CA2137689A1 - Herbicidal pyrazole-(thio)-carboxamides - Google Patents

Abstract

N-substituted pyrazole derivatives of formula (I) wherein R1 represents optionally substituted alkyl or cycloalkyl; op-tionally substituted phenyl or benzyl; optionally substituted alkenyl or alkynyl; or a group selected from -SO2NR61R62, -SO2R71 and -CONR61R62; R2 represents -X-R10; R3 represents hydrogen, halogen, optionally substituted alkyl or cycloal-kyl, cyano, nitro, -S(O)mR6, optionally substituted phenyl or -CO2R6; R4 represents optionally substituted phenyl or pyri-dyl ; R5 represents hydrogen or alkyl; Y represents oxygen or sulphur; R6 represents alkyl or haloalkyl; R61 and R62 inde-pendently represent alkyl br haloalkyl; R7 represents alkyl or haloalkyl; R71 represents alkyl, haloalkyl or optionally substituted phenyl; R8 and R9 independently represents hydrogen, alkyl or haloalkyl; R10 represents optionally substituted phenyl or pyridyl; or optionally substituted alkyl, alkenyl or alkynyl; X represents oxygen atom, -NR11- or -S(O)p-; R11 re-presents hydrogen, alkyl or haloalkyl; m and p independently represent 0, 1 or 2; and their herbicidal properties are de-scribed.

Description

~ W O 93/25535 21 3 7 5 8 9 PCT/EP93/01466 Herbicidal pyrazole-(th~o)-carboxam~des This invention relates to N-substituted pyrazole derivatives, processes for their preparation, compositions cont~ining them and their use as herbicides.
Okajima and Okada, J. Het. Chem., Vol. 27 pages 567-574 describe the preparation of 4-N-phenylcarboxamido-5-methylthio-1,3-dimethylpyrazole. Japanese patent application Number 3119468 discloses a process for preparing certain S-mercaptopyrazole compounds. French patent No. 2,337,997 describes certain fungicidal pyrazole-carboxarnide derivatives, as does Huppatz J. L., Aust. J. Chem Vol.36, ppl35-147 (1982). US
patent No. 4,620,865 and European Patent No. 0151866 disclose certain pyrazole-4-carboxamide derivatives having herbicidal lS properties.
The present invention provides N-substituted pyrazole derivatives of formula I:
y R4R5N ~ , R3 ~1 I

