GB2293380A - Pesticidal heterocyclic and phenyl compounds - Google Patents

Pesticidal heterocyclic and phenyl compounds Download PDF

Info

Publication number
GB2293380A
GB2293380A GB9518703A GB9518703A GB2293380A GB 2293380 A GB2293380 A GB 2293380A GB 9518703 A GB9518703 A GB 9518703A GB 9518703 A GB9518703 A GB 9518703A GB 2293380 A GB2293380 A GB 2293380A
Authority
GB
United Kingdom
Prior art keywords
sch2ch2c
soch2ch2c
so2ch2ch2c
optionally substituted
viii
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Withdrawn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
GB9518703A
Other versions
GB9518703D0 (en
Inventor
Alison Mary Smith
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.)
Syngenta Ltd
Original Assignee
Zeneca Ltd
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
Priority claimed from GB9419083A external-priority patent/GB9419083D0/en
Priority claimed from GB9419085A external-priority patent/GB9419085D0/en
Application filed by Zeneca Ltd filed Critical Zeneca Ltd
Publication of GB9518703D0 publication Critical patent/GB9518703D0/en
Publication of GB2293380A publication Critical patent/GB2293380A/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Withdrawn legal-status Critical Current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
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • 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
    • A01N43/82—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 three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
    • C07C323/02—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/05—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • 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
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C07D277/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical

Abstract

A compound of formula (I), R-S(O)nCH2CH2C(CH3) =CF2 or a salt thereof, wherein n is 0, 1 or 2; and R is a heterocyclic or phenyl group, has nematicidal, insecticidal and acaricidal activity.

