic acids by esterification as is well known in the literature. The 2-hydroxycarboxylic acids can be prepared from ketones or aldehydes by formation of cyanohydrins, then hydrolysis, as is also known. For example, Org. Syntheses . Coll. Vol. 4, 58 (1968) teaches the preparation of atrolactic acid from
acetophenone.
(2) The esters can also be synthesized from aldehyde and ketone cyanohydrins by treatment with alcohols in the presence of HC1 to afford the iminoether
hydrochlorides, followed by hydrolysis.
(3) A third method known for preparing 2-hydroxycarboxylic acids and esters involves treating 2-ketoacids or 2-keto-esters with nucleophilic-organometallic reagents such as Grignard reagents, and alkyl- and aryl-lithium reagents. For example, R. G. Salomon et al. teach the preparation of some esters of Formula 4 by the addition of aryl-Grignard reagents to pyruvate esters ( J. Org. Chem . 1982, 47, 4692).
(4) Another method described in the literature for preparing some 2-aryl-2-hydroxyesters and acids is by acylation of aromatic rings with activated carbonyl compounds in the presence of a protic or Lewis acid. Aromatic substrates capable of undergoing reactions of this type are benzene, diphenyl ether, furan and other aromatic compounds known to be of sufficient reactivity to undergo Friedel-Crafts-type reactions. In the case of mono-substituted benzene derivatives, the acylation occurs preferentially, but not necessarily exclusively, para to the point of attachment of the substituent. For example, see Org. Syntheses, Coll. Vol. 3, 326, (1955), Salomon et al., J. Org. Chem . , 1982, 47, 4692, and U.S. 4,922,010.
Carbonyl compounds known to undergo this reaction include pyruvate esters and acids, glyoxylate esters and acids, and diesters of oxomalonates. The acids used in the acylation reaction can either be protic in nature, for example, a mixture of acetic and sulfuric acid, or a Lewis acid such as aluminum chloride, tin tetrachloride, titanium tetrachloride, or other Lewis acid known to effect Friedel-Crafts-type reactions.
The acid can be used either catalytically or in excess. In some cases, the acid may react destructively with the carbonyl substrate and excess carbonyl compound must be used.
The acylation can be conducted neat or in a solvent known by one skilled in the art to be suitable for Friedel-Crafts reactions, for example, methylene chloride, carbon disulfide, and nitrobenzene. The reaction may be conducted from -50°C to 100°C. The specific choice of acid, solvent, temperature, and reaction time will depend on the carbonyl and aromatic substrates to be reacted.
Several methods are taught in the literature for the preparation of 2, 4-oxazolidinediones of Formula Ib (Equations 1 and 2). Geffken et al. (World Patent
Publication WO 90/12791) discloses the preparation of Ib by treating 2b with a substituted hydrazine 3 as illustrated in Equation 1. The preparation of the starting dioxazinediones 2b is also described therein. WO 90/12791 also describes the desulfurization of
2-thioxo-4-oxazolidinones la to yield 2,4-oxazolidinediones Ib as shown in Equation 2. Suitable
desulfurizing agents include aqueous OXONE® (KHSO5) and aqueous silver nitrate. Equation 2
In addition, compounds of Formula Ib can be prepared by the methods outlined in Equation 3. These procedures involve treatment of a 2-hydroxycarboxylic acid ester 4 with a carbonylating agent 6 to produce compounds of Formula 5, followed by conversion of 5 to Ib by treatment with a substituted hydrazine 3. In
Equation 3, U can be chlorine, 1-imidazolyl, or other suitable leaving group, and the ester group containing Z is as described above for the 2-hydroxycarboxylic esters 4 in Equation 2.
Equation 3
Step 1
Step 2
The compounds of Formula 5 can be prepared by the method illustrated in Step 1, Equation 3. For the preparation of the compounds of Formula 5a (U=Cl), the alcohols of Formula 4 are dissolved in an inert solvent such as methylene chloride or 1-chlorobutane, and treated with a tertiary-amine base such as
triethylamine, pyridine, and N,N-diisopropylethylamine, at a temperature from -60°C to +30°C. To this mixture is added phosgene (6a) to provide products of Formula 5a. The phosgene can be added as a gas or dissolved in a inert solvent such as toluene and added in solution. When the reaction of Step 1 is complete, the resulting mixture is poured into a water-immiscible solvent and washed with dilute aqueous mineral acid, water, and brine. The organic liquid phase is dried and
evaporated to yield products of Formula 5a.
The compounds represented by Formula 5b (U =
1-imidazolyl) can be prepared using 1,1'-carbonyldiimidazole (CDI, 6b) as described below. The alcohols of Formula 4 are dissolved in an inert solvent in which the CDI has sufficient solubility at the reaction temperature. Methylene chloride, 1-chlorobutane and toluene are three of many suitable inert solvents. The CDI is added as a solid or as a solution in an inert solvent at temperatures from 0°C to 100°C. When the synthesis reaction is complete, the resulting mixture is poured into a water-immiscible solvent and washed successively with dilute mineral acid, water, and brine. The organic liquid phase of this mixture is separated, dried, and evaporated to isolate the product.
In some cases, isolation of compounds of Formula 5 is not necessary. For example, after the formation of 5 is complete, the compounds can be treated in situ with a hydrazine of Formula 3 as described below for Step 2.
Furthermore, the use of pure, isolated CDI is not necessary in the synthesis of 5b described in Equation 3, Step 1. The CDI can be first prepared, for example by treatment of a solution of imidazole in an inert solvent with phosgene as described by Staab and Wendel (Org. Syntheses. Coll. Vol. 5, 201, (1973)), and then treated in situ with alcohols 4 to afford 5b.
As illustrated in Step 2 of Equation 3, compounds of Formula 5 can be dissolved in an inert solvent such as methylene chloride, 1-chlorobutane, or THF and treated with a hydrazine of Formula 3 at a temperature from 0°C to 80°C. When U is Cl as shown in Formula 5a, about one equivalent of a tertiary-amine base such as triethylamine, N, N-diethylaniline, N, N-diisopropylethylamine, or a second equivalent of a hydrazine 3 can be added. When U=1-imidazole as in Formula 5b, about one equivalent of a carboxylic acid can be added to accelerate the reaction. Suitable carboxylic acids include acetic acid, pivalic acid, and benzoic acid.
Upon completion of the reaction of Step 2, the product of Formula Ib can be isolated by evaporation of the aforementioned inert solvent, and purified by dissolving the residue in a water-immiscible solvent such as ether or methylene chloride, washing with mineral acid, aqueous base, and water, drying, and evaporating the extraction solvent. Crystallization or chromatography can be utilized for additional
purification if desired.
For reasons of higher yields and lower expense, the methods of preparing compounds of Formula Ib from compounds of Formula 5b (U = 1-imidazolyl) are
preferred to the methods of preparing Ib from 5a.
Compounds of Formula lc wherein in W is N-Q-R12 can be synthesized according to the method schematically illustrated in Equation 4. The 2-thioxo-4-oxazolidinones la are treated with a hydrazine (Q=NR11), hydroxylamine (Q=O), or primary amine (Q=a direct bond) of Formula 7
Equation 4
As shown in Equation 4, the 2-thioxo-4-oxazolidinones la are dissolved in an inert solvent such as methylene chloride, tetrahydrofuran (THF), ethanol or benzene and treated with the hydrazine (Q=NR11), hydroxylamine (Q=O) or primary amine (Q=direct bond) sometimes used in excess, at temperatures from 0°C to 80°C. Acid salts of the hydrazine, hydroxylamine or amine such as dimethylhydrazine hydrochloride and hydroxylamine hydrochloride may also be used, and in these cases an equivalent of additional base is
necessary. Triethylamine, N, N-diisopropylethylamine and other tertiary amine bases are preferred.
The products lc can be isolated by evaporation of the solvent and dissolving the residue in a water- immiscible solvent such as ether. This solution may then be washed with mineral acid, water, and brine, and dried. Evaporation of the solvent followed by
crystallization or chromatography affords the purified products lc.
The hydrazines of Formula 7 (Q=NR11) are
commercially available or can be prepared by methods referenced above for the preparation of hydrazines 3. The preparation of the hydroxylamines like 7 (Q=O) can also be accomplished by methods known in the art. See, for example, Castellino, A. J., et al. J. Org. Chem . 1984, 49, 1348; Murray, R. W., et al. Synthetic Comm . 1989, 19, 3509 and references cited therein; and
Baldol, C, et al. Synthesis 1988, 344.
Compounds of Formula Id wherein R58 is C(=O)R13,
C(=O)OR13, or C(=O)NR13R30 and R30 is not hydrogen, can be prepared by treating compounds of Formula le with the appropriate acylating agent of Formula 8 as set forth in Equation 5.
Equation 5
In Equation 5, the group X in the compounds of Formula 8 may be a halogen, acetate, or other moiety known to be a leaving group in acylation reactions.
Chlorine is the most commonly used leaving group X.
For cases in which X=Cl, the compound of Formula 8 is an acid chloride, chloroformate, or carbamoyl chloride, The iminooxazolidinones of Formula Ie are dissolved in an inert solvent such as methylene chloride,
tetrahydrofuran (THF), or benzene and treated with 8 and a base at a temperature from 0°C to 100°C.
Triethylamine, N, N-diisopropylethylamine, and other tertiary amine bases are preferred.
The products of Formula Id can be isolated by evaporation of the solvent and dissolving the residue in a water-immiscible solvent such as ether. This solution may be washed with a dilute aqueous mineral acid, water, and brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the purified products.
Oxazolidinones of Formula If can be synthesized by reacting a compound of Formula Ie with an isocyanate as described in Equation 6 below.
Equation 6
The iminooxazolidinones of Formula Ie are dissolved in an inert solvent such as toluene, THF, acetonitrile, or 1,2-dichloroethane and treated with an isocyanate at temperatures from 0°C to 50°C. The products of Formula If can be isolated by evaporation of the solvent, and dissolving the residue in a water-immiscible solvent such as methylene chloride. This solution may be washed with dilute aqueous mineral acid, water, brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the products of Formula If.
Specific compounds that can be made by this
invention are described in the Examples and Tables which follow. These are intended to be only exemplary, and are not all-inclusive.
The following are a list of abbreviations and their definitions used in the Tables and Examples which follow. Unless indicated otherwise, alkyl, alkenyl, and alkynyl radicals are the normal isomers. The numbering system for heterocyclic groups is defined in the following way. First, hetero atoms contained in the ring are given the lowest possible numbers using the accepted rules of heterocycle numbering. Then, the point of attachment of the radical is the position assigned the highest priority. For example, the attached group at C-3 in 6-MeOC(=O)-3-pyridyl is higher priority than the MeOC(=O) substituent.
Ac = acetyl
Me = methyl
Et = ethyl
Pr = propyl
Bu = butyl
Bzl = benzyl
BzlO = benzyloxy
c = cyclo
OAc = acetate
CN = cyano
NO2 = nitro
SO2 = sulfonyl
S(O) = sulfinyl
PhO = phenoxy
BuO = butoxy
PrO = propoxy EXAMPLE 1
Preparation of methyl 2-hydroxy-2-methyldecanoate 2-Decanone (10 mL, 52.8 mmol) was dissolved in dry methylene chloride (100 mL), treated at room
temperature with zinc iodide (0.5 g, 1.57 mmol) and then trimethylsilyl cyanide (7.74 mL, 58.0 mmol) was added dropwise. The mixture was stirred at room temperature overnight. The resulting yellow solution was then washed with saturated aqueous NaHCO3 (1 × 100 mL), water (3 × 100 mL) and brine (100 mL). The organic phase was dried (MgSO4), and evaporated to give an orange oil. The resulting, crude trimethylsilyl cyanohydrin (14.9 g) was used in the following step.
All 14.9 g of the crude trimethylsilyl cyanohydrin were dissolved in methanol (200 mL) and cooled to
-78°C. Hydrogen chloride gas was introduced while maintaining a temperature of -30°C or less. When the solution became saturated as evidenced by a drop in temperature, the gas flow was halted. The solution was warmed to 0°C and allowed to stand at 0°C overnight. The reaction mixture was evaporated to a white solid, and the solid was washed with ether and dried. The iminoether hydrochloride was converted to methyl
2-hydroxy-2-methyldecanoate by dissolving in water (200 mL) and steam heating for 10 minutes. The aqueous solution was extracted with ether (2 × 150 mL) and the combined extractions were dried (MgSO4), and evaporated resulting in 8.2 g of the title compound as a colorless oil. 1H NMR (CDCl3, 200 MHz): δ 3.78 (s, 3H, OMe), 3.1 (s, 1H, OH), 1.4 (s, 3H, CH3), 1.26 (s, 10H), 0.9 (t, 3H).
EXAMPLE 2
Preparation of 5-n-octyl-5-methyl-3- (phenylamino)-2,4-oxazolidinedione Methyl 2-hydroxy-2-methyldecanoate (8.3 g,
38.4 mmol) was dissolved in 1-chlorobutane (100 mL), treated with 1,1'-carbonyldiimidazole (11.2 g,
69.1 mmol), and stirred overnight at room temperature. The mixture was filtered and the filtrate was washed with water (3 × 100 mL) and brine (100 mL). The organic phase was dried (MgSO4), and evaporated to a colorless oil (11.3 g). The resulting crude acyl imidazole (5.2 g, 16.6 mmol) was dissolved in 1-chlorobutane (75 mL) and treated sequentially with phenylhydrazine (2.5 mL, 24.9 mmol) and HOAc (1.4 mL,
24.8 mmol). The mixture was stirred overnight at room temperature and then washed with water (3 × 100 mL) and brine. The organic phase was dried (MgSO4), and evaporated to an orange oil. The title compound was obtained as a white solid (1.87 g, mp 63°C) after two recrystallizations from hexanes. 1H NMR (CDCl3, 200
MHz): δ 7.25 (m, 2H), 7.02 (t, 1H), 6.8 (d, 2H), 6.02 (s, 1H, NH), 1.98 (m, 2H), 1.6 (s, 3H, CH3), 1.26 (2, 12H), 0.88 (t, 3H).
EXAMPLE 3
Preparation of ethyl 2-(2-fluoro-6- phenoxy-3-pyridyl)-lactate
To a stirred solution of lithium diisopropylamide (40 mL, 2 M, 80 mmol) in tetrahydrofuran (20 mL) at -70°C under nitrogen, a solution of 2-fluoro-6-phenoxypyridine (13.56 g, 71.7 mmol) in tetrahydrofuran
(10 mL) was added dropwise, keeping the reaction solution temperature below -60°C. After the addition was completed, the solution was further stirred at -70°C for 1 h. Ethyl pyruvate (9.15 g, 78.8 mmol) in tetrahydrofuran (5 mL) was added dropwise, keeping the reaction temperature below -60°C. After the addition, the cool bath was removed and the reaction solution was stirred at ambient temperature. When the reaction solution temperature reached -10°C, the reaction mixture was poured into water (150 mL). The aqueous layer was extracted with EtOAc (3 × 100 mL). The combined organic layers were washed with water
(100 mL), dried (MgSO4), and filtered. The solvent was removed in vacuo to afford a residue which was purified by silica gel chromatography (EtOAc/hexane = 1/2) to afford an oil which upon standing turned into a wax (10 g, 45%) 1H NMR (CDCl3) δ 1.25 (3H, t, J=6.5 Hz), 1.82 (3H, 5), 4.0 (1H, s), 4.20 (2H, q, J=6.5 Hz), 6.72 (1H, d, J=9 Hz), 7.15-7.55 (5H, m), 7.97 (1H, t, J=9 Hz).
EXAMPLE 4
Preparation of 5-(2-fluoro-6-phenoxy-3-pyridyl))-5- methyl-3-(phenylamino)-2,4-oxazolidinedione
To a solution of ethyl 2-(2-fluoro-6-phenoxy-3-pyridyl) lactate (2 g, 6.56 mmol) in anhydrous dichloromethane (40 mL) at room temperature, was added