wherein:
R1 represents:-a straight or branched chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atorns;
a cycloallyl group cont~ining from 3 to 6 carbon atoms optionally substituted by one or more groups R6;
a group -(CH2)n-Ar wherein n represents zero or one and Ar represents a phenyl group optionally substituted by one or more groups selected from halogen, nitro, R6, -OH, -oR6, -S(o)mR7 and -NR8R9;
. a straight or branched chain alkenyl or alkynyl group cont~inin~ up to 6 carbon atoms optionally substituted by one or more groups selected from halogen, R6 and -oR6; or wO 93/25535 ~1 3 7 ~ ~ 9 pcr/Ep93/~i66 a group selected from -SO2NR61R62, -So2R71 and -CONR61R62;
R2 represents:-a group -X-R10;
S R3 represents:-a hydrogen or halogen atom;
a straight or branched chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group cont~ining from 3 to 6 carbon atoms optionally substituted by one or more halogen atoms or groups R6;
a cyano or nitro group;
a group -S(O)mR6;
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, oR6 and cyano; or a group -CO2R6;
R4 represents:
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, oR6, -S(o)mR7 and -NR8R9; or pyridyl optionally substituted by one or more groups selected from halogen, nitro, R6, -oR6, -S(o)mR7 and -NR8R9;
RS represents the hydrogen atom or a straight- or branched-chain alkyl group cont~ining up to 6 carbon atoms;
Y represents the oxygen or sulphur atom;
R6 represents a straight- or branched- chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R61 and R62, which may be the same or different, each represents a straight- or branched- chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R7 represents a straight- or branched- chain alkyl group cont~inin~ up to 4 carbon atoms optionally substituted by one or more halogen atoms;
R71 represents:-a straight- or branched- chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen WO 93/25535 ~ 1 3 7G8 9 PCr/EP93/01466 atoms; or phenyl optionally substituted by one or more groups selected from halogen~ nitro, R6, -oR6, -S(o)mR7 and -NR8R9;
R8 and R9, which may be the same or different, each represents hydrogen or a straight or branched chain alkyl group cont~ining Up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R10 represents:-phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, oR8, -S(o)mR7, -NHCOR6 and -NR8R9;
pyridyl optionally substituted by one or more groups selected from halogen, nitro, R6, oR6, -S(o)mR7, -NHCOR6 and -NR8R9;
a straight- or branched- chain alkyl, alkenyl or alkynyl group cont~ining Up to ten carbon atoms wherein the chain may optionally comprise one or more oxygen or sulphur atoms or -NR5-groups, optionally substituted by one or more groups selected from halogen, -oR8, ~S(O)qR6~ -NR8R9, -CO2R8, -OCOR6, -NHCOR6, -CoNR8R9~ R12, -coR8~ R13 and cyano;
X represents an oxygen atom, -NR11- or -S(O)p-, R11 represents hydrogen or a straight or branched chain alkyl group cont~inin~ up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R12 represents a cycloalkyl group containing from three to seven ring atoms, which may optionally contain from one to three heteroatoms in the ring selected from oxygen, sulphur and -NR5-;
R13 represents:
a cycloalkyl group cont~ining from 3 to 6 carbon atoms which is substituted by one or more groups selected from halogen, R8 and -oR8; or a cycloalkenyl group cont~inin~ S or 6 carbon atorns optionally substituted by one or more groups selected from halogen, R8 and -oR8;
m represents zero, one or two; p represents zero, one or two;
q represents zero, one or two;

WO 93/2S535 ~ ~ 7 ~8~ pcr/Ep93/o~66 ~,vith the proviso that when Y represents oxygen, R2 represents methylthio or N-phenylamino, R4 represents phenyl and R5 represents hvdrogen, Rl and R3 do not simultaneously represent methyl;
and agriculturally acceptable salts thereof, which possess valuable herbicidal properties.
By the term "agriculturally acceptable salts" is meant salts the cations of which are known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably the salts are water-soluble. Suitable salts with bases include alkali metal (eg. sodium and pot~c~ m), ~lk~line earth metal (eg. calcium and magnesium), amrnonium and amine (eg. diethanol~mint, triethanolamine, octyl~min~, morpholine and dioctylmethylamine) salts. Suitable acid addition salts, forrned by compounds of formula I cont~ining an arnino group, include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with orgarlic acids, for example acetic acid.
Certain compounds of formula I have been disclosed, without any indication that they have actually been synthesised, as having fungicidal properties. According to a further feature of the present invention there is provided compounds of formula I as hereinbefore defined excluding compounds of formula I wherein Y represents o~ygen, Rl represents methyl, R3 represents tri~uoromethyl, R5 represents hydrogerl, R2 represents a group selected from methoxy, 2,2,2-trifluoroethoxy, ethylthio, n-propylamino and methanesulphonyl, and R4 represents a group selected from 2-trifluoromethylphenyl, 2-chloro4-nitrophenyl, 2-trifluoromethyl-4-nitrophenyl, 2-bromo-4-nitrophenyl, 2-chloro-5-tri~luoromethylphenyl, 2,5-dichloro-4-nitrophenyl, 2,3,4,5-tetrachlorophenyl, 2,6-dibromo4-trifluoromethoxyphenyl and pentafluorophenyl.