Description

HETEROCYCLIC AND PHENYL COMPOUNDS The present invention relates to novel heterocvclic and phenyl derivatives having nematicidal. insecticidal and acaricidal activity, to processes for their preparation, to compositions containing them, and to methods for killing or controlling nematode, insect or acarid pests using them.
According to the present invention there is provided a compound of formula (I): R-S(O)nCH2CH2C(CH3)=CF2 (I) or a salt thereof, wherein n is 0, 1 or 2; and R is a group of formula (11) to (XXIV):
wherein: the S(O)nCH2CH2C(CH3)=CF2 group is at least one of R1 (when attached to a carbon atom). R'. R3. R4. R5. R6. R7 or R8: R1 (when attached to a carbon atom), R2, R3.R4, R5, R6, R7 and R8 are each independently hydrogen. optionally substituted alkyl optionally substituted alkenyl, alkynyl, cvcloalkyl, alkylcycloalkyl. alkoxy, alkenyloxy, alkynyloxy, hydroxvalkyl, alkoxyalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl. optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxy, optionally substituted heteroarylalkoxy, optionally substituted heteroaryloxyalkyl, haloalkyl, hlloalkenyl, haloalkynyl.
haloalkoxy, haloalkenyloxy, haloalkynyloxy, halogen, hydroxy, cyano, nitro. -NR8R9, -NR9COR10. -NR9CSR10. -NR9SO2R10, -N(SO2R9)(SO2R10), -COR9, -CONR9R10.
-alkylCONR9R10, -CR9NR10. -COOR9, -OCOR9, -SR9, -SOR9, -S02R9, -alkylSR9, -alkylSOR9, -alkylSO9R9. -OSO2R9, -SO2NR9R10, -CSNR9R 10, -SiR9R 1 OR 10, -OCH2CO2R9, -OCH2CH2CO2R9, -CONR9SO2R10, -alkylCONR9SO2R10, -NHCONR9R10, -NHCSNR9R10, or an adjacent pair of R1, R2, R3, R4, R5, R6, R7 and R8 when taken together form a fused 5- or 6-membered carbocyclic or heterocyclic ring; R1 (when attached to a nitrogen atom) is hydrogen, optionally substituted alkyl, cycloalkyl, alkylcycloalkyl, hydroxyalkyl, alkoxvalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryl.
optionally substituted heteroaryl alkyl, optionally substituted heteroaryloxyalkyl, haloalkyl hydroxy, cyano, nitro, -NR9R10, -NR9COR10, NR9CSR10, -NR9COOR10, -NR9SO2R10, -N(SO2R9)(SO2R10), -COR9, -CONR9R10, -alkylCONR9R10, -CR9NR10, -COOR9, OCOR9, -SOR9, -SO'R9. -alkylSR9, -alkylSOR9 -alkylS02R9, -OS02R9, -SO'NR9NR 10. SR9, -SOR9, -SO2R9, -CSNR9R10, -SiR9RlOR10, -OCH2C02R9. -OCH2CH2CO2R9, -CONR9SO2R10, -alkylCONR9SO2R10, -NHCOR9R10, or -NHCSR9R10; and R9, R10 and Ri 1 are each independently hydrogen. optionally substituted alkyl, optionally substituted alkenyl. aikynyl, optionally substituted aryl, optionally substituted arylalkyl.
haloalkyl, haloalkenyl. haloalkynyl, halogen, or hydroxy.
We would explain that. for ease of reference only. the substituents on the R group have been named in accordance with their position on this R group. For example. when R has the formula (II). substituents R2. R3. R4 and R5 are in positions 2, 3. 4, and 5. respectively. on the ring. For the avoidance of doubt, the -S(O)nCH2CH2C(CH3)=CF2 group can be at any of the substituent positions indicated by R1 (when attached to a carbon atom) to RS.
When any one of R1 to RI 1 is an alkyl group, or contains an alkyl moiety, it may be straight or branched chain and is preferably C1-6 alkyl, even more preferably Cl 4 alkyl, for example methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or t-butyl. When the alkyl group is acting as a "linking group, ie R-alkyl- . for example in R-alkylSR8, Cl-4 alkyl or Cl-2 alkyl are particularly preferred.
When any one of R1 to RI I is a substituted alkyl group, or contains a substituted alkyl moiety, it may comprise one or more subsitutents chosen from halogen, nitro, cyano, -COOR9 or a salt thereof, hydroxy, alkoxy, alkoxyimino, alkoxycarbonyl, carbamoyl. mono- or di-alkylcarbamoyl, amino, mono- or di-alkylamino. acylamido (preferably C1-6 acylamido), alkanesulfonyl, and arylsulfonyl, which may itself be substituted with halogen. alkoxy or nitro.
When any one of R1 to R1 1 is an alkenyl or alkynyl group, or contains an alkenyl or alkynyl moiety, it may be straight or branched chain and is preferably C2-6 alkenyl or C2-6 alkynyl, even more preferably C2-4 alkenyl or C24 alkynyl. for example vinyl, allyl, but-3-enyl.
3-methyl-but-3-enyl, ethynyl or propargyl.
When any one of R1 to Rl 1 is a substituted alkenyl group, or contains a substituted alkenyl moietst, it may comprise one or more subsitutents chosen from halogen, COOR9 or a salt thereof, hydroxy, nitro and cyano.
When any one of R 1 to R8 is a cycloalkyl or alkylcycloalkyl group, or contains a cycloalkyl or alkylcycloalkyl moiety, it is preferably C3-6 cycloalkyl or C4-7 alkylcycloalkyl. for example, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclopropyl.
When any one of R1 to R8 is an alkoxy, alkenyloxy, alkynyloxy or alkoxyalkyl group, or contains such a moiety, it is preferably C1-6 alkoxy, for example, methoxy, ethoxy, n-propoxv.
iso-propoxy. n-butoxy, iso-butoxy, sec-butoxy and t-butoxy; C2-6 alkenyloxy, for example, vinyloxy, allyloxy. but-3-enyloxy and 3-methylbut-3-enyloxy; C2-6 alkynyloxy, for example.
propargyloxy; C2-6 monoalkoxyalkyl. for example, methoxymethyl, methoxyethyl and ethoxymethvl: or C3-6 dialkoxylalkyl, for example, dimethoxymethyl and diethoxymethyl.
When any one of RI to R1 l is aryl, or contains an aryl moiety. it is preferably C6-lO aryl.
more preferably it is phenyl. When any one of R1 to R1 1 is arylalkyl. it is preferably C6-lO aryl- methyl or C6-10 aryl-ethyl. even more preferably benzyl or phenethyl.
When any one of R1 to R8 is heteroaryl. or contains a heteroaryl moietv. it is preferably a 5 or ó membered ring containing at least one 0. N or S atom as the heteroatom. for example.
pyridine. pyrrole pyrazine. furan or thiophene. When any one of R1 to R8 is heteroarylalkyl, it is preferably heteroarvl-C1-2 alkyl.
When any one of R1 to R1 lisa substituted aryl, arylalkyl, heteroaryl, or heteroarylalkyl group, it may comprise one or more substituents chosen from alkyl. alkoxy, haloalkvl, haloalkoxy, halogen, hydroxy, COOR9 (or a sSt thereof), arninosulfonyl, cyano or nitro.
Examples of these groups are 4-methylphenyl, 4-chlorophenyl, 4-fluorophenvl, 4-nitrophenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 4-aminosulfonylphenyl, 4-chlorobenzyl, A-fluorobenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 4-nitrobenzyl and A-methylbenzyl.
When any one of R1 to R8 is a aryloxy or arylalkoxy group, it is preferably phenoxy, benzvloxy or phenethoxy.
When any one of Ri to R8 is a substituted aryloxy, arylalkoxy, heteroaryloxy or heteroarylalkoxy group, it may comprise one or more substituents chosen from alkyl, alkoxy, halogen, haloalkyl, haloalkoxy, hydroxy, cyano or nitro. Examples of these groups are 4-methyiphenoxy, 4-chlorophenoxy, 4-fluorophenoxy, 4-nitrophenoxy, 3-trifluoromethylphenoxy, A-trifluoromethylphenoxy 4-chlorobenzyloxy, 4-fluorobenzyloxy, 3-trifluoromethylbenzyloxy, 4-trifluoromethy lbenzyloxy, 4-nitrobenzy loxy and 4-methylbenzyloxy.
When any one of R1 to R 11 is halogen, or contains a halogen moiety, it is preferably fluorine, chlorine, bromine or iodine. Even more preferably, it is fluorine, chlorine or bromine.
When any one of R1 to RI 1 is a haloalkyl, haloalkenyl or haloalkynyl group, it may contain one or more halogen atoms. preferably chlorine, fluorine or bromine. Examples of these groups are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoroethenyl, 3,3-dichloroprop-2-enyl, 2-chloroprop-2-enyl, 3,4,4-trifluorobut-3-enyl, 4-fluorobut-3-enyl, 4,4-difluorobut-3-enyl and 3 -methyl-4,4-difluorobut-3-enyl.
When any one of R1 to R8 is a haloalkoxy group, a haloalkenyloxy group or a haloalkynyloxy group, it may contain one or more halogen atoms, preferably chlorine. fluorine or bromine. Examples of the preferred C1-6 alkoxy, C2-6 alkenvloxv and C2-6 alkynyloxy groups are trichioromethoxy. fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2- fluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2-difluoroethenyloxy, 3,4,4-trifluorobut-3-enyloxy, 4-fluorobut-3-enyloxy, 4,4-difluorobut-3-enyloxy, 3-methyl-4,4-difluorobut-3-enyloxy, 2-chloroprop-2-enyloxy and 3,3-dichloroprop-2-enyloxy.
When any one of R1 to R8 is the group -NR9R10, it is preferably -NH2; a monoalkylarnino group, for example, methylamino and ethylarnino; or a di-alkylamino group, for example, dimethylamino and diethylamino.
When any one of R1 to R8 is the group -NR9CORlO, it is preferably -NHCHC); a C2-6 acts amino group, for example -NHCOCH3, -NHCOC2H5; or benzamido, which may be substituted with one or more substituents chosen from halogen, for example, chlorine, fluorine and bromine; alkyl, for example, methyl and ethyl; alkoxy, for example, methoxy and ethoxy; haloalkyl, for example, chloromethyl, fluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl; haloalkoxy, for example, trifluoromethoxy and 2,2,2-trifluoroethoxy; hydroxy; cyano and nitro.
When any one of R1 to R8 is -NR9CSRIO, R9 and RiO are preferably alkyl for example methyl and ethyl.
When any one of R1 to R8 is the group -NR9SO2R10, it is preferably an alkanesulfonamido group, for example, -NHS02CH3 and -NHS02C2H5.
When any one of R1 to R8 is the group -N(S02R9)(S02R10), it is preferably a di-(alkanesulfonyl)amino group, for example, -N(S02CH3)2 and -N(S02C2H5)2.
When any one of R1 to R8 is the group -COR9, it is preferably a C1-6 acyl group; or an optionally substituted benzoyl group. The benzoyl may be substituted with one or more substituents chosen from halogen, for example, chlorine, fluorine and bromine; alkyl, for example, methyl and ethyl; alkoxy. for example, methoxy and ethoxy; haloalkyl, for example, chloromethyl, fluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl; haloalkoxy, for example, trifluoromethoxy and 2,2,2-trifluoroethoxy; hydroxy; cyano and nitro. Examples of preferred -COR8 groups are acetyl, propionyl, n-butanovl. 4-chlorobenzoyl, 4-fluorobenzoyl, 4-bromobenzoyl, A-methylbenzoyl and 4-trifluoromethylbenzoyl.
When any one of Rl to R8 is the group -CONR9RlO, it is preferably -CONH2; an N-alkwl-carboxamido group, for example -CoNHCH3, -CONHC2H5 and -CONHCH2CH2CH3; or an N,N-dialkyl-carboxamido group, for example -CON(CH3)2, -CON(CH3)(C2H5) and -CON(C2H5)2.
When any one of R1 to R8 is the group -alkylCONR9R10, it is preferably -C1-4 alkylCONR9R 10.
When any one of more of Rl to R8 is the group -CR9NRlO, it is preferably -CH=NOH.
When any one of R1 to R8 is the group -COOR9. it is preferably -COOH: an alkoxycarbonyl group. for example methoxycarbonyl and ethoxycarbonyl: or a haloalkenyloxycarbonyl group, for example 3,4,4-trifluorobut-3-enyloxycarbonyl, 4-fluorobut-3-enyloxycarbonyl, 4,4-difluorobut-3-enyloxycarbonyl and 3-methyl-4,4-difluorobut-3-enyloxycarbonyl.
When any one of R1 to R8 is the group -OCOR9, it is preferably a C2-6 acyloxy group, for example -OCOCH3 and -OCOC2H5; or an optionally substituted benzoyloxy group. The benzoyloxy group may comprise one or more substituents chosen from halogen, for example.
chlorine, fluorine and bromine; alkyl, for example, methyl and ethyl; alkoxy, for example, methoxy and ethoxy; haloalkyl, for example, chloromethyl, fluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl; haloalkoxy, for example, trifluoromethoxy and 2,2,2-trifluoroethoxy; hydroxy; cyano; and nitro.
When any one of R1 to R8 is the group -SR9, R9 is preferably hydrogen, optionally subsituted alkyl, optionally substituted alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, optionally substiuted aryl, or optionally substituted arylalkyl. Examples of the preferred C 1-6 alkylthio (C 1-4 alkyl being especially preferred), C2-6 alkenylthio or C2-6 alkynylthio groups are methylthio, ethylthio. n-propylthio. iso-propylthio, n-butylthio, iso-butylthio, sec-butvlthio, t-butylthio, allylthio, but-3-enylthio, 3-methylbut-3-enylthio and propargylthio.Examples of the preferred Ci-6 haloalkylthio (C14 alkyl being especially preferred), C2-6 haloalkenylthio or C2-6 haloalkynylthio groups are fluoromethylthio, difluoromethylthio, trifluoromethylthio, trichloromethylthio, 2-fluoroethylthio, 2,2,2-trifluoroethylthio, 3-fluoro-n-propylthio, pentafluoroethyithio, 2-c hloroprop- 2-enylthio, 3 ,3-dichloroprop-2 -enyithio, 3,4,4-trifluorobut-3-enylthio, 4-fluorobut-3-enylthio, 4,4-difluorobut-3-enylthio and 3-methyl-4,4-difluorobut-3-enylthio. An example of the preferred C6-10 arylthio and C6-lO aryl C I -'alkylthio groups is 3-trifluoromethylbenzylthio.
When any one of RI to R8 is the group -SOR9, it is preferably an alkanesulfinyl.
alkenylsulfinyl or alkynylsulfinyl group, for example methanesulfinyl or ethanesulfinyl; or a haloalkanesulfinyl, haloalkenylsulfinyl or haloalkynylsulfinyl group. for example trifluoromethanesulfinyl. In another preferred embodiment -SOR9 is preferably -SOF, -SOBr or SOCI.
When any one of R1 to R8 is the group -SO2R9. it is preferably an alkanesulfonyl.
alkenylsulfonyl, alkynylsulfonyl, a haloalkanesulfonyl. haloalkenylsulfonvl, haloalkynylsulfonyl group: or an optionally substituted benzenesulfonyl group. The benzenesulfonyl group may comprise one or more substituents chosen from halogen, for example. chlorine, fluorine and bromine; alkyl, for example, methyl and ethyl; alkoxy, for example, methoxy and ethoxy; haloalkyl, for example, chloromethyl, fluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl; haloalkoxy such as trifluoromethoxy and 2,2,2-trifluoroethoxy; hydroxy; cyano and nitro.
Examples of such groups are methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, and 4-methylbenzenesulfonyl. In another preferred embodiment -SO2R9 is preferably -SO2F, -SO2Br or -SO2Cl.
It will thus be appreciated that the R group of formula (II) to (XXIV) can comprise more than one -S(O)nCH2CH2C(CH3)=CF2 group. Preferably the R group contains one or two such substituents.
When any one of Rl to R8 ss the group -OS02R9, it is preferably an alkanesulfonyloxy group or an optionally substituted benzenesulfonyloxy group. The benzenesulfonyl may be substituted with one or more substituents chosen from halogen, for example, chlorine, fluorine and bromine; alkyl, for example, methyl and ethyl; alkoxy, for example, methoxy and ethoxy; haloalkyl, for example, chloromethyl, fluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl; haloalkoxy, for example, trifluoromethoxy and 2,2,2-trifluoroethoxy; hydroxy; cyano; and nitro.
When any one of Rl to R8 is the group -S02NR9R10, it is preferably -S02NH2; an alkylaminosulfonyl group, for example, -S02NHCH3 and -S02NHC2H5; or a dialkylaminosulfonyl group, for example, -S02N(CH3)2 and -S02N(C2H5)2.
When any one of R1 to R8 is the group -CSINR9R10 it is preferably -CSNH2, -CSNHCH3 or -CSN(CH3)2.
When any one of R1 to R8 is the group -SiR9RIORI 1. it is preferably a trialkylsilyl group, for example. trimethylsilyl and triethylsilyl.
When any one of R1 to R8 is the group -OCH2C02R9, it is preferably an alkoxycarbonylmethoxy group, for example, methoxycarbonvlmethoxy and ethoxycarbonylmethoxy.
When any one of R1 to R8 is the group -OCH2CH2C02R9, it is preferably a alkoxycarbonylethoxy group, for example methoxycarbonylethoxy and ethoxycarbonylethoxy.
','hen any one of Rl to R8 is the group -CONR9SO2R10, it is preferably an N-aikanesulfonylcarboxamido group or an N- alkvl-N-alkanesulfonylcarboxamido group, for example N-( methanesullonyl )-carboxamido and N-methyl-N-( methanesulfonyl )carboxamido.
When any one or more of R1 to R8 is the group -alkylCONR9SO2R 10. R9 and R10 are preferably alkyl groups. for example. ethyl and methyl.
When any one of R1 to R8 is -NHCONR9R10, R9 and R10 are preferably alkyl groups for example, ethyl and methyl.
When any one of Rl to R8 is -NHCSNR9R9, R9 and R10 are preferably alkyl groups, for example ethyl and methyl.
When an adjacent pair of RI, R2, R3, R4, R5, R6, R7 and R8 taken together form a fused 5- or 6-membered carbocyclic or heterocyclic ring, preferably containing two oxygen atoms, the pair of substituents taken together is preferably -(CH2)3-, -(CH2)4-, -CH=CH-CH=CH-, -O-CH2-O-, optionally substituted with one or two halogen atoms or methyl groups, for example -O-CHF-O- or-O-CF2-0-, -O-CH(CH3)-O-, -O-C(CH3)2-O- or -0-(CH2)2-0-.
According to an especially preferred embodiment of the present invention R1 (when attached to a carbon atom) to R8 are each independently hydrogen; nitro; halogen; cyano; -CH=NOH; C14 alkyl; C1-4 haloalkyl; C1-4 alkenyl; C14 haloalkenyl; cyclopropyl; hydroxy; C 1-4 alkoxy; C2-4 alkoxyalkyl; -COOH; C2A alkoxycarbonyl; C24 haloalkenyloxycarbonyl: CONH2; mono or di-C1-2 alkylaminocarbonyl;C24 alkanecarbonyl; -CONHS02 C1-4 alkyl, preferably -CONHS02CH3; phenyl optionally mono- or di- substituted with groups independently chosen from halogen, nitro, C1-4 alkyl, C14 alkoxy or aminosulfonyl; benzyl optionally mono- or di- substituted with groups independently chosen from halogen, nitro, C 1-4 alkyl or C1-4 alkoxy; phenoxy optionally mono- or di- substituted with groups independently chosen from halogen, cyano. C14 alkyl or C1-4 alkoxy; amino optionally mono- or disubstituted with C1-4 alkyl groups; -SH; C1-4 alkylthio; benzylthio optionally mono- or disubstituted with groups independently chosen from halogen or C1-4 haloalkyl; C 1-3 alkenylthio; C2-4 haloalkenylthio; a second S(O)nCH2CH2CH=CF2 group; C1-4 alkanesulfonyl;C1-4 haloalkanesulfonyl; fluorosulfonyl; mono- or di- C1-4 alkylsulfamoyl; a 5 or 6 membered heteroaryl group for example. furyl, pyrazinyl, pyridinyl or thienyl, optionally substituted with halogen; or any adjacent pair forms a fused 5- or 6- carbocyclic or heterocyclic ring; and R1 (when attached to a nitrogen atom) is hydrogen: nitro; cyano: -CH=NOH; C1-4 alkyl; CiA haloalkyl; cyclopropyl; hydroxy; -COOH; C24 alkoxycarbonyl; C2-4 haloalkenyloxycarbonyl; -CONH2; mono or di-C1-2 alkylaminocarbonyl; C2-4 alkanecarbonyl; CONHSO2 Cl-4 alkyl, preferably -CONHSO2CH3; phenyl optionally mono- or di- substituted with groups independently chosen from halogen nitro, C1-4 alkyl. CIA alkoxy or aminosulfonyl: benzyl optionally mono- or di- substituted with groups independently chosen from halogen. nitro.
C 1-4 alkyl or Cl -4 alkoxy: phenoxy optionally mono- or di- substituted with groups independently chosen from halogen, cyano, C 1.4 alkyl or C 14 alkoxy; amino optionally monoor di- substituted with ClA alkyl groups; -SH; C1-4 alkylthlo; benzylthio optionally mono- or disubstituted with groups independently chosen from halogen or C14 haloalkyl; C1-4 alkenylthio: C2--1 haloalkenylthio; a second S(O)nCH2CH2C(CH3)=CF2 group;C1-4 alkanesulfonyl; ClA haloalkanesulfonyl; fluorosulfonyl; mono- or di- Cl-4 alkylsulfamoyl; a 5 or 6 membered heteroaryl group, for example. furyl, pyrazinyl, pyridinyl or thienyl, optionally substituted with halogen.
The following Tables give examples of compounds according to the invention.
Examples of compounds of Formula (II) according to the invention are set out in Table II.
TABLE II No. R2 R3 R4 R5 II.1 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-H II.2 2-SOCH2CH2C(CH3)CF2 3-H 4-H 5-H II.3 2-SO2CH2CH2C(CH3)CF2 3-H 4-H 5-H II.4 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-CH3 II.5 2-SOCH2CH2C(CH3)CF2 3-H 4-H 5-CH3 II.6 2-SO2CH2CH2C(CH3)CF2 3-H 4-H 5-CH3 II.7 2-CH3 3-SCH2CH2C(CH3)CF2 4-H 5-H II.8 2-CH3 3-SOCH2CH2C(CH3)CF2 4-H 5-H II.9 2-CH3 3-SO2CH2CH2C(CH3)CF2 4-H 5-H Examples of compounds of Formula (III) according to the invention are set out in Table III.
TABLE III No. R2 R3 R4 R5 III.1 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-H III.2 2-SOCH2CH2C(CH3)CF2 3-H 4-H 5-H III.3 2-SO2CH2CH2C(CH3)CF2 3-H 4-H 5-H III.4 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-CHO III.5 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-CH2OH III.6 2-SCH2CH2C(CH3)CF2 3-H 4-H (E) 5-CH=NOH III.7 2-SCH2CH2C(CH3)CF2 3-H 4-H (Z) 5-CH=NOH III.8 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-CN III.9 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-COCH3 III.10 2-SCH2CH2C(CH3)CF2 3-H -CH=CH-CH=CH III.11 2-SOCH2CH2C(CH3)CF2 3-H -CH=CH-CH=CH III.12 2-SO2CH2CH2C(CH3)CF2 3-H -CH=CH-CH=CH Examples of compounds of Formula (IV) according to the invention are set out in Table IV.
TABLE IV No. R3 R4 R5 IV. 1 3-C6H5 4-H 5-SCH2CH2C(CH3)CF2 IV.2 3-C6H5 4-H 5-SOCH2CH2C(CH3)CF2 IV.3 3-C6H5 4-H 5-SO2CH2CH2C(CH3)CF2 IV.4 3-CN 4-H 5-SCH2CH2C(CH3)CF2 IV.5 3-Cl 4-H 5-SCH2CH2C(CH3)CF2 IV.6 3-CF3 4-H 5-SCH2CH2C(CH3)CF2 IV.7 3-CH3 4-CONH2 5-SCH2CH2C(CH3)CF2 IV.S 3-CH3 4-COOCH2CH3 5-SCH2CH2C(CH3)CF2 IV.9 3-CH3 4-COOH 5-SCH2CH2C(CH3)CF2 IV.10 3-CH3 4-H 5-SCH2CH2C(CH3)CF2 IV.11 3-H 4-Cl 5-SCH2CH2C(CH3)CF2 IV.12 3-H 4-CN 5-SCH2CH2C(CH3)CF2 IV.13 3-H 4-CN 5-SOCH2CH2C(CH3)CF2 IV.14 3-H 4-CN 5-SO2CH2CH2C(CH3)CF2 IV. 15 3-H 4-CF3 5-SCH2CH2C(CH3)CF2 IV.16 3-H 4-H 5-SCH2CH2C(CH3)CF2 IV. 17 3-H 4-NO2 5-SCH2CH2C(CH3)CF2 IV.18 3-H 4-SCH2CH2C(CH3)CF2 5-CN IV.19 3-H 4-SCH2CH2C(CH3)CF2 5-CF3 IV.20 3-SCH2CH2C(CH3)CF2 4-H 5-Cl IV.21 3-SCH2CH2C(CH3)CF2 4-Cl 5-H IV.22 3-SO2CH2CH2C(CH3)CF2 4-CN 5-SO2CH2CH2C(CH3)CF2 IV.23 3-(5-Cl-Fur-2-yl) 4-H 5-SCH2CH2C(CH3)CF2 IV.24 3-(5-Cl-Fur-2-yl) 4-H 5-SO2CH2CH2C(CH3)CF2 IV.25 3-(Thien-2-yl) 4-H 5-SCH2CH2C(CH3)CF2 IV.26 3-(Thien-2-yl) 4-H 5-SO2CH2CH2C(CH3)CF2 Examples of compounds of Formula (V) according to the invention are set out in Table V.
TABLE V No. R3 R4 R5 V.1 3-CF3 4-H 5-SCH2CH2C(CH3)CF2 V.2 3-Cl 4-CN 5-SCH2CH2C(CH3)CF2 V.3 3-Cl 4-H 5-SCH2CH2C(CH3)CF2 V.4 3-Cl 4-H 5-SO2CH2CH2C(CH3)CF2 V.5 3-H 4-CN 5-SCH2CH2C(CH3)CF2 V.6 3-H 4-CN 5-SO2CH2CH2C(CH3)CF2 V.7 3-H 4-SCH2CH2C(CH3)CF2 5-CF3 V.8 3-H 4-SOCH2CH2C(CH3)CF2 5-CF3 V.9 3-H 4-SCH2CH2C(CH3)CF2 -CN V.10 3-NO2 4-H 5-SCH2CH2C(CH3)CF2 V.11 3-SCH2CH2C(CH3)CF2 4-Cl 5-H V.12 3-SCH2CH2C(CH3)CF2 4-CN 5-SCH2CH2C(CH3)CF2 V.13 3-SO2CH2CH2C(CH3)CF2 4-CN 5-SOCH2CH2C(CH3)CF2 V.14 3-SOCH2CH2C(CH3)CF2 4-CN 5-SO2CH2CH2C(CH3)CF2 V.15 3-SO2CH2CH2C(CH3)CF2 4-CN 5-SO2CH2CH2C(CH3)CF2 V.16 3-SCH2CH2C(CH3)CF2 4-H 5-Cl Examples of compounds of Formula (VI) according to the invention are set out in Table VI.
TABLE VI No. R2 R4 R5 VI. I 2-SCH2CH2C(CH3)CF2 4-H 5-H VI.2 2-SOCH2CH2C(CH3)CF2 4-H 5-H VI.3 2-S02CH2CH2C(CH3)CF2 4-H 5-H VI.4 2-SCH2CH2C(CH3)CF2 4-CF3 5-H VI.5 '-SO'CH2CH2C(CH3)CF' 4-CF3 5-H VI.6 2-SCH2CH2C(CH3)CF2 4-CH3 5-H VI.7 2-SCH2CH2C(CH3)CF2 4-CN 5-H VI.8 2-SCH2CH2C(CH3)CF2 4-CONH2 5-H VI.9 2-SCH2CH2C(CH3 )CF2 4-COOCH2CH3 5-H VI. 10 2-SO2CH2CH2C(CH3 )CF2 4-COOCH2CH3 5-H VI. 11 2-SCH2CH2C(CH3)CF2 4-COOH 5-H VI.12 2-SO2CH2CH2C(CH3)CF2 4-H 5-Br VI.13 2-SCH2CH2C(CH3)CF2 4-H 5-Cl VI.14 2-SO2CH2CH2C(CH3)CF2 4-H 5-Cl VI.15 2-SCH2CH2C(CH3)CF2 4-CH3 VI.16 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-Cl VI. 17 2-SCH'CH2C(CH3)CF' 4-H 5-F VI.18 2-SCH2CH2C(CH3)CF2 4-H 5-C6H5 VI.19 2-SOCH2CH2C(CH3)CF2 4-H 5-C6H5 VI.20 2-SO2CH2CH2C(CH3)CF2 4-H 5-C6H5 VI.21 2-SCH2CH2C(CH3)CF2 4-H 5-CF3 VI.22 '-SCH'CH'CiCH3 )CF2 4-H 5-CS VI.23 2-SOCH2CH2C(CH3)CF2 4-H 5-CN VI.24 2-SO2CH2CH2C(CH3)CF2 4-H 5-CN VI.25 2-SCH2CH2C(CH3)CF2 4-CH3 5-CN VI.26 2-SOCH2CH2C(CH3)CF' 4-CH3 5-CN VI.27 2-SO'CH2CH2C(CH3)CF' 4-CH3 5-CN VI.28 2-SCH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VI.29 2-SOCH2CH2C(CH3)CF2 4-H 5-COOCH'CH3 VI.30 2-SO2CH2CH2C(CH3)CF2 4-H 5-COOCH'CH3 VI.31 2-SCH2CH2C(CH3)CF2 4-CF3 5-COOCH'CH3 VI.32 2-SCH2CH2C(CH3)CF2 4-CH3 5-COOCH3 VI.33 2-SOCH2CH2C(CH3)CF2 4-CH3 5-COOCH3 VI.34 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-COOCH3 VI.35 2-SCH2CH2C(CH3)CF2 4-H 5-COOH VI.36 2-SCH2CH2C(CH3)CF2 4-CF3 5-COOH VI.37 2-SCH2CH2C(CH3)CF2 4-CH3 5-COOH VI.38 2-SCH2CH2C(CH3)CF2 4-CH3 5-CONHS02CH3 VI.39 2-SCH2CH2C(CH3)CF2 4-H 5-CONH2 VI.40 2-SCH2CH2C(CH3)CF2 4-CH3 5-CONH2 VI.41 '-SOCH'CH2C(CH3 CF2 4-CH3 5-CONH2 VI.42 2-SCH2CH2C(CH3 )CF2 4-H 5-NO2 VI.43 2-SOCH2CH2C(CH3)CF2 4-H 5-NO2 VI.44 2-SO2CH2CH2C(CH3)CF2 4-H 5-NO2 VI.45 2-SCH2CH2C(CH3)CF2 4-H 5-SO2F VI.46 2-SOCH2CH2C(CH3)CF2 4-H 5-SO2F VI.47 2-SCH2CH2C(CH3)CF2 4-H 5-SO'NH2 VI.48 2-SO2CH2CH2C(CH3)CF2 4-H 5-S02NH2 VI.49 2-H 4-SCH2CH2C(CH3)CF2 5-Br VI.50 2-H 4-SCH2CH2C(CH3)CF2 5-C6H5 VI.51 2-H 4-SOCH2CH2C(CH3)CF2 5-C6H5 VI.52 2-H 4-SCH2CH2C(CH3)CF2 5-CF3 VI.53 2-H 4-SOCH2CH2C(CH3)CF2 5-CF3 VI.54 2-H 4-SCH2CH2C(CH3)CF2 5-Cl VI.55 2-H 4-SOCH2CH2C(CH3)CF2 5-Cl VI.56 2-H 4-SO2CH2CH2C(CH3)CF2 5-Cl VI.57 2-H 4-SCH2CH2C(CH3)CF' 5-CN VI.58 2-CH3 4-SCH2CH2C(CH3)CF' 5-CN VI.59 2-CH3 4-SOCH2CH2C(CH3)CF2 5-CN VI.60 2-CH3 4-SO2CH2CH2C(CH3)CF2 5-CN VI.61 2-H 4-SCH2CH2C(CH3)CF2 5-CONH2 VI.62 2-CH3 4-SCH2CH'C(CH3)CF2 5-CONH2 VI.63 2-H 4-SCH2CH2C(CH3)CF2 5-COOCH2CH3 VI.64 2-CH3 4-SCH2CH2C(CH3)CF2 5-COOCH3 VI.65 2-CH3 4-SO2CH2CH2C(CH3)CF2 5-COOCH3 VI.66 2-H 4-SCH2CH2C(CH3)CF2 5-COOH VI.67 2-H 4-SCH2CH2C(CH3)CF2 5-F VI.68 2-H 4-SCH2CH2C(CH3)CF2 5-H VI.69 2-H 4-SOCH2CH2C(CH3)CF' 5-H VI.70 2-H 4-SO2CH2CH2C(CH3)CF' 5-H VI.71 2-H 4-SCH2CH2C(CH3)CF2 5-NO2 VI.72 2-H 4-SCH2CH2C(CH3)CF2 5-SO2F VI.73 2-H 4-SCH2CH2C(CH3)CF2 5-SO'NH2 VI.74 2-H 4-Br 5-SCH2CH2C(CH3)CF2 VI.75 2-H 4-C6H5 5-SCH2CH2C(CH3)CF2 VI.76 2-H 4-CF3 5-SCH2CH2C(CH3)CF2 VI.77 2-H 4-CF3 5-SO2CH2CH2C(CH3)CF' VI.78 2-H 4-Cl 5-SCH2CH2C(CH3)CF2 VI.79 2-H 4-CN 5-SCH2CH2C(CH3)CF2 VI.80 2-H 4-CN 5-SOCH2CH2C(CH3)CF2 VI.81 2-H 4-CN 5-SO'CH'CH2C(CH3)CF2 VI.82 2-CH3 4-CN 5-SCH2CH2C(CH3)CF2 VI.83 2-H 4-CONH2 5-SCH2CH2C(CH3)CF2 VI.84 2-H 4-CONH2 5-SOCH2CH2C(CH3)CF2 VI.85 2-H 4-CONH2 5-SO2CH2CH2C(CH3)CF2 VI.86 2-CH3 4-CONH2 5-SCH2CH2C(CH3)CF2 VI.87 2-H 4-COOCH2CH3 5-SCH2CH2C(CH3)CF2 VI.88 2-H 4-COOCH2CH3 5-SOCH2CH2C(CH3)CF2 VI.89 2-H 4-COOCH2CH3 5-SO2CH2CH2C(CH3)CF2 VI.90 2-CH3 4-COOCH3 5-SCH2CH2C(CH3)CF2 VI.91 2-H 4-COOH 5-SCH2CH2C(CH3)CF2 VI.92 2-H 4-F 5-SCH2CH2C(CH3)CF2 VI.93 2-H 4-H 5-SCH2CH2C(CH3)CF2 VI.94 2-H 4-H 5 -SOCH2CH2C(CH3)CF2 VI.95 2-H 4-H 5-SO2CH2CH2C(CH3)CF2 VI.96 2-H 4-NO2 5-SCH2CH2C(CH3)CF2 VI.97 2-H 4-NO2 5-SOCH2CH2C(CH3)CF2 VI.98 2-H 4-SO2F 5-SCH2CH2C(CH3)CF2 VI.99 2-H 4-SO2NH2 5-SCH2CH2C(CH3)CF2 VI.100 2-Br 4-H 5-SCH2CH2C(CH3)CF2 VI.101 2-C6H5 4-H 5-SCH2CH2C(CH3)CF2 VI.102 2-C6H5 4-H 5-SOCH2CH2C(CH3)CF' VI.103 2-C6H5 4-H 5-SO2CH2CH2C(CH3)CF2 VI.104 2-CF3 4-H 5-SCH2CH2C(CH3)CF2 VI.105 2-CF3 4-H 5-SO'CH'CH2C(CH3)CF' VI.106 2-Cl 4-H 5-SCH2CH2C(CH3)CF2 VI.107 '-CN 4-H 5-SCH2CH2C(CH3)CF2 VI.108 2-CN 4-CH3 5-SCH2CH2C(CH3)CF2 VI.109 2-CONH2 4-H 5-SCH2CH2C(CH3)CF2 VI.110 2-CONH2 4-H 5-SOCH2CH2C(CH3)CF2 VI.111 2-CONH2 4-H 5-SO2CH2CH2C(CH3)CF2 VI.112 2-CONH2 4-CH3 5-SO2CH2CH2C(CH3)CF2 VI.113 2-COOCH2CH3 4-H 5-SCH2CH2C(CH3)CF2 VI.114 2-COOCH3 4-CH3 5-SCH2CH2C(CH3)CF2 VI.115 2-COOH 4-H 5-SCH2CH2C(CH3)CF2 VI.116 2-F 4-H 5-SCH2CH2C(CH3)CF2 VI.117 2-F 4-H 5-SOCH2CH2C(CH3)CF2 VI.118 2-NO2 4-H 5-SCH2CH2C(CH3)CF2 VI.119 2-SO2F 4-H 5-SCH2CH2C(CH3)CF2 VI.120 '-SO'NH2 4-H 5-SCH2CH2C(CH3)CF2 VI.121 2-SCH2CH2C(CH3)CF2 4-C6H5 5-H VI.122 2-SOCH2CH2C(CH3)CF2 4-C6H5 5-H VI.123 2-SO2CH2CH2C(CH3)CF2 4-C6H5 5-H Examples of compounds of Formula (VII) according to the invention are set out in Table VII.