carbonyldiimidazole (1.6 g, 9.88 mmol). The mixture was stirred overnight at room temperature and was then poured into water (150 mL). The aqueous layer was extracted with EtOAc (3 × 50 mL). The combined organic layers were washed with water, dried (MgSO4) and filtered, and the solvent removed in vacuo to afford an oil. This oil was dissolved in dichloromethane (20 mL) and HOAc (0.6 g, 10 mmol) and phenylhydrazine (0.78 g, 7.2 mmol) were added. The mixture was stirred at room temperature overnight and was poured into dilute HCl (6N, 100 mL). The aqueous layer was extracted with EtOAc (3 × 50 mL). The combined organic extracts were washed with water (100 ml) and dried (MgSO4). The solvent was removed in vacuo to afford a residue which was recrystallized from 1-chlorobutane to afford the title compound (1.9 g, 75% yield) as a white solid, mp 175°C. 1H NMR (CDCl3) δ 1.85 (3H, 5), 5.85 (1H, 5), 6.50-7.85 (12H, m). EXAMPLE 5
Preparation of 5-methyl-3-(phenylamino)-5-[3- (phenoxypropyl)]-2,4-oxazolidinedione 1,1'-Carbonyldiimidazole (0.96 g, 5.9 mmol) and ethyl 2-(3-phenoxy-1-propyl) lactate (1.0 g, 3.9 mmol) were dissolved in dichloromethane (10 mL). The
reaction solution was stirred at room temperature overnight and was then added to water (20 mL). The aqueous layer was extracted with EtOAc (3 × 50 mL). The combined organic layers were washed with water
(50 mL), dried (MgSO4) and filtered. The solvent was removed in vacuo to afford an oil which was dissolved in dichloromethane (20 mL). Acetic acid (4.7 g,
7.8 mmol) and phenylhydrazine (0.62 g, 5.9 mmol) were added. The reaction mixture was stirred at room temperature overnight and then poured into dilute HCl (1N, 50 mL). The aqueous layer was extracted with EtOAc (3 × 50 mL). The combined organic layers were washed with water (50 mL), dried (MgSO4) and filtered. The solvent was removed in vacuo to afford a residue which was recrystallized from 1-chlorobutane to afford a white solid (1.1 g, 83%) mp 114-5°C, 1H NMR (CDCl3) δ 1.70 (3H,5), 1.78-2.22 (4H, m), 3.98 (2H, t, J=6.5 Hz), 6.10 (1H, 5), 6.80-7.38 (10H, m).
EXAMPLE 6
Preparation of 2-[4-(tert-butyldimethylsilyloxy)phenyl]lactic acid
A round-bottom flask equipped with a magnetic stirbar, addition funnel, condenser and a N2 inlet was charged with Mg (90 mg) and the apparatus was dried under a N2 flow. Once cooled to room temperature, THF (1 mL) was added to the flask along with I2 (1 mg) and BrCH2CH2Br(2 drops). To the flask was then added 2 mL of a solution of 4-t-butyldimethylsilyloxy bromobenzene (1.0 g, 3.48 mmol) in THF (12 mL) and the I2 color discharged within 3-5 min. The remainder of the halide solution was added over a 5 min period and the
resulting mixture was stirred while heated at reflux for 4 h. The flask was cooled to 0°C, sodium pyruvate (420 mg, 3.83 mmol) was added in a single portion, and the resulting mixture was stirred vigorously overnight. The resulting solid mass was broken-up, suspended in Et2O (50 mL) and collected by vacuum filtration. The filter cake was washed with Et2O (2 × 25 mL), allowed to air dry and was then transferred to a flask and suspended in H2O (10 mL). After stirring for 15 min, con HCl (0.7 ml) was added along with EtOAc (25 ml) and the mixture was stirred until the phases cleared. The phases were separated and the aqueous phase was
extracted with EtOAc (2 × 25 mL). All organic phases were washed with H2O (2 × 20 mL), brine (2 × 25 mL), combined and dried (Na2SO4). Solvents were evaporated in vacuo to afford the desired hydroxyacid as a light yellow, dense oil, 660 mg (66%). 1H NMR (CDCl3) : δ 7.45-7.4 (d, 2H), 6.84-6.8 (d, 2H), 1.81 (s, 3H), 0.98 (s, 9H), 0.19 (s, 6H).
EXAMPLE 7
Preparation of Ethyl 2- [4- ( tertbutyldimethylsilyloxy)]-phenyllactate To a solution of 2-[4-(tert-butyldimethylsilyloxy)]phenyllactatic acid (2.14 g, 7.23 mmol) in dry DMF was added N, N-diisopropylethylamine (2.26 g, 14.46 mmol) and Etl (2.26 g, 14.46 mmol) and the resulting mixture was stirred at room temperature overnight. The mixture was diluted with Et2O (100 mL) and washed with H2O (4 × 40 mL), 1N aq. HCl (2 ×
10 mL), saturated aq. NaHC03 (1 × 30 mL) and brine (1 × 50 mL). The aqueous washes were extracted with Et2O (1 × 50 mL) and the Et2O phases were combined, dried
(MgSO4) and concentrated in vacuo to afford a clear yellow oil, 2.32 g. Product was purified by column chromatography on SiO2 to yield the lactate ester as a clear, colorless oil, 1.36 g. 1H NMR (CDCl3) : δ 7.39 (d, 2H), 6.80 (d, 2H), 4.24-4.20 (m, 2H), 3.74 (s, 1H), 1.75 (s, 3H), 1.25 (t, 3H), 0.98 (s, 9H), 0.19 (s, 6H).
EXAMPLE 8
Preparation of 5-(4-t-butyldimethylsilyloxyphenyl)5-methyl-3-(phenylamino)-2,4-oxazolidinedione
To a solution of ethyl 2-[4-tert-butyldimethylsilyloxy)]phenyllactate (7.25 g, 23.3 mmol) in BuCl (65 mL) was added 1,1'-carbonyldiimidazole (6.79 g, 42 mmol) and the resulting mixture was heated at reflux for 3 h. TLC indicated all starting material had been consumed. The mixture was diluted with BuCl (100 mL) and washed with H2O (3 × 50 mL) and brine (1 × 75 mL). The aqueous washes were extracted with BuCl (1 × 75 mL) and the organics were combined and dried (MgSO4).
Solvent was removed in vacuo to yield an oil (9.14 g) which was dissolved in BuCl (65 mL), treated with
PhNHNH2 (4.54 g, 42 mmol) and HOAc (2.5 mL, 42 mmol) and stirred at room temperature overnight. The
solution was then diluted with ether (250 mL) and washed with IN aqueous HCl (2 × 100 mL), saturated aqueous NaHCO3 (2 × 100 mL), and brine (2 × 100 mL). The aqueous washes were extracted with ether (1 ×
100 mL) and the organics were combined and dried
(MgSO4). Evaporation of solvent in vacuo yielded an orange solid which was washed with hot hexane to afford a faint- yellow solid, 7.07 g, (74%), m.p. 150-151°C.1H NMR (CDCl3) : δ 7.43 (d, 2H), 7.26-7.23 (m, 2H), 7.05-7.00 (t, 1H), 6.88 (d, 2H), 6.73 (d, 2H), 6.04 (s, 1H), 1.97 (s, 3H), 0.98 (s, 3H), 0.21 (s, 6H).
EXAMPLE 9
Preparation of 5-(4-hydroxyphenyl)-5-methyl- 3-(phenylamino)-2,4-oxazolidinedione To a solution of the 5-(4-t-butyldimethylsilyloxyphenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione (3.75 g, 9.1 mmol) in CH3CN (50 mL) was added 47% aqueous HF (1 mL) and the resulting mixture was stirred overnight. Acid was quenched by the addition of saturated aqueous NaHCO3 (50 mL), diluted with H2O (30 mL) and extracted with Et20 (3 × 100 mL). The extracts were washed with brine (1 × 75 mL), combined and dried (MgSO4). Evaporation of solvents in vacuo yielded crude material as an oil which solidified upon standing (3.09 g), m.p. 171-174°C. IR (mineral oil): 3270, 3263, 1817, 1744 cm-1; 1H NMR (CDCl3) : δ 8.84 (s, 1H), 7.78 (s, 1H), 7.44 (d, 2H), 7.24 (t, 2H), 6.98-6.85 (m, 3H), 6.80 (d, 2H), 2.00 (s, 3H).
EXAMPLE 10
Preparation of 5-(4-cyanobenzolyloxy)- 5-methyl-3-(phenylamino)-2,4-oxazolidinedione
A flask containing 5-(4-hydroxyphenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione (800 mg, 2.68 mmol) in THF (14 mL) under an N2 atmosphere was cooled to 0°C and to the stirred solution was sequentially added N/.N-diisopropylethylamine (4.33 mg, 3.35 mmol) and 4-cyanobenzoyl chloride (465 mg, 3.35 mmol). The resulting mixture was stirred for 1.5 h at which time the reaction was complete as determined by TLC. The solution was diluted with Et2O (100 mL) and
sequentially washed with 1N aqueous HCl (2 × 30 mL) saturated aqueous NaHCO3 (1 × 50 mL) and brine (2 × 50 mL). The washes were extracted with Et2O (2 ×
50 mL) and the ether phases were combined and dried (MgSO4). Evaporation of solvents in vacuo afforded crude material as a tan-colored solid, 1.08 g.
Purification was effected by column chromatography on SiO2 (30 g) eluting with methylene chloride to return white solid, 950 mg, m.p. 180-182°C. 1H NMR (CDCl3): 8.34-8.30 (d, 2H), 7.86-7.82 (d), 7.74-7.7 (d, 2H); 7.34-7.23 (t, 4H), 7.06-7.02 (t, 1H), 6.78-6.74 (d, 2H) , 6.07 (s, 1H), 2.03 (s, 3H). The compounds illustrated below are subsets of compounds of Formula I referred to in Tables 1-45 which follow.
The groups R1-R59 and A, E, V, G, J, L, m, n, Q, T, W, Y, and Z are as defined in Formula I in the Summary of the Invention. Additional variables are used in the compounds and Tables and are:
R60, which is a structural component of some R19 groups, is R22, R22O, or R22R43N;
R61 and R62, which are the substituents on T, are each independently halogen, C1-C4 alkyl, C1-C4 alkoxy, trifluoromethyl, thiomethyl, or nitro; R63, which is a structural component of some G
groups, is R52 or R37;
E1, which is a structural component of some G
groups, is O, S, or NH;
p, which designates the size of a portion of some substituted R2 alkyl groups, is 1-18;
q, which designates the size of a portion of other substituted R2 alkyl groups, is 1-19; and r and t designate the length of some alkoxyalkyl R2 groups. The sum of r and t is 2-20.
TABLE 3 TABLE 4
Compounds of Formula I wherein Compounds of Formula I wherein W=O, W=O, R2=2-F-6-PhO-3-pyridinyl, R1=Me, and R2=2-F-6-PhO-3-pyridinyl R3=Ph, and R4=H
R1 R3 R4
H 2-Me-Ph H
Me 3-F-Ph H
Et 4-F-Ph H
n-butyl 3-Cl-Ph H
CF3 4-Me-Ph H
CF3CH2CH2CH2 PhCH2 H
cyclopropyl 3,4-diF-Ph H
cyclohexyl 4-(n-butyl)Ph H
CH2=CH 4-NO2-Ph H
CH2=CHCH2 2-cyano-Ph H
CO2CH3 3-CF3-Ph H
n-propyloxy-carbonyl 3-MeO-Ph H
PhCH2 4-(n-butoxy)Ph H
PhC(CH3)H 4-CF3O-Ph H
4'-F-Bzl 2-Me-3-Cl-Ph H
3'-Me-Bzl 2-Me-3-F-Ph H
4'-CF3-Bzl 2-F-3-Cl-Ph H
4'-MeO-Bzl 2,4-diMe-Ph H
4'-MeS-Bzl 2-methoxycarbonyl-Ph H
2-pyridyl H
4-Cl-2-pyridyl H
5-methyl-2-pyridyl H
4-methoxy-2-pyridyl H
2,3-diF-4-pyridyl H
5-pyrimidinyl H
3-pyridazyl H
Ph Me
Ph Ac TABLE 5 TABLE 6
Compounds of Formula I wherein Compounds of Formula I wherein W=S, W=S, R2=n-octyl, R3=Ph, R1=Me, and R2=n-octyl
and R4=H
R1 R3 R4
H 2-Me-Ph H
Me 4-F-Ph H
Et 3-Cl-Ph H
π-butyl 4-Me-Ph H
CF3 3-MeO-Ph H
cyclopropyl 4-CF3O-Ph H
CH2=CH 2-Me-3-Cl-Ph H
CO2CH3 2-F-3-Cl-Ph H
PhCH2 2, 4-diMe-Ph H
4'-F-Bzl Ph Me
3'-Me-Bzl Ph Ac
4'-MeO-Bzl
TABLE 7 TABLE 8
Compounds of Formula I wherein Compounds of Formula I wherein W=O, W=O, R2=n-octyl, R3=Ph, R1=Me, and R2=n-octyl
and R4=H
R1 R3 R4
H 2-Me-Ph H
Me 3-F-Ph H
Et 4-F-Ph H
n-butyl 3-Cl-Ph H
CF3 4-Me-Ph H
CF3CH2CH2CH2 PhCH2 H
cyclopropyl 3,4-diF-Ph H
cyclohexyl 4-(n-butyl)Ph H
CH2=CH 4-NO2-Ph H
CH2=CHCH2 2-cyano-Ph H
CO2CH3 3-CF3-Ph H
n-propyloxy-carbonyl 3-MeO-Ph H
PhCH2 4-(n-butoxy) Ph H
PhC(CH3)H 4-CF3O-Ph H
4'-F-Bzl 2-Me-3-Cl-Ph H
3'-Me-Bzl 2-Me-3-F-Ph H
4'-CF3-Bzl 2-F-3-Cl-Ph H
4'-MeO-Bzl 2,4-diMe-Ph H
4'-MeS-Bzl 2-methoxycarbonyl-Ph H
2-pyridyl H
4-Cl-2-pyridyl H
5-methyl-2-pyridyl H
4-methoxy-2-pyridyl H
2,3-diF-4-pyridyl H
5-pyrimidinyl H
3-pyridazyl H
Ph Me
Ph Ac TABLE 9 TABLE 10
Compounds of Formula I wherein Compounds of Formula I wherein W=S, W=S, R2=4- (3-Cl-benzoyloxy)Ph, R1=Me, and R2=4-(3-Cl-benzoyloxy)Ph R3=Ph, and R4=H
R1 R3 R4
H 2-Me-Ph H
Me 4-F-Ph H
Et 3-Cl-Ph H
n-butyl 4-Me-Ph H
CF3 3-MeO-Ph H
cyclopropyl 4-CF3O-Ph H
CH2=CH 2-Me-3-Cl-Ph H
CO2CH3 2-F-3-Cl-Ph H
PhCH2 2, 4-diMe-Ph H
4'-F-Bzl Ph Me
3'-Me-Bzl Ph Ac
4'-MeO-Bzl
TABLE 11 TABLE 12
Compounds of Formula I wherein Compounds of Formula I wherein W=O, R2=4-(3-Cl-benzoyloxy)Ph, W=O, R1=Me, and R2=4- (3-Cl-R3=Ph, and R4=H benzoyloxy)Ph
R1
H R3 R4
Me 2-Me-Ph H
Et 3-F-Ph H n-butyl 4-F-Ph H
CF3 3-Cl-Ph H
CF3CH2CH2CH2 4-Me-Ph H cyσlopropyl PhCH2 H cyclohexyl 3,4-diF-Ph H
CH2=CH 4-(n-butyl)Ph H
CH2=CHCH2 4-NO2-Ph H
CO2Me 2-cyano-Ph H n-propyloxy-carbonyl 3-CF3-Ph H
PhCH2 3-MeO-Ph H
PhC(CH3)H 4-(n-butoxy)Ph H
4'-F-Bzl 4-CF3O-Ph H
3'-Me-Bzl 2-Me-3-Cl-Ph H
4'-CF3-Bzl 2-Me-3-F-Ph H
4'-MeO-Bzl 2-F-3-Cl-Ph H
4'-MeS-Bzl 2,4-diMe-Ph H
2-methoxycarbonyl-Ph H
2-pyridyl H
4-Cl-2-pyridyl H
5-methyl-2-pyridyl H
4-methoxy-2-pyridyl H
2,3-diF-4-pyridyl H
5-pyrimidinyl H
3-pyridazyl H
Ph Me
Ph Ac TABLE 13 TABLE 14
Compounds of Formula I wherein Compounds of Formula I wherein R1=Me, R3=Ph, and R4=H W=N-O-R58, R1=Me, R2=2-F-6-PhO- 3-pyridinyl, R3=Ph, and R4=H
R2 W R58
2-F-6-PhO-3-pyridinyl N-OH n-octyl
n-octyl N-OH CH2=CHCH2
4- (3-Cl-benzoyloxy) Ph N-OH Bzl
2-F-6-PhO-3-pyridinyl N-OMe Ph
n-octyl N-OMe MeO2CCH2
4- (3-Cl-benzoyloxy) Ph N-OMe 4-F-Ph
2-F-6-PhO-3-pyridinyl N-OAc 4-Me-Ph
n-octyl N-OAc 4-MeO-Ph
4- (3-Cl-benzoyloxy) Ph N-OAc hexanoyl
2-F-6-PhO-3-pyridinyl N-O (C=O) OMe PhC=O
n-octyl N-O (C=O) OMe (4-Me-Ph)C=O
4- (3-Cl-benzoyloxy) Ph N-O (C=O) OMe PhCH2C=0
2-F-6-PhO-3-pyridinyl N-O (C=O) NHPh (4-MeO-Ph)CH2C=O
n-octyl N-O (C=O) NHPh (cyclohexyl) C=O
4- (3-Cl-benzoyloxy) Ph N-O (C=O) NHPh hexyloxycarbonyl
2-F-6-PhO-3-pyridinyl NH (cyclohexyl)OC-O
n-octyl NH PhOC=O
4- (3-Cl-benzoyloxy) Ph NH (4-Me-PhO)C=O
R58 R58 R11
(3-Cl-PhO)C=O 2-pyridinyl H PhCH2OC=O Ac H MeNHC (=O) n-hexanoyl H
(n-hexyl)NHC(=O) (cyclohexyl) C=O H
(cyclohexyl)NHC(=O) PhC=O H
(4-Me-Ph)NHC(=O) (4-Me-Ph)C=O H
(3-Cl-Ph)NHC(=O) (3-Cl-Ph)C=O H PhCH2NHC (=O) PhCH2C=O H Me2NC(=O) (4-MeO-Ph)CH2C=O H PhN(Me)C(=O) MeOC=O H n-hexyloxycarbonyl H
TABLE 15 (cyclohexyl) OC=O H Compounds of Formula I wherein PhOC=O H W=N-NR11R58, R1=Me, R2=2-F-6-PhO- (4-Me-PhO)C=O H
3-pyridinyl, R3=Ph, and R4=H (3-Cl-PhO)C=O H
R58 R 11 PhCH2OC=O H
H H MeNHC(=O) H
Me H (n-hexyl)NHC(=O) H t-butyl H (cyclohexyl) NHC(=O) H n-octyl H PhNHC (=O) H
CH2=CHCH2 H (4-Me-Ph)NHC(=O) H
Bzl H (3-Cl-Ph)NHC(=O) H
4-Cl-Bzl H PhCH2NHC (=O) H
Ph H Me2NC (=O) H
MeO2CCH2 H
4-F-Ph H
4-Me-Ph H
4-MeO-Ph H
2-NO2-Ph H R58 R11 R58
PhN (Me) C (=O) H (3-Cl-Ph) C=O
Me Me PhCH2C=O
MeNHC(=O) Me (4-MeO-Ph) CH2C=O
PhNHC (=O) Me hexyloxycarbonyl
MeOC(=O) Me (cyclohexyl)OC=O
PhOC=O Me PhOC=O
PhC=O Me (4-Me-PhO)C=O
Ac Me (3-Cl-Ph)C=O
-CH2CH2CH2CH2CH2- PhCH2C=O
-CH2CH2OCH2CH2- (4-MeO-Ph) CH2C=O
-CH2CH2N(Me) CH2CH2- hexyloxycarbonyl
(cyclohexyl)OC=O
TABLE 16 PhOC=O
Compounds of Formula I wherein (4-Me-PhO) C=O
W=N-R58, R1=Me, R2=2-F-6-PhO-3- MeNHC (=O)
pyridinyl, R3=Ph, and R4=H (n-hexyl)NHC(=O)
R58 (cyclohexyl) NHC(=O)
Me (4-Me-Ph) NHC(=O)
Et (3-Cl-Ph)NHC(=O) n-octyl PhCH2NHC(=O)
CH2=CHCH2 Me2NC(=O)
Bzl PhN(Me)C(=O)
4-Cl-Bzl
Ph
MeO2CCH2
4-F-Ph
4-Me-Ph
4-MeO-Ph
3-pyridinyl
n-hexanoyl
(cyclohexyl) C=O
PhC=O
(4-Me-Ph) C=O TABLE 17 3-(PhSO2)propyl
Compounds of Formula I wherein (2,6-diMe-PhSO2)(CH2)4 W=O, R1=Me, R3=Ph, R4=H, and: 8-(PhS(O))octyl
R2 7-(4-F-PhS(O))heptyl heptyl (3-Me-PhS(O))CH2CH2
octyl 5-(3-BuO-PhS(O))pentyl decyl (4-pyridyl)CH2
undecyl 8-(2,6-diMe-4-pyridyl)octyl eicosanyl 6-(4-pyridyloxy)hexyl
3-Me-hexyl 3-(2-thienyl)propyl
9,9,9-triF-nonyl 8-(2-pyrimidinyl)octyl 2,4-diCl-octyl 10-(2-furanyl)decyl
8-(c-hexyl)octyl 3-(1-naphthalenyl)propyl 6-Ph-octyl 5-(2-pyrimidinyloxy)pentyl 4-(3-CF3-Ph)Bu 8-(1-naphthalenyloxy)octyl 8-(4-F3CO-Ph)octyl 3-(2-tetrahydropyranyl)propyl 10-(2,4-diF-Ph)decyl 8-(2-tetrahydropyranyloxy) 4-(4-Cl-Ph)Bu octyl
5-(4-Et-Ph)pentyl 2-octenyl
8-(3-propyloxy-Ph)octyl 2-deσenyl
6-(4-(4-F-PhO)Ph)hexyl 4-octenyl
7-(3-(4-Et-PhO)Ph)heptyl Me2N(CH2)6
2-CN-propyl 3-EtS-2-propenyl
3-NO2-propyl 4-c-hexyloxy-2-butenyl 2-MeS-hexyl 6-hydroxy-4-hexenyl
2-(MeS(O))Et 3-(MeC(=O)O)-2-propenyl 2-(EtSO2)Et 3-(4-pyridyl)-2-propenyl EtOC(=O) (CH2)4 5-EtO-2-pentenyl
3-hydroxypropyl 3-CF3-2-propenyl
HO2C(CH2)7 3-Ph-2-propenyl
8-(MeSO3)octyl 4-PhO-2-butenyl
(PhSO3)CH2CH2 7-octynyl
(4-Et-PhSO3) (CH2)4 2-hydroxy-4-butynyl
(Me3N+) (CH2)4-I- 2-EtO-6-heptynyl
(H3N+) (CH2)4Cl- 3-c-hexenyl
MeC(=O)NMe(CH2)4 (CH2CH2OCH2CH2) CH (CH2CH2SCH2CH2) CH TABLE 18
(CH2CH2SO2CH2CH2) CH Compounds of Formula Ig PhOCH2CH2CH2 wherein:
PhO(CH2) 4 q R60
PhO(CH2)5 5 Me
PhO(CH2)8 6 Ph
(2-F-PhO)(CH2)3 8 4-CF3-Ph
(2-Me-PhO)(CH2)3 5 2,4-diCl-Ph
PhS(CH2)3 1 4-F-Ph
(3-CF3-PhS) (CH2)7 2 4-Et-Ph
(4-Et-PhS) (CH2)5 3 3-EtO-Ph
(3-(4-Cl-PhO)PhS)(CH2)7 4 4-(4-F-PhO)Ph
(4-(4-EtO-PhO) PhS)CH2)7 3 4-(3-Et-PhO)Ph FCH2CH2O(CH2)6 1 4-(3-BuO-PhO)Ph
(c-hexyloxy) (CH2)6 8 MeO
(CH2=CHCH2O) (CH2)7 6 PhO
CH≡CCH2OCH2CH2 2 4-F3CO-PhO
CH(=O)CH2CH2 4 3,5-diCl-Ph0 MeC(=O)CH2CH2CH2 6 4-F-PhO
MeC(=NMe)CH2 8 4-Et-PhO
MeC(=NOMe)CH2CH2CH2 2 4-EtO-PhO
MeC(=NNHPh)CH2CH2CH2 1 4-(4-F-PhO)PhO
(CH2CH2N(hexyl)CH2CH2)CH 2 4-(3-Et-PhO)PhO
(CH2CH2N(MeO2C)CH2CH2)CH 3 MeNH
(CH2CH2N[C(=O)NHPh]CH2CH2)CH 4 Me2N
1 PhNH
5 PhN (Me)