In one embodiment the invention provides N-substituted pyrazole derivatives of formula I in which:
R1 represents:-a straight or branched chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms;

W O 93/25S35 ~13 7~ 89 PC~r/EP93/01466 -S -a cvcloalkyl group cont~ining from 3 to 6 carbon atoms optionally substituted by one or more groups R6; or a group -(CH2)n-Ar wherein n represents zero or one and Ar represents phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OH, -oR6, -S(o)mR7 and -NR8R9;
R3 represents:-a hydrogen or halogen atom;
a straight or branched chain allyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloallyl group cont~ining from 3 to 6 carbon atoms optionally substitued by one or more groups R6;
a cyano group;
a group -S(O)mR6;
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, oR6 and cyano, or a group -CO2R6;
R10 represents:-phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, oR8, -S(o)mR7, -NHCOR6 and -NR8R9; or pyridyl optionally sl-bstihlted by one or more groups selected from halogen, nitro, R6, -oR6, -S(o)mR7, -NHCOR6 and -NR8R9.

In this embodiment X preferably represents an oxygen or sulphur atom or a group -NR11.

In a second embodiment the invention provides N-substituted pyrazole derivatives of formula I in which:
R1 represents:-a straight or branched chain allyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group cont~ining from 3 to 6 carbon atoms optionally substituted by one or more groups R6; or WO 93/25s35 ~ ~a9 PCI'/EP93/~,466 a group -(CH2)n-Ar wherein n represents zero or one and Ar represents phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OH, -oR6, -S(o)mR7 and -NR8R9;
S R3 represents:-a hydrogen or halogen atom;
a straight or branched chain alkyl group cont~ining up to 6 carbon atorns optionally substituted by one or more halogen atoms;
a cycloalkyl group cont~ining from 3 to 6 carbon atoms optionally substituted by one or more groups R6;
a cyano or nitro group;
a group -S(O)mR6;
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, oR6 and cyano; or a group -CO2R6;
R10 represents:-straight- or branched- chain alkyl, alkenyl or alkynyl group cont~ining up to ten carbon atoms wherein the chain may optionally comprise one or more oxygen or sulphur atoms or -NRS- groups, optionally substituted by one or more groups selected from halogen, -oR8, ~S~O)qR6~ -NR8R9, -C02R8, -OCOR6, -NHCOR6, -CONR8R9, R12 and cyano.

In a third embodiment the invention provides N-pyrazole derivatives of formula I in which:
R3 represents:-a hydrogen or halogen atom;
a straight or branched chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group cont~ining from 3 to 6 carbon atoms optionally substituted by one or more groups R6;
a cyano or nitro group;
a group -S(O)mR6;
phenyl optionally substituted by one or more groups ~ W O 93/25535 21 3 7 6 8 9 PC~r/EP93/01466 selected from halogen, nitro, R6, oR6 and cyano; or a group -CO2R6;
R10 represents a straight- or branched- chain alkyl, alkenyl or alkynyl group cont~inin~? up to ten carbon atoms wherein the chain S may optionally comprise one or more oxygen or sulphur atoms or -NR5- groups, optionally substituted by one or mpre groups selected from halogen, -oR8, -S(O)qR67 -NR8R9, -CO2R8, -OCOR6, -NHCOR6, -CONR8R9, R12, -COR8, R13 and cyano.