TABLE VII No. R2 R4 R5 VII.1 2-SCH2CH2C(CH3)CF2 4-H 5-H VII.2 2-SOCH2CH2C(CH3)CF2 4-H 5-H VII.3 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VII.4 2-SCH2CH2C(CH3)CF2 4-CF3 5-H VII.5 '-SO'CH'CH2C(CH3)CF2 4-CF3 5-H VII.6 2-SCH2CH2C(CH3)CF2 4-CN 5-H VII.7 2-SCH2CH2C(CH3)CF2 4-CONH2 5-H VII.8 2-SCH2CH2C(CH3)CF2 4-COOCH2CH3 5-H VII.9 2-SO'CH'CH2C(CH3)CF' 4-COOCH2CH3 5-H VII. 10 2-SCH2CH2C(CH3)CF2 4-COOH 5-H VII.11 2-SCH2CH2C(CH3)CF2 4-COOCH2CH3 5-Br VII.12 2-SO2CH2CH2C(CH3)CF2 4-COOCH2CH3 5-Br VII.13 2-SCH2CH2C(CH3)CF2 4-COOH 5-Br VII.14 2-SCH2CH2C(CH3)CF2 4-H 5-Br VII. 15 2-SOCH2CH2C(CH3)CF2 4-H 5-Br VII.16 2-SO2CH2CH2C(CH3)CF2 4-H 5-Br VII.17 2-SCH2CH2C(CH3)CF2 4-H 5-C6H5 VII.18 2-SOCH'CH'C(CH31CFn 4-H 5-C6H5 VII.19 2-SO2CH2CH2C(CH3)CF2 4-H 5-C6H5 VII.20 2-SCH2CH2C(CH3 )CF2 4-H 5-CF3 VII.I 2-SCH2CH2C(CH3)CF2 4-H 5-CH3 VII.22 2-SOCH2CH2C(CH3)CF2 4-H 5-CH3 VII.23 2-SO2CH2CH2C(CH3)CF2 4-H 5-CH3 VII.24 2-SCH2CH2C(CH3)CF2 4-H 5-Cl VII.25 2-SOCH2CH2C(CH3)CF2 4-H 5-Cl VII.26 '-S02CH2CH2C(CH3)CF2 4-H 5-Cl VII.27 2-SCH2CH2C(CH3)CF2 4-CH3 5-Cl VII.28 2-SO'CH'CH'C(CH3)CF' 4-CH3 5-Cl VII.29 2-SCH2CH2C(CH3)CF2 4-H 5-CN VII.30 2-SOCH2CH2C(CH3)CF2 4-H 5-CN VII.3 1 2-SO2CH2CH2C(CH3)CF2 4-H 5-CN VII.32 2-SCH2CH2C(CH3)CF2 4-CH3 5-CN VII.33 2-SOCH2CH2C(CH3)CF2 4-CH3 5-CN VII.34 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-CN VII.35 2-SCH2CH2C(CH3)CF2 4-H 5-CONH2 VII.36 2-SCH2CH2C(CH3)CF2 4-CH3 5-CONH2 VII.3 7 2-SOCH2CH2C(CH3 )CF2 4-CH3 5-CONH2 VII .38 2-SCH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VII.39 2-SOCH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VII.40 2-SO2CH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VII.4 1 2-SCH2CH2C(CH3)CF2 4-CH3 5-COOCH3 VII.42 2-SOCH2CH2C(CH3)CF2 4-CH3 5-COOCH3 VII.43 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-COOCH3 VII .44 2-SCH2CH2C(CH3)CF2 4-H 5-COOH VII.45 2-SCH2CH2C(CH3)CF2 1-CH3 5-COOH VII.46 2-SCH2CH2C(CH3)CF2 4-H 5-F VII.47 2-SCH'CH2C(CH3)CF' 4-H 5-N02 VII.48 2-SOCH2CH2C(CH3)CF2 4-H 5-NO2 VII.49 2-SO2CH2CH2C(CH3)CF2 4-H 5-NO2 VII.50 2-SCH2CH2C(CH3)CF2 4-H 5-SO2F VII.51 2-SOCH2CH2C(CH3)CF2 4-H 5-SO2F VII.52 2-SCH2CH2C(CH3)CF2 4-CH3 5-SO2F VII.53 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-SO2F VII.54 2-SCH2CH2C(CH3)CF2 4-H 5-SO2NH2 VII.55 2-SO2CH2CH2C(CH3)CF2 4-H 5-SO'NH' VII.5 6 2-SCH2CH2C(CH3)CF2 4-CH3 5-S02N(CH2CH3)2 VII.57 2-H 4-SCH2CH2C(CH3)CF2 5-H VII.58 2-H 4-SOCH2CH2C(CH3)CF2 5-H VII.59 2-H 4-SO2CH2CH2C(CH3)CF2 5-H VII.60 2-H 4-SCH'CH2C(CH3)CF' 5-Br VII.61 2-H 4-SCH2CH2C(CH3)CFr 5-C6H5 VII.62 2-H 4-SOCHXCH2C(CH3)CF2 5-C6H5 VII.63 2-H 4-SCH2CH2C(CH3)CF2 5-CF3 VII.64 2-H 4-SOCH2CH2C(CH3)CF2 5-CF3 VII.65 2-H 4-SCH2CH2C(CH3)CF2 5-Cl VII.66 2-H 4-SOCH2CH2C(CH3)CF2 5-Cl VII.67 2-H 4-SO2CH2CH2C(CH3)CF2 5-Cl VII.68 2-H 4-SCH2CH2C(CH3)CF2 5-CN VII.69 2 -CH3 4-SCH2CH2C(CH3)CF2 5-CN VII.70 2-CH3 4-SOCH2CH2C(CH3)CF2 5-CN VII.71 2-CH3 4-SO2CH2CH2C(CH3)CF2 5-CN VII.72 2-H 4-SCH2CH2C(CH3)CF2 5-CONH2 VII.73 2-CH3 4-SCH2CH2C(CH3)CF2 5-CONH2 VII.74 2-H 4-SCH2CH2C(CH3)CF2 5-COOCH2CH3 VII.75 2-CH3 4-SCH2CH2C(CH3)CF2 5-COOCH3 VII.76 2-CH3 4-SO2CH2CH2C(CH3)CF2 5-COOCH3 VII.77 2-H 4-SCH2CH2C(CH3)CF2 5-COOH VII.78 2-H 4-SCH2CH2C(CH3)CF2 5-F VII.79 2-H 4-SCH2CH2C(CH3)CF2 5-N02 VII.80 2-H 4-SCH2CH2C(CH3)CF2 5-SO2F VII.81 2-H 4-SCH2CH2C(CH3)CF2 5-S02NH2 VII.82 2-H 4-H 5-SCH2CH2C(CH3)CF2 VII.83 2-H 4-H 5-SOCH2CH2C(CH3)CF2 VII.84 2-H 4-H 5-SO2CH2CH2C(CH3)CF2 VII.85 2-H 4-Br 5-SCH2CH2C(CH3)CF2 VII.86 2-H 4-C6H5 5-SCH2CH2C(CH3)CF2 VII.87 2-H 4-CF3 5-SCH2CH2C(CH3)CF2 VII.88 2-H 4-CF3 5-SO2CH2CH2C(CH3)CF' VII.89 2-H 4-Cl 5-SCH2CH2C(CH3)CF2 VII.90 2-H 4-CN 5-SCH2CH2C(CH3)CF2 VII.91 2-H 4-CN 5-SOCH2CH2C(CH3)CF2 VII.92 2-H 4-CN 5-SO2CH2CH2C(CH3)CF2 VII.93 2-CH3 4-CN 5-SCH2CH2C(CH3)CF2 VII.94 2-H 4-CONH2 5 -SCH2CH2C(CH3 )CF2 VII 95 2-H 4-CONH2 5-SOCH2CH2C(CH3)CF2 VII.96 2-H 4-CONH2 5-SO2CH2CH2C(CH3)CF2 VII.97 2-CH3 4-CONH2 5-SCH2CH2C(CH3)CF2 VII.98 2-H 4-COOCH2CH3 5-SCH2CH2C(CH3)CF2 VII.99 2-H 4-COOCH2CH3 5-SOCH2CH2C(CH3)CF2 VII.100 2-H 4-COOCH2CH3 5-SO2CH2CH2C(CH3)CF2 VII.101 2-CH3 4-COOCH3 5-SCH2CH2C(CH3)CF2 VII. 102 2-H 4-COOH 5-SCH2CH2C(CH3)CF2 VII. 103 2-H 4-F 5-SCH2CH2C(CH3)CF2 VII.104 2-H 4-N02 5-SCH2CH2C(CH3)CF2 VII. 105 2-H 4-NO2 5-SOCH2CH2C(CH3)CF2 VII.106 2-H 4-SO2F 5-SCH2CH2C(CH3)CF2 VII.107 2-H 4-SO2NH2 5-SCH2CH2C(CH3)CF2 VII. 108 2-Br 4-H 5-SCH2CH2C(CH3)CF2 VII.109 2-C6H5 4-H 5-SCH2CH2C(CH3)CF2 VII.110 2-C6H5 4-H 5-SOCH2CH2C(CH3)CF2 VII.111 2-C6H5 4-H 5-SO2CH2CH2C(CH3)CF2 VII.112 2-CF3 4-H 5-SCH2CH2C(CH3)CF2 VII.113 2-CF3 4-H 5-SO2CH2CH2C(CH3)CF2 VII.114 2-Cl 4-H 5-SCH2CH2C(CH3)CF2 VII.115 2-Cl 4-H 5-SOCH2CH2C(CH3)CF2 VII.116 2-Cl 4-H 5-SO2CH2CH2C(CH3)CF2 VII.117 2-CN 4-H 5-SCH2CH2C(CH3)CF2 VII.118 2-CN 4-CH3 5-SCH2CH2C(CH3)CF2 VII.119 2-CONH2 4-H 5-SCH2CH2C(CH3)CF2 VII.120 2-CONH2 4-H 5-SOCH2CH2C(CH3)CF2 VII.121 2-CONH2 4-H 5-SO2CH2CH2C(CH3)CF2 VII.122 2-CONH2 4-CH3 5-SO2CH2CH2C(CH3)CF2 VII.123 2-COOCH2CH3 4-H 5-SCH2CH2C(CH3)CF2 VII.124 2-COOCH3 4-CH3 5-SCH2CH2C(CH3)CF2 VII.125 2-COOH 4-H 5-SCH2CH2C(CH3)CF2 VII.126 2-F 4-H 5-SCH2CH2C(CH3)CF2 VII.127 2-F 4-H 5-SOCH2CH2C(CH3)CF2 VII.128 2-NH2 4-H 5-SCH2CH2C(CH3)CF2 VII.129 2-NO2 4-H 5-SCH2CH2C(CH3)CF2 VII.130 2-O(4-CN-C6H4) 4-H 5-SCH2CH2C(CH3)CF2 VII.131 2-SO2F 4-H 5-SCH2CH2C(CH3)CF2 VII.132 2-SO2NH2 4-H 5-SCH2CH2C(CH3)CF2 VII.133 2-S-(2)-(5-Cl Thiazole) 4-H 5-SCH2CH2C(CH3)CF2 VII.134 2-SCH2CH2C(CH3)CF2 4-dihydro 5-dihydro Examples of compounds of Formula (VIII) according to the invention are set out in Table VIII.
TABLE VIII No. R1 R2 R4 R5 VIII 1 1 H 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 2 1-H 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 3 1-C6H5 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 4 1-C6H5 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 5 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 6 1 CH3 2-SOCH2CH2C(CH3)CF2 4-H 5-H VIII 7 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 8 1 CH2CH2CHCF2 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 9 1 CH2CH2CHCF2 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 10 1-CH2CH3 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 11 1-CH2CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 12 1-CH2CH2CH3 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 13 1-CH2CH2CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 14 1-CH(CH3)2 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 15 1-CH(CH3)2 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 16 1 C(CH3)3 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 17 1 C(CH3)3 2-SO2CH2CH2C(CH3)CF2 4-H 5-H VIII 18 1-SO2CH3 2-SCH2CH2C(CH3)CF2 4-H 5-H VIII 19 1-H 2-SCH2CH2C(CH3)CF2 4-C6H5 5-H VIII 20 1-H 2-SOCH2CH2C(CH3)CF2 4-C6H5 5-H VIII 21 1 H 2-SO2CH2CH2C(CH3)CF2 4-C6H5 5-H VIII 22 1-CH3 2-SCH2CH2C(CH3)CF2 4-C6H5 5-H VIII.23 1 CH3 2-SOCH2CH2C(CH3)CF2 4-C6H5 5-H VIII.24 1 CH3 2-SO2CH2CH2C(CH3)CF2 4-C6H5 5-H VIII.25 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-Br VIII.26 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-CF3 VIII 27 1 H 2-SCH2CH2C(CH3)CF2 4-CH2CH3 5-CH3 VIII 28 1 H 2-SO2CH2CH2C(CH3)CF2 4-CH2CH3 5-CH3 VIII 29 1-H 2-SCH2CH2C(CH3)CF2 4-CH3 5-CH3 VIII 30 1-H 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-CH3 VIII 31 1-CH3 2-SCH2CH2C(CH3)CF2 4-CH3 5-CH3 VIII.32 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-CH3 VIII 33 1-CH2CH3 2-SCH2CH2C(CH3)CF2 4-CH3 5-CH3 VIII 34 1 CH2CH3 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-CH3 VIII.35 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-CH3 VIII 36 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-CH3 VIII.37 1-CH(CH3)2 2-SCH2CH2C(CH3)CF2 4-H 5-CH3 VIII.38 1-CH(CH3)2 2-SO2CH2CH2C(CH3)CF2 4-H 5-CH3 VIII.39 1 CH3 2-SCH2CH2C(CH3)CF2 4-H 5-Cl VIII.40 1 CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-Cl VIII.41 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-CN VIII.42 1-CH3 2-SOCH2CH2C(CH3)CF2 4-H 5-CN VIII.43 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-CN VIII.44 1-CH3 2-SCH2CH2C(CH3)CF2 4-CH3 5-CN VIII.45 1-CH3 2-SOCH2CH2C(CH3)CF2 4-CH3 5-CN VIII.46 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-CN VIII.47 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-CONH2 VIII.48 1-CH3 2-SCH2CH2C(CH3)CF2 4-CH3 5-CONH2 VIII.49 1-CH3 2-SOCH2CH2C(CH3)CF2 4-CH3 5-CONH2 VIII 50 1-H 2-SOCH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VIII.51 1-H 2-SO2CH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VIII.52 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VIII.53 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-COOCH2CH3 VIII.54 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-COOH VIII 55 1-CH3 2-SCH2CH2C(CH3)CF2 4-CH2CH3 5-COOCH3 VIII.56 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-CH2CH3 5-COOCH3 VIII.57 1 CH3 2-SCH2CH2C(CH3)CF2 4-H 5-F VIII 58 1-H 2-SCH2CH2C(CH3)CF2 4-CH3 5-H VIII.59 1-H 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-H VIII.60 1-CH3 2-SCH2CH2C(CH3)CF2 4-CH3 5-H VIII.61 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-H VIII.62 1-CH(CH3)2 2-SCH2CH2C(CH3)CF2 4-CH3 5-H VIII.63 1 CH(CH3)2 2-SO2CH2CH2C(CH3)CF2 4-CH3 5-H VIII.64 1 H 2-SCH2CH2C(CH3)CF2 4-COOCH2CH3 5-H VIII.65 1-CH3 2-SCH2CH2C(CH3)CF2 4-COOCH2CH3 5-H VIII.66 1-CH3 2-SOCH2CH2C(CH3)CF2 4-COOCH2CH3 5-H VIII.67 1 CH3 2-SO2CH2CH2C(CH3)CF2 4-COOCH2CH3 5-H VIII.68 1-CH3 2-SCH2CH2C(CH3)CF2 4-COOCH3 5-CH2CH3 VIII.69 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-NO2 VIII.70 1-CH3 2-SOCH2CH2C(CH3)CF2 4-H 5-NO2 VIII.71 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-NO2 VIII.72 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-SO2F VIII.73 1-CH3 2-SOCH2CH2C(CH3)CF2 4-H 5-SO2F VIII.74 1-CH3 2-SCH2CH2C(CH3)CF2 4-H 5-SO2NH2 VIII.75 1-CH3 2-SO2CH2CH2C(CH3)CF2 4-H 5-SO2NH2 VIII.76 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-H VIII.77 1-CH3 2-H 4-SOCH2CH2C(CH3)CF2 5-H VIII.78 1-CH3 2-H 4-SO2CH2CH2C(CH3)CF2 5-H VIII 79 1 CH3 2-H 4-SCH2CH2C(CH3)CF2 5-CN VIII.80 1 CH3 2-CH3 4-SCH2CH2C(CH3)CF2 5-CN VIII.81 1-CH3 2-CH3 4-SOCH2CH2C(CH3)CF2 5-CN VIII.82 1 CH3 2-CH3 4-SO2CH2CH2C(CH3)CF2 5-CN VIII.83 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-C6H5 VIII.84 1-CH3 2-H 4-SOCH2CH2C(CH3)CF2 5-C6H5 VIII.85 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-COOCH2CH3 VIII.86 1-CH3 2-CH3 4-SCH2CH2C(CH3)CF2 5-COOCH3 VIII.87 1-CH3 2-CH3 4-SO2CH2CH2C(CH3)CF2 5-COOCH3 VIII.88 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-COOH VIII.89 1-CH3 2-H 4-SCH2CH2C(CH3)CFD2 5-CONH2 VIII.90 1-CH3 2-CH3 4-SCH2CH2C(CH3)CF2 5-CONH2 VIII.91 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-Cl VIII.92 1-CH3 2-H 4-SOCH2CH2C(CH3)CF2 5-Cl VIII.93 1-CH3 2-H 4-SO2CH2CH2C(CH3)CF2 5-Cl VIII.94 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-F VIII.95 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-Br VIII.96 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-SO2NH2 VIII.97 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-SO2F VIII.98 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-NO2 VIII.99 1-CH3 2-H 4-SCH2CH2C(CH3)CF2 5-CF3 VIII 100 1-CH3 2-H 4-SOCH2CH2C(CH3)CF2 5-CF3 VIII.101 1-CH3 2-H 4-H 5-SCH2CH2C(CH3)CF2 VIII.102 1-CH3 2-H 4-H 5-SOCH2CH2C(CH3)CF2 VIII.103 1 CH3 2-H 4-H 5-SO2CH2CH2C(CH3)CF2 VIII.104 1 CH3 2-H 4-CN 5-SCH2CH2C(CH3)CF2 VIII.105 1-CH3 2-H 4-CN 5-SOCH2CH2C(CH3)CF2 VIII.106 1 CH3 2 H 4-CN 5-SO2CH2CH2C(CH3)CF2 VIII.107 1-CH3 2-CH3 4-CN 5-SCH2CH2C(CH3)CF2 VIII.108 1-CH3 2-H 4-C6H5 5-SCH2CH2C(CH3)CF2 VIII.109 1-CH3 2-H 4-COOCH2CH3 5-SCH2CH2C(CH3)CF2 VIII.110 1-CH3 2-H 4-COOCH2CH3 5-SOCH2CH2C(CH3)CF2 VIII.111 1-CH3 2-H 4-COOCH2CH3 5-SO2CH2CH2C(CH3)CF2 VIII.112 1-CH3 2-CH3 4-COOCH3 5-SCH2CH2C(CH3)CF2 VIII.113 1-CH3 2-H 4-COOH 5-SCH2CH2C(CH3)CF2 VIII.114 1-CH3 2-H 4-CONH2 5-SCH2CH2C(CH3)CF2 VIII.115 1-CH3 2-H 4-CONH2 5-SOCH2CH2C(CH3)CF2 VIII.116 1-CH3 2-H 4-CONH2 5-SO2CH2CH2C(CH3)CF2 VIII.117 1-CH3 2-CH3 4-CONH2 5-SCH2CH2C(CH3)CF2 VIII.118 1-CH3 2-H 4-Cl 5-SCH2CH2C(CH3)CF2 VIII.119 1-CH3 2-H 4-F 5-SCH2CH2C(CH3)CF2 VIII.120 1-CH3 2-H 4-Br 5-SCH2CH2C(CH3)CF2 VIII.121 1-CH3 2-H 4-SO2NH2 5-SCH2CH2C(CH3)CF2 VIII.122 1-CH3 2-H 4-SO2F 5-SCH2CH2C(CH3)CF2 VIII 123 1-CH3 2-H 4-NO2 5-SCH2CH2C(CH3)CF2 VIII.124 1 CH3 2-H 4-NO2 5-SOCH2CH2C(CH3)CF2 VIII.125 1 CH3 2-H 4-CF3 5-SCH2CH2C(CH3)CF2 VIII 126 1-CH3 2-H 4-CF3 5-SO2CH2CH2C(CH3)CF2 VIII.127 1 CH3 2-H 4-H 5-SCH2CH2C(CH3)CF2 VIII.128 1-CH3 2-H 4-H 5-SOCH2CH2C(CH3)CF2 VIII.129 1 CH3 2-H 4-H 5-SO2CH2CH2C(CH3)CF2 VIII.130 1-CH3 2-CN 4-H 5-SCH2CH2C(CH3)CF2 VIII.131 1 CH3 2-CN 4-CH3 5-SCH2CH2C(CH3)CF2 VIII.132 1 CH3 2-C6H5 4-H 5-SCH2CH2C(CH3)CF2 VIII.133 1 CH3 2-C6H5 4-H 5-SOCH2CH2C(CH3)CF2 VIII.134 1 CH3 2-C6H5 4-H 5-SO2CH2CH2C(CH3)CF2 VIII.135 1-CH3 2-COOCH2CH3 4-H 5-SCH2CH2C(CH3)CF2 VIII 136 1-CH3 2-COOCH3 4-CH3 5-SCH2CH2C(CH3)CF2 VIII.137 1-CH3 2-COOH 4-H 5-SCH2CH2C(CH3)CF2 VIII.138 1-CH3 2-CONH2 4-H 5-SCH2CH2C(CH3)CF2 VIII.139 1 CH3 2-CONH2 4-H 5-SOCH2CH2C(CH3)CF2 VIII 140 1-CH3 2-CONH2 4-H 5-SO2CH2CH2C(CH3)CF2 VIII 141 1-CH3 2-CONH2 4-CH3 5-SO2CH2CH2C(CH3)CF2 VIII 142 1 CH3 2-Cl 4-H 5-SCH2CH2C(CH3)CF2 VIII 143 1-CH3 2-F 4-H 5-SCH2CH2C(CH3)CF2 VIII 144 1 CH3 2-F 4-H 5-SOCH2CH2C(CH3)CF2 VIII.145 1-CH3 2-Br 4-H 5-SCH2CH2C(CH3)CF2 VIII 146 1-CH3 2-SO2NH2 4-H 5-SCH2CH2C(CH3)CF2 VIII 147 1-CH3 2-SO2F 4-H 5-SCH2CH2C(CH3)CF2 VIII 148 1 CH3 2-NO2 4-H 5-SCH2CH2C(CH3)CF2 VIII.149 1-CH3 2-CF3 4-H 5-SCH2CH2C(CH3)CF2 VIII 150 1-CH3 2-CF3 4-H 5-SO2CH2CH2C(CH3)CF2 VIII.151 1-5 linked 2-SCH2CH2C(CH3)CF2 4-H -CH=CH-CH=CH VIII.152 1-5 linked 2-SO2CH2CH2C(CH3)CF2 4-H -CH=CH-CH=CH VIII.153 1-CH2CH2CH3 2-SCH2CH2C(CH3)=CF2 4-H 5-H VIII 154 1 CH2CH2CH3 2-SOCH2CH2C(CH3)=CF2 4-H 5-H VIII 155 1-CH2CH2CH3 2-SO2CH2CH2C(CH3)=CF2 4-H 5-H Examples of compounds of Formula (IX) according to the invention are set out in Table IX.
TABLE IX No. R1 R3 R4 R5 IX 1 1-CH3 3-H 4-H 5-SCH2CH2C(CH3)CF2 IX 2 1-CH3 3-H 4-H 5-SOCH2CH2C(CH3)CF2 IX.3 1 CH3 3-H 4-H 5-SO2CH2CH2C(CH3)CF2 IX.4 1 CH3 3-Cl 4-H 5-SCH2CH2C(CH3)CF2 IX 5 1 CH3 3-Cl 4-H 5-SOCH2CH2C(CH3)CF2 IX 6 1 CH3 3-Cl 4-H 5-SO2CH2CH2C(CH3)CF2 IX 7 1 CH3 3-COOC2H5 4-H 5-SCH2CH2C(CH3)CF2 IX.8 1-CH3 3-COOC2H5 4-H 5-SOCH2CH2C(CH3)CF2 IX.9 1-CH3 3 COOC2H5 4-H 5-SO2CH2CH2C(CH3)CF2 IX.10 1-CH3 3-COOH 4-H 5-SCH2CH2C(CH3)CF2 IX.11 1 CH3 3-COOH 4-H 5-SOCH2CH2C(CH3)CF2 IX 12 1-CH3 3-COOH 4-H 5-SO2CH2CH2C(CH3)CF2 IX 13 1-CH3 3-CONH2 4-H 5-SCH2CH2C(CH3)CF2 IX 14 1-CH3 3-CONH2 4-H 5-SOCH2CH2C(CH3)CF2 IX.15 1-CH3 3-CONH2 4-H 5-SO2CH2CH2C(CH3)CF2 IX.16 1 CH3 3-CN 4-H 5-SCH2CH2C(CH3)CF2 IX.17 1-CH3 3-CN 4-H 5-SOCH2CH2C(CH3)CF2 IX.18 1 CH3 3-CN 4-H 5-SO2CH2CH2CH-CF2 IX.19 1-CH3 3-SO2F 4-H 5-SCH2CH2C(CH3)CF2 IX.20 1 CH3 3-SO2F 4-H 5-SOCH2CH2CH-CF2 IX.21 1 CH3 3-SO2F 4-H 5-SO2CH2CH2C(CH3)CF2 IX 22 1 CH3 3-SO2NH2 4-H 5-SCH2CH2C(CH3)CF2 IX 23 1-CH3 3-SO2NH2 4-H 5-SOCH2CH2C(CH3)CF2 IX.24 1-CH3 3-SO2NH2 4-H 5-SO2CH2CH2C(CH3)CF2 IX.25 1-CH3 3-H 4-H 5-SCH2CH2C(CH3)CF2 IX.26 1-CH3 3-H 4-H 5-SOCH2CH2C(CH3)CF2 IX.27 1-CH3 3-H 4-H 5-SO2CH2C(CH3)CF2 IX 28 1-CH3 3-H 4-Cl 5-SCH2CH2C(CH3)CF2 IX 29 1-CH3 3-H 4-Cl 5-SOCH2CH2C(CH3)CF2 IX.30 1-CH3 3-H 4-Cl 5-SO2CH2CH2C(CH3)CF2 IX.31 1-CH3 3-H 4-Br 5-SCH2CH2C(CH3)CF2 IX.32 1-CH3 3-H 4-Br 5-SOCH2CH2C(CH3)CF2 IX.33 1-CH3 3-H 4-Br 5-SO2CH2CH2C(CH3)CF2 IX.34 1-CH3 3-H 4-COOC2H5 5-SCH2CH2C(CH3)CF2 IX.35 1-CH3 3-H 4-COOC2H5 5-SOCH2CH2C(CH3)CF2 IX.36 1-CH3 3-H 4-COOC2H5 5-SO2CH2CH2C(CH3)CF2 IX.37 1-CH3 3-H 4-COOCH(CH3)2 5-SCH2CH2C(CH3)CF2 IX.38 1-CH3 3-H 4-COOCH(CH3)2 5-SOCH2CH2C(CH3)CF2 IX.39 1-CH3 3-H 4-COOCH(CH3)2 5-SO2CH2CH2C(CH3)CF2 IX.40 1-CH3 3-H 4-COOCH 5-SCH2CH2C(CH3)CF2 IX.41 1-CH3 3-H 4-COOCH 5-SOCH2CH2C(CH3)CF2 IX.42 1-CH3 3-H 4-COOCH 5-SO2CH2CH2C(CH3)CF2 IX.43 1-CH3 3-H 4-CONH2 5-SCH2CH2C(CH3)CF2 IX.44 1-CH3 3-H 4-CONH2 5-SOCH2CH2C(CH3)CF2 IX 45 1 CH3 3-H 4-CONH2 5-SO2CH2CH2C(CH3)CF2 IX.46 1-CH3 3-H 4-CN 5-SCH2CH2C(CH3)CF2 IX.47 1-CH3 3-H 4-CN 5-SOCH2CH2C(CH3)CF2 IX.48 1-CH3 3-H 4-CN 5-SO2CH2CH2C(CH3)CF2 IX.49 1-CH3 3-H 4-SO2F 5-SCH2CH2C(CH3)CF2 IX.50 1-CH3 3-H 4-SO2F 5-SOCH2CH2C(CH3)CF2 IX.51 1-CH3 3-H 4-SO2F 5-SO2CH2CH2C(CH3)CF2 IX.52 1 CH3 3-H 4-SO2NH2 5-SCH2CH2C(CH3)CF2 IX.53 1 CH3 3-H 4-SO2NH2 5-SOCH2CH2C(CH3)CF2 IX.54 1 CH3 3-H 4-SO2NH2 5-SO2CH2CH2C(CH3)CF2 IX 55 1-CH3 3-CH3 4-H 5-SCH2CH2C(CH3)CF2 IX 56 1 CH3 3-CH3 4-H 5-SOCH2CH2C(CH3)CF2 IX.57 1 CH3 3-CH3 4-H 5-SO2H2CH2C(CH3)CF2 IX 58 1-CH3 3-CH3 4-Cl 5-SCH2CH2C(CH3)CF2 IX.59 1-CH3 3-CH3 4-Cl 5-SOCH2CH2C(CH3)CF2 IX 60 1-CH3 3-CH3 4-Cl 5-SO2CH2CH2C(CH3)CF2 IX.61 1 CH3 3-CH3 4-I 5-SCH2CH2C(CH3)CF2 IX.62 1-CH3 3-CH3 4-I 5-SOCH2CH2C(CH3)CF2 IX.63 1-CH3 3-CH3 4-I 5-SO2CH2CH2C(CH3)CF2 IX.64 1-CH3 3-CH3 4-COOC2H5 5-SCH2CH2C(CH3)CF2 IX.65 1 CH3 3-CH3 4-COOC2H5 5-SOCH2CH2C(CH3)CF2 IX.66 1-CH3 3-CH3 4-COOC2H5 5-SO2CH2CH2C(CH3)CF2 IX.67 1-CH3 3-CH3 4-COOH 5-SCH2CH2C(CH3)CF2 IX.68 1-CH3 3-CH3 4-COOH 5-SOCH2CH2C(CH3)CF2 IX.69 1-CH3 3-CH3 4-COOH 5-SO2CH2CH2C(CH3)CF2 IX.70 1-CH3 3-CH3 4-CONH2 5-SCH2CH2C(CH3)CF2 IX.71 1-CH3 3-CH3 4-CONH2 5-SOCH2CH2C(CH3)CF2 IX.72 1-CH3 3-CH3 4-CONH2 5-SO2CH2CH2C(CH3)CF2 IX.73 1-CH3 3-CH3 4-CN 5-SCH2CH2C(CH3)CF2 IX.74 1-CH3 3-CH3 4-CN 5-SOCH2CH2C(CH3)CF2 IX.75 1-CH3 3-CH3 4-CN 5-SO2CH2CH2C(CH3)CF2 IX.76 1-CH3 3-CH3 4-SO2F 5-SCH2CH2C(CH3)CF2 IX.77 1-CH3 3-CH3 4-SO2F 5-SOCH2CH2C(CH3)CF2 IX.78 1-CH3 3-CH3 4-SO2F 5-SO2CH2CH2C(CH3)CF2 IX.79 1-CH3 3-CH3 4-SO2NH2 5-SCH2CH2C(CH3)CF2 IX.80 1-CH3 3-CH3 4-SO2NH2 5-SOCH2CH2C(CH3)CF2 IX.81 1-CH3 3-CH3 4-SO2NH2 5-SO2CH2CH2C(CH3)CF2 IX.82 1-CH3 3-CH3 4-NO2 5-SCH2CH2C(CH3)CF2 IX.83 1-CH3 3-CH3 4-NO2 5-SOCH2CH2C(CH3)CF2 IX.84 1-CH3 3-CH3 4-NO2 5-SO2CH2CH2C(CH3)CF2 IX.85 1-CH3 3-CF3 4-H 5-SCH2CH2C(CH3)CF2 IX.86 1-CH3 3-CF3 4-H 5-SOCH2CH2C(CH3)CF2 IX.87 1-CH3 3-CF3 4-H 5-SO2CH2CH2C(CH3)CF2 IX.88 1-CH3 3-C6H5 4-H 5-SCH2CH2C(CH3)CF2 IX.89 1-CH3 3-C6H5 4-H 5-SOCH2CH2C(CH3)CF2 IX.90 1 CH3 3-C6H5 4-H 5-SO2CH2CH2C(CH3)CF2 IX.91 1-CH3 3-C6H5 4-CN 5-SCH2CH2C(CH3)CF2 IX.92 1-CH3 3-C6H5 4-CN 5-SOCH2CH2C(CH3)CF2 IX.93 1-CH3 3-C6H5 4-CN 5-SO2CH2CH2C(CH3)CF2 IX.94 1 CH3 3-SCH2CH2C(CH3)CF2 4-CN 5-H IX.95 1 CH3 3-SOCH2CH2C(CH3)CF2 4-CN 5-H IX.96 1 CH3 3-SO2CH2CH2C(CH3)CF2 4-CN 5-H IX.97 1-CH3 3-SCH2CH2C(CH3)CF2 4-H 5-Cl IX.98 1-CH3 3-SOCH2CH2C(CH3)CF2 4-H 5-Cl IX.99 1-CH3 3-SO2CH2CH2C(CH3)CF2 4-H 5-Cl IX.100 1-CH3 3-SCH2CH2C(CH3)CF2 4-H 5-CN IX.101 1 CH3 3-SOCH2CH2C(CH3)CF2 4-H 5-CN IX.102 1 CH3 3-SO2CH2CH2C(CH3)CF2 4-H 5-CN IX.103 1 CH3 3-SCH2CH2C(CH3)CF2 4-H 5-COOC2H5 IX.104 1-CH3 3-SOCH2CH2C(CH3)CF2 4-H 5-COOC2H5 IX.105 1 CH3 3-SO2CH2CH2C(CH3)CF2 4-H 5-COOC2H5 IX.106 1-CH3 3-SCH2CH2C(CH3)CF2 4-H 5-CF3 IX.107 1-CH3 3-SOCH2CH2C(CH3)CF2 4-H 5-CF3 IX 108 1 CH3 3-SO2CH2CH2C(CH3)CF2 4-H 5-CF3 IX 109 1-CH2COOH 3-SCH2CH2C(CH3)CF2 4-H 5-CH3 IX.110 1-CH2COOH 3-SOCH2CH2C(CH3)CF2 4-H 5-CH3 IX.111 1 CH2COOH 3-SO2CH2CH2C(CH3)CF2 4-H 5-CH3 IX 112 1 CH2COOC2H5 3-SCH2CH2C(CH3)CF2 4-H 5-C6H5 IX 113 1 CH2COOC2H5 3 SOCH2CH2C(CH3)CF2 4-H 5-C6H5 IX.114 1-CH2COOC2H5 3-SO2CH2CH2C(CH3)CF2 4-H 5-C6H5 IX 115 1 CH2CN 3-SCH2CH2C(CH3)CF2 4-H 5-(2-Thienyl) IX.116 1-CH2CN 3-SOCH2CH2C(CH3)CF2 4-H 5-(2-Thienyl) IX 117 1 CH2CN 3-SO2CH2CH2C=CF2 4-H 5-(2-Thienyl) IX.118 1-C6H5 3-H 4-H 5-SCH2CH2C(CH3)CF2 IX.119 1-C6H5 3-H 4-H 5-SOCH2CH2C(CH3)CF2 IX 120 1-C6H5 3-H 4-H 5-SO2CH2CH2C(CH3)CF2 IX.121 1 C6H5 3-H 4-CN 5-SCH2CH2C(CH3)CF2 IX 122 1-C6H5 3-H 4-CN 5-SOCH2CH2C(CH3)CF2 IX 123 1-C6H5 3-H 4-CN 5-SO2CH2CH2C(CH3)CF2 IX 124 1-C6H5 3-H 4-COOC2H5 5-SCH2CH2C(CH3)CF2 IX 125 1-C6H5 3-H 4-COOC2H5 5-SOCH2CH2C(CH3)CF2 IX 126 1-C6H5 3-H 4-COOC2H5 5-SO2CH2CH2C(CH3)CF2 IX 127 1-C6H5 3-H 4-COOH 5-SCH2CH2C(CH3)CF2 IX.128 1 C6H5 3 H 4-COOH 5-SOCH2CH2C(CH3)CF2 IX 129 1-C6H5 3-H 4-COOH 5-SO2CH2CH2C(CH3)CF2 IX 130 1 C6H5 3-H 4-Cl 5-SCH2CH2C(CH3)CF2 IX 131 1-C6H5 3-H 4-Cl 5-SOCH2CH2C(CH3)CF2 IX 132 1-C6H5 3-H 4-Cl 5-SO2CH2CH2C(CH3)CF2 IX.133 1-C6H5 3-H 4-SO2F 5-SCH2CH2C(CH3)CF2 IX 134 1 C6H5 3 H 4-SO2F 5-SOCH2CH2C(CH3)CF2 IX 135 1-C6H5 3-H 4-SO2F 5-SO2CH2CH2C(CH3)CF2 IX.136 1-C6H5 3-CH3 4-H 5-SCH2CH2C(CH3)CF2 IX.137 1-C6H5 3-CH3 4-H 5-SOCH2CH2C(CH3)CF2 IX.138 1-C6H5 3-CH3 4-H 5-SO2CH2CH2C(CH3)CF2 IX.139 1-C6H5 3-CH3 4-CN 5-SCH2CH2C(CH3)CF2 IX.140 1-C6H5 3-CH3 4-CN 5-SOCH2CH2C(CH3)CF2 IX 141 1-C6H5 3-CH3 4-CN 5-SO2CH2CH2C(CH3)CF2 IX.142 1-C6H5 3-CH3 4-COOC2H5 5-SCH2CH2C(CH3)CF2 IX.143 1-C6H5 3-CH3 4-COOC2H5 5-SOCH2CH2C(CH3)CF2 IX.144 1-C6H5 3-CH3 4-COOC2H5 5-SO2CH2CH2C(CH3)CF2 IX.145 1 C6H5 3-CH3 4-COOH 5-SCH2CH2C(CH3)CF2 IX 146 1-C6H5 3-CH3 4-COOH 5-SOCH2CH2C(CH3)CF2 IX.147 1-C6H5 3-CH3 4-COOH 5-SO2CH2CH2C(CH3)CF2 IX.148 1-C6H5 3-CH3 4-Cl 5-SCH2CH2C(CH3)CF2 IX 149 1-C6H5 3-CH3 4-Cl 5-SOCH2CH2C(CH3)CF2 IX.150 1-C6H5 3-CH3 4-Cl 5-SO2CH2CH2C(CH3)CF2 IX.151 1-C6H5 3-CH3 4-SO2F 5-SCH2CH2C(CH3)CF2 IX.152 1-C6H5 3-CH3 4-SO2F 5-SOCH2CH2C(CH3)CF2 IX.153 1-C6H5 3-CH3 4-SO2F 5-SO2CH2CH2C(CH3)CF2 IX.154 1-C6H5 3-Cl 4-H 5-SCH2CH2C(CH3)CF2 IX.155 1-C6H5 3-Cl 4-H 5-SOCH2CH2C(CH3)CF2 IX.156 1-C6H5 3-Cl 4-H 5-SO2CH2CH2C(CH3)CF2 IX.157 1-C6H5 3-COOC2H5 4-H 5-SCH2CH2C(CH3)CF2 IX.158 1-C6H5 3-COOC2H5 4-H 5-SOCH2CH2C(CH3)CF2 IX.159 1-C6H5 3-COOC2H5 4-H 5-SO2CH2CH2C(CH3)CF2 IX.160 1-C6H5 3-COOH 4-H 5-SCH2CH2C(CH3)CF2 IX.161 1-C6H5 3-COOH 4-H 5-SOCH2CH2C(CH3)CF2 IX.162 1 C6H5 3-COOH 4-H 5-SO2CH2CH2C(CH3)CF2 IX.163 1 C6H5 3-CONH2 4-H 5-SCH2CH2C(CH3)CF2 IX.164 1-C6H5 3-CONH2 4-H 5-SOCH2CH2C(CH3)CF2 IX.165 1-C6H5 3-CONH2 4-H 5-SO2CH2CH2C(CH3)CF2 IX.166 1-C6H5 3-CN 4-H 5-SCH2CH2C(CH3)CF2 IX.167 1-C6H5 3-CN 4-H 5-SOCH2CH2C(CH3)CF2 IX 168 1 C6H5 3-CN 4-H 5-SO2CH2CH2C(CH3)CF2 IX.169 1-C6H5 3-SO2F 4-H 5-SCH2CH2C(CH3)CF2 IX.170 1-C6H5 3-SO2F 4-H 5-SOCH2CH2C(CH3)CF2 IX.171 1-C6H5 3-SO2F 4-H 5-SO2CH2CH2C(CH3)CF2 IX.172 1-C6H5 3-SO2NH2 4-H 5-SCH2CH2C(CH3)CF2 IX.173 1-C6H5 3-SO2NH2 4-H 5-SOCH2CH2C(CH3)CF2 IX.174 1-C6H5 3-SO2NH2 4-H 5-SO2CH2CH2C(CH3)CF2 IX 175 1 CH3 3 H 4-SCH2CH2C(CH3)CF2 5-CN IX 176 1-CH3 3-H 4-SOCH2CH2C(CH3)CF2 5-CN IX 177 1-CH3 3-H 4-SO2CH2CH2C=CF2 5-CN IX.178 1-CH3 3-H 4-SCH2CH2C(CH3)CF2 5-COOC2H5 IX.179 1-CH3 3-H 4-SOCH2CH2C(CH3)CF2 5-COOC2H5 IX 180 1-CH3 3-H 4-SO2CH2CH2C=CF2 5-COOC2H5 IX 181 1-CH3 3-H 4-SCH2CH2C(CH3)CF2 5-CF3 IX.182 1-CH3 3-H 4-SOCH2CH2C(CH3)CF2 5-CF3 IX.183 1-CH3 3-H 4-SO2CH2CH2C(CH3)CF2 5-CF3 IX.184 1 CH3 3-CN 4-SCH2CH2C(CH3)CF2 5-H IX.185 1 CH3 3-CN 4-SOCH2CH2C(CH3)CF2 5-H IX 186 1 CH3 3-CN 4-SO2CH2CH2C(CH3)CF2 5-H IX 187 1-CH3 3-COOC2H5 4-SCH2CH2C(CH3)CF2 5-H IX 188 1-CH3 3-COOC2H5 4-SOCH2CH2C(CH3)CF2 5-H IX.189 1-CH3 3-COOC2H5 4-SO2CH2CH2C(CH3)CF2 5-H IX 190 1-CH3 3-CF3 4-SCH2CH2C(CH3)CF2 5-H IX.191 1-CH3 3-CF3 4-SOCH2CH2C(CH3)CF2 5-H IX 192 1 CH3 3-CF3 4-SO2CH2CH2C(CH3)CF2 5-H Examples of compounds of Formula (X) according to the invention are set out in Table X.
TABLE X No. R3 R5 X. l 3-c-C3H5 5-SCH2CH2C(CH3)CF2 X.2 3-C CH 5-SCH2CH2C(CH3)CF2 X.3 3-C6H5 5-SCH2CH2C(CH3)CF2 X.4 3-C6H5 5-SOCH2CH2C(CH3)CF2 X.5 3-C6H5 5-SO2CH2CH2C(CH3)CF2 X.6 3-CF2H 5-SCH2CH2C(CH3)CF2 X.7 3-CF3 5-SCH2CH2C(CH3)CF2 X.8 3-CH(CH3)2 5-SCH2CH2C(CH3)CF2 X.9 3-CH=CH2 5-SCH2CH2C(CH3)CF2 X.10 3-CH2Br 5-SCH2CH2C(CH3)CF2 X.11 3-CH2C6H5 5-SCH2CH2C(CH3)CF2 X.12 3-CH2C6H5 5-SOCH2CH2C(CH3)CF2 X.13 3-CH2CF3 5-SCH2CH2C(CH3)CF2 X. 14 3-CH2CF3 5-SOCH2CH2C(CH3)CF2 X.15 3-CH2CF3 5-SO2CH2CH2C(CH3)CF2 X.16 3-CH2CH=CH2 5-SCH2CH2C(CH3)CF2 X.17 3-CH2CH2F 5-SCH2CH2C(CH3)CF2 X.18 3-CH2CH3 5-SCH2CH2C(CH3)CF2 X.19 3-CH2CN 5-SCH2CH2C(CH3)CF2 X.20 3-CH2CN 5-SOCH2CH2C(CH3)CF2 X.21 3-CH2CONH2 5-SCH2CH2C(CH3)CF2 X.22 3-CH2COOCH2CH3 5-SCH2CH2C(CH3)CF2 X.23 3-CH2N(CH3)2 5-SCH2CH2C(CH3)CF2 X.24 3-CH2NHCOCH3 5-SCH2CH2C(CH3)CF2 X.25 3-CH2NHCOOCH3 5-SCH2CH2C(CH3)CF2 X.26 3-CH2OCH3 5-SCH2CH2C(CH3)CF2 X.27 3-CH20CH3 5-S02CH2CH2C(CH3)CF2 X.28 3-CH2OH 5-SCH2CH2C(CH3)CF2 X.29 3-CH2OH 5-SOCH2CH2C(CH3)CF2 X.30 3-CH2S02C6H5 5-SCH2CH2C(CH3)CF2 X.31 3-CH2SO2C6H5 5-SO2CH2CH2C(CH3)CF2 X.32 3-CH3 5-SCH2CH2C(CH3)CF2 X.33 3-CH3 5-SOCH2CH2C(CH3)CF2 X.34 3-CH3 5-S02CH2CH2C(CH3)CF2 X.35 3-COC6H5 5-SCH2CH2C(CH3)CF2 X.36 3-COCH3 5-SCH2CH2C(CH3)CF2 X.37 3-CON(CH3)2 5-SCH2CH2C(CH3)CF2 X.38 3-CONH2 5-SCH2CH2C(CH3)CF2 X.39 3-CONHCH2C6H5 5-SCH2CH2C(CH3)CF2 X.40 3-CONHCH2C6H5 5-SOCH2CH2C(CH3)CF2 X.41 3-CONHCH2CH2CHCF2 5-SCH2CH2C(CH3)CF2 X.42 3-CONHCH3 5-SCH2CH2C(CH3)CF2 X.43 3-CONHS02CH3 5-SCH2CH2C(CH3)CF2 X.44 3-COOC6H5 5-SCH2CH2C(CH3)CF2 X.45 3-COOC6H5 5-SOCH2CH2C(CH3)CF2 X.46 3-COOC6HS 5-S02CH2CH2C(CH3)CF2 X.47 3-COOCH2CH2CHCF2 5-SCH2CH2C(CH3)CF2 X.48 3-COOCH2CH2CHCF2 5-SOCH2CH2C(CH3)CF2 X.49 3-COOCH2CH2CHCF2 5-S02CH2CH2C(CH3)CF2 X.50 3-COOCH2CH2F 5-SCH2CH2C(CH3)CF2 X.51 3-COOCH3 5-SCH2CH2C(CH3)CF2 X.52 3-COOH 5-SCH2CH2C(CH3)CF2 X.53 3-COSCH2CH2CHCF2 5-SCH2CH2C(CH3)CF2 X.54 3-CSNH2 5-SCH2CH2C(CH3)CF' .Y.55 3-H 5-SCH2CH2C(CH3)CF2 X.56 3-H S-SOCH2CH2C(CH3)CF2 X.57 3-H 5-SO2CH2CH2C(CH3)CF2 X.58 3-N(SO2CH3)2 5-SCH2CH2C(CH3)CF2 X.59 3-NHCH2CH3 5-SCH2CH2C(CH3)CF2 X.60 3-NHCHO 5-SCH2CH2C(CH3)CF2 X.61 3-NHCOOCH3 5-SCH2CH2C(CH3)CF2 X.62 3-NHCOCF3 5-SCH2CH2C(CH3)CF2 X.63 3-NHCOCF3 5-SOCH2CH2C(CH3)CF2 X.64 3-NHCOCH3 5-SCH2CH2C(CH3)CF2 X.65 3-NHCOCH3 -"0 -SO2CH2CH2C(CH3)CF2 X.66 3-NHCSCH2CH3 5-SCH2CH2C(CH3)CF2 X.67 3-NHCSNHCH2CH3 5-SCH2CH2C(CH3)CF2 X.68 3-NHS02CH3 5-SCH2CH2C(CH3)CF2 X.69 3-OCF2CF2H 5-SCH2CH2C(CH3)CF2 X.70 3-OCF3 5-SCH2CH2C(CH3)CF2 X.7 1 3-OCF3 5-SOCH2CH2C(CH3)CF2 X.72 3-OCH2C6H5 5-SCH2CH2C(CH3)CF2 X.73 3-OCH2C6H5 5-SO2CH2CH2C(CH3)CF2 X.74 3-OCH2CF3 5-SCH2CH2C(CH3)CF2 X.75 3-OCH2CF3 5-SOCH2CH2C(CH3)CF2 X.76 3-OCH2CF3 5-SO2CH2CH2C(CH3)CF2 X.77 3-OCH2CH=CC12 5-SCH2CH2C(CH3)CF2 X.78 3-OCH2CH2CHCF2 5-SCH2CH2C(CH3)CF2 X.79 3-OCH2CH2CHCF2 5-SOCH2CH2C(CH3)CF2 X.80 3-OCH2CH2CHCF2 5-SO2CH2CH2C(CH3)CF2 X.81 3-OCH2CH'F 5-SCH2CH2CHCF2 X.82 3-OCH2COOH 5-SCH2CH2C(CH3)CF2 X.83 3-OCH3 5-SCH2CH2C(CH3)CF2 X.84 3-OCOC6H5 5-SCH2CH2C(CH3)CF2 X.85 3-OCOCH3 5-SCH2CH2C(CH3)CF2 X.86 3-OC6H5 5-SCH2CH2C(CH3)CF2 X.87 3-OC6H5 5-SOCH2CH2C(CH3)CF2 X.88 3-OC6H5 5-SO2CH2CH2C(CH3)CF2 X.89 3-OSO2CH3 5-SCH2CH2C(CH3)CF2 X.90 3-OSO2CH3 5-SOCH2CH2C(CH3)CF2 X.91 3-SCF3 5-SCH2CH2C(CH3)CF2 X.92 3-SCH2CH2C(CH3)CF2 5-C6H5 X.93 3-SOCH2CH2C(CH3)CF2 5-C6H5 X.94 3-SO2CH2CH2C(CH3)CF2 5-C6H5 X.95 3-SCH2CH2C(CH3)CF2 5-CF2H X.96 3-SCH2CH2C(CH3)CF2 5-CF3 X.97 3-SCH2CH2C(CH3)CF2 5-CH2C6H5 X.98 3-SOCH2CH2C(CH3)CF2 5-CH2C6H5 X.99 3-SCH2CH2C(CH3)CF2 5-CH2CF3 X.100 3-SCH2CH2C(CH3)CF2 5-CH2CH2F X. 101 3-SCH2CH2C(CH3)CF2 5-CH2C1 X.102 3-SCH2CH2C(CH3)CF2 5-CH2CN X.103 3-SCH2CH2C(CH3)CF2 5-CH2OCH3 X. 104 3-SCH2CH2C(CH3)CF2 5-CH20H X.105 3-SCH2CH2C(CH3)CF2 5-CH3 X.106 3-SO2CH2CH2C(CH3)CF2 5-CH3 X. 107 3-SCH2CH2C(CH3)CF2 5-Cl X.108 3-SCH2CH2C(CH3)CF2 5-CN X. 109 3-SCH2CH2C(CH3)CF2 5-CON(CH3)2 X.1 10 3-SCH2CH2C(CH3)CF2 5-COOCH2CH2CHCF2 X. 111 3-SCH2CH2C(CH3)CF2 5-COOCH2CH3C2F X.1 12 3-SCH2CH2C(CH3)CF2 5-COOCH3 X.113 3-SCH2CH2C(CH3)CF2 5-F X. 114 3-SCH2CH2C(CH3)CF2 5-H X. 115 3-SCH2CH2C(CH3)CF2 5-N(S02CH3)2 X.116 3-SCH2CH2C(CH3)CF2 5-NHCHO X.1 17 3-SCH2CH2C(CH3)CF2 5-NHCOCF3 X.118 3-SCH2CH2C(CH3)CF2 5-NHCOOCH3 N.1 19 3-SCH2CH'C(CH3)CF' 5-NHS02CH3 X.120 3-SCH2CH2C(CH3)CF2 5-N02 X.121 3-SCH2CH2C(CH3)CF2 5-OC6H5 X.122 3-SCH2CH2C(CH3)CF2 5-OCF2H X.123 3-SCH2CH2C(CH3)CF2 5-OCF3 X.124 3-SCH2CH2C(CH3)CF2 5-OCH2CF3 X. 125 3-SOCH'CH'C(CH3)CF' 5-OCH2CF3 X. 126 3-SO'CH2CH2C(CH3)CF' 5-OCH2CF3 X.127 3-SCH2CH2C(CH3)CF2 5-OCOCH3 X.128 3-SCH2CH2C(CH3)CF2 5-OS02CH3 X.129 3-SCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 X.130 3-SOCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 X.131 3-SO2CH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 X.132 3-SCH2CH2C(CH3)CF2 5-SCH3 X.133 3-SCH2CH2C(CH3)CF2 5-SO2CF3 X.134 3-SOCH2CH2C(CH3)CF2 5-SO2CH2CH2C(CH3)CF2 X.135 3-SO2CH2CH2C(CH3)CF2 5-SO2CH2CH2C(CH3)CF2 X.136 3-SCH2CH2C(CH3)CF2 5-SO2CH3 X.137 3-SO2CH2CH2C(CH3)CF2 5-SO2CH3 X.138 3-SCH2CH2C(CH3)CF2 5-SO2N(CH3)2 X.139 3-SCH2CH2C(CH3)CF2 5-SOCF3 X.140 3-SOCH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 X.141 3-SCH3 5-SCH2CH2C(CH3)CF2 X.142 3-SO2CF3 5-SCH2CH2C(CH3)CF2 X.143 3-SO2CF3 5-SO2CH2CH2C(CH3)CF2 X.144 3-SO2CH3 5-SCH2CH2C(CH3)CF2 X.145 3-SO2N(CH3)2 5-SCH2CH2C(CH3)CF2 X.146 3-SO2NH2 5-SCH2CH2C(CH3)CF2 X.147 3-SO2NHCH3 5-SCH2CH2C(CH3)CF2 X.148 3-SO2NHCH3 5-SO2CH2CH2C(CH3)CF2 X.149 3-SOCF3 5-SCH2CH2C(CH3)CF2 X.150 3-SOCF3 5-SOCH2CH2C(CH3)CF2 X.151 3-SOCH3 5-SCH2CH2C(CH3)CF2 X.152 3-SOCH3 5-SOC2CH2CH2C(CH3)CF2 X.153 3-(4-CF3-C6H4) 5-SCH2CH2C(CH3)CF2 X.154 3-(4-CF3-C6H4) 5-SO2CH2CH2C(CH3)CF2 X.155 3-(4-CH3-C6H4) 5-SCH2CH2C(CH3)CF2 X. 156 3-(4-CN-C6H4) S-SCH2CH2C(CH3)CF2 X. 157 3-(4-CONH2-C6H4) 5-SCH2CH2C(CH3)CF2 X.158 3-(4-CONH2-C6H4) 5-SO2CH2CH2C(CH3)CF2 X. 159 3-(4-N02-C6H4) 5-SCH2CH2C(CH3)CF2 X.160 3-(4-OCH3-C6H4) 5-SCH2CH2C(CH3)CF2 Examples of compounds of Formula (XI) according to the invention are set out in Table XI.