6 4-CF3-PhNH
3 2,4-diCl-PhNH
8 4-Et-PhNH
4 4-(4-F-PhO)PhNH TABLE 19 TABLE 20
Compounds of Formula Ih Compounds of Formula Ii wherein : wherein :
p A L t r R21
1 O H 2 1 MeS
4 O Et 3 1 FCH2CH2O
2 O Bzl 1 1 c-hexyloxy
5 O Ph 1 1 EtOC(=O)
6 O 4-F-Ph 1 2 OH
7 O 3,5-diMe-Ph 3 1 MeC (=O)O
8 O 4-pyridyl 2 2 Ph0C(=O)O
4 O MeC(=O) 1 3 MeNHC(=O)O
2 O PhC(=O) 2 1 PhNH
6 O 4-pyridyl-C(=O) 3 2 4-pyridyl
4 O BuOC(=O) 1 3 4-pyridyloxy
2 O PhOC(=O) 2 2 2-pyrimidyl
2 O MeNHC(=O) 2 1 c-hexyl
5 O PhNHC(=O) 1 2 EtO
1 O (2-pyridyl)NHC(=O) 1 1 Ph
4 NH Me 2 2 PhO
1 NH Bzl 6 1 H
8 NH Ph 3 5 CF3O
2 NH 4-pyridyl
1 NH EtC(=O) TABLE 21
4 NH PhC(=O) Compounds of Formula Ij
5 NH (4-pyridyl)C(=O) wherein:
6 NH MeOC(=O) Z
3 NH PhOC(=O) 2-Cl-3,5-diF-PhO
1 NH MeNHC(=O) 2,4,6-triBr-PhO
2 N-Me Me 2,3,4-triCl-PhO
3 N-Me Ph 2,3,5-triF-PhO
4 N-Ph Ph 2-CN-PhO
5 --- H 4-CN-PhO
1 --- Me 4-(pentyl)PhO
2 --- Ph 3-(3-hexyl)PhO
2-(octyl)PhO 2-(1-bromoethyl)PhO 3-(2,4-diMe¬3-(CF3CH2)PhO pentyloxycarbonyl)PhO4-(5-Cl-3-hexyl)PhO 3- (2-Cl-PhO)PhO
3-(2-Cl-octyl)PhO 4- (3-Br-PhO)PhO
2-(pentyloxy)PhO 4-(4-F-PhO)PhO
3-(hexyloxy)PhO 3- (3, 5-diCl-PhO)PhO4-(octyloxy)PhO 3-(2-Me-PhO)PhO
4-(CF3O)PhO 3- (4-t-Bu-PhO)PhO
3-(CF3CH2O)PhO 3-(4-EtO-PhO)PhO
2-(5-Cl-2-hexyloxy)PhO 4-(3-CF3-PhO)PhO
2-methanesulfonyl-PhO 3-(2-MeS-PhO)PhO
3-(4-octylsulfonyl)PhO 3-(4-N02-PhO)PhO
4-(2-propylsulfonyl)PhO methoxyethoxymethoxy2-(EtOCH2) PhO ethoxyethoxymethoxy 3-(2-BuOCH2)PhO hexyloxyethoxymethoxy4-(Et2CHOCH2CH2) PhO (2-Cl-Ph) CH2OCH2O
2-(methoxyethoxy) PhO (4-F-Ph)CH2OCH2O
2-((Me)2CHOCH2O)PhO (3, 5-diMe-Ph) CH2OCH2O4-(hexyloxymethoxy)-PhO (2-CF3-Ph)CH2OCH2O 2-(EtS)-PhO (2-propyloxy-Ph)CH2OCH2O3-(3-pentylthio)PhO cyclohexyloxy
4-(octylthio)PhO (Z)-PhCH=CH
4-(2-propenyl)PhO (2-Cl-Ph)CH=CH
3-(4-hexenyl)PhO (4-F-Ph) CH=CH
3-(1-Me-3-heptenyl)PhO (2-Me-Ph) CH=CH
2-(2-Br-2-propenyl)PhO (4-i-Pr-Ph) CH=CH
3-(3-F-2-pentenyl)PhO (Z)-(3-MeO2C-Ph)CH-CH 4-(4-Br-5-octenyl)PhO (Z) -(4-EtO-Ph)CH-CH 3-(2-propynyl)PhO (3-(2-Br-PhO)Ph)CH=CH3-(2-pentynyl)PhO (Z)-(4-(4-F-PhO)Ph)CH=CH 4-(2-methyl-4-hexynyl)PhO (4-(2-Me-PhO)Ph)CH=CH2-(hydroxycarbonyl)PhO (3-(3-i-PrO-PhO)Ph)CH=CH 4-(hydroxycarbonyl)PhO (3-(4-MeS-PhO)Ph)CH=CH 2- (ethoxy carbonyl)PhO
3-(t-butoxycarbonyl)PhO
4-(hexyloxycarbonyl)PhO TABLE 22 3-(4-hexenyl)PhO
Compounds of Formula Ik 3-(1-Me-3-heptenyl)PhO wherein : 2-(2-Br-2-propenyl)PhO
Z 3-(3-F-2-pentenyl)PhO
2- Cl-3,5-diF-PhO 4-(4-Br-5-octenyl)PhO
2,4,6-triBr-PhO 3-(2-propynyl)PhO
2,3,4-triCl-PhO 3-(2-pentynyl)PhO
2,3,5-triF-PhO 4-(2-methyl-4-hexynyl)PhO
2- CN-PhO 2-(hydroxycarbonyl)PhO
4- CN-PhO 4-(hydroxycarbonyl)PhO
4-(pentyl)PhO 2-(ethoxycarbonyl)PhO
3-(3-hexyl)PhO 3-(t-butoxycarbonyl)PhO
2-(octyl)PhO 4-(hexyloxycarbonyl)PhO
2-(1-bromoethyl)PhO 3-(2,4-diMe¬
3-(CF3CH2)PhO pentyloxycarbonyl)PhO
4- (5-Cl-3-hexyl)PhO 3-(2-Cl-PhO)PhO
3- (2-Cl-octyl)PhO 4-(3-Br-PhO)PhO
2- (pentyloxy) PhO 4-(4-F-PhO)PhO
3- (hexyloxy) PhO 3-(3,5-diCl-PhO)PhO
4- (oσtyloxy)PhO 3-(2-Me-PhO)PhO
4- (CF3O)PhO 3-(4-t-Bu-PhO)PhO
3- (CF3CH20)PhO 3-(4-EtO-PhO)PhO
2- (5-Cl-2-hexyloxy) PhO 4-(3-CF3-PhO)PhO
2-methanesulfonyl-PhO 3-(2-MeS-PhO)PhO
3-(4-octylsulfonyl)PhO 3-(4-NO2-PhO)PhO
4-(2-propylsulfonyl)PhO methoxyethoxymethoxy
2-(EtOCH2)PhO ethoxyethoxymethoxy
3-(2-BuOCH2)PhO hexyloxyethoxymethoxy
4-(Et2CHOCH2CH2)PhO (2-Cl-Ph)CH2OCH2O
2-(MeOCH2CH2)PhO (4-F-Ph)CH2OCH2O
2-((Me)2CHOCH2O)PhO cyclopentyloxy
4-(hexyloxymethoxy)-PhO σyclohexyloxy
2-(EtS)-PhO (Z)-PhCH=CH
3-(3-pentylthio)PhO (2-Cl-Ph) CH=CH
4-(octylthio)PhO (4-F-Ph)CH=CH
4-(2-propenyl)PhO TABLE 23 4-C(=O)OR57 2-pyridyl
Compounds of Formula 11 3-C(=O)OR57 3-pyridyl wherein: 4-C(=O)OR57 4-pyridyl
R57
Z 3-C(=O)OR57 3,4-diBr-2-
4-C(=O)OR57 Me pyridyl
4-C(=O)OR57 n-Bu 4-C(=O)OR57 2-Me-5-pyridyl
3-C(=O)OR57 CH3(CH2)11 4-C(=O)OR57 2-furanyl
3-C(=O)OR57 c-Pr 4-C(=O)OR57 3-furanyl
3-C(=O)OR57 CF3 4-C(=O)OR57 5-Br-2-furanyl
4-C(=O)OR57 CF3CH2 4-C(=O)OR57 4,5-diMe-2-
3-C(=O)OR57 H2C=CHCH2 furanyl
4-C(=O)OR57 (Z)-ClCH2- 4-C(=O)OR57 2-thienyl
CH=CHCH2 4-C(=O)OR57 3-thienyl
4-C(=O)OR57 2-propynyl 3-C(=O)OR57 5-Br-2-thienyl
3-C(=O)OR57 CH3CH2C≡C(CH2)2 3-C(=O)OR57 4-methyl-2-
4-C(=O)OR57 3-CF3-Ph thienyl
4-C(=O)OR57 2-F-Ph 4-C(=S)0R57 Me
4-C(=O)OR57 3,5-diCl-Ph 4-C(=S)OR57 Bu
3-C(=O)OR57 3-(MeO2C)Ph 3-C(=S)OR57 CH3CH2CH2CH (Et)
4-C(=O)OR57 3-Et-Ph 3-C(=S)OR57 4-Br-2-CF3-3¬
3-C(=O)OR57 4-t-Bu-Ph thienyl
3-C(=O)OR57 2-(propyloxy)- 4-C(=S)OR57 4,5-diBr-3-
Ph thienyl
4-C(=O)OR57 3-(2-F-PhO)Ph 3-C(=S)OR57 5-Br-2-thienyl
4-C(=O)OR57 4-(3-Br-PhO)Ph 3-C(=S)OR57 4-methyl-2-
3-C(=O)OR57 4-(4-Et-PhO)Ph thienyl
4-C(=O)OR57 3-(3-MeO-PhO)Ph 3-R57(C=O)O CH3
3-C(=O)OR57 3-(2-CF3-PhO)Ph 3-R57(C=S)O CH3
4-C(=O)OR57 5-CF3-1- 3-R57(C=O)O i-Pr
naphthalenyl 3-R57(C=O)O CH(CH3)CH2CH¬
4-C(=O)OR57 4-Cl-6-Br-1- CH2CH3
naphthalenyl 3-R57(C=O)O 3-Et-4-Pr-hexyl
4-C(=O)OR57 4-(2-F-Ph)-1- 3-R57 (C=O)O cyclohexyl
naphthalenyl 4-R57(C=O)O cyclohexyl
4-C(=O)OR57 4-(3-MeO-Ph)-2- 4-R57(C=S)O cyclohexyl
naphthalenyl 4-R57(C=O)O BrCH2 -R57 (C=O)O 6-Cl-OCtyl 4-R57(C=S)O 2-pyridyl-R57(C=O)O 2-propenyl 3-R57(C=O)O 3-pyridyl-R57(C=O)O H2C=CH 3-R57(C=O)O 4-pyridyl-R57 (C=O)O H2C=CH 4-R57(C=O)O 5-CF3-2-pyridyl-R57(C=S)O H2C=CH 4-R57(C=S)O 5-CF3-2-pyridyl-R57 (C=O) O ClCH2C(Me)=CH- 3-R57(C=O)O 3-F-2-pyridyl
CH2CH2 4-R57(C=O)O 2-furanyl-R57(C=O)O ethynyl 3-R57(C=S)O 2-furanyl-R57 (C=O)O 4-Me-2-hexynyl 3-R57 (C=O)O 3-furanyl-R57 (C=O) O 3-Br-2-propynyl 3-R57(C=O)O 3,5-diMe-2--R57(C=O)O Ph furanyl-R57(C=S)O Ph 4-R57(C=O)O 2-thienyl-R57(C=O)O Ph 4-R57(C=O)O 2-thienyl-R57(C=O)O 3-Cl-Ph 4-R57(C=O)O 3-thienyl-R57 (C=O)O 4-Br-Ph 3-R57(C=O)O 4-Cl-2-thienyl-R57(C=O)O 3,5-di-Cl-Ph 3-R57(C=O)O 5-F-3-thienyl-R57(C=O)O 4-NO2-Ph 3-R57 (CO) O 5-propyloxy-3¬-R57(C=O)O 3,5-diMe-Ph thienyl-R57(C=O)O 4-CN-Ph 3-R57O(C=O)O CH3
-R57(C=S)O 4-CN-Ph 3-R57O(C=S)O CH3
-R57(C=O)O 3-(PhO)Ph 3-R57O(C=O)O i-Pr
-R57(C=O)O 4-(PhO)Ph 3-R57O (C-O) O CH(CH3)CH2CH¬-R57(C=O)O 3-(3-Cl-PhO)Ph CH2CH3-R57(C=O)O 4-(3-Et-PhO)Ph 3-R57O(C=O)O 3-Et-4-Pr-hexyl-R57(C=S)O 4-(3-Et-PhO)Ph 3-R57O(C=O)O cyclohexyl-R57(C=O)O 4-(3-CF3-PhO)Ph 3-R57O(C=S)O cyclohexyl-R57(C=O)O 2-naphthalenyl 4-R57O(C=O)O cyclohexyl-R57(C=S)O 2-naphthalenyl 4-R57O(C=O)O cyclohexyl-R57(C=O)O 1-naphthalenyl 4-R57O(C=O)O BrCH2CH2-R57(C=O)O 6-t-butyl-2- 4-R57O(C=O)O 6-Cl-octyl
naphthalenyl 4-R57O(C=O)O 2-propenyl-R57(C=O)O 3-MeS- 3-R57O (C=O) O H2C=CHCH2
naphthalenyl 3-R57O(C=S)O H2C=CHCH2-R57(C=O)O 5-PhO-2- 4-R57O(C=O)O H2C=CHCH2
naphthalenyl 4-R57O(C=S)O H2C=CHCH2-R57(C=O)O 2-pyridyl 4-R57O(C=O)O ClCH2C(Me)=CH- 4-R57O (C=O) O 5-PhO-2-
CH2CH2 naphthalenyl
4-R57O (C=O)O propynyl 4-R57O (C=S) O 5-PhO-2-
4-R57O(C=O)O Ph naphthalenyl
4-R57O(C=S)O Ph 3-R57O (C=O) O 5-PhO-1-
3-R57O(C=O)O Ph naphthalenyl
3-R57O (C=O) O 3-Cl-Ph 4-R57O (C=O) O 4- (2-MeS-PhO)-
4-R57O(C=O)O 4-Br-Ph 2-
4-R57O(C=S)O 4-Br-Ph naphthalenyl
4-R57O(C=O)O 3,5-diMe-Ph 4-R57O (C=O) O 2-pyridyl
4-R57O(C=S)O 3,5-diMe-Ph 4-R57O (C=S) O 2-pyridyl
4-R57O(C=O)O 4-CN-Ph 3-R57O (C=O) O 3-pyridyl
3-R57O (C=O) O 3-(PhO)Ph 3-R57O (C=O) O 4-pyridyl
4-R57O(C=O)O 4-(PhO)Ph 4-R57O (C=O) O 5-CF3-2-pyridyl
4-R57O(C=S)O 4-(PhO)Ph 4-R57O (C=S) O 5-CF3-2-pyridyl
4-R57O(C=O)O 3-(3-Cl-PhO)Ph 3-R57O (C=O) O 3-F-2-pyridyl
3-R57O(C=O)O 3-(2-F-PhO)Ph 4-R57O (C=O) O 2-furanyl
3-R57O(C=O)O 4-(3-Et-PhO)Ph 4-R57O (C=S) O 2-furanyl
3-R57O(C=S)O 4(3-Et-PhO)Ph 3-R57O (C=O) O 3-furanyl
4-R57O(C=O)O 2-naphthalenyl 3-R57O (C=O) O 3,5-diMe-2-
4-R57O(C=S)O 2-naphthalenyl furanyl
4-R57O(C=O)O 1-naphthalenyl 4-R57O (C=O) O 2-thienyl
4-R57O(C=O)O 4-Br-1- 4-R57O (C=S) O 2-thienyl
naphthalenyl 4-R57O (C=O) O 3-thienyl
3-R57O (C=O) O 5-CF3-6-CN-2- 3-R57O (C=O) O 4-Cl-2-thienyl naphthalenyl 3-R57O (C=O) O 5-F-3-thienyl
3-R57O(C=O)O 3-MeSnaphthalenyl
TABLE 24
Compounds of Formula II wherein:
V R39 R57
3-(O(C=V)NR39R57) O Me Me
4-(O(C=V)NR39R57) O H 3-pentyl
4-(O(C=V)NR39R57) O Me 4-Et-hexyl
4-(O(C=V)NR39R57) O i-Pr decyl -(O(C=V)NR39R57 ) S Me cyclohexyl
-(O(C=V)NR39R57 ) S Me 2-propenyl
-(O(C=V)NR39R57 ) O Me 2-propynyl
-(O(C=V)NR39R57 ) O H 7-methyl-3-octynyl-(O(C=V)NR39R57 ) S H 3-Cl-Ph
-(O(C=V)NR39R57) O Me 4-F-Ph
-(O(C=V)NR39R57) O H 2,4-diBr-Ph
-(O(C=V)NR39R57) S Me 3-CF3-Ph
-(O(C=V)NR39R57) S Me 2-Me-Ph
-(O(C=V)NR39R57) O H 4-t-Bu-Ph
-(O(C=V)NR39R57) S Me 3-EtO-Ph
-(O(C=V)NR39R57) O Me 3-(3-Cl-PhO)Ph
-(O(C=V)NR39R57) S Me 3-pyridyl
-(O(C=V)NR39R57) O Et 4-pyridyl
-(O(C=V)NR39R57) O H 3-Cl-2-pyridyl
-(O(C=V)NR39R57) O Bu 5-CF3-2-pyridyl-(O(C=V)NR39R57) O Me 4-(2-Me-PhO)-2-pyridyl-(O(C=V)NR39R57) S Pr 4-F-2-furanyl
-(O(C=V)NR39R57) O H 5-Cl-4-Me-3-fύranyl-(O(C=V)NR39R57) O Me 5-MeS-3-furanyl-(O(C=V)NR39R57) S Me 2-thienyl
-(O(C=V)NR39R57) S Me 3-thienyl
-(O(C=V)NR39R57) O H 4-MeO-2-thienyl-(C=V)NR39R57 O Me Me
-(C=V)NR39R57 O H 3 -pentyl
-(C=V)NR39R57 O Me 4-Et-hexyl
-(C=V)NR39R57 O i-Pr decyl
-(C«=V)NR39R57 S Me cyclohexyl
-(C=V)NR39R57 S Me 2-propenyl
-(C=V)NR39R57 O Me 2-propynyl
-(C=V)NR39R57 S H 3-Cl-Ph
-(C=V)NR39R57 O Me 4-F-Ph
-(C=V)NR39R57 O H 2,4-diBr-Ph
-(C=V)NR39R57 O H 4-t-Bu-Ph
-(C=V)NR39R57 O H 2-MeO-5-CN-Ph
-(C=V)NR39R57 O Me 3-(3-Cl-PhO)Ph 3-(C=V)NR39R57 O Et 4-pyridyl
4-(C=V)NR39R57 O H 3-Cl-2-pyridyl
3-(C=V)NR39R57 O Me 3-CN-2-pyridyl
4-(C=V)NR39R57 O H 5-Cl-4-Me-3-furanyl
3-(C=V)NR39R57 O H 4-MeO-2-thienyl
4-(C=V)NR39R57 O H 5-CF3-2-thienyl
TABLE 25 4-O(CH2)nR59 4 4-F-Ph Compounds of Formula I1 3-O(CH2)nR59 3 2-Me-Ph wherein: 3-O(CH2)nR59 4 3-i-Pr-Ph
Z n R59 3-O(CH2)nR59 3 3-EtO-Ph
3-(CH2)nR59 3 Ph
3-(CH2)nR59 4 Ph TABLE 26
4-(CH2)nR59 3 Ph Compounds of Formula I1
4-(CH2)nR59 4 Ph wherein:
3-(CH2)nR59 3 3-Cl-Ph Z R40
4-(CH2)nR59 4 4-F-Ph 4-OR40 2-pyridyl
3-(CH2)nR59 3 4-Br-2-F-Ph 3-OR40 3-pyridyl
3-(CH2)nR59 3 2-Me-Ph 4-OR40 4-pyridyl
3-(CH2)nR59 4 3-i-Pr-Ph 4-OR40 5-CF3-2-pyridyl
3-(CH2)nR59 3 3-EtO-Ph 3-OR40 3-Cl-5-CF3-2-pyridyl
3-(CH2)nOR59 3 Ph 4-OR40 5-Cl-3-pyridyl
4-(CH2)nOR59 4 Ph 4-OR40 2-N02-4-pyridyl
4-(CH2)nOR59 3 Ph 3-OR40 4-Me02C-2-pyridyl
4-(CH2)nOR59 4 Ph 3-OR40 6-F-2-pyridyl
3-(CH2)nOR59 3 3-Cl-Ph 4-OR40 6-Et-4-N02-2-pyridyl
4-(CH2)nOR59 4 4-F-Ph 4-OR40 5-CN-3-Cl-2-pyridyl
3-(CH2)nOR59 3 2-Me-Ph 4-OR40 5-(4-Br-PhO)-3-
3-(CH2)nOR59 4 3-i-Pr-Ph pyridyl
3-(CH2)nOR59 3 3-EtO-Ph 3-OR40 5-(3,5-diCl-PhO)-2-
3-O(CH2)nR59 3 Ph pyridyl
3-O(CH2)nR59 4 Ph 4-OR40 6-(3-Me-4-NO2-PhO)-
4-O(CH2)nR59 3 Ph 2-pyridyl
4-O(CH2)nR59 4 Ph 4-OR40 6-(5-MeS-PhO)-5-CF3-
3-O(CH2)nR59 3 3-Cl-Ph 3-pyridyl 4-OR40 6-(3-Br-PhO)-4- 3 --OORR40 4-MeS-3-Me-2-thienyl pyridyl 3-OR 40 1-naphthalenyl4-OR40 2-tetrahydropyranyl 4-OR40 2-naphthalenyl3-OR40 2-tetrahydrofuranyl 4-OR 40 4-F-6-NO2-1-3-OR40 2-pyrimidyl naphthalenyl4-OR40 4-pyrimidyl 3-OR40 7-methyl-2- 4-OR40 4-CF3-2-pyrimidyl naphthalenyl 4-OR40 2-EtO-4-pyrimidyl 4-OR40 4-i-butoxy-6-MeS-7-3-OR40 5-CN-4-NO2-2- naphthalenyl
pyrimidyl 4-OR40 2-imidazolyl
3-OR40 5-MeO2C-6-Pr-2- 3-OR40 4-imidazolyl
pyrimidyl 4-OR40 4-Me-4-imidazolyl 4-OR40 4-(3-F-PhO)-2- 4-OR40 4,5-diBr-2- pyrimidyl imidazolyl
3-OR40 6-(3,5-diCl-PhO)-4- 4-OR40 5-CF3-3-imidazolyl
Me-2-pyrimidyl 3-OR40 3-pyrazolyl
3-OR40 2-(2-Pr-PhO)-6-Me-4- 4-OR40 3-pyrazolyl
pyrimidyl 4-OR40 4-F-3-pyrazolyl4-OR40 5-(3-CF3-PhO)-2- 3-OR40 5-CF3-4-N02-3pyrimidyl pyrazolyl
4-OR40 6-(2-NO2-PhO)-3- 4-OR40 5-Br-4-MeO-3- pyrimidyl pyrazolyl
3-OR40 2-furanyl 4-OR40 2-oxazolyl
4-OR40 3-furanyl 3-OR40 5-oxazolyl
4-OR40 5-Br-2-furanyl 4-OR40 4-CF3-2-oxazolyl 3-OR40 3, 5-diMe-2-furanyl 4-OR40 5-MeS-2-oxazolyl 4-OR40 5-propoxy-3-furanyl 3-OR40 5-NO2-4-Me-2- 4-OR40 4-CF3-3-furanyl oxazolyl
3-OR40 5-NO2-2-furanyl 4-OR40 2-thiazolyl
4-OR40 2-thienyl 3-OR40 4-CF3-5-Me-2-3-OR40 3-thienyl thiazolyl
4-OR40 5-methyl-4-Cl-2- 4-OR40 5-NO2-2-thiazolyl thienyl 4-OR40 4-Et-2-thiazolyl 4-OR40 4-EtO-3-thienyl 3-OR40 3-isoxazolyl
4-OR40 5-CF3-3-NO2-2- 4-OR40 5-isoxazolyl
thienyl 4-OR40 5-propyl-3- - - - 3-MeS 2-(hydroxyisoxazolyl carbonyl)PhO
3-OR40 5-NO2-3-isoxazolyl - - - 2-F 2-(ethoxy¬
4-OR40 3-CF3-4-F-5- carbonyl)PhO isoxazolyl - - - 3-C1 3-(t-butoxy¬
3-OR40 3-isothiazolyl carbonyl)PhO
4-OR40 5-isothioazolyl - - - 3-PrO 4-(3-Br-PhO)PhO
4-OR40 5-propyl-3- - - - 2-F 3-(3,5-diCl- isothiazolyl PhO)PhO
3-OR40 5-NO2-3-isothiazolyl - - - 2-F 3- (4-t-Bu-PhO) PhO
4-OR40 3-CF3-4-F-5- - - - 2-F MeOCH2CH2OCH2O isothiazolyl 5-F 2-F MeOCH2CH2OCH2O
- - - 2-F (2-Cl-Ph)CH2OCH2O
TABLE 27 5-Cl 3-F (3-Br-Ph)CH2OCH2O
Compounds of Formula Im - - - 2-F (3,5-diMe- wherein: Ph)CH2OCH2O
R61 R62 Z 5-F 3-NO2 (2-CF3- - - - 2-F 2-Cl-3, 5-diF-PhO Ph) CH2OCH2O - - - 3-Cl 2,3,5-triF-PhO - - - 2-F cyclohexyloxy - - - 2-F 2-CN-PhO 3-Br 2-F (Z)-PhCH-CH - - - 2-F 4-CN-PhO - - - 2-F (4-F-Ph)CH=CH - - - 3-MeO 2-(1-bromoethyl)PhO
- - - 2-F 4- (5-Cl-3- hexyl)PhO
- - - 3-Cl 2-pentyloxy-PhO
- - - 2-F 3-hexyloxy-PhO
- - - 2-F 4-(CF3O)PhO
- - - 3-CH3 2-MeS02-PhO
3-F 2-F 2-(EtOCH2)PhO
- - - 3-NO2 2-(MeOCH2CH2O)PhO
- - - 2-F 2-EtS-PhO
3-F 2-F 4- (2-propenyl) PhO
- - - 3-Et 3- (2-Br-2- propenyl)PhO
5-CF3 2-F 3-(2-propenyl)PhO TABLE 28
Compounds of Formula Io wherein:
R61 R62 Z R57
3-Br 2-F 4-C(=O)OR57 t-Bu
- - - 2-F 4-C (=O) OR57 cyclohexyl
- - - 4-Br 3-C(=O)OR57 CF3CH2
- - - 5-MeS 4-C(=O)OR57 H2C=CHCH2
4-Cl 2-F 3-C(=O)OR57 (Z)-CLCH2CH=CHCH2
3-F 2-F 4-C(=O)OR57 3-CF3-Ph
- - - 3-Br 4-C(=O)OR57 2-propyloxy-Ph
- - - 2-F 4-C(=O)OR57 4-CN-Ph
- - - 5-CF3 3-C(=O)OR57 3-(2-F-PhO)Ph
- - - 5-EtO 3-C(=O)OR57 4-(4-MeS-PhO)Ph
5-F 3-F 4-C(=O)OR57 2-pyridyl
- - - 3-MeO 4-C(=O)OR57 3-furanyl
- - - 2-F 4-C(=O)OR57 4, 5-diMe-2-furanyl - - - 5-NO2 3-C(=O)OR57 4-Br-2-CF3-3-thienyl - - - 3-MeS 4-C(=O)OR57 5-Me-2-thienyl
- - - 6-F 3-R57(C=O)O (CH3)3C
3-Br 2-F 4-R57(C=S)O (CH3)3C
- - - 2-F 4-R57(C=O)O cyclopentyl
- - - 3-C1 4-R57(C=O)O 2-propenyl
- - - 2-F 4-R57(C=S)O H2C=CH
- - - 3-Br 4-R57(C=O)O (Z)-F3CCH=CHCH2 - - - 4-F 4-R57(C=O)O Ph
6-F 4-F 3-R57(C=S)O Ph
- - - 3-PrO 4-R57(C=O)O 4-Br-Ph
- - - 5-C1 4-R57(C=S)O 3-Br-Ph
- - - 2-F 4-R57(C=O)O 3-CF3-Ph
3-Br 2-F 4-R57(C=O)O 4-PhO-Ph
- - - 2-F 3-R57(C=S)O 4-PhO-Ph
- - - 4-EtO 3-R57(C=O)O 3-(3-CF3-PhO)Ph - - - 3-CH3 4-R57(C=O)O 6-t-Bu-2-naphthalenyl - - - 5-CF3 3-R57(C=O)O 5-CF3-3-pyridyl - - - 3-Br 4-R57(C=O)0 4-Cl-2-thienyl - - - 5-NO2 3-R57 (C= S) O 5-i-PrO-3-thienyl 3-Br 2-F 4-R57O(C=S)O (CH3)3C
- - - 5-NO2 3-R57O(C=O)O 3-Et-4-Pr-hexyl
- - - 2-F 4-R57O(C=O)O cyclopentyl
- - - 5-Et 3-R57O(C=O)O HC≡C-CH2
- - - 5-NO2 3-R57O(C=O)O H2C=CHCH2
- - - 2-F 4-R57O(C=O)O Ph
- - - 3-PrO 4-R57OC=O)O 4-Br-Ph
- - - 2-F 4-R57O(C=O)O 3-CF3-Ph
- - - 5-MeS 3-R57O(C=O)O 4-NO2-Ph
- - - 5-CF3 3-R57O(C=S)O 3,5-diMe-Ph
3-Br 2-F 4-R57O(C=O)O 4-PhO-Ph
- - - 2-F 3-R57O(C=S)O 4-PhO-Ph
- - - 2-F 4-R57O(C=O)O 3-MeS-2-naphthalenyl - - - 5-CF3 3-R57O(C=O)O 5-CF3-3-pyridyl
- - - 3-Br 4-R57O(C=O)O 4-Cl-2-thienyl R61 R62 Z R40
- - - 5-CF3 3-OR40 2-pyridyl
- - - 3-Et 4-OR40 3-pyridyl
- - - 2-F 4-OR40 5-CF3-2-pyridyl
- - - 3-Br 4-OR40 5-Br-3-pyridyl
3-Cl 2-F 4-OR40 4-MeO2C-2-pyridyl - - - 6-CF3 3-OR40 6-Et-4-NO2-2-pyridyl - - - 4-F 3-OR40 5-(3,5-diCl-PhO)-2-pyri - - - 3-Cl 4-OR40 2-pyrimidyl
- - - 3-NO2 4-OR40 2-pyrimidyl
- - - 3-MeS 4-OR40 4-pyrimidyl
6-F 2-F 4-OR40 5-CF3-2-pyrimidyl 4-Br 5-Cl 3-OR40 4-(3-F-PhO)-2-pyrimidyl - - - 5-CF3 4-OR40 2-furanyl
- - - 4-i-PrO 3-OR40 5-Br-3-furanyl
6-F 2-F 4-OR40 5-CF3-3-thienyl
- - - 5-NO2 3-OR40 4-Cl-5-methyl-2-thienyl - - - 2-F 4-OR40 2-tetrahydropyranyl - - - 2-F 4-OR40 2-naphthalenyl - - - 3-MeS 4-OR40 4-F-7-Me-1-naphthalenyl - - - 3-Bu 4-OR40 2-imidazolyl
- - - 5-CF3 3-OR40 5-CF3-2-imidazolyl
3-F 2-F 4-OR40 3-pyrazolyl
- - - 5-NO2 3-OR40 4-NO2-2-pyrazolyl
5-F 2-F 4-OR40 5-oxazolyl
- - - 5-CF3 3-OR40 5-MeS-2-oxazolyl
- - - 2-MeS 4-OR40 2-thiazolyl
- - - 3-Br 4-OR40 4-Et-3-thiazolyl
- - - 5-EtO 4-OR40 3-isoxazolyl
3-Cl 2-F 4-OR40 3-isothiazolyl
- - - 3-OBu 4-OR40 5-propyl-3-isothiazolyl
TABLE 29
Compound of Formula Io wherein:
R 61 R62 Z V R39 R57
- - - 2-F 4-(O(C=V)NR39R57) O Me 3-pentyl
- - - 3-N02 4-(P(C=V)NR39R57) O H 2-F-4-Me-heptyl - - - 4-MeS 3-(O(C=V)NR39R57) O Et (Z)-4-Br-2-butenyl - - - 3-CF3 4-(O(C=V)NR39R57) O Me 4-F-Ph
- - - 4-Br 3-(O(C=V)NR39R57) O Pr 3-CF3-Ph