A preferred class of compounds of formula I are those wherein Y represents an oxygen atom.
A further preferred class of compounds of formula I are those wherein Rl represents methyl or ethyl.
A further preferred class of compounds of formula I are those wherein Rl represents methyl.
Compounds in which R3 represents trifluoromethyl are also preferred.
Compounds in which R4 represents 2,4-difluorophenyl are also preferred.
Compounds of formula I in which R4 represents 2,4-difluorophenyl or ~,4,6-trifluorophenyl are also preferred.
- Compounds in which R5 represents the hydrogen atom are also preferred.
A further preferred class of compounds of formula I are those wherein X represents a sulphur atom. Compounds of formula I
wherein X represents an oxygen atom are aiso preferred.
A further preferred class of compounds of formula I are those wherein R10 represents phenyl substituted by at least one halogen atom, preferably fluorine.
A further preferred class of compounds of formula I are those wherein R10 represents a straight- or branched- chain alkyl or alkenyl group cont~ining up to four carbon atorns optionally substituted by one or more halogen atoms.
A further preferred class of compounds of formula I are those in which R2 represents -SR10, wherein R10 represents an alkenyl group cont~ining up to four carbon atoms.
A further preferred class of cornpounds of formula I are those wherein R10 represents a straight- or branched- chain alkyl, alkenyl ~7g89 ~
WO 93/25535 PCI/EP93/3~66 or alkynyl group cont~ining up to six, preferably up to five carbon atoms optionally substituted by one or more halogen atoms.
Where R10 represents a straight- or branched- chain alkyl group which is substituted by one or more groups R12 or R13, S preferably R10 represents a group -CH~R12 or -CH2R13.
A further preferred class of compounds of formula I are those wherein:
R1 represents an alkyl group cont~ining one or two carbon atoms optionally substituted by one or more halogen (preferably fluorine) atoms which may be the same or different;
R3 represents:
an alkyl group cont~inin~ up to three carbon atoms optionally substituted by up to five halogen (preferably fluorine or chlorine) atoms which may be the same or different; or a group -SMe;
R4 represents phenyl optionally substituted by from one to three groups selected from halogen, trifluoromethyl and methoxy;
R5 represents the hydrogen atom or a methyl group;
Y represents an oxygen or sulphur atom;
X represents an oxygen atom or a group -S(O)p-;
R10 represents:
phenyl or pyridyl optionally substituted by a group selected from halogen, methoxy, hydroxy, -NHCOMe, -NH2, -SMe, methyl and trifluoromethyl;
a cycloalkyl group cont~inin~ from 3 to 6 carbon atoms;
a straight- or branch- chained alkyl, alkenyl or alkynyl group cont~ining up to six carbon atoms optionally substituted by one or more groups selected from from halogen, -CO2Et, cyano, cyclopropyl, methoxy, and-CONHMe;
and p represents zero or one.
Particularly important compoundsl because of their herbicidal properties, include the following:
1. 4-N-(2,4-difluorophenyl)carbnx~mido-5-(4-chlorophenylthio)- 1-methyl-3-trifluoromethylpyrazole, 2. 4-N-(2,4-difluorophenyl)carboxamido-5-(4-methoxyphenylthio)-1-methyl-3-trifluoromethylpyrazole, 3. 4-N-(2,4-difluorophenyl3carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, WO 93/25535 ~1 3 7 ~ ~ 9 pcr/Ep93/o1466 4. 4-N-(2,4-difluorophenyl)carboxamido-5-(4-bromophenylthio)- 1-methyl-3-trifluoromethylpyrazole, 5. 4-N-(2,4-difluorophenyl)carboxamido-5-(4-hydroxyphenylthio)- 1-methyl-3-trifluoromethylpyrazole, 56. 4-N-(2,4-difluorophenyl)carboxamido-5-(2-fluorophenylthio)- l-methyl-3-trifluoromethylpyrazole, 7. 4-N-(2,4-difluorophenyl)carboxamido-5-(3-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 8. 4-N-(2,4-difluorophenyl)carbox~mitlo-5-phenylthio-1-10methyl-3-trifluoromethylpyrazole, 9. 4-N-(2,4-difluorophenyl)carboY~miclo-5 (4 acetamidophenylthio)- 1-methyl-3-trifluoromethylpyrazole, 10. 4-N-(2,4-difluorophenyl)carboxamido-5-(4-methylphenylthio)- 1-methyl-3-trifluoromethylpyræole, 1511. 4-N-(3-trifluoromethylphenyl)carboxamido-5-(4-methylphenylthio)-1-methyl-3-trifluoromethylpyrazole, 12. 4-N-(4-methoxyphenyl)carboxamido-5-(4-chlorophenylthio)-1-methyl-3-trifluoromethyl~yl ~ole, 13. 4-N-(2,4-difluorophenyl)carbox~mido-5-(3-20chlorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 14. 4-N-(2,4-difluorophenyl)carbt7x~mido-5-(4-trifluoromethylphenylthio)- 1-methyl-3-tri~luoromethylpyrazole, 15. 4-N-phenylcarb- x~mi-lo-5-(3 trifluoromethylphenylthio)-1,3-dimethylpyræole, 2516. 4-N-(4-fluorophenyl)carboxamido-5-(4-chlorophenylthio)- 1,3-dimethylpyrazole, 17. 4-N-(2,4-difluorophenyl)carbox~rniclo-5-(4-chlorophenylthio)-1,3-dimethylpyrazole, 18. 4-N-(2,4-difluorophenyl~carboxarnido-5-(3-30chlorophenylthio)-1,3-dimethylpyrazole, 19. 4-N-(2,4-difluorophenyl)carboxamido-5-(4-fluorophenoxy)-1-methyl-3-trifluoromethylpyrazole, 20. 4-N-(4-fluorophenyl)carboxamido-5-(3-trifluoromethylphenoxy)- 1-methyl-3-trifluoromethylpyrazole, 3521. 4-N-(2,4-difluorophenyl)carboxamido-5-(3-chlorophenoxy)-1-methyl-3-trifluoromethylpyrazole, 22. 4-N-phenylcarboxamido-5-(4-chlorophenoxy)- 1,3-dimethylpyrazole, WO 93/25~35 ' ~ PCI/EP93/Q~466 ~37~8~ ~