TABLE XI No. R3 R5 XI.1 3-Br 5-SCH2CH2C(CH3)CF2 XI.2 3-c-C5H9 5-SCH2CH2C(CH3)CF2 XI.3 3-c-C5H9 5-SOCH2CH2C(CH3)CF2 XI.4 3-C CH 5-SCH2CH2C(CH3)CF2 XI.5 3-C6HS 5-SCH2CH2C(CH3)CF2 XI.6 3-C6H5 5-SOCH2CH2C(CH3)CF2 XI.7 3-C6H5 5-SO2CH2CH2C(CH3)CF2 XI.8 3-CF2H 5-SCH2CH2C(CH3)CF2 XI.9 3-CF3 5-SCH2CH2C(CH3)CF2 XI.10 3-CH=CH2 5-SCH2CH2C(CH3)CF2 XI. 11 3-CH=CHCH3 5-SCH2CH2C(CH3)CF2 XI.12 3-CH=CHCN 5-SCH2CH2C(CH3)CF2 XI. 13 3-CH=CHNO' 5-SCH2CH2C(CH3)CF2 XI. 14 3-CH=NOCH3 5-SCH2CH2C(CH3)CF2 XI.15 3-CH2(3-CF3-C6H4) 5-SCH2CH2C(CH3)CF2 XI. 16 3-CH2(3-CF3-C6H4) 5-SCH2CH2C(CH3)CF2 XI.17 3-CH2C6H5 5-SCH2CH2C(CH3)CF2 XI.18 3-CH2C6H5 5-SOCH2CH2C(CH3)CF2 XI.19 3-CH2C6H5 5-SO2CH2CH2C(CH3)CF2 XI.20 3-CH2CF3 5-SCH2CH2C(CH3)CF2 XI.21 3-CH2CF3 5-SOCH2CH2C(CH3)CF2 XI.22 3-CH2CH=CH2 5-SCH2CH2C(CH3)CF2 XI.23 3-CH2CH3 5-SCH2CH2C(CH3)CF2 XI.24 3-CH2CH3 5-SO2CH2CH2C(CH3)CF2 XI.25 3-CH2C1 5-SCH2CH2C(CH3)CF2 XI.26 3-CH2CN 5-SCH2CH2C(CH3)CF2 XI.27 3-CH2CONH2 5-SCH2CH2C(CH3)CF2 XI.28 3-CH2N(CH3 )2 5-SCH2CH2C(CH3)CF2 XI.29 3-CH2NHCOCH3 5-SCH2CH2C(CH3)CF2 XI.30 3-CH20CH2CH2CH2CH3 5-SCH2CH2C(CH3)CF2 XI.3 1 3-CH20CH2CH2CH3 5-SCH2CH2C(CH3)CF2 XI.32 3-CH20CH2CH3 5-SCH2CH2C(CH3)CF2 XI.33 3-CH20CH'CH3 5-SOCH2CH2C(CH3)CF2 XI.34 3-CH20CH3 5-SCH2CH2C(CH3)CF2 XI.35 3-CH2OCH3 5-SOCH2CH2C(CH3)CF2 XI.36 3-CH2OCH3 5-SO2CH2CH2C(CH3)CF2 XI.37 3-CH2OH 5-SCH2CH2C(CH3)CF2 XI.3 8 3-CH2SCH2CH2C(CH3 )CF2 5-SCH2CH2C(CH3)CF2 XI.39 3-CH2SO2C6H5 5-SCH2CH2C(CH3)CF2 XI.40 3-CH3 5-SCH2CH2C(CH3)CF2 XI.4l 3-CH3 S-SOCH2CH2C(CH3)CF2 XI.42 3-CH3 5-SO2CH2CH2C(CH3)CF2 XI.43 3-Cl 5-SCH2CH2C(CH3)CF2 XI.44 3-Cl 5-SO2CH2CH2C(CH3)CF2 XI.45 3-CN 5-SCH2CH2C(CH3)CF2 XI.46 3-COC6H5 5-SCH2CH2C(CH3)CF2 XI.47 3-COCH3 5-SCH2CH2C(CH3)CF2 XI.48 3-CON(CH3)2 5-SCH2CH2C(CH3)CF2 XI.49 3-CON( CH3 )C2HS 5-SCH2CH2C(CH3 )CF2 XI.50 3-CONH2 5-SCH2CH2C(CH3)CF2 NI.S 1 3-CONHCH2C6HS 5-SCH2CH2C(CH3 )CF2 XI.52 3-CONHCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XI.53 3-CONHCH2CH2CH3 5-SCH2CH2C(CH3)CF2 XI.54 3-CONHCH3 5-SCH2CH2C(CH3)CF2 XI.55 3-CONHCH3 5-SOCH2CH2C(CH3)CF2 XI.56 3-CONHCH3 5-SO'CH2CH2C(CH3)CF2 XI.57 3-CONHSO'CH3 5-SCH2CH2C(CH3)CF2 XI.58 3-COOC6H5 5-SCH2CH2C(CH3)CF2 XI.59 3-COOCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XI.60 3-COOCH2CH2F 5-SCH2CH2C(CH3)CF2 XI.61 3-COOCH2CH3 5-SCH2CH2C(CH3)CF2 XI.62 3-COOCH3 5-SCH2CH2C(CH3)CF2 XI.63 3-COOH 5-SCH2CH2C(CH3)CF2 XI.64 3-COSCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XI.65 3-CSNH2 5-SCH2CH2C(CH3)CF2 XI.66 3-F 5-SCH2CH2C(CH3)CF2 XI.67 3-H 5-SCH2CH2C(CH3)CF2 XI.68 3-H 5-SOCH2CH2C(CH3)CF2 XI.69 3-H 5-SO2CH2CH2C(CH3)CF2 XI.70 3-N(S02CH3)2 5-SCH2CH2C(CH3)CF2 XI.71 3-NHCHO 5-SCH2CH2C(CH3)CF2 XI.72 3-NHCOC2H5 5-SCH2CH2C(CH3)CF2 XI.73 3-NHCOCF3 5-SCH2CH2C(CH3)CF2 XI.74 3-NHCOCH3 5-SCH2CH2C(CH3)CF2 XI.75 3-NHCSCH2CH3 5-SCH2CH2C(CH3)CF2 XI.76 3-NHCSNHCH2CH3 5-SCH2CH2C(CH3)CF2 XI.77 3-NHSO2CH3 5-SCH2CH2C(CH3)CF2 XI.78 3-N02 5-SCH2CH2C(CH3)CF2 XI.79 3-OC6H5 5-SCH2CH2C(CH3)CF2 XI.80 3-OCF2CF2H 5-SCH2CH2C(CH3)CF2 XI.81 3-OCF2H 5-SCH2CH2C(CH3)CF2 XI.82 3-OCF3 5-SCH2CH2C(CH3)CF2 XI.83 3-OCH2CF3 5-SCH2CH2C(CH3)CF2 XI.84 3-OCH2CF3 5-SOCH2CH2C(CH3)CF2 XI.85 3-OCH2CF3 5-S02CH2CH2C(CH3)CF2 XI.86 3-OCH2CH=CC12 5-SCH2CH2C(CH3)CF2 XI.87 3-OCH3 5-SCH2CH2C(CH3)CF2 XI.88 3-OCOC2H5 5-SCH2CH2C(CH3)CF2 XI.89 3-OCOC6H5 5-SCH2CH2C(CH3)CF2 XI.90 3-OCOCH3 5-SCH2CH2C(CH3)CF2 XI.91 3-OSO2CH3 5-SCH2CH2C(CH3)CF2 XI.92 3-SCF3 5-SCH2CH2C(CH3)CF2 XI.93 3-SCH2CH2C(CH3)CF2 5-CF3 XI.94 3-SCH2CH2C(CH3)CF2 5-CH2C6H5 XI.95 3-SCH2CH2C(CH3)CF2 5-CH2CF3 XI.96 3-SCH2CH2C(CH3)CF2 5-CH2CH=CH2 XI.97 3-SCH2CH2C(CH3)CF2 5-CH2CN XI.98 3-SCH2CH2C(CH3)CF2 5-CH2CONH2 XI.99 3-SCH2CH2C(CH3)CF2 5-CH2NHCOCH3 XI.100 3-SCH2CH2C(CH3)CF2 5-CH2OCH3 XI.101 3-SCH2CH2C(CH3)CF2 5-CH3 XI.102 3-SCH2CH2C(CH3)CF2 5-Cl XI.103 3-SCH2CH2C(CH3)CF2 5-CN XI. 104 3-SCH2CH2C(CH3)CF2 5-COOCH3 XI.105 3-SCH2CH2C(CH3)CF2 5-NHCHO XI.106 3-SCH2CH2C(CH3)CF2 5-OC6H5 XI. 107 3-SCH2CH2C(CH3)CF2 5-OCH2CF3 XI.108 3-SCH2CH2C(CH3)CF2 5-OCH3 XI.109 3-SCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XI.110 3-SCH3 5-SCH2CH2C(CH3)CF2 XI.111 3-SO2C2H5 5-SCH2CH2C(CH3)CF2 XI.112 3-SO2CF3 5-SCH2CH2C(CH3)CF2 XI.113 3-SO2CH2CH2C(CH3)CF2 5-OCH2CF3 XI.114 3-SO2CH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XI.115 3-SO2CH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 XI.116 3-SO2F 5-SCH2CH2C(CH3)CF2 XI.117 3-S02N(CH3)2 5-SCH2CH2C(CH3)CF2 XI. 118 3-S02NH2 5-SCH2CH2C(CH3)CF2 XI.119 3-SO2NHCH3 5-SCH2CH2C(CH3)CF2 XI.1 120 3-SOCF3 5-SCH2CH2C(CH3)CF2 XI.121 3-SOCH2CH2C(CH3)CF2 5-CH2CN XI. 122 3-SOCH2CH2C(CH3)CF2 5-OCH2CF3 XI.123 3-SOCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XI.124 3-SOCH3 5-SCH2CH2C(CH3)CF2 XI. 125 3-(2-Pyrazinyl) 5-SCH'CH2C(CH3)CF2 XI.126 3-(3-F-C6H4) 5-SCH2CH2C(CH3)CF2 XI.127 3-(3-NO2-C6H4) 5-SCH2CH2C(CH3)CF2 XI.128 3-(3-NO2-C6H4) 5-SOCH2CH2C(CH3)CF2 XI.129 3-(3-NO2-C6H4) 5-SO2CH2CH2C(CH3)CF2 XI.130 3-(4-F-C6H4) 5-SCH2CH2C(CH3)CF2 XI.131 3-(4-F-C6H4) 5-SOCH2CH2C(CH3)CF2 XI.132 3-(4-F-C6H4) 5-SO2CH2CH2C(CH3)CF2 Examples of compounds of Formula (XII) according to the invention are set out in Table XII.
TABLE XII No. R2 R5 XII.1 2-SCH2CH2C(CH3)CF2 5-c-C3H5 XII.2 2-SCH2CH2C(CH3)CF2 5-C CH XII.3 2-SCH2CH2C(CH3)CF2 5-C6H5 XII.4 2-SOCH2CH2C(CH2)CF2 5-C6H5 XII.5 2-SO2CH2CH2C(CH3)CF2 5-C6H5 XII.6 2-SCH2CH2C(CH3)CF2 5-CF2H XII.7 2-SCH2CH2C(CH3)CF2 5-CF3 XII.8 2-SCH2CH2C(CH3)CF2 5-CH(CH3)2 XII.9 2-SO2CH2CH2C(CH3)CF2 5-CH(CH3)2 XII.10 2-SCH2CH2C(CH3)CF2 5-CH=CH2 XII.1 1 2-SCH2CH2C(CH3)CF2 5-CH2(2,6-di F -C6H3) XII.12 2-SCH2CH2C(CH3)CF2 5-CH2(4-NO2-C6H4) XII. 13 '-SO'CH'CH2C(CH3)CF2 5-CH2(4-N02-C6H4) XII.14 2-SOCH2CH2C(CH3)CF2 5-CH2(4-OCH3-C6H4) XII. 15 2-SO2CH2CH2C(CH3)CF2 5-CH2(4-OCH3-C6H4) XII. 16 2-SCH2CH2C(CH3)CF2 5-CH2Br XII.17 2-SCH2CH2C(CH3)CF2 5-CH2C6H5 XII.18 2-SOCH2CH2C(CH3)CF2 5-CH2C6H5 XII. 19 2-SO2CH2CH2C(CH3)CF2 5-CH2C6H5 XII.20 2-SCH2CH2C(CH3)CF2 5-CH2CF3 XII.2 1 2-SOCH2CH2C(CH3)CF2 5-CH2CF3 XII.22 2-SO2CH2CH2C(CH3)CF2 5-CH2CF3 XII.23 2-SCH2CH2C(CH3)CF2 5-CH2CH(CH3)2 XII.24 2-SCH2CH2C(CH3)CF2 5-CH2CH=CH2 XII.25 2-SCH2CH2C(CH3)CF2 5-CH2CH2CH2CH2CH3 XII.26 2-SOCH2CH2C(CH3)CF2 5-CH2CH2CH2CH2CH3 XII.27 2-SO2CH2CH2C(CH3)CF2 5-CH2CH2CH2CH2CH3 XII.28 2-SCH2CH2C(CH3)CF2 5-CH2CH2CH2CH3 XII.29 2-SOCH2CH2C(CH3)CF2 5-CH2CH2CH2CH3 XII.30 2-SO2CH2CH2C(CH3)CF2 5-CH2CH2CH2CH3 XII.3 1 2-SCH2CH2C(CH3)CF2 5-CH2CH2CH3 XII.32 2-SOCH2CH2C(CH3)CF2 5-CH2CH2CH3 XII.33 2-SO2CH2CH2C(CH3)CF2 5-CH2CH2CH3 XII.34 2-SCH2CH2C(CH3)CF2 5-CH2CH2F XII.35 2-SCH2CH2C(CH3)CF2 5-CH2CH3 XII.36 2-SCH2CH2C(CH3)CF2 5-CH2CN XII.37 2-SOCH2CH2C(CH3)CF2 5-CH2CN XII.38 2-SCH2CH2C(CH3)CF2 5-CH2CONH2 XII.39 2-SCH2CH2C(CH3)CF2 5-CH2COOCH2CH3 XII.40 2-SCH2CHSC(CH3)CF2 5-CH2N(CH3)2 XII.4 1 2-SCH2CH2C(CH3)CF2 5-CH2NHCOCH3 XII.42 2- SCH2CH2C(CH3)CF2 5-CH2NHCOOCH3 XII.43 2- SCH2CH2C(CH3)CF2 5-CH20CH3 XII.44 2- SO2CH2CH2C(CH3)CF2 5-CH20CH3 XII.45 2-SCH2CH2C(CH3)CF2 5-CH2OH XII.46 2-SOCH2CH2C(CH3)CF2 5-CH2OH XII.47 2-SCH2CH2C(CH3)CF2 5-CH2S02C6H5 XII.48 2- SO2CH2CH2C(CH3)CF2 5-CH2S02C6H5 XII.49 2- SCH2CH2C(CH3)CF2 5-CH3 XII.SO 2- SOCH2CH2C(CH3)CF2 5-CH3 XII.51 2-SO2CH2CH2C(CH3)CF2 5-CH3 XII.52 2-SCH2CH2C(CH3)CF2 5-COC6H5 XII.53 2- SCH2CH2C(CH3)CF2 5-COCH3 XII.54 2- SCH2CH2C(CH3)CF2 5-CON(CH3)2 XII.55 2-SCH2CH2C(CH3)CF2 5-CONH2 XII.56 2- SCH2CH2C(CH3)CF2 5-CONHCH2C6H5 XII.57 2-SOCH2CH2C(CH3)CF2 5-CONHCH2C6H5 XII.58 2-SCH2CH2C(CH3)CF2 5-CONHCH2CH2C(CH3)CF2 XII.59 2- SCH2CH2C(CH3)CF2 5-CONHCH3 XII.60 2- SCH2CH2C(CH3)CF2 5-CONHS02CH3 XII.61 2- SCH2CH2C(CH3)CF2 5-COOC6H5 XII.62 2-SOCH2CH2C(CH3)CF2 5-COOC6H5 XII.63 2-SO2CH2CH2C(CH3)CF2 5-COOC6H5 XII.64 2-SCH2CH2C(CH3)CF2 5-COOCH2CH2C(CH3)CF2 XII.65 2-SOCH2CH2C(CH3)CF2 5-COOCH2CH2C(CH3)CF2 XII.66 2-SO2CH2CH2C(CH3)CF2 5-COOCH2CH2C(CH3)CF2 XII.67 2-SCH2CH2C(CH3)CF2 5-COOCH2CH2F XII.68 2-SCH2CH2C(CH3)CF2 5-COOCH2CH3 XII.69 2-SCH2CH2C(CH3)CF2 5-COOCH3 XII.70 2-SCH2CH2C(CH3)CF2 5-COOH XII.71 2-SCH2CH2C(CH3)CF2 5-COSCH2CH2C(CH3)CF2 XII.72 2-SCH2CH2C(CH3)CF2 5-CSNH2 XII.73 2-SCH2CH2C(CH3)CF2 5-H XII.74 2-SOCH2CH2C(CH3)CF2 5-H XII.75 2-SO2CH2CH2C(CH3)CF2 5-H XII.76 2-SCH2CH2C(CH3)CF2 5-N(S02CH3)2 XII.77 2-SCH2CH2C(CH3)CF2 5-NHCH2CH3 XII.78 2-SCH2CH2C(CH3)CF2 5-NHCHO XII.79 2-SCH2CH2C(CH3 )CF2 5-NHCOOCH3 XII.80 2-SCH2CH2C(CH3)CF2 5-NHCOCF3 XII.8 1 2-SOCH2CH2C(CH3 )CF2 5-NHCOCF3 XII.82 2-SCH2CH2C(CH3)CF2 5-NHCOCH3 XII.83 2-SO2CH2CH2C(CH3)CF2 5-NHCOCH3 XII.84 2-SCH2CH2C(CH3)CF2 5-NHCSCH2CH3 XII. 85 2-SCH2CH2C(CH3)CF2 5-NHCSNHCH2CH3 XII.86 2-SCH2CH2C(CH3 )CF2 5-NHS02CH3 XII.87 2-SCH2CH2C(CH3)CF2 5-OCF2CF2H XII.88 2-SCH2CH2C(CH3)CF2 5-OCF3 XII.89 2-SOCH2CH2C(CH3)CF2 5-OCF3 XII.90 2-SCH2CH2C(CH3)CF2 5-OCH2C6H5 XII.91 2-SO2CH2CH2C(CH3)CF2 5-OCH2C6H5 XII.92 2-SCH2CH2C(CH3)CF2 5-OCH2CF3 XII.93 2-SOCH2CH2C(CH3)CF2 5-OCH2CF3 XII.94 2-SO2CH2CH2C(CH3)CF2 5-OCH2CF3 XII.95 2-SCH2CH2C(CH3)CF2 5-OCH2CH=CC12 XII.96 2-SCH2CH2C(CH3)CF2 5-OCH2CH2C(CH3)CF2 XII.97 2-SOCH2CH2C(CH3)CF2 5-OCH2CH2C(CH3)CF2 XII.98 2-SO2CH2CH2C(CH3)CF2 5-OCH2CH2C(CH3)CF2 XII.99 2-SCH2CH2C(CH3)CF2 5-OCH2CH2F XII. 100 2-SCH2CH2C(CH3)CF2 5-OCH2COOH XII.101 2-SCH2CH2C(CH3)CF2 5-OCH3 XII.102 2-SCH2CH2C(CH3)CF2 5-OCOC6H5 XII.103 2-SCH2CH2C(CH3)CF2 5-OCOCH3 XII.104 2-SCH2CH2C(CH3)CF2 5-OC6H5 XII. 105 2-SOCH2CH2C(CH3)CF2 5-OC6H5 XII. 106 2-S02CH2CH2C(CH3)CF2 5-OC6H5 XII.107 2-SCH2CH2C(CH3)CF2 5-OS02CH3 XII. 108 2-SOCH2CH2C(CH3)CF2 5-OS02CH3 XII. 109 2-SCH2CH2C(CH3)CF2 5-SCF3 XII.110 2-SCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XII.111 2-SCH2CH2C(CH3)CF2 5-SCH3 XII. 112 2-SCH2CH2C(CH3)CF2 5-S02CF3 XII. 113 2-SO2CH2CH2C(CH3)CF2 5-S02CF3 XII. 114 2-SCH2CH2C(CH3)CF2 5-S02CH2CH2C(CH3)CF2 XII.115 2-SO2CH2CH2C(CH3)CF2 5-SO2CH2CH2C(CH3)CF2 XII. 116 2-SCH2CH2C(CH3)CF2 5-S02CH3 XII.1 117 2-SCH2CH2C(CH3)CF2 5-S02N(CH3)2 XII. 118 '-SCH2CH2C(CH3)CF2 5-SO'NH2 XII. 119 2-SCH2CH2C(CH3)CF2 5-S02NHCH3 XII. 120 2-SO2CH2CH2C(CH3)CF2 5-S02NHCH3 XII. 121 2-SCH2CH2C(CH3)CF2 5-SOCF3 XII. 122 2-SOCH2CH2C(CH3)CF2 5-SOCF3 XII. 123 2-SCH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 XII. 124 2-SOCH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 XII. 125 2-SO2CH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 XII. 126 2-SCH2CH2C(CH3)CF2 5-SOCH3 XII. 127 2-SO2CH2CH2C(CH3)CF2 5-SOCH3 XII. 128 2-SCH2CH2C(CH3)CF2 5-(2-CH3-C6H4) XII. 129 2-SOCH2CH2C(CH3)CF2 5-(2-CH3-C6H4) XII.130 2-SO2CH2CH2C(CH3)CF2 5-(2-CH3-C6H4) XII. 131 2-SCH2CH2C(CH3)CF2 5-(2-Furyl) XII.132 2-SCH2CH2C(CH3)CF2 5-(2-OCH3-C6H4) XII.133 2-SCH2CH2C(CH3)CF2 5-(2-Thiophenyl) XII. 134 2-SCH2CH2C(CH3)CF2 5-(3-Furyl) XII.135 2-SCH2CH2C(CH3)CF2 5-(4-CF3-C6H4) XII. 136 2-SO2CH2CH2C(CH3)CF2 5-(4-CF3-C6H4) XII. 137 2-SCH2CH2C(CH3)CF2 5-(4-CH3-C6H4) XII.138 2-SCH2CH2C(CH3)CF2 5-(4-CN-C6H4) XII. 139 2-SCH2CH2C(CH3)CF2 5-(4-CONH2-C6H4) XII. 140 2-SO2CH2CH2C(CH3)CF2 5-(4-CONH2-C6H4) XII.141 2-SCH2CH2C(CH3)CF2 5-(4-NO2-C6H4) XII. 142 2-SOCH2CH2C(CH3)CF2 5-(4-N02-C6H4) XII.143 2-SO2CH2CH2C(CH3)CF2 5-(4-NO2-C6H4) XII. 144 2- SCH2CH2C(CH3)CF2 5-(4-OCH3-C6H4) XII. 145 2-SOCH2CH2C(CH3 )CF2 5-(4-OCH3-C6H4) XII. 146 2-S02CH2CH2C(CH3)CF2 5-(4-OCH3-C6H4) XII. 147 2-SCH2CH2C(CH3)CF2 5-(4-OH-C6H4) XII. 148 2-SCH2CH2C(CH3 )CF2 5-(4-Pyridinyl) Examples of compounds of Formula (XIII) according to the invention are set out in Table XIII.
TABLE XIII No. R2 R5 XIII. 1 2-SCH2CH2C(CH3)CF2 5-Br XIII.2 2-SO2CH2CH2C(CH3)CF2 5-Br XIII.3 2-SCH2CH2C(CH3)CF2 5-C(CH3)3 XIII.4 2-SO2CH2CH2C(CH3)CF2 5-C(CH3)3 XIII.S 2-SCH2CH2C(CH3)CF2 5-C(O)C6H5 XIII.6 2-SCH2CH2C(CH3)CF2 5-c-C3H5 XIII.7 2-SO2CH2CH2C(CH3)CF2 5-c-C3H5 XIII.8 2 SCH2CH2C(CH3)CF2 5-C CH XIII.9 2-SCH2CH2C(CH3)CF2 5-C6H5 XIII. 10 2-SOCH2CH2C(CH3)CF2 S-C6H5 XIII.1 11 2-SO2CH2CH2C(CH3)CF2 5-C6H5 XIII.12 2-SCH2CH2C(CH3)CF2 5-CF2H XIII. 13 2-SOCH2CH2C(CH3 )CF2 S-CF2H XIII. 14 2-SCH2CH2C(CH3)CF2 5-CF3 XIII. 15 2-S02CH2CH2C(CH3)CF2 5-CF3 XIII.16 16 2-SCH2CH2C(CH3)CF2 5-CH(CH3)2 XIII. 17 '-S02CH2CH2C(CH3)CF2 5-CH(CH3)2 XIII.18 18 2-SCH2CH2C(CH3)CF2 5-CH=CH2 XIII.19 19 2-SCH2CH2C(CH3)CF2 5-CH2Br XIII.20 2-SCH2CH2C(CH3)CF2 5-CH2C6H5 XIII.21 2-SOCH2CH2C(CH3)CF2 5-CH2C6H5 XIII.22 2-SO2CH2CH2C(CH3)CF2 5-CH2C6H5 XIII.23 2-SCH2CH2C(CH3)CF2 5-CH2CF3 XIII.'4 2- SCH2CH2C(CH3)CF2 5-CH2CH2F XIII.25 2-SOCH2CH2C(CH3)CF2 5-CH2CH2F XIII.26 2- SO2CH2CH2C(CH3)CF2 5-CH2CH2F XIII.27 2- SCH2CH2C(CH3)CF2 5-CH2CH3 XIII.28 2- SOCH2CH2C(CH3)CF2 5-CH2CH3 XIII.29 2-SO2CH2CH2C(CH3)CF2 5-CH2CH3 XIII.30 2-SCH2CH2C(CH3)CF2 5-CH2CHCH2 XIII.3 1 2- SCH2CH2C(CH3)CF2 5-CH2CN XIII.32 2- SCH2CH2C(CH3)CF2 5-CH2CONH2 XIII.33 2-SCH2CH2C(CH3)CF2 5-CH2COOCH2CH3 XIII.34 2- SCH2CH2C(CH3)CF2 5-CH2N(CH3)2 XIII.35 2-SCH2CH2C(CH3)CF2 5-CH2OCH3 XIII.36 2-SOCH2CH2C(CH3)CF2 5-CH2OCH3 XIII.37 2- SO2CH2CH2C(CH3)CF2 5-CH20CH3 XIII.38 2-SCH2CH2C(CH3)CF2 5-CH2OH XIII.39 2-SCH2CH2C(CH3)CF2 5-CH2SO2C6H5 XIII.40 2-SCH2CH2C(CH3)CF2 5-CH3 XIII.41 2-SOCH2CH2C(CH3)CF2 5-CH3 XIII.42 2-SO2CH2CH2C(CH3)CF2 5-CH3 XIII.43 2-SCH2CH2C(CH3)CF2 5-COCH3 XIII.44 2-SCH2CH2C(CH3)CF2 S-CON(CH3)2 XIII.45 2-SCH2CH2C(CH3)CF2 5-CONH2 XIII.46 2-SCH2CH2C(CH3)CF2 5-CONHCH2C6H5 XIII.47 2-SCH2CH2C(CH3)CF2 5-CONHCH2CH2C(CH3)CF2 XIII.48 2-SOCH2CH2C(CH3 )CF2 5-CONHCH2CH2C(CH3)CF2 XIII.49 2-SO2CH2CH2C(CH3)CF2 5-CONHCH2CH2C(CH3)CF2 XIII.SO 2-SCH2CH2C(CH3)CF2 5-CONHCH3 XIII.5 1 2-SCH2CH2C(CH3)CF2 5-CONHS02CH3 XIII.52 2-S02CH2CH2C(CH3)CF2 5-CONHS02CH3 XIII.53 2-SCH2CH2C(CH3)CF2 5-COOC6H5 XIII.54 2-SOCH2CH2C(CH3)CF2 5-COOC6H5 XIII.55 2-SCH2CH2C(CH3)CF2 5-COOCH2CH2C(CH3 )CF2 XIII.5 6 2-SOCH2CH2C(CH3)CF2 5-COOCH2CH2C(CH3)CF2 XIII.57 2-SO2CH2CH2C(CH3)CF2 5-COOCH2CH2C(CH3)CF2 XIII.58 2-SCH2CH2C(CH3)CF2 5-COOCH2CH2F XIII.59 2-SCH2CH2C(CH3)CF2 5-COOCH3 XIII.60 2-SCH2CH2C(CH3)CF2 5-COOH XIII.6 1 2-SCH2CH2C(CH3)CF2 5-COSCH2CH2C(CH3)CF2 XIII.62 2-SCH2CH2C(CH3)CF2 5-CSNH2 XIII.63 2-SCH2CH2C(CH3)CF2 5-H XIII.64 2-SOCH2CH2C(CH3)CF2 5-H XIII.65 2-SO2CH2CH2C(CH3)CF2 5-H XIII.66 2-SCH2CH2C(CH3)CF2 5-N(CH3)2 XIII.67 2-SCH2CH'C(CH3)CF2 5-N(S02CH3)2 XIII.68 2-SO2CH2CH2C(CH3)CF2 S-N(SO2CH3)2 XIII.69 2-SCH2CH2C(CH3)CF2 5-NH2 XIII.70 2-SCH2CH2C(CH3)CF2 5-NHCH3 XIII.71 2-SOCH2CH2C(CH3)CF2 5-NHCH3 XIII.72 2-SO2CH2CH2C(CH3)CF2 5-NHCH3 XIII.73 2-SCH2CH2C(CH3)CF2 5-NHCHO XIII.74 2-SOCH2CH2C(CH3)CF2 5-NHCHO XIII.75 2-SCH2CH2C(CH3)CF2 5-NHCOCF3 XIII.76 2-SO2CH2CH2C(CH3)CF2 5-NHCOCF3 XIII.77 2-SCH2CH2C(CH3)CF2 5-NHCOCH3 XIII.78 2-SCH2CH2C(CH3)CF2 5-NHCOOCH3 XIII.79 2-SOCH2CH2C(CH3)CF2 5-NHCOOCH3 XIII.80 2-SCH2CH2C(CH3)CF2 5-NHCSCH2CH3 XIII.8 1 2-SCH2CH2C(CH3)CF2 5-NHCSNHCH2CH3 XIII.82 2-SCH2CH2C(CH3)CF2 5-NHS02CH3 XIII.83 2-S02CH2CH2C(CH3)CF2 5-NHS02CH3 XIII.84 2-SCH2CH2C(CH3)CF2 5-OC6H5 XIII.85 2-SOCH2CH2C(CH3)CF2 5-OC6H5 XIII.86 2-SO2CH2CH2C(CH3)CF2 5-OC6H5 XIII.87 2-SCH2CH2C(CH3)CF2 5-OCF2CF2H XIII.88 2-SCH2CH2C(CH3)CF2 5-OCF3 XIII.89 2-SOCH2CH2C(CH3)CF2 5-OCF3 XIII.90 2-SO2CH2CH2C(CH3)CF2 5-OCF3 XIII.9 1 2-SCH2CH2C(CH3)CF2 5-OCH2C6H5 XIII.92 2-SCH2CH2C(CH3)CF2 5-OCH2CF3 XIII.93 2-SOCH2CH2C(CH3)CF2 5-OCH2CF3 XIII.94 2-S02CH2CH2C(CH3)CF2 5-OCH2CF3 XIII.95 2-SCH2CH2C(CH3)CF2 5-OCH2CH=CC12 XIII.96 2-SCH2CH2C(CH3)CF2 5-OCH2CH2C(CH3 )CF2 XIII.97 2-SOCH2CH2C(CH3)CF2 5-OCH2CH2C(CH3)CF2 XIII.98 2-S02CH2CH2C(CH3)CF2 5-OCH2CH2C(CH3)CF2 XIII.99 2-SCH2CH2C(CH3)CF2 5-OCH2CH2F XIII. 100 2-SCH2CH2C(CH3)CF2 5-OCH2COOCH3 XIII. 101 2-SCH2CH2C(CH3)CF2 5-OCH3 XIII. 102 2-SOCH2CH2C(CH3)CF2 5-OCH3 XIII.103 2-SO2CH2CH2C(CH3)CF2 5-OCH3 XIII. 104 2-SCH2CH2C(CH3)CF2 5-OCOC6H5 XIII. 105 2-SCH2CH2C(CH3)CF2 5-OCOCH3 XIII. 106 2-SCH2CH2C(CH3)CF2 5-OS02CH3 XIII. 107 2-SOCH2CH2C(CH3)CF2 S-OSO2CH3 XIII. 108 '-SO'CH'CH'C(CH3)CF' S-OSO2CH3 XIII. 109 2-SCH2CH2C(CH3)CF2 5-SCF3 XIII. 110 2-SCH2CH2C(CH3)CF2 5-SCH2(3-CF3C6H4) XIII. 111 2-SOCH2CH2C(CH3)CF2 5-SCH2(3-CF3C6H4) XIII. 112 '-SO'CH'CH2C(CH3)CF2 5-SCH2(3-CF3C6H4) XIII.113 2-SCH2CH2C(CH3)CF2 5-SCH2(4-CF3-C6H4) XIII.1 14 2-SCH2CH2C(CH3)CF2 5-SCH2(c-C3H5) XIII. 115 2-SCH2CH2C(CH3)CF2 5-SCH2C CH XIII.1 116 2-SCH2CH2C(CH3)CF2 5-SCH2CH=CH2 XIII. 117 2-SCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XIII. 118 2-SOCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 XIII. 119 2-SCH2CH2C(CH3)CF2 5-SCH3 XIII. 120 2-SOCH2CH2C(CH3)CF2 5-SCH3 XIII.121 2-SO2CH2CH2C(CH3)CF2 5-SCH3 XIII. 122 2-SCH2CH2C(CH3)CF2 5-SH XIII. 123 2-SCH2CH2C(CH3)CF2 5-S02CH2CH2C(CH3)CF2 XIII. 124 '-SO'CH'CH2C(CH3)CF2 5-S02CH2CH2C(CH3)CF2 XIII. 125 2-SCH2CH2C(CH3)CF2 5-SO2CH3 XIII.126 2-SO2CH2CH2C(CH3)CF2 5-SO2CH3 XIII. 127 2-SCH2CH2C(CH3)CF2 5-S02N(CH3)2 XIII. 128 2-SCH2CH2C(CH3)CF2 5-S02NH2 XIII.129 2-SCH2CH2C(CH3)CF2 5-SO2NHCH3 XIII. 130 2-SCH2CH2C(CH3)CF2 5-SOCF3 XIII. 13 1 2-SOCH2CH2C(CH3)CF2 5-SOCF3 XIII.132 2-SCH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 XIII. 133 2-SOCH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 XIII.134 2-SO2CH2CH2C(CH3)CF2 5-SOCH2CH2C(CH3)CF2 XIII. 135 2-SCH2CH'C(CH3)CF2 5-SOCH3 XIII.136 2-SCH2CH2C(CH3)CF2 5-(4-CF3-C6H4) XIII. 137 2-SO2CH2CH2C(CH3)CF2 5-(4-CF3-C6H4) XIII.138 2-SCH2CH2C(CH3)CF2 5-(4-CH3-C6H4) XIII.139 2-SO2CH2CH2C(CH3)CF2 5-(4-CH3-C6H4) XIII. 140 2-SCH2CH2C(CH3)CF2 5-(4-CN-C6H4) XIII.141 2-SOCH2CH2C(CH3)CF2 5-(4-CN-C6H4) XIII. 142 2-SCH2CH2C(CH3)CF2 5-(4-CONH2-C6H4) XIII. 143 2-SCH2CH2C(CH3)CF2 5-(4-H2NS02-C6H4) XIII. 144 2-SCH2CH2C(CH3)CF2 5-(4-N02-C6H4) XIII. 145 2-SCH2CH2C(CH3)CF2 5-(4-OCH3-C6H4) XIII. 146 2-SOCH2CH2C(CH3)CF2 5-(4-OCH3-C6H4) XIII.147 2-SO2CH2CH2C(CH3)CF2 5-(4-OCH3-C6H4) Examples of compounds of Formula (XIV) according to the invention are set out in Table XIV.
TABLE XIV No. R1 R5 XIV. 1 1-CH3 5-SCH2CH2C(CH3)CF2 Examples of compounds of Formula (XV) according to the invention are set out in Table XV.
TABLE XV No. R1 R2 R3 R4 XV. 1-SCH2CH2C(CH3)CF2 2-H 3-H 4-N02 Examples of compounds of Formula (XVI) according to the invention are set out in Table XVI.
TABLE XVI No. R2 R3 R4 R5 R6 XVI 1 1 2-Cl 3-H 4-SCH2CH2C(CH3)CF2 5-H 6-H XVI 2 2 F 3-F 4-SCH2CH2C(CH3)CF2 5-F 6-F XVI.3 2-F 3-F 4-SOCH2CH2C(CH3)CF2 5-F 6-F XVI 4 2 F 3 F 4-SO2CH2CH2C(CH3)CF2 5-F 6-F XVI 5 2 H 3-H 4-SCH2CH2C(CH3)CF2 5-H 6-H XVI.6 2-H 3-H 4-SO2CH2CH2C(CH3)CF2 5-H 6-H XVI 7 2-SCH2CH2C(CH3)CF2 3-CF3 4-H 5-H 6-H XVI.8 2 SCH2CH2C(CH3)CF2 3-CN 4-H 5-H 6-H XVI 9 2 SCH2CH2C(CH3)CF2 3-CONH2 4-H 5-H 6-H XVI 10 2-SCH2CH2C(CH3)CF2 3-COOCH2CH2C(CH3)CF2 4-H 5-H 6-H XVI.11 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-CF3 6-H XVI 12 2-SO2CH2CH2C(CH3)CF2 3-H 4-H 5-CF3 6-H XVI 13 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-Cl 6-H XVI 14 2-SO2CH2CH2C(CH3)CF2 3-H 4-H 5-Cl 6-H XVI 15 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-CN 6-H XVI 16 2-SO2CH2CH2C(CH3)CF2 3-H 4-H 5-CN 6-H XVI.17 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-CONH2 6-H XVI.18 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-COOH 6-H XVI.19 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-H 6-H XVI.20 2-SO2CH2CH2C(CH3)CF2 3-H 4-H 5-H 6-H XVI.21 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-NO2 6-H XVI.22 2-SCH2CH2C(CH3)CF2 3-H 4-H S-SCH2CH2C(CH3)CF2 6-H XVI.23 2-SCH2CH2C(CH3)CF2 3-H 4-H 5-H 6-F XVI.24 2-SCH2CH2C(CH3)CF2 3-NO2 4-H 5-H 6-H Examples of compounds of Formula (XVII) according to the invention are set out in Table XVII.
TABLE XVII No. R3 R4 R5 R6 XVII.1 3-SCH2CH2C(CH3)CF2 4-H 5-H 6-CH3 XVII.2 3-SCH2CH2C(CH3)CF2 4-H 5-H 6-Cl XVII.3 3-SCH2CH2C(CH3)CF2 4-H 5-H 6-OCH3 XVII .4 3-SCH2CH2C(CH3)CF2 4-H 5-H 6-C6H5 XVII.S 3-SOCH2CH2C(CH3)CF2 4-H 5-H 6-C6H5 XVII.6 3-SO2CH2CH2C(CH3)CF2 4-H 5-H 6-C6H5 XVII.7 3-SCH2CH2C(CH3)CF2 -CH=CH-CH=CH- 6-H Examples of compounds of Formula (XVIII) according to the invention are set out in Table XVIII.
TABLE XVIII No. R2 R3 R5 R6 XVIII. 1 2-SCH2CH2C(CH3)CF2 3-H -CH=CH-CH=CH XVIII.2 2-SOCH2CH2C(CH3)CF2 3-H -CH=CH-CH=CH XVIII.3 2-SO2CH2CH2C(CH3)CF2 3-H -CH=CH-CH=CH XVIII.1 '-SCH2CH2C(CH3)CF2 3-H -CH=C(CI)CH=CH XVIII.S 2-SOCH2CH2C(CH3)CF2 3-H -CH=C(C1)CH=CH XVIII.6 2-SO2CH2CH2C(CH3)CF2 3-H -CH=C(CI)CH=CH XVIII.7 2-SCH2CH2C(CH3)CF2 3-H 5-H 6-H XVIII.8 2-SOCH2CH2C(CH3)CF2 3-H 5-H 6-H XVIII.9 2-SO2CH2CH2C(CH3)CF2 3-H 5-H 6-H XVIII.10 2-SCH2CH2C(CH3)CF2 3-Cl 5-H 6-H XVIII.11 2-SOCH2CH2C(CH3)CF2 3-Cl S-H 6-11 XVIII.12 2-SO2CH2CH2C(CH3)CF2 3-Cl 5-H 6-H XVIII.13 2-SCH2CH2C(CH3)CF2 3-SCH2CH2C(CH3)CF2 5-H 6-H XVIII.14 2-SCH2CH2C(CH3)CF2 3-H 5-H 6-Cl XVIII.15 2-SOCH2CH2C(CH3)CF2 3-H 5-H 6-Cl XVIII.16 '-SO'CH2CH2C(CH3)CF2 3-H 5-H 6-Cl Examples of compounds of Formula (XIX) according to the invention are set out in Table XIX.
TABLE XIX No. R4 R5 R6 XIX. 1 4-SCH2CH2C(CH3)CF2 -CH=CH-CH=CH Examples of compounds of Formula (XX) according to the invention are set out in Table XX.
TABLE XX No. R3 R5 R6 XX. 1 3-SCH2CH2C(CH3)CF2 5-Br 6-H XX.2 3-SCH2CH2C(CH3)CF2 5-c-C3H5 6-H XX.3 3-SOCH2CH2C(CH3)CF2 5-c-C3H5 6-H XX.4 3-SCH2CH2C(CH3)CF2 5-C6H5 6-CH3 XX.5 3-SOCH2CH2C(CH3)CF2 5-C6H5 6-CH3 XX.6 3-SO'CH2CH2C(CH3)CF' 5-C6H5 6-CH3 XX.7 3-SOCH2CH2C(CH3)CF2 5-C6H5 6-CN XX.8 3-SCH2CH2C(CH3)CF2 5-C6H5 6-H XX.9 3-SO2CH2CH2C(CH3)CF2 5-C6H5 6-H XX.10 3-SCH2CH2C(CH3)CF2 5-(4-F-C6H4) 6-H XX.l I 3-SOCH2CH2C(CH3)CF2 5-(4-F-C6H4) 6-H XX.12 3-SCH2CH2C(CH3)CF2 5-CF2H 6-CH3 NX.13 3-SCH2CH2C(CH3)CF2 5-CF3 6-H XX. 14 3-SOCH2CH2C(CH3)CF2 5-CF3 6-OC6H5 XX.15 3-SCH2CH2C(CH3)CF2 5-CH(CH3)2 6-H XX. 16 3-SCH2CH2C(CH3)CF2 S-CH=CH' 6-H XX.17 3-SCH2CH2C(CH3)CF2 5-CH=CHCN 6-H XX.18 3-SCH2CH2C(CH3)CF2 5-CH=CHN02 6-H XX.19 3-SCH2CH2C(CH3)CF2 5-CH=NOCH3 6-CH3 XX.2O 3-SCH2CH2C(CH3)CF2 5-CH2C CH 6-H XX.21 3-SCH2CH2C(CH3)CF2 5-CH2C6H5 6-H XX.22 3-SOCH2CH2C(CH3)CF2 5-CH2C6H5 6-H XX.23 3-SCH2CH2C(CH3)CF2 5-CH2CF3 6-H XX.'4 3-SCH2CH2C(CH3)CF2 5-CH2CH=CH2 6-H XX.25 3-SCH2CH2C(CH3 )CF2 5-CH2CH2CH2CH3 6-H XX.2 6 3-SO2CH2CH2C(CH3)CF2 5-CH2CH2CH2CH3 6-H XX.27 3-SCH2CH2C(CH3)CF2 5-CH2CH2CH3 6-H XX.28 3-SO2CH2CH2C(CH3)CF2 5-CH2CH2CH3 6-H XX.29 3-SCH2CH2C(CH3)CF2 5-CH2CH2F 6-H XX.30 3-SCH2CH2C(CH3)CF2 5-CH2CH3 6-H XX.31 3-SCH2CH2C(CH3)CF2 5-CH2CN 6-CH3 XX.32 3-SCH2CH2C(CH3)CF2 5-CH2CONH2 6-H XX.33 3-SCH2CH2C(CH3)CF2 5-CH2N(CH3)2 6-CH3 XX.34 3-SCH2CH2C(CH3)CF2 5-CH2NHCOCH3 6-H XX.35 3-SCH2CH2C(CH3)CF2 5-CH20CH2CH3 6-H XX.36 3-SOCH2CH2C(CH3)CF2 5-CH20CH2CH3 6-H XX.37 3-SCH2CH2C(CH3)CF2 5-CH20CH3 6-CH3 XX.38 3-SCH2CH2C(CH3)CF2 5-CH2OH 6-H XX.39 3-SCH2CH2C(CH3)CF2 5-CH2SO2C6H5 6-H XX.40 3-SCH2CH2C(CH3)CF2 5-CH3 6-CF2H XX.41 3-SCH2CH2C(CH3)CF2 5-CH3 6-CH=CH2 XX.42 3-SCH2CH2C(CH3)CF2 5-CH3 6-CH2CH2F XX.43 3-SCH2CH2C(CH3)CF2 5-CH3 6-CH2CN XX.44 3-SCH2CH2C(CH3)CF2 5-CH3 6-CH2N(CH3)2 XX.45 3-SCH2CH2C(CH3)CF2 5-CH3 6-CH2OH XX.46 3-SCH2CH2C(CH3)CF2 5-CH3 6-CH3 XX.47 3-SCH2CH2C(CH3)CF2 5-CH3 6-CONH2 XX.48 3-SCH2CH2C(CH3)CF2 5-CH3 6-CONHCH3 XX.49 3-SCH2CH2C(CH3)CF2 5-CH3 6-CONHSO'CH3 XX.50 3-SCH2CH2C(CH3)CF2 5-CH3 6-COOCH2CH3 XX.51 3-SCH2CH2C(CH3)CF2 5-CH3 6-COOCH3 XX.52 3-SCH2CH2C(CH3)CF2 5-CH3 6-H XX.53 3-SOCH2CH2C(CH3)CF' 5-CH3 6-H XX.54 3-SO2CH2CH2C(CH3)CF2 5-CH3 6-H XX.55 3-SCH2CH2C(CH3)CF2 5-CH3 6-NHCHO XX.56 3-SCH2CH2C(CH3)CF2 5-CH3 6.NHCOCH3 XX.57 3-SCH2CH2C(CH3)CF2 5-CH3 6-NHCONH2 XX.58 3-SCH2CH2C(CH3)CF2 5-CH3 6-OCF2H XX.59 3-SCH2CH2C(CH3)CF2 5-CH3 6-OCH2CF3 XX.60 3-SCH2CH2C(CH3)CF2 5-CH3 6-OCH2CH'F XX.61 3-SCH2CH2C(CH3)CF2 5-CH3 6-OCOCH3 XX. 62 3-SCH2CH2C(CH3)CF2 5-CH3 6-OS02CH3 XX.63 3-SCH2CH2C(CH3)CF2 5-CH3 6-S02NH2 XX.64 3-SCH2CH2C(CH3)CF2 5-CH3 6-SOCH3 XX.65 3-SCH2CH2C(CH3)CF2 5-CHCl2 6-H XX.66 3-SCH2CH2C(CH3)CF2 5-CHO 6-CH3 XX.67 3-SCH2CH2C(CH3)CF2 5-Cl 6-H XX.68 3-SO2CH2CH2C(CH3)CF2 5-Cl 6-H XX.69 3-SCH2CH2C(CH3)CF2 5-CN 6-H XX.70 3-SOCH2CH2C(CH3)CF2 5-CN 6-H XX.71 3-SCH2CH2C(CH3)CF2 5-COCH3 6-H XX.72 3-SCH2CH2C(CH3)CF2 5-CON(CH3)2 6-H XX.73 3-SCH2CH2C(CH3)CF2 5-CONH2 6-H XX.74 3-SCH2CH2C(CH3)CF2 5-CONHCH2C6H5 6-H XX.75 3-SOCH2CH2C(CH3)CF2 5-CONHCH2CH2C(CH3)CF2 6-H XX.76 3-SCH2CH2C(CH3)CF2 5-CONHCH3 6-H XX.77 3-SCH2CH2C(CH3)CF2 5-CONHSO2CH3 6-CH3 XX.78 3-SO2CH2CH2C(CH3)CF2 5-COOCH2CH2C(CH3 )CF2 6-H XX.79 3-SCH2CH2C(CH3)CF2 5-COOCH2CH2F 6-H XX. 80 3-SCH2CH2C(CH3 )CF2 5-COOCH2CH3 6-H XX.81 3-SCH2CH2C(CH3)CF2 5-COOCH3 6-CH3 XX.82 3-SOCH2CH2C(CH3)CF2 5-COOCH3 6-H XX.83 3-SCH2CH2C(CH3)CF2 5-COOH 6-H XX.84 3-SOCH2CH2C(CH3 )CF2 5-COOH 6-H XX.85 3-SCH2CH2C(CH3)CF2 5-F 6-H XX.86 3-SCH2CH2C(CH3)CF2 5-H 6-(1-CH3-cC3H4) XX.87 3-SCH2CH2C(CH3)CF2 5-H 6-(4-F-C6H4) XX.88 3-S02CH2CH2C(CH3)CF2 5-H 6-(4-F-C6H4) XX.89 3-SCH2CH2C(CH3)CF2 5-H 6-Br XX.90 3-SCH2CH2C(CH3)CF2 5-H 6-C(CH3)3 XX.91 3-SCH2CH2C(CH3)CF2 5-H 6-c-C3H5 XX.92 3-SCH2CH2C(CH3)CF2 5-H 6-c-CSH9 XX.93 3-SCH2CH2C(CH3)CF2 5-H 6-C CH XX.94 3-SCH2CH2C(CH3)CF2 5-H 6-C6H5 XX.95 3-SOCH2CH2C(CH3)CF2 5-H 6-C6H5 XX.96 3-SCH2CH2C(CH3)CF2 5-H 6-CF3 XX.97 3-SO2CH2CH2C(CH3)CF2 5-H 6-CF3 XX.98 3-SCH2CH2C(CH3)CF2 5-H 6-CH(CH3)2 XX.99 3-SCH2CH2C(CH3)CF2 5-H 6-CH=CHCN XX. 100 3-SCH2CH2C(CH3)CF2 5-H 6-CH=CHN02 XX. 101 3-SCH2CH2C(CH3)CF2 5-H 6-CH=NOCH3 XX. 102 3-SOCH2CH2C(CH3)CF2 5-H 6-CH2(4-CF3-C6H4) XX.103 3-SCH2CH2C(CH3)CF2 5-H 6-CH2C CH XX.104 3-SCH2CH2C(CH3)CF2 5-H 6-CH2C6H5 XX.105 3-SOCH2CH2C(CH3)CF2 5-H 6-CH2C6H5 XX.106 3-SCH2CH2C(CH3)CF2 5-H 6-CH2CF3 XX.107 3-SCH2CH2C(CH3)CF2 5-H 6-CH2CH=CH2 XX.108 3-SCH2CH2C(CH3)CF2 5-H 6-CH2CH2CH2CH3 XX.109 3-SCH2CH2C(CH3)CF2 5-H 6-CH2CH2CH3 XX. 110 3-SCH2CH2C(CH3)CF2 5-H 6-CH2CH3 XX.111 3-SCH2CH2C(CH3)CF2 5-H 6-CH2CONH2 XX.112 3-SCH2CH2C(CH3)CF2 5-H 6-CH2NHCOCH3 XX. 113 3-SCH2CH2C(CH3)CF2 5-H 6-CH20CH2CH3 XX. 114 3-SCH2CH2C(CH3)CF2 5-H 6-CH'OCH3 XX.115 3-SCH2CH2C(CH3)CF2 5-H 6-CH2SO2C6H5 XX.116 3-SCH2CH2C(CH3)CF2 5-H 6-CH3 XX.117 3-SOCH2CH2C(CH3)CF2 5-H 6-CH3 XX. 118 3-S02CH2CH2C(CH3)CF2 5-H 6-CH3 XX.ll9 3-SCH2CH2C(CH3)CF2 5-H 6-CHO XX.120 3-SCH2CH2C(CH3)CF2 5-H 6-Cl XX.121 3-SOCH2CH2C(CH3)CF2 5-H 6-Cl XX.122 3-SCH2CH2C(CH3)CF2 5-H 6-CN XX.123 3-SCH2CH2C(CH3)CF2 5-H 6-COCH3 XX.124 3-SCH2CH2C(CH3)CF2 5-H 6-CON(CH3)2 XX.125 3-S02CH2CH2C(CH3)CF2 5-H 6-CON(CH3)C2H5 XX. 126 3-SCH2CH2C(CH3)CF2 5-H 6-CONHCH2C6H5 XX. 127 3-SCH2CH2C(CH3)CF2 5-H 6-CONHCH2CH2C(CH3)CF2 XX.128 3-SCH2CH2C(CH3)CF2 5-H 6-CONHCH2CH2CH3 XX.129 3-SCH2CH2C(CH3)CF2 5-H 6-COOC6H5 XX. 130 3-SCH2CH2C(CH3)CF2 5-H 6-COOCH2CH2C(CH3)CF2 XX.131 3-SCH2CH2C(CH3)CF2 5-H 6-COOCH2CH2F XX.132 3-SCH2CH2C(CH3)CF2 5-H 6-COOCH3 XX.133 3-SOCH2CH2C(CH3)CF2 5-H 6-COOCH3 XX.135 3-SO'CH'CH'C(CH3)CF' 5-H 6-COOH XX.136 3-SCH2CH2C(CH3)CF2 5-H 6-F XX.137 3-SCH2CH2C(CH3)CF2 5-H 6-H XX.138 3-SCH2CH2C(CH3)CF2 5-H 6-NHCH2CH3 XX.139 3-SOCH2CH2C(CH3)CF2 5-H 6-NHCH2CH3 XX. 140 3-SCH2CH2C(CH3)CF2 5-H 6-NHCOC2H5 XX.141-3-SCH2CH2C(CH3)CF2 5-H 6-NHCOC6H5 XX.142 3-SCH2CH2C(CH3)CF2 5-H 6-NHCOCF3 XX.143 3-SCH2CH2C(CH3)CF2 5-H 6-NHCOCH3 XX. 144 3-SCH2CH2C(CH3)CF2 5-H 6-NHCOOCH3 XX.145 3-SCH2CH2C(CH3)CF2 5-H 6-NH--WSCH2CH3 XX. 146 3-SCH2CH2C(CH3 )CF2 5-H 6-NHCSNHCH2CH3 XX.147 3-SCH2CH2C(CH3)CF2 5-H 6-NHS02CH3 XX. 148 3-SCH2CH2C(CH3)CF2 5-H 6-N02 XX. 149 3-SCH2CH2C(CH3)CF2 5-H 6-OC4H9 XX. 150 3-SOCH2CH2C(CH3)CF2 5-H 6-OC5Hll XX.151 3-SCH2CH2C(CH3)CF2 5-H 6-OC6H5 XX.152 3-SOCH2CH2C(CH3)CF2 5-H 6-OC6H5 XX. 153 3-SCH2CH2C(CH3)CF2 5-H 6-OCF2CF2H XX.154 3-SCH2CH2C(CH3)CF2 5-H 6-OCF3 XX.155 3-SOCH2CH2C(CH3)CF2 5-H 6-OCF3 XX.156 3-SO2CH2CH2C(CH3)CF2 5-H 6-OCH(CH3)C2H5 XX.157 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2(4-C1-C6H4) XX. 158 3-S02CH2CH2C(CH3)CF2 5-H 6-OCH2(4-C1-C6H4) XX.159 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2C6H5 XX.160 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2CCl=CH2 XX.161 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2CH=CCl2 XX. 162 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2CH=CH2 XX. 163 3-S02CH2CH2C(CH3)CF2 5-H 6-OCH2CH=CH2 XX.164 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2CH2CH3 XX. 165 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2CH2COOCH3 XX. 166 3-SOCH2CH2C(CH3)CF2 5-H 6-OCH2CH2COOCH3 XX. 167 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2CH2C(CH3)CF2 XX.168 3-SCH2CH2C(CH3)CF2 5-H 6-OCH2CH3 XX.169 3-SCH2CH2C(CH3)CF2 S-H 6-OCH2COOH XX.170 3-SCH2CH2C(CH3)CF2 5-H 6-OCH3 XX.171 3-SOCH2CH2C(CH3)CF2 5-H 6-OCH3 XX.172 3-SCH2CH2C(CH3)CF2 5-H 6-OCOC2H5 SX.173 3-SCH2CH2C(CH3)CF2 5-H 6-OCOC6H5 XX.174 3-SCH2CH2C(CH3)CF2 5-H 6-OH XX.175 3-SOCH2CH2C(CH3)CF2 5-H 6-OH XX.176 3-SCH2CH2C(CH3)CF2 5-H 6-SCF3 XX.177 3-SOCH2CH2C(CH3)CF2 5-H 6-SCF3 XX.178 3-SCH2CH2C(CH3)CF2 5-H 6-SCH2CH2CH3 XX. 179 3-SCH2CH2C(CH3)CF2 5-H 6-SCH2CH2C(CH3)CF2 XX.180 3-SCH2CH2C(CH3)CF2 5-H 6-SCH3 XX.181 3-SOCH2CH2C(CH3)CF2 5-H 6-SCH3 XX.182 3-SCH2CH2C(CH3)CF2 5-H 6-S02NHCH3 XX.183 3-SCH2CH2C(CH3)CF2 5-H 6-SOCF3 XX. 184 3-SCH2CH2C(CH3)CF2 5-H 6-SOCH2CH2C(CH3)CF2 XX. 185 3-SCH2CH2C(CH3)CF2 5-NH2 6-CH3 XX. 186 3-SO'CH2CH'C(CH3)CF' 5-NHCH2CH3 6-C6H5 XX. 187 3-SCH2CH2C(CH3)CF2 5-NHCH2CH3 6-H XX.188 3-SCH2CH2C(CH3)CF2 5-NHCHO 6-H XX. 189 3-SCH2CH2C(CH3)CF2 5-NHCOCF3 6-CH3 XX.190 3-SOCH2CH2C(CH3)CF2 5-NHCOCH3 6-C6H5 XX.191 3-SCH2CH2C(CH3)CF2 5-NHCOCH3 6-H XX.192 3-SCH2CH2C(CH3)CF2 5-NHCONH2 6-CH3 XX. 193 3-SCH2CH2C(CH3)CF2 5-NHCOOCH3 6-H XX. 194 3-SCH2CH2C(CH3)CF2 5-NHS02CH3 6-CH3 XX. 195 3-SCH2CH2C(CH3)CF2 5-NMe2 6-H XX.196 3-SOCH2CH2C(CH3)CF2 5-N02 6-C6H5 XX.197 3-SCH2CH2C(CH3)CF2 5-N02 6-H XX.198 3-SCH2CH2C(CH3)CF2 5-OC6H5 6-H XX.199 3-SOCH2CH2C(CH3)CF2 5-OC6H5 6-H XX.200 3-SOCH2CH2C(CH3)CF2 5-OC6H5 6-NHCOCH3 XX.201 3-SCH2CH2C(CH3)CF' 5-OCF2CF2H 6-CH3 XX.202 3-SCH2CH2C(CH3)CF2 5-OCF2H 6-H XX.203 3-SCH2CH2C(CH3)CF2 5-OCF3 6-H XX.204 3-SOCH2CH2C(CH3)CF2 5-OCF3 6-H XX.205 3-SCH'CH'C(CH3)CF' 5-OCH(CH3)2 6-H XX.206 3-SOCH2CH2C(CH3)CF2 S-OCH(CH3)C2H5 6-H XX.207 3-SCH2CH2C(CH3)CF2 5-OCH2(4-Cl-C6H4) 6-H XX.208 3-SO2CH2CH2C(CH3)CF2 5-OCH2(4-Cl-C6H4) 6-H XX.209 3-SCH2CH2C(CH3)CF2 5-OCH2C6H5 6-H XX. 210 3-SCH2CH2C(CH3)CF2 5-OCH2CC1=CH2 6-H XX.2 11 3-SCH2CH2C(CH3)CF2 5-OCH2CF3 6-H XX.2 12 3-SCH2CH2C(CH3)CF2 5-OCH2CH=CH2 6-H XX.213 3-SO2CH2CH2C(CH3)CF2 5-OCH2CH2COOCH3 6-CH3 XX .214 3-SCH2CH2C(CH3)CF2 5-OCH2CH2COOCH3 6-H XX.2 15 3-SO2CH2CH2C(CH3)CF2 5-OCH2CH2COOCH3 6-H XX.216 3-SCH2CH2C(CH3)CF2 5-OCH2CH2C(CH3)CF2 6-H XX.217 3-SCH2CH2C(CH3 )CF2 5-OCH2CH2F 6-CH3 XX.2 18 3-SCH2CH2C(CH3)CF2 5-OCH2CH3 6-H XX.219 3-SCH2CH2C(CH3)CF2 5-OCH2COOCH3 6-H XX.220 3-SCH2CH2C(CH3)CF2 5-OCH2COOH 6-H XX.221 3-SCH2CH2C(CH3)CF2 5-OCH3 6-H XX.222 3-SCH2CH2C(CH3)CF2 5-OCOC2H5 6-H XX.223 3-SOCH2CH2C(CH3)CF2 5-OCOC6H5 6-H XX.224 3-SCH2CH2C(CH3)CF2 5-OCOCH3 6-CH3 XX.225 3-SOCH2CH2C(CH3)CF2 5-OH 6-C6H5 XX .226 3-SCH2CH2C(CH3)CF2 5-OH 6-CH3 XX.227 3-SCH2CH2C(CH3 )CF2 5-OH 6-H XX.228 3-SCH2CH2C(CH3)CF2 5-OS02CH3 6-H XX.229 3-SCH2CH2C(CH3)CF2 5-SCF3 6-H XX.230 3-SOCH2CH2C(CH3)CF2 5-SCF3 6-H XX.23 1 3-SCH2CH2C(CH3 )CF2 5-SCH2CH2C(CH3)CF2 6-H XX.232 3-SCH2CH2C(CH3)CF2 5-SCH2CH2CH3 6-H XX.233 3-SCH2CH2C(CH3)CF2 5-SCH2CH2C(CH3)CF2 6-H XX.'34 3-SCH2CH2C(CH3-)CF2 5-SCH3 6-H XX.'35 3-SOCH2CH2C(CH3)CF2 5-SCH3 6-H XX.236 3-SCH2CH2C(CH3)CF2 5-SO2NH2 6-CH3 XX.237 3-SCH2CH2C)CH3)CF2 5-SO2NHCH3 6-H XX.238 3-SCH2CH2C(CH3)CF2 5-SOCF3 6-H XX.239 3-SCH2CH2C(CH3)CF2 5-SOCH3 6-CH3 XX.240 3-CH3 5-CH3 6-SCH2CH2C(CH3)CF2 XX.241 3-CH3 5-H 6-SCH2CH2C(CH3)CF2 XX.242 3-CH3 5-OC4H9 6-SO2CH2CH2C(CH3)CF2 XX.243 3-CH3 5-SCH2CH2C(CH3)CF2 6-CH3 XX.244 3-CH3 5-SCH2CH2C(CH3)CF2 6-H XX.245 3-H 5-CH3 6-SCH2CH2C(CH3)CF2 XX.246 3-H 5-H 6-CH2CH2C(CH3)CF2 XX.247 3-H 5-SCH2CH2C(CH3)CF2 6-CH3 XX.248 3-H 5-SCH2CH2C(CH3)CF2 6-H XX.249 3-H 5-SOCH2CH2C(CH3)CF2 6-CH3 XX.250 3-H 5-S02CH2CH2C(CH3)CF2 6-CH3 XX.251 3-SCH2CH2C(CH3)CF2 -(CH2CH2CH2CH2 )- XX.252 3-SOCH2CH2C(CH3 )CF2 -(CH2CH2CH2CH2) XX. 253 3-S02CH2CH2C(CH3)CF2 -(CH2CH2CH2CH2) Examples of compounds of Formula (XXI) according to the invention are set out in Table XXI.