- - - 3-C1 4-(O(C=V)NR39R57) O H 2-MeO-5-CN-Ph - - - 2-F 3-(O(C=V)NR39R57) O Me 3-(3-CF3O-PhO)Ph - - - 3-Br 4-(O(C=V)NR39R57) O Et 3-Cl-2-pyridyl - - - 2-F 4- O(C=V)NR39R57) S Pr 4-F-3-furanyl - - - 4-EtO 3- O(C=V)NR39R57) O Et 2-thienyl
3-Cl 2-F 4- O(C=V)NR39R57) O Me 4-MeO-2-thienyl - - - 2-F 4- (C=V)NR39R57) O Me 3-pentyl
- - - 2-F 3- (C=V)NR39R57) S Me cyclohexyl
3-Br 2-F 4- (C=V)NR39R57) S H 2-propenyl
- - - 4-MeS 3- (C=V)NR39R57) O Et (Z)-4-Br-2-butenyl - - - 6-F 3- (C=V)NR39R57) S H 3-Cl-Ph
- - - 3-CF3 4- (C=V)NR39R57) O Me 4-F-Ph
- - - 4-Br 3-((C=V)NR39R57) O Pr 3-CF3-Ph
- - - 3-NO2 4-((C=V)NR39R57) S H 4-t-Bu-Ph
- - - 3-NO2 4-((C=V)NR39R57) S H 4-t-Bu-Ph - - - 3-Cl 4-((C=V)NR39R57 O H 2-MeO-5-CN-Ph - - - 3-Br 4-((C=V)NR39R57 O Et 3-Cl-2-pyridyl - - - 4 -Me 3-((C=V)NR39R57 S H 5-CF3-3-pyridyl - - - 2-F 4-((C=V)NR39R57 S Pr 4-F-3-furanyl - - - 4-EtO 3-((C=V)NR39R57 O Et 2-thienyl
3-Cl 2-F 4-((C=V)NR39R57 O Me 4-MeO-2-thienyl
TABLE 30
Compounds of Formula lo wherein:
R61 R62 Z n R59
6-F 2-F 3-(CH2)nR 59 3 Ph
- - - 2-F 4-(CH2)nR59 3 Ph
- - - 3-MeO 4-(CH2)nR59 4 Ph
- - - 4-CF3 3- (CH2)nR59 3 3-Cl-Ph - - - 2-F 4-(CH2)nR59 4 4-F-Ph
- - - 4-MeS 3-(CH2)nR59 3 4-Br-2-F-Ph
5-Cl 2-F 3-(CH2)nR59 3 2-Me-Ph - - - 5-i-Pr 3-(CH2)nR59 4 3-i-Pr-Ph - - - 2-F 4-(CH2)nR59 3 4-t-Bu-Ph - - - 4-Me 3-(CH2)nR59 3 3-EtO-Ph - - - 2-F 3-(CH2)nR59 4 2-CF3-4-EtO-Ph - - - 3-EtO 4-(CH2)nR59 4 3-NO2-5-F-Ph
6-F 2-F 3-O(CH2)nR59 3 Ph
- - - 4-Br 3-O(CH2)nR59 4 Ph
- - - 2-F 4-O(CH2)nR59 3 Ph
- - - 3-MeO 4-O(CH2)nR59 4 Ph
- - - 2-F 4-O(CH2)nR59 4 4-F-Ph
5-Cl 2-F 3-O(CH2)nR59 3 2-Me-Ph - - - 5-i-Pr 3-O(CH2)nR59 4 3-i-Pr-Ph - - - 2-F 4-O(CH2)nR59 3 4-t-Bu-Ph - - - 5-Me 3-O(CH2)nR 59 3 3-EtO-Ph - - - 2-F 3-O(CH2)nR59 4 2-CF3-4-EtO-Ph - - - 5-CF3 3-O(CH2)nR 59 4 2-MeS-4-Bu-Ph
6-F 2-F 3-(CH2)n-OR59 3 Ph
- - - 2-F 4-(CH2)n-OR59 3 Ph
- - - 3-MeO 4-(CH2)n-OR59 4 Ph - - - 2-F 4- (CH2 ) n-OR59 4 4-F-Ph
- - - 5-i-Pr 3- (CH2 ) n-OR59 4 3-i-Pr-Ph - - - 2-F 4- (CH2 ) n-OR59 3 4-t-Bu-Ph - - - 4-Me 3- (CH2 ) n-OR59 3 3-EtO-Ph - - - 2-F 3- (CH2 ) n-OR59 4 2-CF3-4-EtO-Ph - - - 5-CF3 3- (CH2 ) n-OR59 4 2-MeS-4-Bu-Ph
TABLE 31
Compounds of Formula I wherein W=O, R1=CH3, R3=Ph, R4=H, and:
R2 6-(F2C=CHCH2O)-3-pyridyl
6-(C5H11)-3-pyridyl 6-(CH=CCH2O)-3-pyridyl
6-(C12H25)-3-pyridyl 6-(C8H17C=CCH2CH20)-3-pyridyl
3-(CF3CH2)-3-pyridyl 6-MeSO2-3-pyridyl
6-(CH3(CH2)10C(Cl)2)-3-pyridyl 6-(C8H17SO2)-3-pyridyl
6-(CH3CH(CH3)CH2CH2O)-3- 6-(CH2ClSO2)-3-pyridyl pyridyl 6-(MeOCH2O)-3-pyridyl
6-(C12H25O)-3-pyridyl 6-(C8H17CH(CH3)O(CH2)2O)-3- 6-CF3O-3-pyridyl pyridyl
6-(CF3CH2CH2O)-3-pyridyl 6-(EtOC(=O))-3-pyridyl 6-EtS-3-pyridyl 6-(CH3CH(CH3)(CH2)8OC(=O))-3-
6-(CH3CH(CH3)(CH2)9)-3-pyridyl pyridyl
6-CF3S-3-pyridyl 6-NMe2-3-pyridyl
6-(CH3(CH2)10CH(Cl)S)-3- 5-CF3CH2-3-pyridyl
pyridyl 5-CF3O-3-pyridyl
6-(CH2=CH)-3-pyridyl 5-C2H5S-3-pyridyl
6-(C6H13CH=CHCH2)-3-pyridyl 5-CF3S-3-pyridyl
6-(C(Br)H=CH)-3-pyridyl 5-(MeC≡C)-3-pyridyl
6-(C10H21CH=C(Cl))-3-pyridyl 5-(CH2=CHCH2O)-3-pyridyl 6-(MeC≡C)-3-pyridyl 5-(CH≡CCH2O)-3-pyridyl 6-(C9H19C≡CCH2)-3-pyridyl 5-MeSO2-3-pyridyl
6-(CH2(Cl)C≡C)-3-pyridyl 4-(C5H11O)-2-pyridyl
6-(CH2=CHCH2O)-3-pyridyl 4-CF3O-2-pyridyl
6-(C8H17CH=CH(CH2)2O)-3- 4-(CH2=CH)-2-pyridyl
pyridyl 4-(MeC≡C)-2-pyridyl 4- (C (Cl) 2=CHCH20) -2-pyridyl 2-(Me(CH2)3CH(Me))-5-F- 4- (EtOCH2O) -2-pyridyl oxazolyl
6- (C5H1 1) -2-pyridyl 2-EtO-4-oxazolyl
6-CF3O-2-pyridyl 2-(3-CF3-PhO)-4-oxazolyl 6- (CCl3CH2S) -2-pyridyl 2-Me-4-F-5-oxazolyl
6- (ClCH2CH=CHCH2) -2-pyridyl 2-EtO-5-oxazolyl
6-MeSO2-2-pyridyl 2-hexyl-4-F-5-oxazolyl 5- (C5H11) -2-pyridyl 2-CF3-5-oxazolyl
5- (CH (CH3) 2 (CH2) 3 ) -2-pyridyl 2-thiazolyl
5- (ClCH2CH2) -2-pyridyl 4-F-5-Me-2-thiazolyl 5-CF3O-2-pyridyl 4-MeO-5-CF3-2-thiazolyl 5- (C5H1 1O) -2-pyridyl 4-(Me(CH2)3CH(Me))-5-EtO-2- 5-EtS-2-pyridyl thiazolyl
5-CF3S-2-pyridyl 4-hexyloxy-5-Cl-2-thiazolyl 5-(CBr2=CH)-2-pyridyl 5-(2-Me-PhO)-2-thiazolyl 5-(MeC≡C)-2-pyridyl 2-Cl-4-thiazolyl
5-(CH2=CHCH2O)-2-pyridyl 2-Me-5-F-4-thiazolyl 5-MeSO2-2-pyridyl 2-EtO-4-thiazolyl
5-(MeOCH2O)-2-pyridyl 2-Cl-5-F-4-thiazolyl 2-CF3O-4-pyridyl 2-Br-5-thiazolyl
2-(MeC≡C)-4-pyridyl 4-F-5-thiazplyl
2-EtSO2-4-pyridyl 2-hexyl-5-thiazolyl
3-F-2-PhO-4-pyridyl 2-Et-4-F-5-thiazolyl 5-F-2-PhO-4-pyridyl 2-Br-4-F-5-thiazolyl 6-C1-2-(2-F-PhO)-4-pyridyl 5-Cl-3-isoxazolyl
2-(2-F-PhO)-6-Me-4-pyridyl 4-F-5-Me-3-isoxazolyl 4-Br-2-oxazolyl 4-F-5-hexyloxy-3-isoxazolyl 4-Et-5-Me-2-oxazolyl 5-MeO-3-isoxazolyl
4-(Et2CHO)-5-Cl-2-oxazolyl 5-(4-EtO-PhO)-3-isoxazolyl 4-Me-5-CF3-2-oxazolyl 4-isoxazolyl
4-F-5-MeO-2-oxazolyl 5-F-4-isoxazolyl
5-(2-Me-PhO)-2-oxazolyl 3-F-4-isoxazolyl
4-(4-Cl-PhO)-5-EtO-2-oxazolyl 3,5-diF-4-isoxazolyl 2-hexyl-4-oxazolyl 3-hexyl-5-isoxazolyl 2-Br-5-F-oxazolyl 3-Br-4-F-5-isoxazolyl 2-Me-4-oxazolyl 3-(Et2CHO)-5-isoxazolyl 3-Et-4-F-5-isoxazolyl 6-Cl-5-(4-Et-PhO)-3- 3-CF3-5-isoxazolyl pyridazinyl
3-(4-F-PhO)-5-isoxazolyl 4-pyridazinyl
3-(4-Br-PhO)-4-F-5-isoxazolyl 6-Et-5-F-4-pyridazinyl
5-Cl-3-isothiazolyl 3,5-diF-4-pyridazinyl
4-F-5-Me-3-isothiazolyl 5-F-6-PhO-4-pyridazinyl 5-hexyloxy-3-isothiazolyl 6-(4-Et-BzlO)-4-pyridazinyl 4-F-3-isothiazolyl 2-pyrimidyl
4-F-5-MeO-3-isothiazolyl 4-Br-5-Me-2-pyriιrtidyl
5-(2-Me-BzlO)-3-isothiazolyl 5-Et-2-pyrimidyl
4-isothiazolyl 4-hexyl-6-CF3-2-pyrimidyl 5-F-4-isothiazolyl 4,6-cUMeO-2-pyrimidyl
3-F-4-isothiazolyl 5-(2-MeO-PhO)-2-pyrimidyl 3, 5-diF-4-isothiazolyl 6-(4-Et-BzlO)-4-Me-2-pyrimidyl 3-Br-5-isothiazolyl 4-pyrimidyl
3-MeO-4-F-5-isothiazolyl 5-F-2-hexyl-4-pyrimidyl 3-CF3-5-isothiazolyl 6-Et-4-pyrimidyl
3-(Me(CH2)2CH(Et))-4-F-5- 2-EtO-6-Me-4-pyrimidyl
isothiazolyl 6-(2-F-PhO)-4-pyrimidyl 3-Cl-4-F-5-isothiazolyl 5-pyrimidyl
3-(2-MeO-BzlO)-4-F-5- 4,6-diF-2-Me-5-pyrimidyl isothiazolyl 2-hexyloxy-5-pyriπtidyl
3-(4-F-PhO)-5-isothiazolyl 2-CF3-5-pyrimidyl
3-(3-Et-BzlO)-5-isothiazolyl 2-(4-Cl-PhO)-5-pyrimidyl 3-(4-Br-PhO)-5-isothiazolyl 4-F-2-(2-Me-PhO)-5-pyrimidyl 2-pyrazinyl 4-F-2-(3-EtO-BzlO)-5-pyrimidyl 5-Br-6-MeO-2-pyrazinyl
5-hexyl-6-Me-2-pyrazinyl TABLE 32
5-(2-Cl-PhO)-3-F-2-pyrazinyl Compounds of Formula Ip 5-(3-Me-PhO)-2-pyrazinyl wherein E1=0 and:
6-(4-EtO-BzlO)-3-F-2-pyrazinyl E63
3-pyridazιnyl 4-Cl-2,6-diF
6-hexyloxy-5-Me-3-pyridazinyl 2,4,6-triF
6-Cl-5-MeO-3-pyridazinyl 3-C5H11
6-hexyl-4-F-3-pyridazinyl 4-CH3CH(CH3)(CH2)5
6-(2-F-BzlO)-3-pyridazinyl 3-CF3CH2 O 4-C7H15C (Cl) 2 Compounds of Formula Ip 4-C5H11O wherein
3-C6H13CH(CH3)O E1=S and:
3-CHF20 R63
4-C6H13CH(Cl)CH2O 4-Cl-2,6-diF
3-MeSO2 4-C5H11
4-CH3C(CH3)2(CH2)4SO2 3-CF3CH2
2-MeOCH2 3-C6H13CH(CH3)O
3-C4H9CH(CH3)O(CH2)2O 4-CF3O
3-MeOCH2O 3-MeSO2
4-C5H11O(CH2)2O 3-C4H9CH (CH3) O(CH2)2O4-CH3CH(CH3) (CH2)5S 3-MeOCH2O
3-cyclopentyl 4-cyclohexyl
4-cyclohexyl 3-cyclopentyloxy
4-cycloρentyloxy 2-CH2=CH
3-cyclohexyloxy 3-CF2=CH
4-C6H13CH=CH 2-CH=C
4-C4H9C (CH3)=CHCH2 4-MeOC(=O)
2-HCsC 3-(4-Cl-PhO)
3-C5H11C≡CCH2 4-(2-Me-PhO)
3-HOC (=O) 3-(3-MeO-PhO)
3-MeOC (=O) 4-(2-CF3-PhO)
4-CH3CH(CH3)(CH2)4OC(=O)
3-(4-Cl-PhO) Compounds of Formula Ip 4-(2,4-diF-PhO) wherein
3-(2-Me-PhO) E1=NH and:
4-(4-C4H9-PhO) R63
3-(3-MeO-PhO) 2-CF3
4-(4-(C2H5CH(CH3)0)-PhO) 3-NO2
4-(2-CF3-PhO) 3-Br
3-(4-CH3S-PhO) 4-Et
4-(4-NO2-PhO) 3-(3-Br-PhO)
4-(4-Me-PhO)
3-(2-F-PhO) Compounds of Formula Ix 4-NO2-2-F
wherein: R18 =2- F and: 3-MeOC(=O)
R37 2-Me
H 4-C4H9
2-F 4-CN
3-F 4-CH3CH(CM3)CH2
3-Cl 2-MeO
4-Cl 3-C4H9O
4-Br 3-(2-Cl-PhO)
2-Me 4-(3-Br-PhO)
4-C4H9 3-(4-F-PhO)
3-CH3CH(CH3)CH2 4-(2-Me-PhO)
3-MeO 3-(4-(butyl)PhO)
3-C4H9O 4-(3-MeO-PhO)
2-CN 2-(2-CF3-PhO)
3-(3-Cl-PhO) 3-(4-MeS-PhO)
2-(2-Me-PhO) 4-(3-CN-PhO)
4-(3-MeO-PhO)
2,3-diCl TABLE 33
2,3-diF Compounds of Formula Iq
4-Br-2-F wherein:
4-Cl-2-F G
4-Cl-2-Me 5- (4-Cl-2, 6-diF-PhO)
4-CF3-2-Cl 5- (2-CN-PhO)
4-EtO-2-CN 5- (4-C5H11O-PhO)
5-(3-CF3O-PhO)
Compounds of Formula Ix 5-(4-MeSO2-PhO) wherein R10,=4 -F, and: 5-(3-(MeOCH2O)-PhO)
E37 5-(2-(CH2=CHCH2)PhO)
H 5-(3-PhO-PhO)
2-F 5-(4-(4-Cl-PhO)PhO)
3-C1 4-(4-Cl-2,6-diF-PhO)
4-Br 4-(3-CN-PhO)
4-C1-2-F 4-(3-CF3O-PhO)
3-CF3 6-(4-Cl-2,4-diF-PhO)
4-CF3O 6-(3-CN-PhO) 6-(4-CF3O-PhO) 4-(3-isoxazolylthio)
5-(6-F-2-pyridyloxy) 5-(3-F-4-isoxazolylthio) 5-(2-Cl-3-pyridyloxy) 5-(3-Me-5-isoxazolylthio) 5-(3-Cl-4-pyridyloxy) 6-(4-Cl-3-isoxazolylthio) 5- 5-F-2-pyrimidyloxy) 4-(2-oxazolylthio)
5-(2-Cl-3-thienyloxy) 5-(4-Cl-2-oxazolylthio) 5-(4-Me-3-thienyloxy) 5-(2-F-4-oxazolylthio)
5-(5-F-3-thienyloxy) 6-(5-Me-2-oxazolylthio) 4-(2-Cl-3-thienyloxy) 4-(5-Cl-3-pyrazolylthio) 5-(4-Me-3-furanyloxy) 5-(4-pyrazolylthio)
4-(5-F-3-furanyloxy) 4-(6-Cl-2-pyridylamino) 5-(4-Cl-2-oxazolyloxy) 5-(2-F-3-pyridylamino)
4-(5-F-4-oxazolyloxy) 6-(2-Me-4-pyridylamino) 6-(2-Me—5-oxazolyloxy) 4-(2-MeS-3-thienylamino) 5-(5-Me-3-isoxazolyloxy) 5-(4-NO2-3-thienylamino) 4-(3-Cl-4-isoxazolyloxy) 6-(3-thienylamino)
6-(3-F-5-isoxazolyloxy) 4-(2,5-diCl-3-furanylamino) 6- 3-pyrazolyloxy) 5-(2-F-3-furanylamino)
6-(3-Me-4-pyrazolyloxy) 6-(2-Et-3-furanylamino) 5-PhS 4-(5-MeO-3-isoxazolylamino) 5-(3-CF3-PhS) 6-(3-MeS-5-isoxazolylamino) 4-(3-CF3O-PhS) 4-(2-oxazolylamino)
6-(2,3,4-triF-PhS)
5-(6-Cl-2-pyridylthio) TABLE 34
5- 3-pyridylthio) Compounds of Formula Ir 5- 3-Me-4-pyridylthio) wherein:
6-[2-MeO-3-pyridylthio) G
4- 5-Cl-2-pyrimidylthio) 5-(2,4,6-triF-PhO)
5- 2-F-4-pyrimidylthio) 5-(3-CN-PhO)
5- 2-pyrimidylthio) 5-(4-CF3O-PhO)
6- 5-Me-2-pyrimidylthio) 5-(2-(CF2=CH)-PhO)
5-(2-Cl-4-thienylthio) 5-(3-EtS-PhO)
5-(3-thienylthio) 6-(4-CF3-2-pyridyloxy) 6-(2-F-3-thienylthio) 6-(3-CF3O-2-pyridyloxy) 4-(3-furanylthio) 6-(5-(MeOC(=O))-2-pyridyloxy) 6-(3-Me-3-furanylthio) 6-(6-F-2-pyridyloxy) 6- 6-Me-2-pyridyloxy) 5-(3-thienylthio)
6- 6-(4-Cl-PhO)-2-pyridyloxy) 6-(2-F-3-thienylthio) 6- 2-F-3-pyridyloxy) 6-(4-Br-3-thienylthio) 6- 4-CF3-3-pyridyloxy) 6-(2-Me-4-thienylthio) 6- 2-Cl-4-pyridyloxy) 5-(4-CF3-3-furanylthio) 6- 2-(2-Cl-PhO)-4-pyridyloxy) 6-(3-furanylthio)
6- 5-Cl-2-pyrimidyloxy) 6-(2-Cl-3-furanylthio) 6- 2-Cl-3-thienyloxy) 6-(2-Me-4-furanylthio) 6- 4-Me-3-thienyloxy) 5-(5-Cl-4-isoxazolylthio) 6- 5-CF3-3-thienyloxy) 6-(5-Me-3-isoxazolylthio) 6- 2-NO2-3-thienyloxy) 6-(3-isoxazolylthio) 5- 2-Br-3-thienyloxy) 5-(2-oxazolylthio)
6- 2-F-3-furanyloxy) 6-(2-Cl-3-oxazolylthio) 6- 4-Me-3-furanyloxy) 5-(5-F-3-pyrazolylthio) 5- 2-Cl-3-furanyloxy) 6-(3-Br-4-pyrazolylthio) 6- 4-Cl-2-όxazolyloxy) 5-(2-F-4-pyridylamino) 6- 5-F-4-oxazolyloxy) 6-(6-Me-2-pyridylamino) 6- 2-Me-5-oxazolyloxy) 6-(3-pyridylamino)
5- 4-CF3-2-oxazolyloxy) 5-(2-CF3-3-thienylamino) 6- 5-Me-3-isoxazolyloxy) 6-(2,5-diF-3-thienylart-ino) 6- 3-Cl-4-isoxazolyloxy) 5-(4-Me-3-furanylamino) 6- 3-F-5-isoxazolyloxy) 6-(3-furanylamino)
5- 3-isoxazolyloxy) 5-(5-MeO-3-isoxazolylamino) 6- 5-Cl-3-pyrazolyloxy) 6-(3-CF3-4-isoxazolylamino) 6- 3-Me-4-pyrazolyloxy) 5-(2-EtS-4-oxazolylamino) 5- 2,4,6-triF-PhS) 6-(3-NO2-4-pyrazolylamino) 5-PhS
5- 4-CF3O-PhS) TABLE 35
6- 6-CF3-2-pyridylthio) Compounds of Formula Is 6- 2-pyridylthio) wherein:
6- 2-F-3-pyridylthio) G
6- 2-Cl-4-pyridylthio) 2-(2,4,6-triF-PhO)
5- 2-Cl-2-pyridylthio) 2-PhO
5- 2-F-3-pyridylthio) 2-(4-CF3O-PhO)
6- 5-MeO-2-pyrimidylthio) 2-(5-CF3-3-thienyloxy) 6- 2-Cl-4-pyrimidylthio) 2-(2-Cl-3-furanyloxy) 2-(2-oxazolyloxy) 2- (4,5-diCl-2-oxazolylthio)
2-(4-Me-3-isoxazloyloxy) 2-(4-F-3-pyrazolylthio)
2-(2,4,6-triF-PhS) 2-(3-pyridylamino)
2-(4-CF3O-PhS) 2-(2,5-diF-3-thienylamino)
2-(2-F-3-pyridylthio) 2-(2-Me-3-furanylamino)
2-(5-Me-2-pyrimidylthio) 2-(5-MeO-3-isoxazolylamino)
2-(3-thienylthio) 2-(2-CF3-2-oxazolylamino)
2-(2-Cl-3-furanylthio) 2-(5-Me-3-pyrazolylamino)
4-(3-isoxazolylthio)
TABLE 36
Compounds of Formula Iq wherein:
G R28
5-(R28NMe) 2-(MeOC(=O)Ph
5-(R28NMey 3-(2-F-PhO)Ph
5-(R28NMe) 6-F-2-pyridyl
5-(R28NMe) 4-F-2-pyrimidyl
5-(R28NMe) 5-MeS-2-thienyl
5-(R28NMe) 2-NO2-3-furanyl
5-(R28NMe) 3-CF3-4-isoxazolyl
(Z)-5-(R28CH=CH) 2-F-Ph
5-(R28CH=CH) 3-Me-2-furanyl
5-(R28OC(=O) 4-PhO-Ph
5-(R28OC(=S) 4-Cl-Ph
5-(R28OC(=S) 5-MeO-2-pyrimidyl
5-(R28OC(=S) 3-F-pyrazolyl
5-(R28C(=O)O 2,4-diF-Ph
5-(R28C(=S)O 2-furanyl
5-(R28N(C3H7)C(=S)O) 2,5-diCl-3-thienyl
5-(R280C(=S)0) 3-isoxazolyl
5-(R28NHC(=O)O) 4-Me-2-imidazolyl
5-(R28N(Et)C(=S)O) 5-MeS-3-pyrazolyl
6-(R28NMe) 4-CF3O-Ph
6-(R28NMe) 4-pyridyl
6-(R28NMe) 2-Cl-4-pyrimidyl
6-(R28NMe) 3-NO2-2-thienyl
6-(R28NMe) 4-F-2-furanyl 6- R28NMe) 2-Me-4-pyrazolyl
(Z)-6-(R28CH=CH) 3-pyridyl
(Z) -6-(R28CH=CH) 4-Cl-2-oxazolyl 6- R28CH=CH) 5-F-3-pyrazolyl 6-(R28OC(=O)) 4-Et-Ph
6-[R28OC(=O)) 2, 5-diCl-3-thienyl 6- (R28OC(=O)) 4-oxazolyl
6-(R28C(=O)O) 3-MeO-Ph
6-(R28C(=S)O) 3-Me-pyrazolyl
6-(R28N(C4H9)C(=O)O) 3-furanyl
6-(R28NHC(=S)O) 5-MeS-3-isoxazolyl 6-(R28OC(=O)O) 5-F-3-pyrazolyl 6-(R28N(C3H7)C(=S)O) 6-Br-2-pyridyl
6-(R28N(Me)C(=O)O) 2-oxazolyl
4-(R28NMe) Ph
4-(R28NMe) 6-Me-2-pyridyl
4-(R28NMe) 4-pyrimidyl
4-(R28NMe) 4-Br-3-thienyl
4-(R28NMe) 3-CF3-2-furanyl 4-(R28NMe) 2-Cl-4-oxazolyl
(Z)-4-(R28CH=CH) 4-Et-Ph
4-(R28CH=CH) 2-thienyl
4-(R28OC(=O)) 3-Cl-Ph
4-(R28OC(=O)) 6-F-2-pyridyl
4-(R28OC(=S)) 3-furanyl
4-(R28C(=O)O) 3-NO2-Ph
4-(R28C(=O)O) 2,5-diCl-3-thienyl 4-(R28C(=S)O) 5-CF3-3-isoxazolyl 4-(R28N(Et)C(=O)O) 2-PhO-5-pyrimidyl 4-(R28OC(=O)O) 6-(MeOC(=O)-2-pyridyl
4-(R28OC(=S)O) 2-oxazolyl
4-(R28N(Et)C(=S)O) 2-thienyl G R59
5-(R59O(CH2)4) 2-pyrimidyl
5-(R59OCH2) 4-N02-2-oxazolyl 5-(R59(CH2)4O) 2-furanyl
5-(R59CH2O) 2-Cl-4-pyrimidyl
5-(R59CH2) 4-Me-Ph
5-(4-NO2-Ph) - - -
6-(R59O(CH2)2) 2-Me-3-furanyl
6-(R59CH2O) 3-thienyl
6-(R59(CH2)2) 5-MeS-2-oxazolyl
6-(3-MeS-Ph) - - -
4-(R590(CH2)3) 4,5-diCl-pyrazolyl
4-(R59(CH2)2O) 5-Me-3-isoxazolyl
4-(R59CH2) 3-furanyl
4-(4-EtO-Ph) - - -
TABLE 37
Compounds of Formula Ir wherein:
G R28
6-(R28N(Me)) 4-(4-CF3-Ph)
6-(R28N(Me)) 2-Me-Ph
6-(R28N(Me)) 2-pyridyl
6- (R28N (Me) ) 2-Cl-5-pyrimidyl
6-(R28N(Me)) 2,5-diCl-3-thienyl
6-(R28N(Me)) 2-NO2-3-f uranyl
6-(R28N(Me)) 5-MeO-3-isoxazolyl
6-(R28CH=CH) Ph
(Z)-6-(R28CH=CH) 2-EtS-5-pyrimidyl
6-(R28OC(=O)) 2-F-Ph
6-(R28OC(=O)) 3-pyrazolyl
6-(R28OC(=S)) 4-(4-Cl-PhO)Ph
6-(R28OC(=S)) 2 -Me-3-thienyl
6-(R28C(=O)O) 3-F-Ph
6-(R28C(=S)O) 2-pyrimidyl
6-(R28N(Me)C(=S)O) 4-Et-3-pyridyl
6-(R28OC(S)O) 4-PhO-Ph
6-(R28OC(O)O) 2-furanyl
6-(R28NHC(=O)O) 4-EtO-3-isoxazolyl
5-(R28N(Me)) Ph 5-(R28N(Me)) 3-Cl-Ph
5-(R28N(Me)) 3-Me-4-pyridyl
5-(R28N(Me)) 2-pyrimidyl
5-(R28N(Me)) 2-Et-3-thienyl
5-(R28N(Me)) 3-furanyl
5-(R28N(Me)) 4-Me-2-oxazolyl
5-(R28N(Me)) 5-NO2-3-pyrazolyl
(Z)-5-(R28CH=CH) 4-Cl-Ph
5-(R28CH=CH) 6-Me-2-ρyridyl
5-(R28OC(=O)) Ph
5-(R28OC(=O)) 4-EtO-2-pyridyl
5-(R28OC(=S)) 3-F-2-oxazolyl
5-(R28C(=O)O) 4-Br-Ph
5-(R28C(=S)O) 6-Et-2-pyridyl
5-(R28NHC(=O)O) 4-CF3-Ph
5-(R28N(Me2CH)C(=S)O) 2-oxazolyl
5-(R28OC(=O)O) 4-CF3-2-pyrimidyl
5-(R28N(Me)C(=O)O) 5-Me-2-furanyl
G R59
6-(R59OCH2) 3-F-Ph
6-(R59O(CH2)2) 3-isoxazolyl
6-(R59CH2O) 2,4-diF-Ph
6-(R59CH2O) 4-Et-Ph
6-(R59CH2) 3-(4-Cl-PhO)Ph
6-(R59(CH2)2) 2-F-Ph
6-(CF3-Ph) - - -
5-(R59O(CH2)2) 3-pyridyl
5-(R59(CH2)3O) 4-Cl-3-pyrazolyl
5-(R59(CH2)3) 2-Br-3-thienyl
5-(2-Cl-4-Me-Ph) - - -
TABLE 38
Compounds of Formula Is wherein:
G R 28
3-(R28N(Me)) Ph 3-(R28N(Me)) 2-F-Ph
3-(R28N(Me)) 4-(4-Cl-PhO)Ph
3-(R28N(Me)) 3-pyridyl
3-(R28N(Me)) 4-Me-2-pyrimidyl 3-(R28N(Me)) 2-F-3-thienyl
3-(R28N(Me)) 2-EtS-3-furanyl
33-(R28N(Me)) 4-NO2-2-oxazolyl
33-(R28N(Me) ) 5-Cl-3-isoxazolyl 3-(R28N(Me)) 3-pyrazolyl
(Z)-3-(R28CH=CH) 4-PhO-Ph
3-(R28CH=CH) 4-CF3-Ph
(Z)-3-(R28CH=CH) 3-isoxazolyl
3-(R28OC(=O)) 4-CF3-Ph
3-(R28OC(=O)) 2-Cl-5-pyrimidyl
3-(R28OC(=O)) 5-Me-2-furanyl
3-(R28OC(=S)) 5-NO2-3-isoxazolyl
3-(R28C(=O)O) 4-(4-butyl)Ph
3-(R28C(=S)O) 2-oxazolyl
3-(R28NHC(=S)O) 4-EtS-3-pyrazolyl
3-(R28OC(=S)O) 2,5-diF-3-thienyl
3-(R28N(Me)C(=O)O) 4-NO2-Ph G R59
3-(R59OCH2) 3-thienyl
3-(R59CH2O) 5-F-2-oxazolyl
3-(R59(CH2)4) 4-pyrazolyl
3-(2-Cl-Ph) - - -
TABLE 39
Compounds of Formula I wherein W=O, R1=Me, R3=Ph, R4=H, and:
R26
5-R26-3-F-2-furanyl 2-F-PhO
5-R26-3-F-2-furanyl 3-Br-PhO
5-R26-3-F-2-furanyl 2-Me-PhO
5-R26-3-F-2-furanyl 4-Et-PhO
5-R26-3-F-2-furanyl 2-MeO-PhO 5-R26-3-F-2-furanyl 4-EtO-PhO 5-R26-3-F-4-Cl-2-furanyl 2-F-PhO 5-R26-3-F-4-Cl-2-furanyl 4-Me-PhO 5-R26-4-CF3-2-furanyl 3-EtO-PhO 5-R26-4-Me-2-furanyl 4-Cl-PhO 5-R26-4-EtO-2-furanyl 3-Me-PhO 4-R26-3-F-2-furanyl 2-F-PhO 4-R26-3-F-2-furanyl 4-Cl-PhO 4-R26-5-Cl-2-furanyl 4-Et-PhO 4-R26-3-F-2-furanyl (2-Me-Ph)CH2O 4-R26-5-Me-2-furanyl (4-MeO-Ph)CH2O 5-R26-3-F-2-furanyl (2-F-Ph)CH2O 5-R26-3-F-2-furanyl (4-Et-Ph)CH2O 5-R26-2-F-3-furanyl 4-F-PhO 5-R26-2-F-3-furanyl 3-Cl-PhO 5-R26-2-F-3-furanyl 2-Me-PhO 5-R26-4-F-3-furanyl 3-Br-PhO 5-R26-2-F-3-furanyl (4-Br-Ph)CH2O 5-R26-2-F-3-furanyl (2-Me-Ph)CH2O 5-R26-4-F-3-furanyl (4-Et-Ph)CH2O 3-F-4-Me-2-furanyl