23. 4-N-(4-fluorophenyl)carboxamido-5-(4-chlorophenoxy)-1,3-dimethylpyrazole, 24. 4-N-(2,4-difluorophenyl)carboxamido-5-(4-chlorophenoxy)- 1-methyl-3-trifluoromethylpyrazole, 525. 4-N-(2,4-difluorophenyl)carboxamido-5-(n-butylthio)-1-methyl-3-trifluoromethylpyrazole, 26. 4-N-(2,4-difluorophenyl)carboxamido-5-(2-propenylthio)-1-methyl-3-trifluoromethylpyrazole, 27. 4-N-(2,4-difluorophenyl)carboxamido-5-isopropylthio-1-methyl-3-trifluoromethylpyrazole, 28. 4-N-(2,4-difluorophenyl)carboxamido-5-ethylthio-1-methyl-3-trifluoromethylpyrazole, 29. 4-N-(2,4-difluorophenyl)carboxamido-5-(3-chloropl o~ylthio)-1-methyl-3-trifluoromethylpyrazole 1530. 4-N-(2,4-difluorophenyl)carbox~mi~lo-5-methylthio-1-methyl-3 -trifluoromethylpyrazole, 31. 4-N-(2,4-difluorophenyl)carbox~miclo-5-(2,2,2-trifluoroethoxy)-1-methyl-3-trifluoromethylpyrazole.
32. 4-N-(2,4-difluorophenyl)carbo~r~miclo-5-20(ethoxycarbonylmethylthio)-1-methyl-3-trifluoromethylpyrazole, 33. 4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-5-(1-methylbutylthio)-3-trifluoromethylpyrazole, 34. 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluorometllyl~yl azole, 2535. 4-N-(2,4-difluorophenyl)carboxamido-5-(n-hexylthio)-1-methyl-3 -trifluoromethylpyrazole, 36. 5-cyclopentylthio-4-N-(2,4-difluorophenyl)carbox~mir~o-1-methyl-3-trifluoromethylpyrazole, 37. 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(n-propylthio)-3-trifluoromethylpyrazole, 38. 5-cyclohexylthio-4-N-(2,4-difluorophenyl)carboxamido-1 -methyl-3 -trifluoromethylpyrazole, 39. 4-N-(2,4-difluorophenyl)carboxamido-1 methyl 5 (1-methylpropylthio)-3-trifluoromethylpyrazole, 3540. 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(3-methylbutylthio)-3-trifluoromethylpyrazole, 41. 4-N-(2,4-difluorophenyl)carboxamido-5-(1,1-dimethylethylthio)-1-methyl-3-trifluoromethylpyrazole, WO 93/25535 ~137 ~8 9 PCI/EP93/01466 42. 4-N-(2,4-difluorophenyl)carbox~Tnido-S-ethoxy-1-methyl-3-trifluoromethylpyrazole, 43. 4-N-(2,4-difluorophenyl)carboxamid~-1-methyl-5-(2-propynylthio)-3-trifluoromethylpyrazole, S44. 