TABLE XXI No. R2 R4 R6 XXI.l 2-SCH2CH2C(CH3)CF2 4-H 6-H TABLE XXII No. R2 R5 R6 R7 R8 XXII 1 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-H XXII.2 2- 5-H 6-H 7-H 8-F SO2CH2CH2C(CH3)CF2 XXII 3 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-CH3 8-H XXII.4 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NHCOCH3 8-H XXII.5 2-SOCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-H XXII.6 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-COOH 8-H XXII.7 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-F 8-H XXII.8 2-SCH2CH2C(CH3)CF2 4-CH3 6-H 7-H 8-H XXII.9 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-CN XII.10 2-SCH2CH2C(CH3)CF2 5-H 6-CH3 7-H 8-H XXII.11 2 SOCH2CH2C(CH3)CF2 5-H 6-Cl 7-H 8-H XXII.12 2-SCH2CH2C(CH3)CF2 5-H 6-Cl 7-Cl 8-H XXII.13 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-cC3H5-1-CH3 8-H XXII.14 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OH 8-Cl XXII.15 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH2CF3 8-H XXII.16 2-SOCH2CH2C(CH3)CF2 5-H 6-H 7-OCH2CH3 8-H XXII.17 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-CH2OCH3 XXII.18 2-SCH2CH2C(CH3)CF2 5-H -CH=CH-CH=CH- 8-H XXII.19 2 SCH2CH2C(CH3)CF2 5-H 6-H 7-Cl 8-H XXII.20 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NHCOC2H5 8-H XXII.21 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NHSO2CH3 8-H XXII.22 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NO2 8-H XXII.23 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OC2H5 8-H XXII.24 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH3 8-H XXII.25 2-SCH2CH2C(CH3)CF2 5-Cl 6-H 7-OCH3 8-H XXII.26 2-SCH2CH2C(CH3)CF2 5-H 6-Br 7-H 8-H XXII.27 2-SCH2CH2C(CH3)CF2 5-H 6-CF3 7-H 8-H XXII.28 2-SCH2CH2C(CH3)CF2 5-H 6-Cl 7-H 8-H XXII.29 2 SCH2CH2C(CH3)CF2 5-H 6 COOCH2CH2CHCF2 7-H 8-H XXII.30 2-SCH2CH2C(CH3)CF2 5-H 6-CONH2 7-H 8-H XXII.31 2-SCH2CH2C(CH3)CF2 5-H 6-COCNCH2CH2CH3 7-H 8-H XXII.32 2-SCH2CH2C(CH3)CF2 5-H 6-CON(CH3)2 7-H 8-H XXII.33 2-SCH2CH2C(CH3)CF2 5-H 6-COOH 7-H 8-H XXII.34 2-SCH2CH2C(CH3)CF2 5-H 6-F 7-H 8-H XXII 35 2-SCH2CH2C(CH3)CF2 5-H 6-NHCOC6H5 7-H 8-H XXII 36 2-SCH2CH2C(CH3)CF2 5-H 6-OCH3 7-H 8-H XXII 37 2-SCH2CH2C(CH3)CF2 5-H 6-SCH3 7-H 8-H XXII 38 2-SCH2CH2C(CH3)CF2 5-H 6-SO2CH3 7-H 8-H XXII.39 2-SCH2CH2C(CH3)CF2 5-H 6-SO2N(CH3)2 7-H 8-H XXII.40 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-Cl XXII.41 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-SCH3 8-H XXII.42 2-SOCH2CH2C(CH3)CF2 5-H 6-Br 7-H 8-H XXII.43 2- 5-H 6-Br 7-H 8-H SO2CH2CH2C(CH3)CF2 XXII.44 2-SCH2CH2C(CH3)CF2 5-H 6-CN 7-H 8-H XXII.45 2-SOCH2CH2C(CH3)CF2 5-H 6-COOCH2CH2CHCF2 7-H 8-H XXII.46 2 5-H 6-COOCH2CH2CHCF2 7-H 8-H SO2CH2CH2C(CH3)CF2 XXII.47 2-SOCH2CH2C(CH3)CF2 5-H 6-F 7-H 8-H XXII.48 2-SCH2CH2C(CH3)CF2 5-H 6-OCF3 7-H 8-H XXII.49 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-SO2NH2 8-H XXII.50 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-SO2NH2 8-H XXII.51 2-SCH2CH2C(CH3)CF2 5-H 6-OCH3 7-H 8-H XXII.52 2-SCH2CH2C(CH3)CF2 5-H 6 CONHCH3 7-H 8-H XXII.53 2-SCH2CH2C(CH3)CF2 5-H 6-SO2NHCH3 7-H 8-H XXII.54 2-SCH2CH2C(CH3)CF2 5-H 6-SO2C3H5 7-H 8-H XXII.55 2-SCH2CH2C(CH3)CF2 5-H 6-CSNH2 7-H 8-H XXII.56 2-SCH2CH2C(CH3)CF2 5-H 6-NO2 7-H 8-H XXII.57 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-NO2 XXII.58 2-SCH2CH2C(CH3)CF2 5-H -O-CH2-O- 8-H XXII.59 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-SO2F 8-H XXII.60 2-SCH2CH2C(CH3)CF2 5-OCH3 6-H 7-H 8-H XXII.61 2-SCH2CH2C(CH3)CF2 5-H 6-OCH3 7-OCH3 8-H XXII.62 2-SCH2CH2C(CH3)CF2 5-H 6-CCH 7-H 8-H XXII.63 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-SO2CH3 8-H XXII.64 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NHCOC6H5 8-H XXII.65 2-SCH2CH2C(CH3)CF2 4-Cl 6-H 7-H 8-H XXII.66 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-Br XXII.67 2-SCH2CH2C(CH3)CF2 5-H 6-SCF3 7-H 8-H XXII.68 2-SCH2CH2C(CH3)CF2 5-H 6-SOCF3 7-H 8-H XXII.69 2-SCH2CH2C(CH3)CF2 5-H 6-COCH3 7-H 8-H XXII.70 2-SCH2CH2C(CH3)CF2 5-H 6-SCH2CH2CH3 7-H 8-H XXII.71 2-SCH2CH2C(CH3)CF2 5-H 6-1 7-H 8-H Examples of compounds of Formula (XXIII) according to the present invention are set out in Table XXIII.
TABLE XXIII NO. R2 R5 R6 R7 R8 XXIII.1 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-H XXIII.2 2-SCH2CH2C(CH3)CF2 5-H 6-F 7-H 8-H XXIII.3 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NO2 8-H XXIII.4 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NH2 8-H XXIII.5 2-SCH2CH2C(CH3)CF2 5-H 6-F 7-H 8-F XXIII.6 2-SOCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-H XXIII.7 2-SCH2CH2C(CH3)CF2 5-H 7-CO2CH3 8-H XXIII.8 2-SO2CH2CH2(CH3)CF2 5-H 6-H 7-H 8-H XXIII.9 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-CH3 XXIII.10 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-CH2CH=CH2 XXIII.11 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-cC3H5 XXIII.12 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-Cl XXIII.13 2-SCH2CH2C(CH3)CF2 5-H 6-CH2CH=CH2 7-H 8-H XXIII.14 2-SCH2CH2C(CH3)CF2 5-H 6-cC3H5 7-H 8-H XXIII.15 2-SCH2CH2C(CH3)CF2 5-H 6-C6H5 7-H 8-H XXIII.16 2-SCH2CH2C(CH3)CF2 5-H 6-CH3 7-CH3 8-H XXIII.17 2-SCH2CH2C(CH3)CF2 5-H 6-Cl 7-F 8-H XXIII.18 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH3 8-NHCOCH3 XXIII.19 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH3 8-OCH3 XXIII.20 2-SCH2CH2C(CH3)CF2 5-H 6-OCH3 7-OCH3 8-H XXIII.21 2-SCH2CH2C(CH3)CF2 5-H 6-F 7-OH 8-H XXIII.22 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-CO2CH3 XXIII.23 2-SO2CH2CH2C(CH3)CF2 5-H 6-H 7-OCH3CF3 8-H XXIII.24 2-SCH2CH2C(CH3)CF2 5-H 6-CH3 7-H 8-H XXIII.25 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-CN XXIII.26 2-SCH2CH2C(CH3)CF2 5-H -CH=CH-CH=CH- 8-H XXIII.27 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-Cl 8-H XXIII.28 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-F 8-H XXIII.29 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-CH3 8-H XXIII.30 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NHCOCH3 8-H XXIII.31 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-N(SO2CH3)2 8-H XXIII.32 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OH 8-H XXIII.33 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCOCH3 8-H XXIII.34 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH3 8-H XXIII.35 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OSO2CH3 8-H XXXII.36 2-SCH2CH2C(CH3)CF2 5-H 6-SO2C2H5 7-H 8-H XXXII 37 2 SCH2CH2C(CH3)CF2 5-H 6-SO2N(C2H5)2 7-H 8-H XXIII 38 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-F XXIII.39 2-SCH2CH2C(CH3)CF2 5-CH3 6-H 7-H 8-H XXIII.40 2-SCH2CH2C(CH3)CF2 5-NH2 6-H 7-H 8-H XXIII.41 2-SCH2CH2C(CH3)CF2 5-NO2 6-H 7-H 8-H XXIII.42 2-SCH2CH2C(CH3)CF2 5-OH 6-H 7-H 8-H XXIII.43 2-SCH2CH2C(CH3)CF2 5-OCH2CH2F 6-H 7-H 8-H XXIII.44 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-COOH 8-H XXIII.45 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-NHCHO 8-H XXIII.46 2-SCH2CH2C(CH3)CF2 5-H 6-Cl 7-H 8-H XXIII.47 2-SCH2CH2C(CH3)CF2 5-H 6-CN 7-H 8-H XXIII.48 2-SCH2CH2C(CH3)CF2 5-H 6-COOH 7-H 8-H XXIII.49 2-SCH2CH2C(CH3)CF2 5-COOH 6-H 7-H 8-H XXIII.50 2-SCH2CH2C(CH3)CF2 5-NHCOC2H5 6-H 7-H 8-H XXIII.51 2-SCH2CH2C(CH3)CF2 5-NHSO2CH3 6-H 7-H 8-H XXIII.52 2-SCH2CH2C(CH3)CF2 5-OCOC2H5 6-H 7-H 8-H XXIII.53 2-SCH2CH2C(CH3)CF2 5-OCH2CH2CHCF2 6-H 7-H 8-H XXIII.54 2-SCH2CH2C(CH3)CF2 5-OCH3 6-H 7-H 8-H XXIII.55 2-SCH2CH2C(CH3)CF2 5-H 6-NH2 7-H 8-H XXIII.56 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH2CCl=CH2 8-H XXIII.57 2-SCH2CH2C(CH3)CF2 5-H 6-OCH2CH=OCl2 7-H 8-H XXIII.58 2-SCH2CH2C(CH3)CF2 5-H 6-OCH2CO2C2H5 7-H 8-H XXIII.59 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-CN 8-H XXIII.60 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-CONH2 8-H XXIII.61 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-CON(CH3)C2H5 8-H XXIII.62 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH2CH2F 8 H XXIII.63 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH2CH2CH3 8-H XXIII.64 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-OCH(CH3)C2H5 8-H XXIII.65 2-SCH2CH2C(CH3)CF2 5-H 6-SCH3 7-H 8-H XXIII.66 2-SCH2CH2C(CH3)CF2 5-H 6-H 7-H 8-NO2 XXIII.67 2-SCH2CH2C(CH3)CF2 5-H 6-NO2 7-H 8-NO2 XXIII.68 2-SCH2CH2C(CH3)CF2 5-H 6-CF3 7-H 8-H XXIII.69 2-SCH2CH2C(CH3)CF2 5-H 6-NO2 7-H 8-H XXIII.70 2-SCH2CH2C(CH3)CF2 5-H 6-CO2CH2CH2CHCF2 7-H 8-H XXIII.71 2-SCH2CH2C(CH3)CF2 5-NHCOCF3 6-H 7-H 8-H Examples of compounds of Formula (XXIV) according to the present invention are set out in Table XXIV.
TABLE XXIV COMPOUND R4 R5 R6 R2 XXIV.1 4-H 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.2 4-H 5-H 6-H 2-S(O)CH2CH2C(CH3)=CF2 XXIV.3 4-CF3 5-H 6-OCH3 2-SCH2CH2C(CH3)=CF2 XXIV.4 4-C6H5 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.5 4-SCH2CH2C(CH3)=CF2 5-H 6-H 2-H XXIV.6 4-OC2H5 5-CH3 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.7 4-OCH3 5-H 6-n-C3H7 2-SCH2CH2C(CH3)=CF2 XXIV.8 4-OC5H11 5-H 6-H 2-S(O)2CH2CH2C(CH3)=CF2 XXIV.9 4-OC4H9 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.10 4-OCH2CH=CHCH3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.11 4-OH 5-H 6-n=C3H@ 2-SCH2CH2C(CH3)=CF2 XXIV 12 4-CF3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV 13 4-SCH2CH2C(CH3)=CF2 5-H 6-OCH2CF3 2-H XXIV.14 4-CH3 5-H 6-OCH2CH3 2-SCH2CH2C(CH3)=CF2 XXIV.15 4-Cl 5-H 6-n-C3H7 2-SCH2CH2C(CH3)=CF2 XXIV.16 4-OCH2C6H5 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.17 4-OCH2CO2CH3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.18 4-n-C3H7 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.19 4-OCH2(4-Cl-C6H4) 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.20 4-OCH2CO2H 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.21 4-OCH2CF3 5-H 6-CH(CH3)2 2-SCH2CH2C(CH3)=CF2 XXIV.22 4-Cl 5-H 6-CH(CH3)2 2-SCH2CH2C(CH3)=CF2 XXIV.23 4-O(CH2)2CO2CH3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.24 4-COH3 5-H 6-CH(CH3)2 2-SCH2CH2C(CH3)=CF2 XXIV.25 4-CH(CH3)2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.26 4-SCH2CH2C(CH3)=CF2 5-H 6-CH3 2-C6H5 XXIV.27 4-SCH2CH2C(CH3)=CF3 5-H 6-H 2-CH3 XXIV.28 4-OCH3 -----(CH2)4----- 2-SCH2CH2C(CH3)=CF2 XXIV.29 4-CH3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.30 4-CH3 5-H 6-H 6-H 2-S(O)CH2CH2C(CH3)=CF2 XXIV.31 4-H 5-C(CH3)3 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.32 4-H 5-CF3 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.33 4 H 5-CH(CH3)2 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.34 4-H 5-Cl 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.35 4-H 5-C6H5 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.36 4-SCH2CH2CH=CF2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.37 4-OCH2CH2CH=CF2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.38 4-H -----(CH2)3----- 2-SCH2CH2C(CH3)=CF2 XXIV.39 4-CH3 5 CH3 6-CH3 2-SCH2CH2C(CH3)=CF2 XXIV.40 4-SCH2CH2CH=CF2 5-CH3 6-SCH2CH2C(CH3)=CF2 2-H XXIV.41 4-C#CH 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.42 4-CN 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.43 4-(4 F-C6H4) 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.44 4-(3-F-C6H4) 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.45 4-(4-F3-C6H4CH2) 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.46 4-@C3H5 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.47 4-(1-CH3-@C3H5) 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.48 4-CH2CF3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.49 4-OCH2CF3 5-H 6-Cl 2-SCH2CH2C(CH3)=CF2 XXIV.50 4-CH2OCH3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.51 4-Cl 5-H 6-Cl 2-SCH2CH2C(CH3)=CF2 XXIV.52 4-SCH2CH2C(CH3)=CF2 5-H 6-OCH2CH2CH=CF2 2-H XXIV.53 4-F 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.54 4-SCH3 5-H 6-F 2-SCH2CH2C(CH3)=CF2 XXIV.55 4-C(CH3)3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.56 4-C(CH3)3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.57 4-H --CH==CH--CH==CH-- 2-SCH2CH2C(CH3)=CF2 XXIV.58 4-H --CH==CH--CH==CH-- 2-S(O)CH2CH2C(CH3)=CF2 XXIV.59 4 H --CH==CH--CH==CH-- 2-S(O)2CH2CH2(CH3)=CF2 XXIV.60 4-OH --CH==CH--CH==CH-- 2-SCH2CH2C(CH3)=CF2 XXIV.61 4-CF2CF3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.62 4-CH(OCH3)2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.63 4-Cl 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.64 4-NH2 5-NH2 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.65 4-OCH2CF3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.66 4-OCH2CF3 5-H 6-H 2-S(O)CH2CH2C(CH3)=CF2 XXIV.67 4-OCH2CH=CH2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.68 4-OCH2CH2CH=CF2 5-H 6-CF3 2-SCH2CH2C(CH3)=CF2 XXIV.69 4-OC2H5 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.70 4-OH 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.71 4-OH 5-CH3 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.72 4-OH 5-H 6-CF3 2-SCH2CH2C(CH3)=CF2 XXIV.73 4-OCH(CH3)2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.74 4-OCH6H5 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.75 4-C6H5 5-H 6-OC2H5 2-SCH2CH2C(CH3)=CF2 XXIV.76 4-(3-CF3-C6H@) 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.77 4-(4-NO2-C6H4) 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.78 4-SCH2CH2C(CH3)=CF2 5-H 6-SCH3 2-H XXIV.79 4-CH=CF2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.80 4-CHO 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.81 4-CONH2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.82 4-COOH 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.83 4-COOCH3 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.84 4-H 5-NO2 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.85 4-H 5-SCH2CH2C(CH3)=CF2 6-H 2-H XXIV.86 4-CH3 5-CH2C6H5 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.87 4-CH3 5-COC6H5 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.88 4-OCH2CCl=CH2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.89 4-OCH2CH=CCl2 5-H 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.90 4-C6H5 5-CO2C2H5 6-H 2-SCH2CH2C(CH3)=CF2 XXIV.91 4 H 5-H 6-H 2-SO2CH2CHC(CH3)CF2 indicates a cyclic substituent The compounds of formula (I) wherein n is 0 may be prepared by a variety of methods.
Compounds of Formula (I) may be prepared by dehydrobromination of the corresponding compound of Formula (XXV):
for example by treatment of the compound of Formula (XXV) with a base such as an alkali metal hydroxide, for example potassium or sodium hydroxide, in the presence of an inert solvent, for example dimethylformamide.Compounds of Formula (XXV) may be prepared from the corresponding thiol compound of Formula (XXVI): R SH (XXVI) by reaction of the compound of Formula (XXVI) with a compound of Formula (XXVII):
wherein L is a readily displaceable leaving group such as iodo, bromo, methanesulphonyloxy and especially para-toluenesulphonyloxy, under conditions well known in the art for such displacement reactions, for example in the presence of a mild base such as an alkali metal carbonate, for example potassium or sodium carbonate, in an inert solvent. at a temperature in the range from 0 "C to 200 "C. preferably 40 C to 100 "C, and most conveniently at the reflux temperature of a suitable inert solvent such as acetone which has a boiling point within this range.
Compounds of Formula (XXVII) may be prepared by the following sequence of reactions. Crotonic acid (CH.CH=CHCO2H, commerciallv available) is reacted with dibromodifluoromethane (CF2Br2) under the conditions described by Rong and Keese in Tetrahedon Letters, 1990. page 5616, in the presence of acetonitrile, water, sodium dithionite (Na.S OJ) and sodium bicarbonate, to give the compound of Formula XXVIII):
The compound of Formula (XXIX)::
is then prepared by reduction of the compound of Formula (XXVIII) under conditions well known in the art for the reduction of an acid group to a primary alcohol, for example using lithium aluminium hydride in the presence of an inert solvent such as tetrahydrofuran.
Compounds of Formula (XXVII) may then be prepared from the compound of Formula (XXIX) by standard methods for the conversion of a primary hydroxyl group to a displaceable leaving group. In the case of compounds of Formula (XXVII) where L is methanesulphonyloxy or paratoluenesulphonyloxy, the compound of Formula (XXIX) may be reacted with methanesulphonyl chloride or para-toluenesulphonyl chloride. In the case of the compound of Formula (XXVII) where L is iodo or bromo, the compound of Formula (XXIX) may be reacted with an alkali metal iodide or bromide, for example sodium or potassium iodide or bromide, under acidic conditions.
It will be appreciated by those skilled in the art that compounds of Formula (XXVI) may exist in tautomeric equilibrium between the equivalent mercapto and thione forms. For the sake of convenience, these compounds are referred to herein in their mercapto form unless otherwise stated.
Compounds of Formula (XXVI) are commercially available or may be prepared from commercially available precursors by standard procedures well known in the art. For example, typical procedures suitable for the preparation of many of the relevant compounds of Formula (XXVI) where R is (XXII) or (XXIII) and their precursors may be found in the following standard references: Comprehensive Heterocyclic Chemistry (Publishes by Pergamon. Edited by Katritzky and Rees), 1984, e.g. pages 177-331; Journal of Organic Chemistry, 19 758-766 ( 1954); Heterocyclic Compounds (Published by Wiley, Edited by Elderfield)* Volume S; Organic Compounds of Sulphur. Selenium and Tellurium (Published bv The Chemical Society Specialist Reports), Volumes 3.4 and 5: Warburton et al.Chemical Reviews, 57, 1011-1020 (1957). By wav of example, many of the compounds of formula (XXVI), where R is (XXIII) may be prepared by reacting a correspondingly substituted 2-aminophenol or a salt thereof, with thiophosgene, in an inert solvent such as diethyl ether or chloroform, and optionally in the presence of a base, such as potassium carbonate, and/or water.Also by way of example, many of the compounds of formula (XXVI) where R is (XXII) may be prepared by the Herz Reaction (Warburton et al, Chemical Reviews, 57 1011-1020(1957)) in which appropriately substituted anilines are reacted sequentially with disulphur dichloride and aqueous sodium hydroxide to product the corresponding 2-mercapto aniline derivative, which is then reacted with carbon disulphide to produce the 2-mercaptobenzthiazole of formula (XXVI).Benzthiazoles of formula (XXVI) may also be prepared from appropriately substituted N-phenylthioureas by oxidation (for example in the presence of molecular bromine) and replacement of the amino group of the resulting 2-aminobenzthiazole with a 2-mercapto group by reaction with a base and carbon disulphide or by diazotisation, reaction with a halide and displacement of the 2-halo group using NaSH. N-phenylthioureas are available by reaction of the corresponding anilines with ammonium thiocyanate.Compounds of Formula (XXVI) may also be prepared by reaction of the correspondingly substituted 2-halonitrobenzene by reaction with sodium sulphide, sulphur (Ss), and carbon disulphide, or by reaction of the correspondingly substituted phenyl isothiocyanate with sulphur (S8) to produce the corresponding 2-keto benzthiazole which may be readily converted to the corresponding 2-mercaptobenzthiazole of Formula (XXVI). All of these reactions are well documented in the chemical literature. The choice of the appropriate procedure will depend upon the particular nuclear substitution pattern required and is within the normal skill of the art. Typical examples are provided in the experimental examples.
Alternatively, the compounds of formula (I) may be prepared by reacting a corresponding compound of formula (XXX): R L (XXX) here L is again a good leaving group, with a mercapto compound of formula (XXXI):
under conditions well known In the art for such displacement reactions. with subsequent dehydrobrnmintion. Preferably, L is halogen or a nitro group. Conveniently the reaction may be carried out using a two phase solvent system, such as water/dichloromethane, in the presence of a phase transfer catalyst, for example tetra-n-butyl ammonium bromide. at ambient temperature under a nitrogen atmosphere.
The mercapto compound of formula (XXXI) is conveniently reacted in the form of its S-acetyl or its isothiouronium hydrogen bromide salt, which compounds are readily hydrolysed to the mercapto compound of formula (XXXI).
The compounds of formula (I) where n is 1 or 2, may be prepared by oxidising the correspondingly substituted compound of formula (I) when n is 0, using conventional methods, for example by treatment with a suitable oxidising agent in an inert organic solvent. In general, oxidation of a compound of Formula (I) with one equivalent of a suitable oxidising agent provides the corresponding compound wherein n is 1, and oxidation using two equivalents of the oxidising agent provides the corresponding compound wherein n is 2. Suitable oxididising agents include organic and inorganic peroxides such as peroxy carboxylic acids. or their salts, for example, meta-chloroperbenzoic acid, perbenzoic acid, magnesium monoperoxy-phthalic acid or potassium peroxymono-sulfate.
Thus, according to a further aspect of the present invention there is provided a process for the preparation of compounds of formula (I) where n is 1 or 2, which comprises oxidation of the correspondingly substituted compound of formula (I) when n is 0.
As well as the compounds of formula (I) being prepared from the corresponding substituted compounds, it will be appreciated that subsequent functional group transformations may be carried out using known chemistry to obtain the required ring substitution. Examples of such functional group transformations include the reduction of nitro groups to amine groups, halogenation, e.g. chlorination, hydrolysis of an ester to the acid, oxidation of an alcohol to the acid, salt formation.
Various further preferred features and embodiments of the present invention will now be described in futher detail with reference to the following illustrative examples in which percentages are by weight and the following abbreviations are used: mp = melting point: bp = boiling point: g = grammes; gc = gas chromatography; NMR = nuclear magnetic resonance; s = singlet; d = doublet: dd = double doublet: t = triplet: q = quartet: m = multiplet: br = broad; M=mole; mM=millimoles: CDCl = deuteriochloroform. Chemical shifts (o) are measured in parts per million from tetramethvlsilane. CDCI; was used as solvent for NNIR spectra unless otherwise stated. M = molecular ion as determined by mass spectrometry; FAB = fast atom bombardment; tIc = thin layer chromatography.
Preparation 1 This describes the three-stage preparation of 4-bromo-4,4-difluoro-3-methylbutyl 2methylbenzenesulphonate.
Step (a) - Preparation of 4-bromo-4,4-difluoro-3-methylbutanoic acid.
Two identical reactions were set up as follows. To a solution of 2-butenoic acid (3.44g) in acetonitrile (160cm3) was added sodium dithionite (8.36g), sodium bicarbonate (4. 15g), water (40cm3), and finally dibromodifluoromethane ( lOcm3). The reaction mixture, which consisted of a biphasic solution containing solid inorganic salts, was stirred at room temperature for 4 hours after which the solid had dissolved and gc analysis indicated complete reaction. The combined reaction mixture from the two reactions was saturated with solid sodium chloride and the two phases separated. The organic phase was dried over MgSO4, filtered and evaporated under reduced pressure to give a pale yellow oil.This oil was taken up in ethyl acetate and filtered through silica to remove inorganic salts, leaving a bright yellow solution which was dried with MgSO4 and evaporated as before to give 4-bromo-4,4-difluoro-3-methylbutanoic acid as a yellow oil (13.12g). 'H NMR (CDCI3) 6 (ppm): 2.70-2.90(2H,m); 2.37(lH,brq); 1.23(3H,d).
Step (b) - Preparation of 4-bromo4.4-difluoro-3-methvlbutanol To a stirred solution of 4-bromo-4,4-difluoro-3-methylbutanoic acid (6g) in dry tetrahydrofuran (120cm3) at 0 C under nitrogen was added portionwise solid lithium aluminium hydride (1.156g), causing effervescence. The solution was stirred at 0 C for I hour and then allowed to warm to the ambient temperature, with stirring, over one hour. The reaction was quenched by the addition of water (1.2cm3), 15% weight/volume aqueous sodium hydroxide (1.2cm3) and water (3.6cm"), which left a white precipitate and a clear organic phase.The reaction mixture was filtered through Celite (Trade Mark) which was washed copiously with ethyl acetate and the filtrate was evaporated under reduced pressure to give 4-bromo-4,4-difluoro-3-methylbutanol as a pale yellow oil (4.255g). 'H NMR (CDCl3) 8 (ppm): 3.65-390(2H,t); 2.40(1H,m); 2.00(1H.m); 1.80(1H,m); 1.50(1H,m); 1.15(3H,d).