3-F-5-C6H13-2-furanyl
3-F-4-MeO-2-furanyl
4, 5-diMe-3-F-2-furanyl
4-EtO-3-F-5-MeO-2-furanyl
5-EtO-4-Cl-2-furanyl
2-F-5-Me-3-furanyl
2-F-5-MeO-3-furanyl
5-Et-4-F-3-furanyl
2, 4-diF-5-Me-3-furanyl
TABLE 40 6-(Z)-PhCH=CH Compounds of Formula It 6-PhC(=S)O wherein R18=2-F, and: 6-PhOC(=O)
R50 6-PhN(Me)C(=O)O 6-PhS 6-PhNHC(=S)O 6-PhOC(=O)O 6-(2-F-Ph)CH2
6-PhNHC(=S) 6-(3-Cl-Ph)C(=O)O 6-PhO(CH2)3 6-(4-CF3-Ph)OCH2 6-Ph(CH2)2O 6-(4-CF3-Ph)CH2O 6-PhCH2 6-(4-Et-Ph)OCH2
6-Ph(CH2)4 6-(4-Et-Ph)CH2O
6-PhNH 6-(4-PhO-Ph)CH2O 6-PhCH=CH 6-Me
6-PhOC(=O) 6-CH3CH(CH3) (CH2)3 6-PhOC(=S) 6-CF3(CH2)5
6-PhN(C4H9)C(=O)O 6-C2H5CH(CH3) (CH2)2O 6-PhN(Me)C(=S)O 5-C6H13S
6-PhOC(=S)O 6-(C4H9)C(CH3) (C1)S 6-PhOCH2 5-C2H5C (CH3) =CHCH2 6-PhO(CH2)4 6-CH3CH (CH3) C (Br) =CHCH2 6-Ph(CH2)3O 5-CH3CH (CH3) C=C (CH2) 2 6-Ph(CH2)2 6-CF3(CH2)3C=C
6-PhN(Me) 6-CH2=CH (CH2) 2CH(CH3)O 6-PhC(=O)O 6-C2H5C (Cl) =C(CH3)CH2O 6-PhOC(=S) 5-C2H5C=CCH(CH3)O 6-PhNHC(=O)O 6-C6H13
6-PhN(CH3CH(CH3)CH2)C(=O)O 6-CF3
6-PhN(C4H9)C(=S)O 5-CF3O
6-PhNHC(=O) 6-MeS
6-PhO(CH2)2 5-CF3S
6-PhCH2O 6-CH2=CH
6-Ph(CH2)4O 6-CH (Cl) =CH
6-Ph(CH2)3 6-MeC≡C
6-(2-F-PhS) 6-CH≡CCH2Cl
6-(2-F-Ph)CH=CH 5-CH2=CHCH2O
6-(2-F-Ph)C(=O)O 6-CF2=CHCH2O
6-(2-F-Ph)C(=S)O 6-CHC≡CCH2O
6-(2-F-Ph)OCH2 5-cyclopropyloxy 6-(2-F-Ph)O(CH2)2 6-cyclohexyloxy
6-(2-F-Ph)CH2O 5-cyclohexyl
6-(26F-Ph) (CH2)2O 5-MeSO2 6-C2H5CH(CH3)CH(CH3)SO2 5-PhO 4-Cl
6-C4H9O(CH2)2 5-PhO 6-Cl
5-C4H9OC(CH3)O 5-PhO 3-F-4-Cl
6-C5H11OC(=O) 5-PhO 6-F-4-Cl
6-cyclopropyl 5-PhO 6-CF3
6-C6H13SO2 5-PhO 4-Me
6-CH2ClSO2 5-PhO 6-Et
5-MeOCH2 5-PhO 4-MeO
6-MeOCH2O 5-PhO 6-EtO
6-MeOC(=O) 5-(2-F-PhO) 3-F
5-NMe2 5-(2-F-PhO) 4-MeO
5-(2-F-PhO) 6-Cl
TABLE 41 5-(2-F-PhO) 6-Me Compounds of Formula It 6-PhO 3-F wherein: R50=6-PhO 6-PhO 4-Cl
R 18 6-PhO 3-F-5-Cl
2,5-diF 6-(2-F-PhO) 5-Me
2,4-diF 6-(2-F-PhO) 5-MeO
5-Et 4-PhO 3-F
5-EtO 4-PhO 6-Cl
5-Cl-2-F 4-(2-F-PhO) 4-Et
5-Cl-4-F 3-F 5-Me
5-CF3 3-F 5-CF3
5-F 3-F 5-CHF2
5-Br-2-F 3-F-4-Br 5-MeO
5-Me 4-Br-6-Cl 5-CF3O
5-MeO
2-F-5-Me TABLE 43
Compounds of Formula Iv
TABLE 42 wherein:
Compounds of Formula R18 R50
wherein: 3-F 5-NMe2
R50 R18 3-F 5-MeSO2
5-PhO 3-F 3-F 5-MeOCH2O
5-PhO 4-F 3-F 5-MeC=CCH2O
5-PhO 6-F 3-F 2-MeOC(=O) 3-F 2-CH2=CHCH2O NHR28 5-NO2-4-
3-F 2-CH≡CCH2 isoxazolyl
3-F 2-CH2=CH NHR28 3-Me-5- isoxazolyl
TABLE 44 NHR28 2-oxazolyl
Compounds of Formula Iw NHR28 2-MeO-4-oxazolyl wherein: NHR28 5-Br-3-pyrazolyl
R50 R28 NHR28 4-pyrazolyl
SR28 4-Me-2-thienyl NHR28 6-Cl-2-pyridyl
SR28 2-CH3CH(CH3)CH2- NHR28 2,5-diF-3- 3-thienyl pyridyl
SR28 2-furanyl NHR28 3-Me-4-pyridyl
SR28 4-MeO-3-furanyl NHR28 3-Bu-2-pyrimidyl
SR28 5-(C4H9O)-3- NHR28 2-CN-5-pyrimidyl isoxazolyl NHR28 3-(2-MeS-PhO)-4-
SR28 3-CF3-4- pyrimidyl
isoxazolyl (Z)-R28CH=CH 5-isoxazolyl
SR28 4-MeS-5- (Z)-R28CH=CH 4-Cl-2-oxazolyl isoxazolyl (Z)-R28CH=CH 2-Et-4-oxazolyl
SR28 4-oxazolyl (Z)-R28CH=CH 3-Cl-4-pyrazolyl
SR28 2-F-5-oxazolyl (Z)-R28CH=CH 6-MeO-2-pyridyl
SR28 4-Cl-3-pyrazolyl (Z)-R28CH=CH 2-Bu-3-pyridyl
SR28 3-Br-4-pyrazoly1 (Z)-R28CH=CH 4-F-5-pyrimidyl
SR28 2-pyridyl (Z)-R28CH=CH 2-PhO-5-
SR28 2-CF3-3-pyridyl pyrimidyl
SR28 2-CF3O-4-pyridyl R28CH-CH 2-thienyl
SR28 2-F-4-pyrimidyl R28CH-CH 4-(CH3CH(CH3)CH)-
NHR28 2-thienyl 3-isoxazolyl
NHR28 2,4-diCl-3- R28CH=CH 5-MeO-4- thienyl isoxazolyl
NHR28 3-Cl-4-F-2- R28CH=CH 2-MeS-2-oxazolyl furanyl R28CH=CH 2-Br-5-oxazolyl
NHR28 4-CF3-3-furanyl R28CH=CH 3-Me-4-pyrazolyl
NHR28 4-MeS-3- R28CH=CH 4-Me-2-pyridyl isoxazolyl R28CH=CH 5-BuO-3-pyridyl
R28CH=CH 3-Br-4-pyridyl R28CH=CH 2-(4-MeO-PhO)-5- R59CH2O 3-MeO-Ph
pyrimidyl R59CH2O 4-BuO-Ph
R59(CH2)2O 3-F-Ph
R50 R59 R59(CH2)2O 2-Me-Ph
R59CH2 2-F-Ph R59(CH2)2O 3-MeO-Ph
R59CH2 2-Cl-Ph R59(CH2)3O 2-F-Ph
R59CH2 3-Br-Ph R59(CH2)3O 3-Me-Ph
R59CH2 4-Cl-2-F-Ph R59(CH2)3O 4-BuO-Ph
R59CH2 4-Cl-Ph R59(CH2)4O 2-MeO-Ph
R59CH2 3-CF3-Ph R59(CH2)4O 3-F-Ph
R59CH2 4-MeS-Ph R59(CH2)4O 4-Cl-Ph
R59CH2 4-NO2-Ph R59OCH2 2-Cl-Ph
R59CH2 2-Me-Ph R59OCH2 4-Cl-Ph
R59CH2 4-Bu-Ph R59OCH2 3-Br-Ph
R59CH2 3-MeO-Ph R59OCH2 2,4-diF-Ph
R59CH2 4-BuO-Ph R59OCH2 2-Cl-Ph
R59CH2CH2 3-Br-Ph R59OCH2 4-CF3-Ph
R59CH2CH2 4-MeS-Ph R59OCH2 3-MeSrPh
R59CH2CH2 4-Cl-2-F-Ph R59OCH2 4-NO2-Ph
R59CH2CH2 2,3-diF-Ph R59OCH2 2-Me-Ph
R59CH2CH2 2-Me-Ph R59OCH2 4-Bu-Ph
R59(CH2)3 4-Br-Ph R59OCH2 2-MeO-Ph
R59(CH2)3 4-(CH3CH(CH3)- .59 'OCH2 3-(CH3CH(CH3)CH2O)'
CH2) Ph Ph
R59(CH2)4 4-F-Ph R59O(CH2)2 2-Cl-Ph
R59(CH2)4 .2-MeO-Ph R59O(CH2)2 3-CF3-Ph
R59CH2O 2-F-Ph R59O(CH2)2 3-MeO-Ph
R59CH2O 2-Cl-Ph R59O(CH2)2 4-BuO-Ph
R59CH2O 3-Br-Ph R59O(CH2)2 4-Bu-Ph
R59CH2O 4-Cl-2-F-Ph R59O(CH2)2 2-F-Ph
R59CH2O 4-Cl-Ph R59O(CH2)3 2,4-diF-Ph
R59CH2O 3-CF3-Ph R59O(CH2)3 4-Cl-Ph
R59CH2O 4-MeS-Ph R59O(CH2)4 2-Me-Ph
R59CH2O 2-Me-Ph R59O(CH2)4 4-BuO-Ph
R59CHoO 4-Bu-Ph TABLE 45
Compounds of Formula Iw wherein:
R50 V R28
R28OC(=V) O 4-NO2-2-thienyl
R28OC(=V) O 2-furanyl
R28OC(=V) O 4-Cl-3-isoxazolyl
R28OC(=V) O 4-Me-5-isoxazolyl
R28OC(=V) S 5-Bu-2-oxazolyl
R28OC(=V) O 5-CF3-3-pyrazolyl
R28OC(=V) O 4-CF3-2-pyridyl
R28OC(=V) O 5-Me-3-pyridyl
R28OC(=V) O 3-CF3O-2-pyrimidyl
R28OC(=V) O 2-MeOC (=O) -5-pyrimidyl
R28OC(=V) O 6-Cl-4-pyrimidyl
R28C(=V)O O 5-CF3-2-furanyl
R28C(=V)O S 4-(C2H5CH(CH3)O)-3-furanyl
R28C(=V)O S 3-Me-4-isoxazolyl
R28C(=V)O O 4-C4H9-5-isoxazolyl
R28C(=V)O O 2-Br-4-oxazolyl
R28C(=V)O O 3-pyrazolyl
R28C(=V)O S 3-Et-4-pyrazolyl
R28C(=V)O O 3-CN-2-pyridyl
R28C(=V)O O 4-(Me)3C-3-pyridyl
R28C(=V)O O 2-MeO-4-pyridyl
R28C(=V)O O 4,6-diCl-2-pyrimidyl
R28C(=V)O O 4-F-5-pyrimidyl
R28C(=V)O O 2-(4-Cl-PhO)-4-pyrimidyl
R28OC(=V)O O 5-CF3-2-thienyl
R28OC(=V)O O 4-NO2-2-furanyl
R28OC(=V)O O 4-Br-3-isoxazolyl
R28OC(=V)O S 5-Me-4-isoxazolyl
R28OC(=V)O O 5-isoxazolyl
R28OC(=V)O S 4-Bu-2-oxazolyl
R28OC(=V)O O 5-BuO-3-pyrazolyl
R28OC(=V)O O 4-(2-F-PhO)-2-pyridyl
R28OC(=V)O O 2-Cl-4-pyridyl R28OC(=V)O O 3-Br-2-pyrimidyl
R28OC(=V)O O 4-Me-5-pyrimidyl
R28OC(=V)O O 5-(EtCHMe)-4-pyrimidyl
R50 V R28 R39
R28R39NC(=V)O O 2-thienyl H
R28R39NC(=V)O S 2-F-3-thienyl Me
R28R39NC(=V)O O 3-Br-2-furanyl Et
R28R39NC(=V)O S 4-Me-3-furanyl Pr
R28R39NC(=V)O O 5-Bu-3-isoxazolyl Bu
R28R39NC(=V)O O 4-(EtCH(CH3))-5-isoxazolyl H
R28R39NC(=V)O O 2-MeS-4-oxazolyl Et
R28R39NC(=V)O O 3-pyrazolyl Bu
R28R39NC(=V)O O 5-MeOC(=O)-2-pyridyl H
R28R39NC(=V)O O 4-(2-F-PhO)-2-pyridyl Me
R28R39NC(=V)O O 4-CF3-3-pyridyl Et
R28R39NC(=V)O O 4-Bu-2-pyrimidyl Bu
R28R39NC(=V)O O 6-Et-5-pyrimidyl H
R28R39NC(=V)O O 5-Br-4-pyrimidyl Me
R28R39NC(=V) O 4-Cl-3-thienyl H
R28R39NC(=V) S 3-Br-2-furanyl H
R28R39NC(=V) O 2,4-diCl-3-furanyl Me
R28R39NC(=V) S 4-CF3-5-isoxazolyl C2H5CH(CH3)
R28R39NC(=V) O 4-MeS-2-oxazolyl H
R28R39NC(=V) O 2-Bu-5-oxazolyl Et
R28R39NC(-V) S 3-pyrazolyl Bu
R28R39NC(=V) O 5-MeO-3-pyridyl H
R28R39NC(=V) O 4-(4-Me-PhO)-3-pyridyl H
R28R39NC(=V) O 3-Bu-4-ρyridyl H
R28R39NC(=V) S 4-F-2-pyrimidyl H
R28R39NC(=V) O 5-pyrimidyl H Formulation/utility
Compounds of this invention will generally be used in formulation with an agriculturally suitable
composition. The fungicidal compositions of the present invention comprise an effective amount of at least one compound of Formula I as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent. Useful formulations can be prepared in conventional ways.
They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further
formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.
Weight Percent
Active
Ingredient Diluent Surfactant
Wettable Powders 25-90 0-74 1-10
Oil Suspensions, 5-50 40-95 0-15
Emulsions, Solutions,
(including Emulsifiable
Concentrates)
Dusts 1-25 70-99 0-5
Granules, Baits and 0.01-99 5-99.99 0-15
Pellets
High Strength 90-99 0-10 0-2
Compositions
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and
Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon ' s Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
Methods for formulating such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S.
3,060,084. Granules and pellets can be made by
spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-148, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in DE 3,246,493.
For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;
U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132,
138-140, 162-164, 166, 167 and 169-182; U.S.
2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are worked up in
conventional ways. Compound numbers refer to Index Table A hereinafter.
Example A
Wettable Powder
Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example B
Granule
Compound 1 10.0% attapulgite granules (low volative
matter, 0.71/0.30 mm; U.S.S. No.
25-50 sieves) 90.0%.
Example C
Extruded Pellet
Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
Example D
Emulsifiable Concentrate
Compound 1 20.0% blend of oil soluble sulfonates
and polyoxyethylene ethers 10.0% isophorone 70.0%.
The compounds of this invention are useful as plant disease control agents. The present invention
therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens
comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of Formula I or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete,
Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera
leucotricha, Venturia inaequalisr Erysiphe graminis, Uncinula necatur, Pυccinia recondita, Puccinia
graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma and other generea and species closely related to these pathogens.
Compounds of this invention can also be mixed with one or more other insecticides, fungicides,
nematocides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of other
agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monocrotophos, carbofuran, tetrachlorvinphos,
malathion, parathion—methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate,
esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate,
tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin,
kasugamycin, myclobutanil, tebuconazole,
difenoconazole, diniconazole, fluquinconazole,
ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox,
fenarimol, triadimenol, diclobutrazol, copper
oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole,
pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and
fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as Bacillus thuringiensis, baculovirus and avermectin B.
In certain instances, combinations with other fungicides having a similiar spectrum of control but a different mode of action will be particularly
advantageous for resistance management.
Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to the seed to protect the seed and seedling.
Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions.
Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be
protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.
The following Tests demonstrate the control
efficacy of compounds of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not limited, however, to these
species. See Index Table A for compound descriptions.
Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following tests.
TEST A
The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20 °C for 6 days, after which disease ratings were made.
TEST B
The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27 °C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.
TEST C
The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
TEST D
The test suspension was sprayed to the point of run-off on potato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and potato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
TEST E
The test suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings were made.
Index Table 1
Compounds of Formula I wherein:
Cmpd
No. R1 R2 R3 R4 W mp(ºC)1
1 Me 2-F-6-PhO-3-pyridyl Ph H O 175
2 Me 2,6-diF-3-pyridyl Ph H O 127
3 Me 2-F-6-PhO-3-pyridyl Ph H S 145
4 Me 2,6-diF-3-pyridyl Ph H S 131
5 Me PhOCH2CH2CH2 Ph H O 115
6 Me (E)-PhOCH2CH=CHCH2 Ph H O 102
7 Me 2-F-6-(2-Cl-PhO)-3-pyridyl Ph H O 160
8 Me 2-F-6-(2-Cl-PhO)-3-pyridyl P.h H S 141
9 Me 2-F-6-(2-F-PhO)-3-pyridyl Ph H O 160
10 Me 2-F-6-(2-F-PhO)-3-pyridyl Ph H S 125
11 Me (2-F-PhO)CH2CH2CH2 Ph H O 85
12 Me (2-Me-PhO)CH2CH2CH2 Ph H O 110
13 Me 2-F-6-(2-Me-PhO)-3-pyridyl Ph H O 169
14 Me (4-PhO-PhO)CH2CH2CH2 Ph H O 132
15 Me 2-F-6-(2,3-diF-PhO)-3-pyridyl Ph H O 142
16 Me 2-F-6-(2,3-diCl-PhO)-3-pyridyl Ph H O 206
17 Me 2-F-6-(2-pyridylthio)-3-pyridyl Ph H O 182
18 Me 2-F-6-(3-PhO-PhO)-3-pyridyl Ph H O 125
19 Me 2-F-6-(2-MeO-PhO)-3-pyridyl Ph H O 149
20 Me 3-(PhCH2CH2CH2O)Ph Ph H O 110
21 Me PhO(CH2)4 Ph H O 97
22 Me 2-F-6-PhCH2O-3-pyridyl Ph H O 111
23 H PhOCH2CH2CH2 Ph H O 123
24 Me CH3(CH2)8CH2 Ph H O 76
25 Me CH3(CH2)6CH2 Ph H O 63
26 Me 4-(5-CF3-2-pyridyloxy)Ph Ph H S oil
27 Me 4-(3-Cl-5-CF3-2-pyridyloxy)Ph Ph H S 134
28 Me 4-(3-Cl-5-CF3-2-pyridyloxy)Ph Ph H O 77
29 Me 4-[PhC(=O)O]Ph Ph H O 156 Cmpd
No. R1 R2 R3 R4 W mp(°C)1
30 Me 4-[(3-F-Ph)C(=O)O]Ph Ph H O 179
31 Me 4-[(4-MeO-Ph)C(=O)O]Ph Ph H O 162
32 Me 4-[(4-CN-Ph)C(=O)O]Ph Ph H O 182
33 Me 4-[(3-Cl-Ph)C(=O)O]Ph Ph H O 129
34 Me 3-[PhC(=O)O]Ph Ph H O 112
35 Me 3-[(3-F-Ph)C(=O)O]Ph Ph H O 108
36 Me 3-[(4-MeO-Ph)C(=O)O]Ph Ph H O 76
37 Me 3-[(4-CN-Ph)C(=O)O]Ph Ph H O 93
38 Me 3-[(3-Cl-Ph)C(=O)O]Ph Ph H O 78
39 Me 3-[MeC(=O)O]Ph Ph H O oil
40 Me 3-[PrC(=O)O]Ph Ph H O 90
41 Me 3-[i-PrC(=O)O]Ph Ph H O 120
42 Me 3-[Me3CC(=O)O]Ph Ph H O 132
43 Me 4-[MeC(=O)O]Ph Ph H o 109
44 Me 4-[PrC(=O)O]Ph Ph H O 136
45 Me 4-[ϊ-PrC(=O)O]Ph Ph H O 158
46 Me 4-[Me3CC(=O)O]Ph Ph H O 120
47 Me 4-(MeOCH2CH2OCH2O)Ph Ph H O oil
48 Me 4-(2-tetrahydropyranyloxy)Ph Ph H O 162
49 Me 3-(MeOCH2CH2OCH2O)Ph Ph H O Oil
50 Me 3-(PhCH2OCH2O)Ph Ph H O 100
51 Me (2-tetrahydropyranyloxy)CH2CH2CH2 Ph H O 76
52 Me HOCH2CH2CH2 Ph H O 122
53 Me CH3(CH2)6CH2 3-Cl-Ph H o 82
54 Me CH3(CH2)6CH2 3-F-Ph H o 84
55 Me CH3(CH2)6CH2 2-Me-Ph H O 65
56 Me PhO(CH2)5 Ph H O 67
57 Me 4-(2-Me-Ph)Ph Ph H O 139
58 Me PhSO3(CH2)3 Ph H O 67
59 Me (O=)CHCH2CH2 Ph H O 73
60 Me MeSO3(CH2)3 Ph H O 115
61 Me (E)-(CH2=CHCH2O-N=)CHCH2CH2 Ph H O 80 Cmpd
No . R1 R2 R3 R4 W mp (ºC )1
62 Me (Z) - (CH2=CHCH2O-N=) CHCH2CH2 Ph H O oil
63 Me (Z) -PhOCH2CH=CHCH2 Ph H O 69
64 Me (E) -PhCH=CHCH2 Ph H O 141
1 1H NMR data for oils listed in Index Table 2
Index Table 2
Cmpd No. 1H NMR Data1
26 6.43 (s, 1H), 6.76 (d, J=7.6, 2H), 7.94 (d,
J=8.6, 1H), 8.44 (s, 1H)
39 2.05 (s, 3H), 2.32 (s, 3H), 6.04 (s, 1H, NH) 47 3.38 (s, 3H), 5.29 (s, 2H), 6.08 (s, 1H, NH) 49 3.36 (s, 3H), 5.28 (s, 2H), 6.34 (s, 1H, NH) 62 1.67 (s, 3H), 2.10-2.60 (m, 4H), 4.58 (d,
J=4, 2H), 5.22-5.35 (m, 2H), 5.95 (m, 1H),
6.26 (s, 1H), 6.66 (t, J=4, 1H), 6.80-7.28
(m, 5H).
1 Unless indicated otherwise, spectra were obtained in CDCl3 at 400 MHz. s = singlet, d = doublet, m =
multiplet, coupling constants (J) are in Hertz.
Results for Tests A to E are given in Table 1. In the table, a rating of 100 indicates 100% disease
control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls). NT
indicates that no test was performed.
TABLE 1
Cmpd Test Test Test Test Test
No . A B C D E
1 100 47 64 99 100
2 75 0 86 79 100
3 100 94 93 97 100 4 100 84 0 77 100
5 0 0 96 100 100
6 59 0 0 0 100
7 100 90 84 100 100
8 100 91 73 97 100
9 100 91 73 91 100 10 100 87 0 62 100 11 0 0 61 88 100 12 22 14 75 72 100 13 86 86 75 91 100 14 22 0 43 88 100 15 100 0 NT 97 100 16 100 0 43 85 100 17 0 0 16 NT 0 18 92 39 70 33* 100 19 81 39 53 56* 100 20 0 0 12 NT 0 21 0 0 84 NT 100 22 100 61 99 NT 100 23 0 0 16 NT 60 24 16 13 76 87 100 25 96 13 97 100 100 26 77 0 77 97 100 27 77 26 26 NT 100 28 95 0 97 NT 100 29 86 0 75 16 100 30 90 0 43* 9 100 31 80 0 43* 0 100 32 86 0 0 95 100 33 90 0 43 54 100 34 28 0 0 9 100 35 41 48 43 9 85 36 66 0 0 0 75 37 24 25 0 0 92 38 66 0 0 26 100 39 66 24* 0 0 46 40 80 0 24 NT 99
41 86 0 24 NT 99
42 41 0 24 NT 93
43 86 0 24 NT 99
44 93 24 76 34 99
45 93 0 76 34 100
46 97 48 63 59 100
* = Plants were sprayed at a concentration of 40 ppm.