5-(3-butenylthio)~-N-(2,4-difluorophenyl)-carboxamido-1-methyl-3-trifluoromethylpyrazole, 45. 5-(2-bromo-2-propenylthio)-4-N-(2,4-difluorophenyl)-carboxamido-1-methyl-3-trifluoromethylpyrazole, 46. 5-(3-bromo-2-propenylthio)-4-N-(2,4-difluorophenyl)-10carbox~miclo-1-methyl-3-trifluoromethylpyrazole, 47. S-(cyanomethylthio)-4-N-(2,4-difluorophenyl)-carboxamido- 1-methyl-3-trifluoromethylpyrazole, 48. 5-(3-methyl-2-butenylthio)-4-N-(2,4-difluorophenyl)-carboxamido- 1-methyl-3-trifluoromethylpyrazole, 1549. S-(cyclopropylmethylthio)-4-N-(2,4-difluorophenyl)-carboY~mido-l-methyl-3-trifluoromethylpyrazole, 50. 5-(3-butynylthio)-4-N-(2,4-difluorophenyl)carboxarnido-1 -methyl-3 -trifluoromethylpyrazole, 5 1. 5-(2-chloropropylthio)-4-N-(2,4-difluorophenyl)-20carboxamido-1-methyl-3-trifluoromethylpyrazole, 52. 4-N-(2,4-difluorophenyl)carboxamido-5-(2,2-dimethoxyethylthio)- 1-methyl-3-trifluoromethylpyrazole, 53. 5-(2-butenylthio)-4-N-(2,4-difluorophenyl)-carboxamido-1-methyi-3-trifluoromethylpyrazole, 2554. 4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-5-(n-pentylthio)-3-trifluoromethylpyrazole, 55. 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-S-(2-methylbutylthio)-3-trifluoromethylpyrazole, 56. 4-N-(2,4-difluorophenyl)carbox~mido-1-methyl-S-30(2-methyl-2-propenylthio)-3-trifluoromethylpyrazole, 57. 5-(2-chloro-2-propenylthio)-4-N-(2,4-difluorophenyl)-carboxamido-1-methyl-3-trifluoromethylpyrazole, 58. 4-N-(2,4-difluorophenyl)carboxamido-5-(2-methoxyethyl)-1-methyl-3-trifluoromethylpyrazole, 3559. 5-(3-chloro-2-propenylthio)-4-N-(2,4-difluorophenyl)-carboxarnido- 1-methyl-3-trifluoromethylpyrazole, . 60. S-ethylthio-1-ethyl-4-N-(2,4-difluorophenyl)-carboxamido-3-trifluoromethyl pyrazole, wo93/2ss35 ~ 7689` PCr/EP93/~66 ~1hylll~io-1-et~yl~N-(2,4,6-trIfluorophenyl)-~ 5 (N methy~ n~ ~o~ ~yl~ ~l~io) 4 N (2~4 d~Cluorophcnyl)carb~ m~d~l-me~~ uor~ .cLL~l~ l~olc, 563 4-N~ oropho~yV-5-~4~ orop~o~r~ o~
1-met~1-3-t~i~1UO~O~ l~Lazo~
64. 3~ ro-lifh~l rom~t~yl 5 (4 ~uorophe~?1~hio) 1 N-t~.~d~uoroPheny})~l~A~ o l-metllyl~