Step (c) - Preparation of 4-bromo4,4-difluoro-3-methylbutvlsulphonate To a stirred solution of 4-bromo-4.4-difluoro-3-methylbutanol (2.63g) and tosyl chloride (ptoluenesulphonyl chloride, 2.58g) in dicliloromethane (25cm?) at the ambient temperature was added triethylamine (3.85cm?) and dimethylaminopyridine (0.330g). The reaction was stirred for 45 minutes, during which time a white precipitate formed, and after which gc indicated complete consumption of tosyl chloride. The reaction mixture was partitioned between ethyl acetate and 2M HCI and the layers separated.The aqueous layer was extracted twice with ethyl acetate and the combined organic phases were washed with 2M HCI, water, brine and dried over MgSO.
Filtration and evaporation under reduced pressure gave 4-bromo-4,4-difluoro-3-methylbutyl ptolysulphonate as a pale yellow oil (4.34g). 1H NMR (CDCl3) 8 (ppm): 7.80(2H,d); 7.37(2H,d); 4.05-4.20 (2H,m); 2.45(3H,s); 2.00-2.40(2H,m); 1.60(1H,m); 1.08(3H,d).
Example 1: Preparation of 2-(4,4-difluoro-3-methvl-but-3-env!thio)-5-chlorobenzothiazole.
(Compound XÌ.28) To a solution of 4-bromo4,4-difluoro-3-methylbutyl p-methylbenzenesulfonate (O.5g) in acetone (7ml) was added 2-mercapto-5-chlorobenzothiazole (0.296g)and potassium carbonate(O.39g), which resulted in formation of a beige suspension. The reaction was heated at reflux for I hour after which ge analysis indicated complete consumption of staring material to give a single peak. The reaction was cooled and poured in to ethyl acetate and water. The layers were separarted and the aqueous layer was extracted into ethyl acetate (2x). The combined organic layers were washed with 2M HCl, water and brine.The organic layer was dried (MgSO4), filtered and evaporated under reduced pressure to give crude 2-(4-bromo-4,4-difluoro-3-methyl-butylthio)-5-chlorobenzothiazole as a brown oil (0.560g).
The above oil was then dissolved in dimethylformanide (semi) and powdered potassium hydroxide (0.800g) was added resulting in a dark brown solution. The reaction was stirred at rt and gc analysis after 45 minutes indcated complete loss of starting material. The reaction mixture was poured into ethyl acetate and 2M HCl and the layers separated. The aqueous layer was extracted with ethyl acetate (2x). The combined organic layers were washed with 2M HCI, water and brine and dried (MgSO4). The organic layer was then filtered and evaporated under reduced pressure to give a brown oil. Purification by column chromatography on silica gel using 6% diethylether in hexane as eluent gave of 2-(4,4-dinuoro-3-methyl-but-3-enylthio)-5-chlorobenzothiazole, (0.215g). 'H nmr (CDCl3) 5 1.65 (3H,t); 2.50 (2H,m); 3.40 ('H,t); 7.30 (lH,dd); 7.65 (lH,d); 7.85 (1H,d).
The iollowing compounds were prepared using the general method described above: 2-(4,4-difluoro-3-methyl-but-3-enylthio)-5-trifluoromethylbenzothiazole (Compound XXII.27). 1H nmr (CDCl3) # 1. 70 (3H,t); 2.50 (2H,m); 3.45 (2H,t); 7.55 (lH,d); 7.90 (1H,d); 8.10 (1H,bs).
(ii) 2-(4,sdi9uoro-3-methyl-but-3-enylthio)benzothiazole (Compound XXII. 1). 'H nmr (CDCI;) # 1. 70 (3H,t); 2.50 (2H,m); 3.40 (2H,t); 7.30 (lH.t); 7.40 (1H,t); 7.75 (1H,d); 7.85 (1H,d).
2-(4,4-di9uoro-3-methyl-but-3-enylthio)-6-methoxybenzoxazole (Compound XXIII.34). 'H nmr (CDCl3) # 1. 70 (3H,t); 2.50 (2H,m); 3.35 (2H,t); 3.85(3H,s); 6.89 (lH,dd); 7.00(1H,d); 7.50 (1H,d).
2-(4,4-difluoro-3-methyl-but-3-enylthio)-6-nitrobenzothiazole (Compound XXII.22). 1H nmr (CDCl3) 8 1. 70 (3H,t); 2.55 (2H.m); 3.50 (2H,t); 3.85(3H,s); 7.90 (1H,d); 8.30 (lH,dd); 8.70 (lH,d).
2-(4,4-difluoro-3-methyl-but-3-enylthio)benzoxazole (Compound XXIII.1). 1H nmr (CDCl3) # 1.70 (3H.t); 2.50 (2H,m); 3.40 (2H,t); 7.20-7.35 (2H,m); 7.45 (1H,dd); 7.60 (1H,dd).
2-(4,4-difluoro-3-methyl-but-3-enylthio)pyrimidine (Compound XXIV.1). 1H nmr (CDCl3) # 1.65 (3H,t); 2.40(2H,m); 3.20 (2H,t); 6.95 (1H, t); 8.50 (2H, d).
2-(4,4-difluoro-3-methyl-but-3-enylthio)-5-methyl-1,3,4-oxadiazole (Compound XII.49). 1H nmr (CDCl3) # 1. 60 (3H,t); 2.45-2.50 (2H,m); 2.50 (3H,s); 3.30 (2H, t).
2-(4,4-difluoro-3-methyl-but-3-enylthio)-5-phenyloxazole (Compound VI. 121). 'H nrnr (CDCl3) 6 1.
60 (3H,t); 2.45-2.55 (2H,m); 3.40 (2H, t); 7.30 (lH,s); 7.30 (lH,t); 7.40 (2H,t); 7.60 (2H,d).
2-(4,4-difluoro-3-methyl-but-3-enylthio)-5-phenyl-1,3,4-oxadiazole (Compound XII.3). 1H nmr (CDCl3) # 1. 65 (3H,t); 2.50-2.60 (2H,m); 3.30-3.40 (2H, t); 7.95-8.05 (2H,m); 7.45-7.60 (3H,m).
2-(4,4-difluoro-3-methyl-but-3-enylthio)thiazole (Compound VII.1). 1H nmr (CDCl3) # 1.65 (3H,t); 2.40-2.50 (2H,m); 3.30 (2H, t); 7.25 (1H,d); 7.70 (1H,m).
The following compounds were made according to the procedure outlined above but were not purified prior to oxidation in Examples (3.1. 3.11. 3.111 and 3.IV (via Example 2); 2-(4,4-difluoro-3-methyl-but-3-enylthio)-5-cyclopropyl-1,3,4-thiadiazole (Compound XIII.6). 1H nmr (CDCl3) # 1.60 (3H,t);1.10-1.15 (2H,m); 1.15-1.25 (2H,m); 2.40-2.50 (2H,m); 2.30 (1H,m); 40 (2H. t).
2-(4,4-difluoro-3-methyl-but-3-enylthio)pyridine (Compound XVI. 19). 'H nmr (CDCl3) # 1. 60 (3H,t); 2.35-2.40(2H,m); 3.25 (2H,t); 7.00 (lH,dt); 7.20 (1H, d); 7.50 (lH,dt); 8.40-8.45 (lH,m).
2-(4,4-difluoro-3-methyl-but-3-enylthio)imidazole (Compound VIII.1). 1H nmr (CDCl3) # 1.65 (3H,t); 2.40-2.50 (2H,m); 3.30 (2H, t); 7.25 (1H,d); 7.70 (lH,m).
4-(4,4-difluoro-3-methyl-but-3-enylthio)pyridine (Compound XVI.S). 'H nmr (CDCl3) 6 1. 65 (3H.t); 2.40-2.50 (2H,m); 3.30 (2H, t); 7.25 (1H,d); 7.70 (1H,m).
Example 2 - Preparation of 2-(4,4-difluoro-3-methyl-but-3-enylthio)-1-propylimidazole. (Compound VIII.153 To a solution of 2-(4,4-difluoro-3-methyl-but-3-enylthio)imidazole(0.220g) in dimethylformamaide (5ml) was added sodium hydride (0.038g of an 80% suspension in oil) and the reaction was stirred at rt for 30 minutes. Propyl iodide (0.200g) was added and the reaction stirred at rt for 1 hour after which ge analysis indicated complete reaction. The reaction was poured into ethylacetate and water and the layers separated. The aqueous layer was extracted with ethyl acetate (2x). The combined organic fractions were washed alternately with water and brine (3x) and dried (MgS04). Filtration and evaporation under reduced pressure gave a yellow oil.
This material was carried forward to the oxidation step (Example 3.IV) without purification Example 3 - Preparation of 2-(4,4-difluoro-3-methyl-but-3-enylsulfonyl)pyrimidine, (Compound XXIV.91) To a stirred solution of 2-(4,4-difluoro-3-methyl-but-3-enylthio)pyrirnidine (0.371g) in dichloromethane (15ml) at rt was added, portionwise, meta-chloroperbenzoic acid (1.244g). The reaction mixture was stirred at room temperature for 2 hours and then left to stand at rt overnight.
The reaction mixture was poured into aqueous sodium bicarbonate and extracted with dichloromethane. The combined organic layers were then dried (MgSO4), filtered and evaporated under reduced pressure to give a yellow oil which crystallised on standing. The solid was triturated with hexane to give 2-(4,4-difluoro-3-methyl-but-3-envlsulfonvl)pyrimidine, (compound XXlV.9) ) as a yellow solid (0.309g). 'H nmr (CDCl3) 8 1. 60 (3H.t); 2.50-2.60 (2H,m); 3.60-3.70 (2H,t); 7.60 (1 H.
t); 9.00 (2H. d).
The following compounds were made using the method described above and using the appropriate unoxidised starting materials: (I) r-(4,4-difluoro-3-methvl-but-3-enylsulfonyl)pyndine (Compound XV1.20). 'H nmr (CDCl?,) 8 1. 55 (3H.t); 2.40-2.50(2H,m); 3.45-3.50 (2H,m); 7.60 (1H,dt); 7.80 (1H. dt); 8.10 (1H,d); 8.80 (1H,dd).
(II) 2-(4,4-difluoro-3-methyl-but-3-enylsulfonyl)-5-cyclopropyl-1,3,4-thiadiazole (Compound XIII.7). 'H nmr (CDCl3) # 1. 60 (3H,t);1.25-1.30 (2H,m); 1.30-1.45 (2H,m); 2.45-2.50 (lH,m); 2.50-2.60 (2H,m); 3.60-3.65 (2H, t).
(III) 4-(4,4-difluoro-3-methyl-but-3-enylsulfonyl)pyridlne (Compound XVI. 6). 'H nmr (CDCl3) 6 1. 60 (3H,t); 2.45 (2H,m); 3.20 (2H,t); 7.80 (2H,m); 8.30 (2H, m).
(IV) 2-(4,4-difluoro-3-methyl-but-3-enylsulfonyl)-1-propylimidazole (Compound VIII.155). 1H nmr (CDCl3) # 0.95 (3H,t); 1.60 (3H,t); 1.90 (2H,m); 2.50 (2H,m); 3.60 (2H,m); 4.30 (2H,dd); 7.05 (lH.s); 7.20 (1H, s)..
Example 4 - Preparation of 2-(4,4-difluoro-3-methyl-but-3-enylthio)-5-chlorothiazole. (Compound VII.24).
To a solution of 2-(4,4-difluoro-3-methyl-but-3-enylthio)thiazole (0.8g) in carbon tetrachloride (25ml) was added N-chlorosuccinirnide (0.575g) and the reaction was heated to reflux for 3 hours and then allowed to cool. The reaction was filtered and the residue washed with carbon tetrachloride. The filtrate was evaporated under reduced pressure to give a yellow oil. Purification by column chromatography on silica gel using 5% diethylether in hexane gave 2-(4,4-difluoro-3-methyl-but-3enylthio)-5-chlorothiazole. compound VII.24, as an oil (0.35g). 'H nmr (CDCl3) 6 1. 65 (3H.t); 2.40 (2H.m); 3.25 (2H, t); 7.43(1H,s).
Example 5 - Preparation of gave 2-(4,4-difluoro-3-methyl-but-3-enylsulfonyl )-5-chlorothiazole (Compound VII.26).
To a solution of 2-(4,4-difluoro-3-methyl-but-3-enythio)-5-chlorothiazole (0.128g) in methanol (5ml), cooled in a methanol ice bath. was added magnesium monoperoxyphthalate (MMPP) (0.556g). After stirring for 1.5 hours tl@ analysis indicated no starting material present. but some suffoxide still remaining. A funher 0. ig of MMPP was added and the reaction stirred for a further 1 hour after which tlc analysis indicated complete reaction. The reaction was flooded with diethylether and the white ppt filtered off and washed with diethylether. The diethylether filtrate was then washed with water and brine and dried (MgSO4).Filtration and evaporation under reduced pressure gave a soild which was repeatedly washed with chloroform. The chloroform washings were evaporated under reduced pressure to give an oil. Purification by column chromatography on silica gel using a gradient of 10% by 15% diethylether in hexane gave 2-(4,4-difluoro-3-methyl-but-3-enylsulfonyl)-5- chlorothiazole, compound VI1.26, as an oil (0.04g). 'H nmr (CDCI3) d 1. 60 (3H,t); 2.50-2.55 (2H,m); 3.40-3.50 (2H, m); 7.85 (1H,s).
The compounds of formula (I) are nematicidal and can be used to control nematodes in plants. Thus, in a further aspect of the present invention, there is provided a method of killing or controlling nematodes, which comprises applying a compound of formula (I) to the nematode.
The term "controlling" extends to non-lethal effects which result in the prevention of damage to the host plant and the limitation of nematode population increase. The effects may be the result of chemical induced disorientation, immobilisation, or hatch prevention or induction.
The chemical treatment may also have deleterious effects on nematode development or reproduction.
The compounds of the present invention can be used against both plant parasitic nematodes and nematodes living freely in the soil.
Examples of plant-parasitic nematodes are: ectoparasites, for example, Xiphinema spp., Longidorus spp., and Trichodorus spp.; semi-parasites, for example, Tvlenchulus spp.; migratory endoparasites, for example. Pratylenchus spp., Radopholus spp. and Scutellonema spp.; sedentary parasites, for example, Heterodera spp., Globodera spp. and Meloidogyne spp.; and stem and leaf endoparasites, for example, Ditylenchus spp., Aphelenchoides spp. and Hirshmaniella spp The compounds of formula (I) also display activity against different types of nematodes including cyst nematode.
The compounds of the present invention also exhibit activity against other pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals. nursery crops, stored food and fibre products. These pests include: Heteroptera/Homoptera including Myzus persicae, Aphis gossvpii, Aphis fabae, Rhopalosiphum cadiz Aonidiella spp.. Trialeurodes spp,. Bemisia tabaci, Nilaparvata lugens, Nephotettix cincticeps, Nezara viridula. Dvsdercus suturellus, Dvsdercus fasciatus,and Lv gus lineoralis.
Diptera including Ceratitis capitata, Tipula spp., Oscinella frit, Liriomyza spp., Delia spp., and Peromva spp.
Lepidoptera including Pieris brassicae, Plutella xylostella, Spodoptera littoralis and other Spodoptera spp., Heliothis virescens and other Heliothis and Helicoverpa spp., and Chilo partellus.
Coleoptera including Phaedon cochleariae, Diabrotica spp., Agrotis spp., and Leptinotarsa decemlineata.
Blattodea including Blattella germanic, Periplaneta americana, and Blatta orientalis. Orthoptera including Chortiocetes terminifera, Schistocerca spp., Locusta spp. and Scapteriscus spp..
Acan including Panonychus ulmi, Panoychus citri, Tetranychus urticae, Tetranvchus cinnabarinus, Phyliocoptruta oleivora, and Brevipaipus spp.
The compounds can also be used against livestock, household, public and animal health pests such as: Siphonaptera including Ctenocephaiides felis. Ctenocephaiides canis, Xenopsylla cheopis, and Pulex irritans.
Mallophaga including Menopon gallinae, and Cuclotogaster heterographus.
Anoplura including Pediculus humanus capitis, Pediculus humanus humanus, and Phthirus pubis.
Diptera including Musca domestica. Aedes aegypti. Anopheles gambia, Culex quinquefasciatus, Chrysops discalis, and Tabanus nigroviflatus.
Sarcophagidae including Sarcophaga haemorrhoidalis and Wohlfahrtia magnifica.
Calliphoridae including Lucilia cuprina and Cordvlobia anthropophaga.
Oestridae including Oestrus ovis.
Generally, the compounds may be used to combat and control pests injurious to and/or associated with the transmission of diseases of man and animals. The pests which may be combated and controlled by the use of the compounds of the invention parasitic nematodes of animals, including mammals, which may be found in the gastrointestinal tract, the air passages or blood vessels of the respiratory tract and the heart, together with the associated blood vessels.
The compounds of formula (I) may be used to treat vertebrates, such as mammals (for example. man, pigs, sheep, cattle, equines. cats and dogs), birds (for example, chicken, ducks, turkeys, geese, canaries and budgerigars), and fish (for example, salmon, trout and ornamental fish).
The nematode and other pests may be killed/controlled by applying an effective amount of one or more of the compounds of the present invention to the environment of the pests, to the area to be protected, as well as directly on the pests.
In order to apply the compound to the locus of the nematode, insect or acarid pest. or to a plant susceptible to attack by the nematode, insect or acarid pest, the compound is usually formulated into a composition which includes in addition to the compound of formula (I) suitable inert diluent or carrier materials, and/or surface active agents. Thus in ;wo further aspects of the invention there is provided a nematicidal, insecticidal or acaricidal composition comprising an effective amount of a compound of formula (I) as defined herein and an inert diluent or carrier material and optionally a surface active agent.
The amount of composition generally applied for the control of nematode pests gives a rate of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 to 6 kg per hectare.
The compositions can be applied to the soil, plant, seed, or other area to be protected, to the locus of the pests, or to the habitat of the pests, in the form of dusting powders, wettable powders, granules (slow or fast release), emulsion or suspension concentrates, liquid solutions, emulsions, seed dressings, fogging/smoke formulations or controlled release compositions, such as microencapsulated granules or suspensions.
Dusting powders are formulated by mixing the active ingredient with one or more finelv divided solid carriers and/or diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers.
Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths, ground corn cobs, and the like, or on to hard core materials such as sands, silicates, mineral carbonates. sulfates, phosphates, or the like. Agents which are commonly used to aid in impregnation, binding or coating the solid carriers include aliphatic and aromatic petroleum solvents. alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones. esters, dextrins, sugars and vegetable oils. with the active ingredient. Other additives may also be included, such as emulsifying agents. wetting agents or dispersing agents.
Microencapsulated formulations (microcapsule suspensions CS) or other controlled release formulations may also be used, particularly for slow release over a period of time, and for seed treatment.
Alternatively the compositions may be in the form of liquid preparations to be used as dips, irrigation additives or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents). The compositions which ,ir-e to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients. An EC is a homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non-volatile organic solvent. An SC is a fine particle size dispersion of solid active ingredient in water.To apply the concentrates they are diluted in water and are usually applied by means of a spray to the area to be treated. For agricultural or horticultural purposes, an aqueous preparation containing between 0.0001% and 0. 1% by weight of the active ingredient (approximately equivalent to from 5-2000g/ha) is particularly useful.
Suitable liquid solvents for ECs include methyl ketone, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).
Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide. Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters of sulfuric acid, for example sodium lauryl sulfate, salts of sulfonated aromatic compounds, for example sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, or butylnaphthalene sulfonate, and a mixture of the sodium salts of diisopropyl- and triisopropylnaphthalene sulfonates.Suitable agents of the non ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol. nonyl phenol and octyl cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethvlene oxide, and the lecithins.
These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 1-85% by weight of the active ingredient or ingredients. When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.
The compounds of formula (I) may also be formulated as powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS), or microcapsule suspensions CS for use in seed treatments. The formulations can be applied to the seed by standard techniques and through conventional seed treaters. In use the compositions are applied to the nematodes, to the locus of the nematodes, to the habitat of the nematodes, or to growing plants liable to infestation by the nematodes, by any of the known means of applying pesticidal compositions, for example, by dusting, spraying, or incorporation of granules.
The compounds of the invention may be the sole active ingredient of the composition or they may be admixed with one or more additional active ingredients such as nematicides or agents which modify the behaviour of nematodes such as hatching factors, insecticides, synergists, herbicides, fungicides or plant growth regulators where appropriate.
Suitable additional active ingredients for inclusion in admixture with the compounds of the invention may be compounds which will broaden the spectrum of activity of the compounds of the invention or increase their persistence in the location of the pest. They may synergise the activity of the compound of the invention or complement the activity for example by increasing the speed of effect or overcoming repellency. Additionally multi-component mixtures of this type may help to overcome or prevent the development of resistance to individual components.
The particular additional active ingredient included will depend upon the intended utility of the mixture and the type of complementary action required. Examples of suitable insecticides include the following: a) Pyrethroids such as permethrin, esfenvalerate, deltamethrin. cyhalothrin in particular lambda-cyhalothrin, bifenthrin, fenpropathrin. cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin. tetramethrin, s-bioallethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethyl-(E)-( IR.3S)-9 R,35)-2.2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl) c clopropane carboxylate:: b) Organophosphates such as profenofos, sulprofos, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chloropyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pyrimiphos-methyl, pyrimiphos-ethyl, fenitrothion or diazinon: c) Carbamates (including aryl carbamates) such as pirimicarb, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur or oxamyl; d) Benzoyl ureas such as triflumuron, or chlorofluazuron; e) Organic tin compounds such as cyhexatin, fenbutatin oxide, azocyclotin; f) Macrolides such as avermectins or milbemycins, for example such as abamectin, ivermectin and milbemycin; g) Hormones and pheromones; h) Organochlorine compounds such as benzene hexachloride, DDT, endosulphan, chlordane or dieldrin; i) Amidines, such as chlordimeform or amitraz j) Fumigant agents; k) Nitromethylenes such as imidacloprid.
In addition to the major chemical classes of insecticide listed above, other insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture. For instance selective insecticides for particular crops, for example stemborer specific insecticides for use in rice such as cartap or buprofezin can be employed. Alternatively insecticides specific for particular insect species/stages for example ovo-larvicides such as clofentezine, flubenzimine, hexythiazox and tetradifon, motilicides such as dicofol or propargite, general acaricides such as bromopropylate, chlorobenzilate, or growth regulators such as hydramethylnon, cyromazine, methoprene, chlorfluazuron and diflubenzuron may also be included in the compositions.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamax, safroxan and dodecyl imidazole.
Suitable herbicides. fungicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicides which can be included is propanil, an example of a plant growth regulator for use in cotton is "Pix", and examples of fungicides for use in rice include blasticides such as blasticidin-S. The ratio of the compound of the invention to the other active ingredient in the composition will depend upon a number of factors including type of target, effect required from the mixture etc. However in general the additional active ingredient of the composition will be applied at about the rate as it is usually employed, or at a slightly lower rate if synergism occurs.
EXAMPLE 6 In order to illustrate the nematicidal properties of the compounds of formula (I), the in vitro activity of compounds according to the invention against the root-know nematode, Meloidogyne incognita, was evaluated by placing an aqueous suspension of freshly hatched (024 hours old), second stage juveniles into a solution of candidate nematicide over a series of test rates. Test Chemicals were diluted to double the rate required in 1% of a mixture of ethanol and acetone (1:1) and 99% deionised water. 0.5 cm3 of chemical solution was then mixed with 0.5 cm 3 of the nematode suspension (at 200 nematodes/cm3) in a glass vial. Each chemical was evaluated in a series of treatments over a range of application rates of 1.65-0.02 ppm (parts per million). Each treatment was replicated twice.The vials were capped and left for 72 hours in a constant environment room at 23"C. The numbers of dead and line nematodes were assessed visually for each treatment using a stereomicroscope. Results are express in Table A in terms of the observed mortality at the given application rate of the test chemical (meaned over the replicate treatments). Where appropriate, the results for a test chemical were statistically analysed to generate LC 50 and LC 90 values (the concentration of test chemical causing 50% and 90% mortality respectively).
TABLE A Compound No Mortality Rate LC50 LC90 (%) (ppm) (ppm) (ppm) XXIV. I 90.1 1.65 XXIV. 1 77.7 0.55 XXIV.I 27.8 0.185 0.34 1.13 XXIV. I 5.1 0.06 XXIV . I 2.8 0.02 XXII. I 96.9 1.65 XXII. 1 94.7 0.55 XXII. 1 92.9 0.185 0.013 0.156 XXII. 1 89.6 0.06 XXII. 1 54.2 0.02 EXAMPLE 7 This example demonstrates granules suitable for soil application. The granules can be made by standard techniques such as impregnation, coating, extrusion or agglomeration.
%wlw Impregnated granule : Active ingredient 5 Wood Rosin 2.5 Gypsum granules 92.5 (2040 mesh) Coated granule : Active ingredient 0.5 Solvesso'* 200 0.4 Calcium carbonate granules 99. 1 (30-60 mesh) Slow release granule: Active ingredient 10 Polyvinylacetate/vinyl 5 chloride copolymer latex Attapulgus granules 85 EXAMPLE 8 This Example demonstrates formulations for use as a spray. The compounds can be formulated as wettable powders, water dispersible granules, suspension concentrates, emulsifiable concentrates, emulsions or microcapsule suspensions for application diluted in water.
g/l Emulsifiable concentrate: Active ingredient 250 Calcium dodecyl- 50 benzene sulfonate Nonyl phenol ethoxylate 50 Alkylberizene solvent to I litre CTow/w Wettable powder Liquid active ingredient 40 lignosulfonate dispersant 5 silica 25 sodium lauryl sulfate 3 china clay (kaolin) 27 Microcapsule suspension: Liquid active ingredient 250 toluene diisocyanate 10 polymethylene polyphenyl 20 isocyanate nonyl phenol ethoxylate 6 lignosulfonate dispersant 15 xanthan gum bentonite 10 biocide 'Proxel'* 0.1 sodium carbonate 5 water to 1 litre The microcapsule suspensions can be used as a spray, soil drench or as an intermediate to prepare slow release granules for application to the soil.
Suspension concentrate: Solid active ingredient 400 lignosulfonate dispersant 50 sodium lauryl sulfate 30 xanthan gum biocide 'Proxel'* 0.1 bentonite 10 water to I litre EXAMPLE 9 This Example demonstrates formulations suitable for use as seed treatments in conventional application machinery.
%w/w Dry seed treatment Active ingredient 20 dodecyl benzene 3 Rubine Toner (dyestuff) 2.7 Talc 53.3 Silica to 100% The suspension concentrate and microcapsule suspension of Example 10 can be used as flowable concentrates for seed treatment.
EXAMPLE 10 This Example demonstrates the formulation of the compounds for electrostatic spraying.
Active ingredient 200 N-methylpyrrolidone 50 Soyabean oil 120 Solvesso'* 200 to 1 litre EXAMPLE 11 This Example demonstrates a formulation suitable for use as a bait.
%w/w Active ingredient 0.25 Icing sugar 99.65 Butylated hydroxy toluene 0.10 EXAMPLE 12 This Example demonstrates a formulation suitable for use as a bolus.
mg Active ingredient 1300 Sodium starch glycollate 300 Microcrystalline cellulose 1200 Lactose 2920 Povidone 250 Magnesium stearate 30 EXAMPLE 13 This Example demonstrates a formulation suitable for use as an injectable suspension.
mg Active ingredient 40 Sodium metabisulfite Polysorbate 80 1 Sodium methyl hydroxybenzoate 2 Water to lml EXAMPLE 14 This Example demonstrates a formulation suitable for use as an injectable solution.
mg Active ingredient 20 Sodium citrate 6 Citric acid Sodium chloride 7 Chlorcresol Water to lml EXAMPLE 15 This Example demonstrates a formulation suitable for use as an oral suspension.
g Active ingredient 100.0 Polysorbate 80 2.0 Xanthan gum 5.0 Colloidal silicon dioxide 10.0 Methyl hydroxybenzoate 1.5 Citric acid monohydrate 10.0 Sodium citrate 10.0 Purified water to lOOO.Oml