Claims

CLAIMS We Claim:
1. A compound comprising Formula I
wherein:
R1 is H; C1-C4 alkyl; C1-C4 haloalkyl; C3-C6
cycloalkyl; C2-C4 alkenyl; C2-C4
alkoxycarbonyl; or phenylmethyl optionally substituted on the phenyl ring with R6 and on the benzylic carbon with R7;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C4-C17 alkyl substituted with C3-C6 cycloalkyl; C4-C12 alkyl substituted with phenyl optionally substituted with R31 on the phenyl ring; C3-C14 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C20 alkyl substituted with R19; C2-C6 alkoxyalkyl substituted with R21; C7-C20 alkoxyalkyl optionally substituted with R21; C7-C20 alkenyl; C2-C20 alkenyl substituted with R20; C7-C20 alkynyl; C2-C20 alkynyl substituted with R48; C5-C7 cycloalkenyl; (CH2CH2OCH2CH2)CH-;
(CH2CH2N(R15)CH2CH2)CH-; (CH2CH2SCH2CH2)CH-;
(CH2CH2SO2CH2CH2)CH-; pyrimidyl, pyrazinyl, pyridazinyl, oxazolyl, isoxazolyl, isothiazolyl or thiazolyl each optionally substituted with R26 and R18; furanyl substituted with one substituent selected from R26 and one from R18; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl, pyridyl, pyrimidinyl or pyridazyl
each optionally substituted with R10; or phenylmethyl;
R4 is H, methyl, or acetyl;
R5, R7, R11, R14, R23, R24, R30, R39, R43, and R55 are each independently H or C1-C4 alkyl;
R6, R29, R34, R38, R42, R44, and R56 are each
independently 1-2 halogen; C1-C4 alkyl; C1-C4 alkoxy; trifluoromethyl; methylthio; or nitro; R8 is C2-C19 alkyl; C2-C19 alkylcarbonyl; C2-C19
alkoxycarbonyl; (R9R14N)C=O; phenyl optionally substituted with R27; or phenoxycarbonyl optionally substituted with R17;
R9 is C1-C18 alkyl; or phenyl optionally
substituted with R17;
R10, R27, and R45 are each independently 1-2
substituents selected from the group consisting of trifluoromethyl, trifluoromethoxy, nitro,
CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano;
R12 is H; C1-C8 alkyl optionally substituted with C2-C7 alkoxycarbonyl; C3-C8 alkenyl;
phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5; phenyl optionally substituted with R34; or pyridyl optionally substituted with R34; or
R11 and R58 can be taken together as -CH2 (CH2)2CH2-, -CH2(CH2)3CH2-, -CH2(CH2)4CH2-, -CH2CH2OCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2N(R5)CH2CH2- or
-CH2CH2N(R5)CH2CH2CH2- along with the nitrogen to which they are attached to form a ring;
R13 is C1-C6 alkyl; C3-C6 cycloalkyl; phenyl
optionally substituted with R45; or phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5;
R15 is C1-C12 alkyl; C2-C12 alkylcarbonyl; benzoyl optionally substituted with R16 on the phenyl ring; C2-C12 alkoxycarbonyl; C2-C12 alkylaminocarbonyl substituted with R55 on nitrogen;
phenoxycarbonyl optionally substituted with R46 on the phenyl ring; or phenylaminocarbonyl optionally substituted with R46 on the phenyl ring and with R55 on nitrogen;
R16 is 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8
alkoxyalkoxy; C2-C8 alkylthio; C2-C8 alkenyl;
C2-C8 haloalkenyl; C2-C8 alkynyl;
hydroxycarbonyl; C2-C8 alkoxy-carbonyl; or phenoxy substituted with R29;
R17, R18, R32, R35, R47, and R53 are each
independently 1-2 halogen; C1-C2 alkyl;
trifluoromethyl; or C1-C2 alkoxy;
R19 is cyano; nitro; C1-C19 alkylthio; C1-C19
alkylsulfinyl; C1-C19 haloalkoxy; C5-C6
cycloalkyloxy; C3-C19 alkenyloxy; C3-C19 alkynyloxy; C1-C19 alkylsulfonyl; C2-C19 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC(=O)O; R8R43N; (C1-C4 alkoxy) 2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenyl-sulfinyl, pyridyl or pyridyloxy each optionally substituted with
R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38; tetrahydropyranyl; 2-tetrahydropyranyloxy; or
C(=J)R24; R20 is cyano; nitro; C1-C17 alkylthio; C1-C17 alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17 haloalkynyl; C3-C17 alkynyloxy; C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; R8R43N; (C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+; phenyl-sulfonyl,
phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl, naphthalenyl,
pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38; tetrahydropyranyl;
2-tetrahydropyranyloxy; C1-C17 alkoxy; 1-3 halogen; C2-C17 alkoxy-alkoxy; C3-C17 alkynyl;
C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R21 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C2-C17 haloalkenyl; C3-C17 alkenyloxy; C3-C17 haloalkynyl; C3-C17
alkynyloxy; C1-C17 alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O) O; R8R43N; (C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C 1-C17 alkoxy; C2-C17 alkoxyalkoxy; C3-C17 alkynyl; C3-C6 cycloalkyl; phenyl or phenoxy each optionally substituted with R31; or C2-C17 haloalkoxyalkoxy; R22 is C1-C16 alkyl; phenyl optionally substituted with R36; or pyridyl optionally substituted with R36;
R25 is H; C1-C6 alkyl; or phenyl optionally
substituted with R35;
R26 is C1-C6 alkyl; C1-C6 alkoxy; phenoxy
substituted with R53, or benzyloxy substituted on the phenyl ring with R53;
R28 is phenyl, pyridyl or pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl or pyrazolyl each
optionally substituted with R38;
R31, R36, R37, R41, R46 are independently 1-2
substituents selected from the group consisting of trifluoromethyl, trifluoromethoxy, nitro,
CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano; or phenoxy substituted with R44;
R33 is C1-C6 alkyl; or phenyl optionally
substituted with R32;
R40 is pyridyl or pyrimidyl each optionally
substituted with R37; or thienyl, furanyl, pyrazolyl, naphthalenyl, isothiazolyl,
thiazolyl, imidazolyl, oxazolyl, or isoxazolyl each optionally substituted with R38; 2-tetrahydropyranyl; or 2-tetrahydrofuranyl;
R48 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17 alkynyloxy; C1-C17 alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC(=O)O; R8R43N; (C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C1-C17 alkoxy; 1-3 halogen; C2-C17 alkoxyalkoxy; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R49 is C5-C12 alkyl; C2-C12 haloalkyl; C5-C12 alkoxy;
C1-C12 haloalkoxy; C2-C12 alkylthio; C1-C12 haloalkylthio; C2-C12 alkenyl; C2-C12
haloalkenyl; C3-C12 alkynyl; C2-C12 haloalkynyl; C3-C12 alkenyloxy; C3-C12 haloalkenyloxy; C3-C12 alkynyloxy; C1-C12 alkylsulfonyl; C1-C12
haloalkylsulfonyl; C2-C12 alkoxyalkyl; C2-C12 alkoxyalkoxy; C2-C12 alkoxycarbonyl; N(CH3)2; or G;
R50 is C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy;
C1-C6 haloalkoxy; C1-C6 alkylthio; C1-C6
haloalkylthio; C2-C6 alkenyl; C2-C6 haloalkenyl; C3-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6
alkynyloxy; C3-C6 cycloalkyl; C3-C6 cycloalkyloxy; C1-C6 alkylsulfonyl; C1-C6 haloalkylsulfonyl; C2-C6 alkoxyalkyl; C2-C6
alkoxyalkoxy; C2-C6 alkoxycarbonyl; N(CH3)2; or
Y;
R51 is phenyl substituted with R52; pyridyl or
pyrimidyl each optionally substituted with R37; .or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazolyl each optionally substituted with R38; R52 1S 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8 alkoxyalkoxy; C2-C8 alkylthio; C5-C6 cycloalkyl; C5-C6 cycloalkyloxy; C2-C8 alkenyl; C2-C8 haloalkenyl; C2-C8 alkynyl; hydroxycarbonyl; C2-C8 alkoxycarbonyl; or phenoxy optionally
substituted with R29; R54 is phenyl substituted with R37; pyridyl or pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazolyl each optionally substituted with R38; R57 is C1-C12 alkyl; C3-C6 cycloalkyl; C1-C12
haloalkyl; C3-C12 alkenyl; C3-C12 haloalkenyl; C3-C12 alkynyl; C3-C12 haloalkynyl; phenyl, naphthalenyl or pyridyl each optionally
substituted with R41; or furanyl or thienyl each optionally substituted with R42;
R58 is R12, C(=O)R13, C(=0)OR13 or C(=O)NR13R30;
R59 is phenyl optionally substituted with R38;
A is O, NR25, or a direct bond;
E and V are independently O or S;
G is -OR51; -SR51; -NHR28; -N(CH3)R28; -CH=CHR28 (cis or trans); -C(=V)OR28; -OC(=V)R28;
R28NR39C(=V)O-; -OC(=V)OR28; -C(=V)NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -{CH2)mR59. or phenyl optionally substituted with R38;
J is O or N-A-L;
L is H; C1-C8 alkyl, C3-C8 alkenyl; phenylmethyl optionally substituted with R47 on the phenyl ring and R55 on the benzylic carbon; phenyl optionally substituted with R47; pyridyl optionally substituted with R47; C(=O)R22;
C(=O)OR22; or C(=O)NR22R7;
m is 1-4;
n is 3-4;
Q is O, NR11, or a direct bond;
T is phenyl optionally substituted with 1-2
halogen; C1-C4 alkyl; C1-C4 alkoxy;
trifluoromethyl; methylthio; or nitro;
W is O, S, or N-Q-R58;
Y is -OR28; -SR28; -NHR28; -N(CH3)R28; -CH=CHR28 (cis or trans); -C(=V)OR28; -OC(=V)R28; R28NR39C(=V)O-; -OC(=V)OR28; -C(=V)NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -(CH2)mR59; or phenyl optionally substituted with R38; and
Z is phenoxy substituted with R16; C3-C12
alkoxyalkoxyalkoxy; benzyloxymethoxy optionally substituted on the phenyl ring with R56; C5-C6 cycloalkyloxy; styryl optionally substituted on the phenyl ring with R41; -C(=V)OR57;
-OC(=V)R57; -OC(=V)NR39R57; -OC(=V)OR57; -C(=V)NR39R57; -(CH2)nR59; -(CH2)nOR59;
-O(CH2)nR59; or -OR40;
and the agriculturally suitable salts thereof;
provided that :
i) when W is N-Q-R58, Z is other than phenoxy
substituted with R16, C5-C6 cycloalkyloxy, or
-C(=O)(C1-C5 alkoxy);
ii) when R2 is an optionally substituted phenyl or heterocyclic ring, only H or F can be
substituted on the carbon atom(s) of the phenyl or heterocyclic ring adjacent to the carbon bearing the oxazolidinone ring; iii) when two substituents are selected from the
alkyl and alkoxy groups in R10, R27, R31, R36, R37, R41, R45 or R46, then at least one of said substituents contains only one carbon atom; and iv) when R2 is alkyl substituted with optionally substituted phenyl, then the phenyl group is not attached to the alkyl carbon attached to the oxazolidinone ring.
2. A compound of Claim 1, wherein
R1 is H; C1-C2 alkyl; or vinyl;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C3-C8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C16 alkyl substituted with R19; C2-C6 alkoxyalkyl substituted with R21; C7-C16 alkoxyalkyl optionally substituted with R21; C7-C20 alkenyl; C2-C16 alkenyl substituted with R20; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl optionally substituted with C1-C2
alkyl or halogen;
R4 is H or methyl;
R12 is C1-C8 alkyl; phenylmethyl; or phenyl;
R19 is C1-C19 alkylthio; C1-C19 haloalkoxy; C5-C6 cycloalkyloxy; C3-C19 alkenyloxy; C1-C19
alkylsulfonyl; C2-C19 alkoxycarbonyl;
hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with
R31; thienyl or furanyl each optionally
substituted with R38; 2-tetrahydropyranyloxy; or CH(=N-A-L);
R20 is C1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl;
hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl optionally substituted with R38; 2-tetrahydropyranyloxy; C1-C17 alkoxy; 1-3 halogen; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31; R21 is C1-C17 alkylthio; C-L-C^ haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C1-C17 alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxycarbonyl; R22C(=O)O; R22OC(=O)O; R22R43NC (=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl each optionally substituted with R38;
2-tetrahydropyranyloxy; C1-C17 alkoxy; C2-C17 alkoxyalkoxy; or phenyl or phenoxy each
optionally substituted with R31;
R28 is phenyl or pyridyl each optionally
substituted with R37; or thienyl or furanyl each optionally substituted with R38;
R40 is pyridyl or pyrimidyl each optionally
substituted with R37; or thienyl or furanyl each optionally substituted with R38;
2-tetrahydropyranyl; or 2-tetrahydrofuranyl; R51 is phenyl substituted with R52; pyridyl
optionally substituted with R37; or thienyl or furanyl each optionally substituted with R38; R57 is C1-C12 alkyl; C3-C6 cycloalkyl; C1-C12
haloalkyl; phenyl, naphthalenyl or pyridyl each optionally substituted with R41; or furanyl or thienyl each optionally substituted with R42; R58 is R12;
A is 0 or NR25;
G is -OR51 or -SR51;
L is H; C1-C8 alkyl; phenylmethyl optionally
substituted with R47 on the phenyl ring; phenyl optionally substituted with R47; or C(=O)R22; Q is OH, NH, or a direct bond;
Y is -OR28 or -SR28; and
Z is phenoxy substituted with R16; -C(=0)OR57;
-OC(=O)R57; -OR40; or -OC(=O) NHR57.
provided that the total number of carbons in R2 is less than or equal to 20;
3. A compound of Claim 2, wherein
R1 is methyl;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C3-C8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C16 alkyl substituted with R19; C2-C6 alkoxyalkyl substituted with R21; C7-C16 alkoxyalkyl optionally substituted with R21; C7-C20 alkenyl; C2-C16 alkenyl substituted with R20; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl optionally substituted with F, Cl, or methyl;
R4 is H;
R16 is 3 halogen; C5-C8 alkyl; C2-C8 haloalkyl;
C5-C8 alkoxy; C1-C8 haloalkoxy; C2-C8 alkylthio; C2-C8 alkenyl; or phenoxy substituted with R29;
R19 is C1-C19 alkylthio; C1-C19 haloalkoxy; C5-C6 cycloalkyloxy; C3-C19 alkenyloxy; C2-C19
alkoxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; pyridyl optionally substituted with R31; or CH(=N-A-L);
R20 is C1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C2-C17
alkoxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; C1-C17 alkoxy; 1-3 halogen; or phenyl or phenoxy each optionally substituted with R31;
R21 is C1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C2-C17
alkoxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC (=O)O; C1-C17 alkoxy; C2-C17
alkoxyalkoxy; or phenyl or phenoxy each
optionally substituted with R31;
R22 is C1-C16 alkyl; or phenyl optionally
substituted with R36;
R28 is phenyl or pyridyl each optionally
substituted with R37; or thienyl optionally substituted with R38;
R29, R38, R42, and R44 are independently 1-2 halogen selected from the group consisting of F and Cl; C1-C4 alkyl; or C1-C4 alkoxy; R31, R36, R37, and R41 are independently
trifluoromethyl; 1-2 halogen; cyano; C1-C4 alkyl; C1-C4 alkoxy; or phenoxy substituted with R44;
R40 is pyridyl substituted with R37; or thienyl
optionally substituted with R38;
R49 is C5-C8 alkyl; C2-C8 haloalkyl; C5-C8 alkoxy;
C2-C8 alkylthio; or thienyloxy optionally substituted with R38;
R50 is C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy;
C1-C6 haloalkoxy; C1-C6 alkylthio; C2-C6
alkenyl; C3-C6 alkenyloxy; C3-C6 cycloalkyloxy; C2-C6 alkoxycarbonyl; or -OR28;
R57 is C1-C12 alkyl; phenyl or pyridyl optionally substituted with R41; or thienyl optionally substituted with R42;
A is O or NH;
L is C1-C8 alkyl; phenylmethyl; or phenyl;
T is phenyl optionally substituted with 1-2 halogen selected from the group consisting of F and Cl, or C1-C2 alkyl;
W is O or S; and
Z is phenoxy optionally substituted with R16;
-C(=O)OR57; -OC(=O)R57; -OR40; or -OC(=O)NHR57.
4. A compound of Claim 3, wherein
R2 is C7-C12 alkyl; C7-C12 haloalkyl comprised of fewer than 7 halogens from the group consisting of F and Cl; C3-C8 alkyl substituted with phenoxy optionally substituted with R31; C1-C12 alkyl substituted with R19; C7-C12 alkoxyalkyl;
C7-C12 alkenyl; C2-C12 alkenyl substituted with R20; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R18 is F, Cl, Br, or methoxy; R19 is C1-C12 alkylthio; C5-C6 cycloalkyloxy;
pyridyloxy optionally substituted with R31; or
CH(=N-A-L);
R20 is C1-C12 alkylthio; C5-C6 cycloalkyloxy; C1-C12 alkoxy; 1-3 halogen; phenyl or phenoxy each optionally substituted with R31;
R31, R37, and R41 are 1-2 halogen selected from the group consisting of F and Cl; cyano, C1- C4 alkyl, or C1-C4 alkoxy; or phenoxy;
R38 is 1-2 halogen selected from the group
consisting of F and Cl; methyl; or methoxy; R49 is C5-C8 alkyl; C2-C8 haloalkyl; C5-C8 alkoxy; or C2-C8 alkylthio;
R50 is C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy;
C1-C6 alkylthio; C3-C6 cycloalkyloxy; or phenoxy optionally substituted with R37;
R57 is C1-C8 alkyl; or phenyl optionally
substituted with R41;
L is C1-C8 alkyl or phenylmethyl when A is O; or C1-C8 alkyl or phenyl when A is NH;
T is phenyl optionally substituted with fluorine or methyl; and
Z is -OC(=O)R57 or -OR40.
5. A compound of Claim 4, wherein
R2 is C7-C12 alkyl; C7-C12 haloalkyl; C4-C6 alkyl substituted with phenoxy optionally substituted with R31; C1-C12 alkyl substituted with R19;
C7-C12 alkoxyalkyl; C7-C12 alkenyl; pyridyl substituted with one group from R50 and one halogen from the group consisting of F and Cl; or -T-Z;
R19 is C1-C19 alkylthio; C5-C6 cycloalkyloxy; or
pyridyloxy optionally substituted with R31;
R50 is C1-C6 alkyl; trifluoromethyl; C1-C6 alkoxy; or phenoxy optionally substituted with R37; and R57 is C2-C8 alkyl; or phenyl optionally
substituted with R41.
6. A compound of Claim 5 comprising
5-methyl-5-octyl-3-(phenylamino)-2,4- oxazolidinedione and the (S)-enantiomer thereof;
5-(2-fluoro-6-phenoxy-3-pyridinyl)-5-methyl- 3-(phenylamino)-2,4-oxazolidinedione and the (S)-enantiomer thereof;
5-methyl-5-(3-phenoxypropyl)-3-(phenylamino)-2,4-oxazolidinedione and the (S)-enantiomer thereof;
4-[5-methyl-2,4-dioxo-3-(phenylamino)-5- oxazolidinyl]phenyl 3-chlorobenzoate and the (S)-enantiomer thereof; and
4-[5-methyl-2,4-dioxo-3-(phenylamino)-5- oxazolidinyl]phenyl 4-cyanobenzoate and the (S)-enantiomer thereof.
7. A method of controlling fungal diseases in plants; comprising treating the locus to be protected with an effective amount of a compound of Formula I
wherein
R1 is H; C1-C4 alkyl; C1-C4 haloalkyl; C3-C6
cycloalkyl; C2-C4 alkenyl; C2-C4 alkoxycarbonyl; or phenylmethyl optionally
substituted on the phenyl ring with R6 and on the benzylic carbon with R7;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C4-C17 alkyl substituted with C3-C6 cycloalkyl; C4-C12 alkyl substituted with phenyl optionally substituted with R31 on the phenyl ring; C3-C14 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C20 alkyl substituted with R19; C2-C6 alkoxyalkyl
substituted with R21; C7-C20 alkoxyalkyl
optionally substituted with R21; C7-C20 alkenyl; C2-C20 alkenyl substituted with R20; C7-C20 alkynyl; C2-C20 alkynyl substituted with R48; C5-C7 cycloalkenyl; (CH2CH2OCH2CH2) CH-;
(CH2CH2N (R15) CH2CH2) CH-; (CH2CH2SCH2CH2) CH-;
(CH2CH2SO2CH2CH2) CH-; pyrimidyl, pyrazinyl, pyridazinyl, oxazolyl, isoxazolyl, isothiazolyl or thiazolyl each optionally substituted with R26 and R18; furanyl substituted with one substituent selected from R26 and one from R18; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl, pyridyl, pyrimidinyl or pyridazyl
each optionally substituted with R10; or phenylmethyl;
R4 is H, methyl, or acetyl;
R5, R7, R11, R14, R23, R24, R30, R39, R43, and R55 are each independently H or C1-C4 alkyl;
R6, R29, R34, R38, R42, R44, and R56 are each
independently 1-2 halogen; C1-C4 alkyl; C1-C4 alkoxy; trifluoromethyl; methylthio; or nitro; R8 is C1-C19 alkyl; C2-C19 alkylcarbonyl; C2-C19
alkoxycarbonyl; (R9R14N) C=O; phenyl optionally substituted with R27; or phenoxycarbonyl optionally substituted with R17;
R9 is C1-C18 alkyl; or phenyl optionally
substituted with R17;
R10, R27, and R45 are each independently 1-2
substituents selected from the group consisting of trifluoromethyl, trifluoromethoxy, nitro, CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano;
R12 is H; C1-C8 alkyl optionally substituted with C2-C7 alkoxycarbonyl; C3-C8 alkenyl;
phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5; phenyl optionally substituted with R34; or pyridyl optionally substituted with R34; or
R11 and R58 can be taken together as -CH2 (CH2)2CH2-, -CH2(CH2)3CH2 _, -CH2(CH2)4CH2-, -CH2CH2OCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2N(R5)CH2CH2- or
-CH2CH2N(R5)CH2CH2CH2- along with the nitrogen to which they are attached to form a ring;
R13 is C1-C6 alkyl; C3-C6 cycloalkyl; phenyl
optionally substituted with R45; or
phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5;
R15 is C1-C12 alkyl; C2-C12 alkylcarbonyl; benzoyl optionally substituted with R16 on the phenyl ring; C2-C12 alkoxycarbonyl; C2-C12 alkylaminocarbonyl substituted with R55 on nitrogen;
phenoxycarbonyl optionally substituted with R46 on the phenyl ring; or phenylaminocarbonyl optionally substituted with R46 on the phenyl ring and with R55 on nitrogen;