Claims (1)

  1. Claims 1. A compound of formula (I), R-S(O)nCH2CH2C(CH3)=CF2 or a salt thereof, wherein n is 0 1 or 2; and R is a group of formula (II) to (XXIV), wherein:
    the S(O)nCH2CH2C(CH3)=CF2 group is at least one of R1 (when attached to a carbon atom), R2, R3, R4. RS. R6, R7 or R8: R1 (when attached to a carbon atom), R2. R3. R4. RS. R6, R7 and R8 are each independently hydrogen. optionally substituted alkyl. optionally substituted alkenyl.
    alkynyl, cycloalkyl, alkylcycloalkyl, alkoxy, alkenyloxy, alkynyloxy, hydroxyalkyl, alkoxyalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxy, optionally substituted heteroarylalkoxy. optionally substituted heteroaryloxyalkyl, haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, haloalkenyloxy, haloalkynyloxy, halogen, hydroxy, cyano, nitro -NR9R 10, -NR9COR 10, -NR9CSR 10, -NR9SO2R 10, -N(S02R9)(S02R 10), -COR9, -CONR9R 10, -alkylCONR9R 10, CR9NR10, -COOR9, -OCOR9, -SR9, -SOR9, -S02R9, -alkylSR9, -alkylSOR9, alkylS02R9, -OS02R9, -SO2NR9R10, -CSNR9R 10, -SiR9R1OR1O, -OCH2C02R9, -OCH2CH2CO2R9, -CONR9SO2R10, -alkylCONR9SO2R10, -NHCONR9R10, -NHCSNR9R1O, or an adjacent pair of R1, R2, R3, R4, R5, R6, R7 and R8 when taken together form a fused 5- or 6-membered carbocyclic or heterocyclic ring;; R1 (when attached to a nitrogen atom) is hydrogen, optionally substituted alkyl, cycloalkyl, alkylcycloalkyl, hydroxyalkyl, alkoxyalkyl, optionally substituted aryl, optionally substituted arylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryl, optionally substituted heteroarylalkyl, optionally substituted heteroaryloxyalkyl, haloalkyl, hydroxy, cyano, nitro, -NR9R10, -NR9COR10, NR9CSR 10, -NR9COOR 10, -NR9S02R 10, -N(S02R9)(S02R10), -COR9, CONR9R10, -alkylCONR9R10, -CR9NR10, -COOR9, -OCOR9, -SOR9, -SO2R9, alkylSR9, -alkylSOR9, -alkylS02R9, -OS02R9, -SO'NR9NR 10, -SR9, -SOR9, S02R9, -CSNR9R 10, -SiR9R10R9, -OCH2C02R9, -OCH2CH2C02R9, -CONR9SO2R10, -alkylCONR9SO2R10, -NHCOR9R10, or -NHCSR9R10; and R9, R10 and R11 are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl. alkynyl, optionally substituted aryl. optionally substituted arylalkyl. haloalkyl. haloalkenyl. haloalkynyl halogen. or hydroxy.
    2. A compound according to claim 1. wherein: Ri (when attached to a carbon atom) to R8 are each independently hydrogen; nitro; halogen; cyano; -CH=NOH; CiA alkyl; ClA haloalkyl; C1-4 alkenyl: C1-4 haloalkenyl; cyclopropyl; hydroxy; C1-4 alkoxy; C2-4 alkoxyalkyl; -COOH; C2-4 alkoxycarbonyl; C2-4 haloalkenyloxycarbonyl; -CONH2; mono or di-C1-2 alkylaminocarbonyl; C'-4 alkanecarbonyl; -CONHSO2 ClA alkyl.
    preferably -CONHS02CH3; phenyl optionally mono- or di- substituted with groups independently chosen from halogen, nitro, C1-4 alkyl, C14 alkoxy or aminosulfonyl; benzyl optionally mono- or di- substituted with groups independently chosen from halogen, nitro, C14 alkyl or C14 alkoxy; phenoxy optionally mono- or di- substituted with groups independently chosen from halogen, cyano, C 1-4 alkyl or C 14 alkoxy; amino optionally mono- or di- substituted with C1-4 alkyl groups; -SH; C14 alkylthio; benzylthio optionally mono- or di- substituted with groups independently chosen from halogen or C1-4 haloalkyl; C14 alkenylthio; C24 haloalkenylthio; a second S(O)nCH2CH2CH=CF2 group;C14 alkanesulfonyl; C14 haloalkanesulfonyl; fluorosulfonyl; mono- or di- C1-4 alkylsulfamoyl; a 5 or 6 membered heteroaryl group, for example, furyl, pyrazinyl, pyridinyl or thienyl, optionally substituted with halogen; or any adjacent pair forms a fused 5- or 6- carbocyclic or heterocyclic ring; and R1 (when attached to a nitrogen atom) is hydrogen; nitro; cyano; -CH=NOH; C14 alkyl; C14 haloalkyl; cyclopropyl; hydroxy; -COOH; C2-4 alkoxycarbonyl;C2-4 haloalkenyloxycarbonyl; -CONH2; mono or di-Cl-2 alkylaminocarbonyl; C2-4 alkanecarbonyl; -CONHS02 C1-4 alkyl, preferably -CONHS02CH3; phenyl optionally mono- or di- substituted with groups independently chosen from halogen, nitro, C1-4 alkyl, C14 alkoxy or aminosulfonyl; benzyl optionally mono- or di- substituted with groups independently chosen from halogen, nitro, C1-4 alkyl or C1-4 alkoxy; phenoxy optionally mono- or di- substituted with groups independently chosen from halogen, cyano, C1-4 alkyl or C14 alkoxy; amino optionally mono- or di- substituted with C1-4 alkyl groups; -SH; C14 alkylthio; benzylthio optionally mono- or di- substituted with groups independently chosen from halogen or C1-4 haloalkyl; CIA alkenylthio; C2A haloalkenylthio; a second S(O)nCH2CH2C(CH3)=CF2. group; C 1-4 alkanesulfonvl; C 1-4 haloalkanesulfonyl; fluorosulfonyl; mono- or di- C14 alkylsulfamoyl; a 5 or 6 membered heteroaryl group, for example, furyl, pyrazinyl, pyridinyl or thienyl, optionally substituted with halogen.
    A . A process for the preparation of a compound of either of claims 1 and 2, where n is 0.
    comprising reacting a compound of formula (XXVI) R-SH (XXVI) with a compound of formula (XXVII)
    where R is as defined in claims 1 and 2, and L is a good leaving group, and then conducting a dehydrobromination step.
    4. A process for the preparation of a compound of either of claims 1 and 2, where n is 0.
    comprising reacting a compound of formula (XXX) R-L (XXX) with a compound of formula (XXXI)
    where R is as defined in claims 1 and 2, and L is a good leaving group, and then conducting a dehydrobromination step.
    5. A process for the preparation of a compound of either of claims 1 and 2, when n is 1 or 2, which comprises oxidation of the correspondingly substituted compound of formula (I) when n is 0.
    6. An agricultural composition comprising a compound of either of claims 1 and 2 as the active ingredient in admixture with an agriculturally acceptable diluent or carrier.
    7. An agricultural composition according to claim 6, further comprising a surface active material.
    S. An agricultural composition according to either of claims 6 and 7, further comprising at least one other active ingredient which is an insecticide, fungicide, bactericide, acaricide or other biologically active compound.
    9. A process for preparing an agricultural composition of any one of claims 6 to 8, comprising admixing the compound of either of claims 1 and 2 and the agriculturally acceptable diluent or carrier.
    10. A method for killing or controlling nematode, insect or acarid pests comprising applying a compound of either of claims 1 and 2, or a composition of any one of claims 6 to 8, to the pests, their habitat, or a plant susceptible to attack by the pests.
GB9518703A 1994-09-22 1995-09-13 Pesticidal heterocyclic and phenyl compounds Withdrawn GB2293380A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9419083A GB9419083D0 (en) 1994-09-22 1994-09-22 Heterocyclic compounds
GB9419085A GB9419085D0 (en) 1994-09-22 1994-09-22 Heterocyclic compounds