R16 is 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8
alkoxyalkoxy; C2-C8 alkylthio; C2-C8 alkenyl; C2-C8 haloalkenyl; C2-C8 alkynyl;
hydroxycarbonyl; C2-C8 alkoxy-carbonyl; or phenoxy substituted with R29; R17, R18, R32, R35, R47, and R53 are each
independently 1-2 halogen; C1-C2 alkyl;
trifluoromethyl; or C1-C2 alkoxy;
R19 is cyano; nitro; C1-C19 alkylthio; C1-C19
alkylsulfinyl; C1-C19 haloalkoxy; C5-C6
cycloalkyloxy; C3-C19 alkenyloxy; C3-C19 alkynyloxy; C1-C19 alkylsulfonyl; C2-C19 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O)O; R8R43N; (C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenyl-sulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphtha-lenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy; or C(=J)R24;
R20 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17
haloalkynyl; C3-C17 alkynyloxy;. C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; R8R43N; (C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+; phenyl-sulfonyl,
phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl, naphthalenyl,
pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38; tetrahydropyranyl;
2-tetrahydropyranyloxy; C1-C17 alkoxy; 1-3 halogen; C2-C17 alkoxy-alkoxy; C3-C17 alkynyl; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R21 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C2-C17 haloalkenyl; C3-C17 alkenyloxy; C3-C17 haloalkynyl; C3-C17
alkynyloxy; C1-C17 alkylsulfonyl; C2-C17
alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O)O; R8R43N;
(C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C1-C17 alkoxy; C2-C17 alkoxyalkoxy; C3-C17 alkynyl; C3-C6 cycloalkyl; phenyl or phenoxy each optionally substituted with R31; or C2-C17 haloalkoxyalkoxy;
R22 is C1-C16 alkyl; phenyl optionally substituted with R36; or pyridyl optionally substituted with R36;
R25 is H; C1-C6 alkyl; or phenyl optionally
substituted with R35;
R26 is C1-C6 alkyl; C1-C6 alkoxy; phenoxy
substituted with R53, or benzyloxy substituted on the phenyl ring with R53;
R28 is phenyl, pyridyl or pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl or pyrazolyl each
optionally substituted with R38;
R31, R36, R37, R41, R46 are independently 1-2
substituents selected from the group consisting of trifluoromethyl, trifluoromethoxy, nitro, CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano; or phenoxy substituted with R44;
R33 is C1-C6 alkyl; or phenyl optionally
substituted with R32; R40 is pyridyl or pyrimidyl each optionally
substituted with R37; or thienyl, furanyl, pyrazolyl, naphthalenyl, isothiazolyl,
thiazolyl, imidazolyl, oxazolyl, or isoxazolyl each optionally substituted with R38;
2-tetrahydropyranyl; or 2-tetrahydrofuranyl; R48 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17
alkynyloxy; C1-C17 alkylsulfonyl; C2-C17
alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O) O; R8R43N;
(C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with
R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranylbxy;
C1-C17 alkoxy; 1-3 halogen; C2-C17 alkoxyalkoxy;
C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R49 is C5-C12 alkyl; C2-C12 haloalkyl; C5-C12 alkoxy;
C1-C12 haloalkoxy; C2-C12 alkylthio; C1-C12 haloalkylthio; C2-C12 alkenyl; C2-C12
haloalkenyl; C3-C12 alkynyl; C2-C12 haloalkynyl; C3-C12 alkenyloxy; C3-C12 haloalkenyloxy; C3-C12 alkynyloxy; C1-C12 alkylsulfonyl; C1-C12
haloalkylsulfonyl; C2-C12 alkoxyalkyl; C2-C12 alkoxyalkoxy; C2-C12 alkoxycarbonyl; N(CH3)2; or
G;
R50 is C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy;
C1-C6 haloalkoxy; C1-C6 alkylthio; C1-C6
haloalkylthio; C2-C6 alkenyl; C2-C6
haloalkenyl; C3-C6 alkynyl; C2-C6 haloalkynyl;
C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 cycloalkyl; C3-C6 cycloalkyloxy; C1-C 6 alkylsulfonyl; C1-C6 haloalkylsulfonyl; C2-C6 alkoxyalkyl; C2-C6
alkoxyalkoxy; C2-C6 alkoxycarbonyl; N(CH3)2; or Y;
R51 is phenyl substituted with R52; pyridyl or
pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazolyl each optionally substituted with R38; R52 is 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8
alkoxyalkoxy; C2-C8 alkylthio; C5-C6
cycloalkyl; C5-C6 cycloalkyloxy; C2-C8 alkenyl; C2-C8 haloalkenyl; C2-C8 alkynyl;
hydroxycarbonyl; C2-C8 alkoxycarbonyl; or phenoxy optionally substituted with R29;
R54 is phenyl substituted with R37; pyridyl or
pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazolyl each optionally substituted with R38;
R57 is C1-C12 alkyl; C3-C6 cycloalkyl; C1-C12
haloalkyl; C3-C12 alkenyl; C3-C12 haloalkenyl; C3-C12 alkynyl; C3-C12 haloalkynyl; phenyl, naphthalenyl or pyridyl each optionally
substituted with R41; or furanyl or thienyl each optionally substituted with R42;
R58 is R12, C(=O)R13, C(=O)OR13 or C (=O)NR13R30;
R59 is phenyl optionally substituted with R38;
A is O, NR25, or a direct bond;
E and V are independently O or S;
G is -OR51; -SR51; -NHR28; -N(CH3)R28; -CH=CHR28 (cis or trans); -C(=V)OR28; -OC(=V)R28;
R28NR39C (=V)O-; -OC(=V)OR28; -C(=V)NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -(CH2)mR59; or phenyl optionally substituted with R38; J is O or N-A-L;
L is H; C1-C8 alkyl, C3-C8 alkenyl; phenylmethyl optionally substituted with R47 on the phenyl ring and R55 on the benzylic carbon; phenyl optionally substituted with R47; pyridyl optionally substituted with R47; C(=O)R22;
C(=O)OR22; or C(=O)NR22R7;
m is 1-4;
n is 3-4;
Q is O, NR11, or a direct bond;
T is phenyl optionally substituted with 1-2
halogen; C1-C4 alkyl; C1-C4 alkoxy;
trifluoromethyl; methylthio; or nitro; W is O, S, or N-Q-R58;
Y is -OR28; -SR28; -NHR28; -N(CH3)R28; -CH=CHR28 (cis or trans); -C(=V)OR28; -OC(=V)R28;
R28NR39C(=V)O-; -OC(=V)OR28; -C (=V) NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -(CH2)mR59; or phenyl optionally substituted with R38; and
Z is phenoxy substituted with R16; C3-C12
alkoxyalkoxyalkoxy; benzyloxymethoxy optionally substituted on the phenyl ring with R56; C5-C6 cycloalkyloxy; styryl optionally substituted on the phenyl ring with R41; -C(=V)OR57;
-OC(=V)R57; -OC (=V)NR39R57; -OC(=V)OR57;
-C(=V)NR39R57; -(CH2)nR59; -(CH2)nOR59;
-O(CH2)nR59; or -OR40;
and the agriculturally suitable salts thereof;
provided that:
i) when W is N-Q-R58, Z is other than phenoxy
substituted with R16, C5-C6 cycloalkyloxy, or -C(=O) (C1-C5 alkoxy);
ii) when R2 is an optionally substituted phenyl or heterocyclic ring, only H or F can be
substituted on the carbon atom(s) of the phenyl or heterocyclic ring adjacent to the carbon bearing the oxazolidinone ring;
iii) when two substituents are selected from the
alkyl and alkoxy groups in R10, R27, R31, R36, R37, R41, R45 or R46, then at least one of said substituents contains only one carbon atom; and iv) when R2 is alkyl substituted with optionally
substituted phenyl, then the phenyl group is not substituted on the alkyl carbon attached to the oxazolidinone ring.
8. The method of Claim 7, wherein
R1 is H; C1-C2 alkyl; or vinyl;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C3-C8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C^C^ alkyl substituted with R19; C2-C6 alkoxyalkyl
substituted with R21; C7-C16 alkoxyalkyl
optionally substituted with R21; C7-C20 alkenyl; C2-C16 alkenyl substituted with R20; pyridyl substituted with one substituent selected from
R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl optionally substituted with C1-C2
alkyl or halogen;
R4 is H or methyl;
R12 is C1-C8 alkyl; phenylmethyl; or phenyl;
R19 is C1-C19 alkylthio; C1-C19 haloalkoxy; C5-C6 cycloalkyloxy; C3-C19 alkenyloxy; C1-C19 alkylsulfonyl; C2-C19 alkoxycarbonyl;
hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl each optionally
substituted with R38; 2-tetrahydropyranyloxy; or CH(=N-A-L); R20 is C1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl;
hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl optionally substituted with R38; 2-tetrahydropyranyloxy; C1-C17 alkoxy; 1-3 halogen; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R21 is C1-C17 alkylthio; C1-C17 haloalkoxy; C5-C6 cycloalkyloxy; C3-C17 alkenyloxy; C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl;
hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; phenylsulfonyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl or furanyl each optionally
substituted with R38; 2-tetrahydropyranyloxy; C1-C17 alkoxy; C2-C17 alkoxyalkoxy; or phenyl or phenoxy each optionally substituted with R31;
R28 is phenyl or pyridyl each optionally.
substituted with R37; or thienyl or furanyl each optionally substituted with R38;
R40 is pyridyl or pyrimidyl each optionally
substituted with R37; or thienyl or furanyl each optionally substituted with R38;
2-tetrahydropyranyl; or 2-tetrahydrofuranyl; R51 is phenyl substituted with R52; pyridyl
optionally substituted with R37; or thienyl or furanyl each optionally substituted with R38;
R57 is C1-C12 alkyl; C3-C6 cycloalkyl; C1-C12
haloalkyl; phenyl, naphthalenyl or pyridyl each optionally substituted with R41; or furanyl or thienyl each optionally substituted with R42; R58 is R12;
A is O or NR25; G is -OR51 or -SR51;
L is H; C1-C8 alkyl; phenylmethyl optionally
substituted with R47 on the phenyl ring; phenyl optionally substituted with R47; or C(=O)R22; Q is OH, NH, or a direct bond;
Y is -OR28 or -SR28; and
Z is phenoxy substituted with R16; -C(=O)OR57;
-OC(=O)R57; -OR40; or -OC(=O)NHR57.
provided that the total number of carbons in R2 is less than or equal to 20;
9. The method of Claim 7, wherein the fungal diseases are caused by the plant pathogens Phytophthora infestans, and Plasmopara viticola .
10. A fungicidal composition comprising at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent, and an effective amount of a compound of Formula I
wherein:
R1 is H; C1-C4 alkyl; C1-C4 haloalkyl; C3-C6
cycloalkyl; C2-C4 alkenyl; C2-C4
alkoxycarbonyl; or phenylmethyl optionally substituted on the phenyl ring with R6 and on the benzylic carbon with R7;
R2 is C7-C20 alkyl; C7-C20 haloalkyl; C4-C17 alkyl substituted with C3-C6 cycloalkyl; C4-C12 substituted with phenyl optionally substituted with R31 on the phenyl ring; C3-C14 alkyl substituted with phenoxy or phenylthio each optionally substituted with R31; C1-C20 alkyl substituted with R19; C2-C6 alkoxyalkyl
substituted with R21; C7-C20 alkoxyalkyl
optionally substituted with R21; C7-C20 alkenyl; C2-C20 alkenyl substituted with R20; C7-C20 alkynyl; C2-C20 alkynyl substituted with R48;
C5-C7 cycloalkenyl; (CH2CH2OCH2CH2)CH-;
(CH2CH2N(R15)CH2CH2)CH-; (CH2CH2SCH2CH2)CH-;
(CH2CH2SO2CH2CH2)CH-; pyrimidyl, pyrazinyl, pyridazinyl, oxazolyl, isoxazolyl, isothiazolyl or thiazolyl each optionally substituted with
R26 and R18; furanyl substituted with one substituent selected from R26 and one from R18; pyridyl substituted with one substituent selected from R49, or one group from R50 and one from R18; or -T-Z;
R3 is phenyl, pyridyl, pyrimidinyl or pyridazyl
each optionally substituted with R10; or phenylmethyl;
R4 is H, methyl, or acetyl;
R5, R7, R11, R14, R23, R24, R30, R39, R43, and R55 are each independently H or C1-C4 alkyl;
R6, R29, R34, R38, R42, R44, and R56 are each
independently 1-2 halogen; C1-C4 alkyl; C1-C4 alkoxy; trifluoromethyl; methylthio; or nitro; R8 is C1-C19 alkyl; C2-C19 alkylcarbonyl; C2-C19
alkoxycarbonyl; (R9R14N) C=O; phenyl optionally substituted with R27; or phenoxycarbonyl optionally substituted with R17;
R9 is C1-C18 alkyl; or phenyl optionally
substituted with R17;
R10, R27, and R45 are each independently 1-2
substituents selected from the group consisting of trifluoromethyl, trifluoromethoxy, nitro, CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano; R12 is H; C1-C8 alkyl optionally substituted with
C2-C7 alkoxycarbonyl; C3-C8 alkenyl;
phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5; phenyl optionally substituted with
R34; or pyridyl optionally substituted with
R34; or
R11 and R58 can be taken together as -CH2(CH2)2CH2-,
-CH2(CH2)3CH2-, -CH2(CH2)4CH2-, -CH2CH2OCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2N(R5)CH2CH2- or
-CH2CH2N(R5)CH2CH2CH2- along with the nitrogen to which they are attached to form a ring;
R13 is C1-C6 alkyl; C3-C6 cycloalkyl; phenyl
optionally substituted with R45; or
phenylmethyl optionally substituted on the phenyl ring with R34 and on the benzylic carbon with R5;
R15 is C1-C12 alkyl; C2-C12 alkylcarbonyl; benzoyl optionally substituted with R16 on the phenyl ring; C2-C12 alkoxycarbonyl; C2-C12 alkylaminocarbonyl substituted with R55 on nitrogen;
phenoxycarbonyl optionally substituted with R46 on the phenyl ring; or phenylaminocarbonyl optionally substituted with R46 on the phenyl ring and with R55 on nitrogen;
R16 is 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8
alkoxyalkoxy; C2-C8 alkylthio; C2-C8 alkenyl; C2-C8 haloalkenyl; C2-C8 alkynyl;
hydroxycarbonyl; C2-C8 alkoxy-carbonyl; or phenoxy substituted with R29;
R17, R18, R32, R35, R47, and R53 are each
independently 1-2 halogen; C1-C2 alkyl;
trifluoromethyl; or C1-C2 alkoxy; R19 is cyano; nitro; C1-C19 alkylthio; C1-C19 alkylsulfinyl; C1-C19 haloalkoxy; C5-C6
cycloalkyloxy; C3-C19 alkenyloxy; C3-C19 alkynyloxy; C1-C19 alkylsulfonyl; C2-C19 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O) O; R8R43N; (C1-C4 alkoxy) 2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenyl-sulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38; tetrahydropyranyl; 2-tetrahydropyranyloxy; or
C(=J)R24;
R20 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17 haloalkynyl; C3-C17 alkynyloxy; C1-C17
alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl; R22C(=O)O; R22OC(=O)O;
R22R43NC(=O)O; R8R43N; (C1-C4 alkoxy) 2P (=E)O; R33SO3; R43R14R23N+; phenyl-sulfonyl,
phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl, naphthalenyl,
pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38; tetrahydropyranyl;
2-tetrahydropyranyloxy; C1-C17 alkoxy; 1-3 halogen; C2-C17 alkoxy-alkoxy; C3-C17 alkynyl; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R21 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C2-C17 haloalkenyl; C3-C17 alkenyloxy; C3-C17 haloalkynyl; C3-C17
alkynyloxy; C1-C17 alkylsulfonyl; C2-C17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC(=O)O; R8R43N;
(C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with
R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C1-C17 alkoxy; C2-C17 alkoxyalkoxy; C3-C17 alkynyl; C3-C6 cycloalkyl; phenyl or phenoxy each optionally substituted with R31; or C2-C17 haloalkoxyalkoxy;
R22 is C1-C16 alkyl; phenyl optionally substituted with R36; or pyridyl optionally substituted with R36;
R25 is H; C1-C8 alkyl; or phenyl optionally
substituted with R35;
R26 is C1-C6 alkyl; C1-C6 alkoxy; phenoxy
substituted with R53, or benzyloxy substituted on the phenyl ring with R53;
R28 is phenyl, pyridyl or pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl or pyrazolyl each
optionally substituted with R38;
R31, R36, R37, R41, R46 are independently 1-2
substituents selected from the group consisting of trifluoromethyl, trifluoromethoxy, nitro,
CO2CH3, halogen, C1-C4 alkyl, C1-C4 alkoxy, and cyano; or phenoxy substituted with R44;
R33 is C1-C6 alkyl; or phenyl optionally
substituted with R32;
R40 is pyridyl or pyrimidyl each optionally
substituted with R37; or thienyl, furanyl, pyrazolyl, naphthalenyl, isothiazolyl,
thiazolyl, imidazolyl, oxazolyl, or isoxazolyl each optionally substituted with R38; 2-tetrahydropyranyl; or 2-tetrahydrofuranyl;
R48 is cyano; nitro; C1-C17 alkylthio; C1-C17
alkylsulfinyl; C1-C17 haloalkoxy; C5-C6
cycloalkyloxy; C3-C17 alkenyloxy; C3-C17
alkynyloxy; C1-C17 alkylsulfonyl; C2-C17
alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
R22C(=O)O; R22OC(=O)O; R22R43NC (=O)O; R8R43N;
(C1-C4 alkoxy)2P(=E)O; R33SO3; R43R14R23N+;
phenylsulfonyl, phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R31; thienyl, pyrimidinyl, furanyl,
naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R38;
tetrahydropyranyl; 2-tetrahydropyranyloxy;
C1-C17 alkoxy; 1-3 halogen; C2-C17 alkoxyalkoxy; C3-C6 cycloalkyl; or phenyl or phenoxy each optionally substituted with R31;
R49 is C5-C12 alkyl; C2-C12 haloalkyl; C5-C12 alkoxy;
C1-C12 haloalkoxy; C2-C12 alkylthio; C1-C12 haloalkylthio; C2-C12 alkenyl; C2-C12
haloalkenyl; C3-C12 alkynyl; C2-C12 haloalkynyl; C3-C12 alkenyloxy; C3-C12 haloalkenyloxy; C3-C12 alkynyloxy; C1-C12 alkylsulfonyl; C1-C12
haloalkylsulfonyl; C2-C12 alkoxyalkyl; C2-C12 alkoxyalkoxy; C2-C12 alkoxycarbonyl; N(CH3)2; or G;
R50 is C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy;
C1-C6 haloalkoxy; C1-C6 alkylthio; C1-C6
haloalkylthio; C2-C6 alkenyl; C2-C6 haloalkenyl; C3-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6
alkynyloxy; C3-C6 cycloalkyl; C3-C6 cycloalkyloxy; C1-C6 alkylsulfonyl; C1-C6 haloalkylsulfonyl; C2-C6 alkoxyalkyl; C2-C6 alkoxyalkoxy; C2-C6 alkoxycarbonyl; N(CH3)2; or
Y;
R51 is phenyl substituted with R52; pyridyl or
pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazolyl each optionally substituted with R38;
R52 is 3 halogen; cyano; C5-C8 alkyl; C2-C8
haloalkyl; C5-C8 alkoxy; C1-C8 haloalkoxy; C1-C8 alkylsulfonyl; C2-C8 alkoxyalkyl; C2-C8 alkoxyalkoxy; C2-C8 alkylthio; C5-C6 cycloalkyl; C5-C6 cycloalkyloxy; C2-C8 alkenyl; C2-C8 haloalkenyl; C2-C8 alkynyl; hydroxycarbonyl; C2-C8 alkoxycarbonyl; or phenoxy optionally
substituted with R29;
R54 is phenyl substituted with R37; pyridyl or
pyrimidyl each optionally substituted with R37; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazolyl each optionally substituted with R38;
R57 is C1-C12 alkyl; C3-C6 cycloalkyl; C1-C12
haloalkyl; C3-C12 alkenyl; C3-C12 haloalkenyl;
C3-C12 alkynyl; C3-C12 haloalkynyl; phenyl, naphthalenyl or pyridyl each optionally
substituted with R41; or furanyl or thienyl each optionally substituted with R42;
R58 is R12, C(=O)R13, C(=O)OR13 or C (=O)NR13R30;
R59 is phenyl optionally substituted with R38;
A is O, NR25, or a direct bond;
E and V are independently 0 or S;
G is -OR51; -SR51; -NHR28; -N(CH3)R28; -CH=CHR28 (cis or trans); -C(=V)OR28; -OC(=V)R28;
R28NR39C(=V)0-; -OC(=V)OR28; -C(=V)NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -(CH2)mR59; or phenyl optionally substituted with R38;
J is O or N-A-L;
L is H; C1-C8 alkyl, C3-C8 alkenyl; phenylmethyl optionally substituted with R47 on the phenyl ring and R55 on the benzylic carbon; phenyl optionally substituted with R47; pyridyl optionally substituted with R47; C(=O)R22;
C(=O)OR22; or C(=O)NR22R7;
m is 1-4;
n is 3-4;
Q is O, NR11, or a direct bond;
T is phenyl optionally substituted with 1-2
halogen; C1-C4 alkyl; C1-C4 alkoxy;
trifluoromethyl; methylthio; or nitro;
W is O, S, or N-Q-R58;
Y is -OR28; -SR28; -NHR28; -N(CH3)R28; -CH=CHR28 (cis or trans); -C(=V)OR28; -OC(=V)R28;
R28NR39C (=V) O-; -OC(=V)OR28; -C (=V) NR39R28;
-(CH2)mOR59; -O(CH2)mR59; -(CH2)mR59; or phenyl optionally substituted with R38; and
Z is phenoxy substituted with R16; C3-C12
alkoxyalkoxyalkoxy; benzyloxymethoxy optionally substituted on the phenyl ring with R56; C5-C6 cycloalkyloxy; styryl optionally substituted on the phenyl ring with R41; -C(=V)OR57;
-OC(=V)R57; -OC(=V)NR39R57; -OC(=V)OR57; -C(=V)NR39R57; -(CH2)nR59; -(CH2)nOR59;
-O(CH2)nR59; or -OR40;
and the agriculturally suitable salts thereof;
provided that:
i) when W is N-Q-R58, Z is other than phenoxy
substituted with R16, C5-C6 cycloalkyloxy, or -C(=O) (C1-C5 alkoxy);
ii) when R2 is an optionally substituted phenyl or heterocyclic ring, only H or F can be
substituted on the carbon atom(s) of the phenyl or heterocyclic ring adjacent to the carbon bearing the oxazolidinone ring; iii) when two substituents are selected from the alkyl and alkoxy groups in R10, R27, R31, R36, R37, R41, R45 or R46, then at least one of said substituents contains only one carbon atom; and iv) when R2 is alkyl substituted with optionally substituted phenyl, then the phenyl group is not attached to the alkyl carbon attached to the oxazolidinone ring.
EP93907384A 1992-03-11 1993-03-10 Fungicidal oxazolidinones Withdrawn EP0630370A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US84956392A 1992-03-11 1992-03-11
US849563 1992-03-11
PCT/US1993/002164 WO1993018016A1 (en) 1992-03-11 1993-03-10 Fungicidal oxazolidinones

Publications (1)

Publication Number Publication Date
EP0630370A1 true EP0630370A1 (en) 1994-12-28

Family

ID=25306005

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93907384A Withdrawn EP0630370A1 (en) 1992-03-11 1993-03-10 Fungicidal oxazolidinones

Country Status (2)

Country Link
EP (1) EP0630370A1 (en)
WO (1) WO1993018016A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU674042B2 (en) * 1992-11-13 1996-12-05 E.I. Du Pont De Nemours And Company Processes for preparing 2,4-oxazolidinediones
USH1401H (en) * 1993-11-15 1995-01-03 E. I. Du Pont De Nemours And Company, Inc. Fungicidal oxazolidinones
GB9607784D0 (en) * 1996-04-15 1996-06-19 Zeneca Ltd Fungicides
GB9607785D0 (en) * 1996-04-15 1996-06-19 Zeneca Ltd Fungicides
EP2316458A1 (en) 2004-09-20 2011-05-04 Xenon Pharmaceuticals Inc. Pyridazine derivatives for inhibiting human stearoyl-coa-desaturase
MX2007003321A (en) 2004-09-20 2007-06-05 Xenon Pharmaceuticals Inc Heterocyclic derivatives and their use as therapeutic agents.
CN101084207A (en) 2004-09-20 2007-12-05 泽农医药公司 Heterocyclic derivatives and their use as stearoyl-coa desaturase inhibitors
US7592343B2 (en) 2004-09-20 2009-09-22 Xenon Pharmaceuticals Inc. Pyridazine-piperazine compounds and their use as stearoyl-CoA desaturase inhibitors
CN101084212A (en) 2004-09-20 2007-12-05 泽农医药公司 Heterocyclic derivatives and their use as mediators of stearoyl-coa desaturase
EP2289510A1 (en) 2004-09-20 2011-03-02 Xenon Pharmaceuticals Inc. Heterocyclic derivatives for the treatment of diseases mediated by stearoyl-coa desaturase enzymes
WO2006034440A2 (en) 2004-09-20 2006-03-30 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-coa desaturase inhibitors
CN101208089A (en) 2005-06-03 2008-06-25 泽农医药公司 Aminothiazole derivatives as human stearoyl-CoA desaturase inhibitors
US9090604B2 (en) 2006-07-27 2015-07-28 E I Du Pont De Nemours And Company Fungicidal azocyclic amides
WO2008013622A2 (en) 2006-07-27 2008-01-31 E. I. Du Pont De Nemours And Company Fungicidal azocyclic amides
EP2501678B1 (en) * 2009-11-17 2015-09-23 Novartis AG Aryl-pyridine derivatives as aldosterone synthase inhibitors
ES2948192T3 (en) 2013-06-27 2023-09-01 Pfizer Heteroaromatic compounds and their use as dopamine D1 ligands
CN114835700A (en) * 2022-04-20 2022-08-02 中国农业大学 Pyrazolidone compound with high anti-candida activity, preparation method thereof and application of pyroxapyroxalone compound as medical antifungal agent

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0393911B1 (en) * 1989-04-21 1994-08-31 E.I. Du Pont De Nemours And Company Fungicidal oxazolidinones
WO1991019703A2 (en) * 1990-06-11 1991-12-26 E.I. Du Pont De Nemours And Company Fungicidal iminooxazolidinones

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9318016A1 *

Also Published As

Publication number Publication date
WO1993018016A1 (en) 1993-09-16

Similar Documents

Publication Publication Date Title
US6096895A (en) Heterocyclic dihydrazole compounds and their use for controlling fungal plant diseases
US5977149A (en) Dihydrotriazole compounds and their use for controlling fungal plant diseases
US6057352A (en) Fungicidal cyclic amides
EP0836384A1 (en) Arthropodicidal and fungicidal cyclic amides
WO1998023156A1 (en) Methyl substituted fungicides and arthropodicides
WO1998023155A1 (en) Arthropodicidal and fungicidal cyclic amides
WO1993018016A1 (en) Fungicidal oxazolidinones
WO1996036229A1 (en) Fungicidal cyclic amides
EP0642502B1 (en) Fungicidal imidazolinones
WO1995007278A1 (en) Fungicidal, miticidal and arthropodicidal aminopyrimidines
US5962436A (en) Fungicidal cyclic amides
JP2622427B2 (en) Bactericidal oxazolidinones
WO1999028305A1 (en) Fungicidal cyclic amides
WO1993022311A1 (en) Fungicidal 1,3,4-oxadiazines and 1,3,4-thiadiazines
US5223523A (en) Fungicidal oxazolidinones
WO1999011129A1 (en) Enantiomerically enriched compositions and their pesticidal use
EP0869963A1 (en) Arthropodicidal and fungicidal organosilanes and organogermanes
EP0937051A1 (en) Fungicidal cyclic amides
US5356908A (en) Fungicidal oxazolidinones
USH1401H (en) Fungicidal oxazolidinones
EP0637301A1 (en) Fungicidal oxazolidinones
EP0577712B1 (en) Fungicidal 4-thioxooxazolidin-2-ones and 4-iminooxazolindin-2-ones
US6255311B1 (en) Fungicidal fused bicyclic pyrimidinones
WO1996022286A2 (en) Arthropodicidal oxazines and thiazines
EP0821677A1 (en) Oxazoline and thiazoline arthropodicides

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19940817

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19960823