Publications (2)

Publication Number Publication Date
GB9518703D0 GB9518703D0 (en) 1995-11-15
GB2293380A true GB2293380A (en) 1996-03-27

Family

ID=26305666

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9518703A Withdrawn GB2293380A (en) 1994-09-22 1995-09-13 Pesticidal heterocyclic and phenyl compounds

Country Status (1)

Country Link
GB (1) GB2293380A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6297198B1 (en) 1996-05-14 2001-10-02 Syngenta Participations Ag Isoxazole derivatives and their use as herbicides
WO2002006257A1 (en) * 2000-07-13 2002-01-24 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (iii)
US6448262B1 (en) 1998-11-16 2002-09-10 American Cyanamid Company Pesticidal and parasiticidal use of 2-(substituted thio) thiazolo-[4,5-b]pyridine compounds
WO2003039258A1 (en) * 2001-09-10 2003-05-15 Basf Aktiengesellschaft Pesticidal and parasitical di-and trifluorosubstituted alkene compounds
WO2003049541A2 (en) * 2001-12-13 2003-06-19 Bayer Cropscience Ag Nematicidal trifluorobutenyl imidazole thioether derivatives
US6645990B2 (en) 2000-08-15 2003-11-11 Amgen Inc. Thiazolyl urea compounds and methods of uses
US6723720B2 (en) 1999-04-05 2004-04-20 Novartis Animal Health Us, Inc. Pesticidal triazine-derivatives
US7034026B2 (en) 2001-04-10 2006-04-25 Merck & Co., Inc. Inhibitors of Akt activity
WO2006079480A1 (en) * 2005-01-26 2006-08-03 Merial Ltd. Pesticidal substituted thioethers
US7223738B2 (en) 2002-04-08 2007-05-29 Merck & Co., Inc. Inhibitors of Akt activity
US8901311B2 (en) 2002-07-03 2014-12-02 Makhteshim Chemical Works, Ltd. Method for producing heterocyclic fluoroalkenyl sulfones

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6297198B1 (en) 1996-05-14 2001-10-02 Syngenta Participations Ag Isoxazole derivatives and their use as herbicides
US6448262B1 (en) 1998-11-16 2002-09-10 American Cyanamid Company Pesticidal and parasiticidal use of 2-(substituted thio) thiazolo-[4,5-b]pyridine compounds
US6723720B2 (en) 1999-04-05 2004-04-20 Novartis Animal Health Us, Inc. Pesticidal triazine-derivatives
WO2002006257A1 (en) * 2000-07-13 2002-01-24 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (iii)
US6645990B2 (en) 2000-08-15 2003-11-11 Amgen Inc. Thiazolyl urea compounds and methods of uses
US7196104B2 (en) 2000-08-15 2007-03-27 Amgen, Inc. Thiazolyl urea compounds and methods of uses
US7034026B2 (en) 2001-04-10 2006-04-25 Merck & Co., Inc. Inhibitors of Akt activity
WO2003039258A1 (en) * 2001-09-10 2003-05-15 Basf Aktiengesellschaft Pesticidal and parasitical di-and trifluorosubstituted alkene compounds
US7105524B2 (en) 2001-09-10 2006-09-12 Basf Aktiengesellschaft Pesticidal and parasiticidal di-and trifluorosubstituted alkene compounds
WO2003049541A2 (en) * 2001-12-13 2003-06-19 Bayer Cropscience Ag Nematicidal trifluorobutenyl imidazole thioether derivatives
US6930076B2 (en) 2001-12-13 2005-08-16 Bayer Cropscience Ag Nematicidal trifluorobutenyl imidazole thioether derivatives
WO2003049541A3 (en) * 2001-12-13 2004-08-12 Bayer Cropscience Ag Nematicidal trifluorobutenyl imidazole thioether derivatives
US7223738B2 (en) 2002-04-08 2007-05-29 Merck & Co., Inc. Inhibitors of Akt activity
US8901311B2 (en) 2002-07-03 2014-12-02 Makhteshim Chemical Works, Ltd. Method for producing heterocyclic fluoroalkenyl sulfones
WO2006079480A1 (en) * 2005-01-26 2006-08-03 Merial Ltd. Pesticidal substituted thioethers
JP2008538199A (en) * 2005-01-26 2008-10-16 メリアル リミテッド Substituted thioethers as pesticides.

Also Published As

Publication number Publication date
GB9518703D0 (en) 1995-11-15

Similar Documents

Publication Publication Date Title
US5952359A (en) Thiazoles and their agricultural compositions
US5684011A (en) Pyrimidine derivatives useful as nematicides
US5451594A (en) Heterocyclic compounds
GB2331748A (en) Insecticidal thiazole derivatives
GB2293380A (en) Pesticidal heterocyclic and phenyl compounds
US5273988A (en) 2-(3,4,4,-trifluorobutenylmercapto) alkoxy or nitro benzoxazoyl compounds
US5246938A (en) Heterocyclic compounds
WO1994006783A1 (en) Benzoxazole and benzothiazole derivatives
US5270318A (en) Heterocyclic compounds
US5246933A (en) Nematicidal quinoxaline derivatives
GB2281295A (en) (2-Fluoroethyl) thio-substituted pyrimidines as nematicides
US5187176A (en) 1-phenyl substituted pyrimidone derivatives
IL119810A (en) Intermediates in the preparation of fluoroalkenylthio-substituted benzoaxazoles and benzthiazoles
EP0481604A1 (en) Heterocyclic compounds
CZ352592A3 (en) benzoxazole derivatives, process of their preparation and nematocidal composition in which said derivatives are comprised

Legal Events

Date Code Title Description
WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)