6~. 3-chloro~iflnoromethyl-5~ uorophen~ io) l-10me~hyl~N-(~,4,~-triiluorophe~yl)carbo~s,mi~lopy~ e~
66. 4-N-(2~4-di~uoropheny~ rboy~mitlo l~ yl-S-pyridylt~io)-3-tr~llorome~ ~le, 67. S-~q ~.~ ...~henylthio) 1 N-~2,~di~uorophe~yl)-ca~bo~ l-methyl-~ luorometl"~ ylz~ole, 15C~. 5 (3 chl~ro-4-flu-~,v~h~l~o)~ ~ (~,4-d;~luorDphcnyl)c~l,~ d~ ~ctl~ orom~t~l~.~ole, 6~. 4-N-(2,4~ uorophen~l)c~bt~a~;do-5-(4-ilu~rop~ h;o~-1-methyl.3~(n~pr~1)pyra~o1e, 70. 4 N-~2~4 di~uorc~ o ~ lh 5 (4 fluol~ph~ io)~ u~roethyl)-3-l~ uoLo~ y~ e~
71. 4-N-~4-dinu~ophenyl)c~ m;~ -(4-~orophc~ io3 1-methyl 3 me~ h;opyrazole, 7~. 4-N~3 chloro~ uoruphenyl)carl.~ ln.5.(4.
fluoropl~c~ io~ me~yl-3-~luoromeL~yl~ylazole, 73. 4-N-(3~4-di~llorophe uo~ophc~l~io)-l-me~hyl-3-~uorometh~ly~ zole~
74. 5-s~fluoroph~ylL~io)~l~me~y~-3-~rifLuGromeL~
(2,4,~~ l,.o~phc~yl)c~1,ç ~ razole, 75. 4-N-(~fluoropho~yl)carbt~Y~ o-5-~4-fluorophuly~thio) l-methyl ~-tri~uoromethylpyra~ole, 76. 4-~ (4~c~10rophenyl)c~rhn~mi~lo~5.(4.
fluorophe~yltl~io)-l-methyl-3-tri~uorom~ .yl~Olc, 77. 4-~-(4~hloro-2 ~uorophenyI)carbo~mldo-5-(4- , fluorophenylthio)-l-mct~yl-3-~uoromesh,~lpr~a~ole, 78. ~-(4-~uorophenylthio)-1-mcthyl-3-trifluoromo~. 4-N
(~,4,6 trifluorophenyl)~l.u~ do~ole, 7Y. ~N-(Z-c~loro4-~uorophenyl3c~1,o~ ;do-5-(4-iluorophcD ylthio)~ ~yl-3-tri~uvrum~yl~yr~ole, WO 93/2553~ 2~J. ~ 768 9 pcr/Ep93/ol466 80. 4-~-(4-fluorophenyl)carboxamido-5-t4-fluorophenylthio)- 1-methyl-3-trifluoromethylpyrazole, 8 1. 4-N-(2,4-dichlorophenyl)carboxamido-5-(4-fluorophenylthio)- 1-methyl-3-trifluoromethylpyrazole, 582. 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4-N-(2,3,4-trifluorophenyl)carboxamidopyrazole, 83. 4-N-(4-bromo-2-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 84. 5-(4-fluorophenylthio)-4-N-(2-fluoro-4-10methylphenyl)carbox~mi~lo-1-methyl-3-trifluoromethylpyrazole, 85. 4-N-(3-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 86. 4-N-(2,3-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 1587. 4-N-(2,5-difluorophenyl)carboxamido-5-(4-fluorophenylthio)- 1-methyl-3-trifluoromethylpyrazole, 88. 4-N-(2,6-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 89. 4-N-(3,5-difluorophenyl)carboxamido-5-(4-20fluorophenylthio)- 1-methyl-3-trifluoromethylpyl ~ole, 90. 5-(4-fluorophenylthio)- 1-methyl-3-trifluoromethyl-4-N-(2,3,6-trifluorophenyl)carboxamidopyrazole, 91. 5-(4-fluorophenylthio)-1-methyl~-N-(phenyl)carboxamido-3-trifluoromethylpyrazole, 2592. 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(4-methylthiophenylthio)-3-trifluoromethylpyrazole, 93. 5-(4-fluorophenylthio)- 1-methyl-4-N-methyl-N-(2,4-difluorophenyl)carboxamido-3-trifluoromethylpyrazole, 94. 5-(4-chlorophenylsulphinyl)-4-N-(2,4-30difluorophenyl)carboxarnido- 1-methyl-3-trifluoromethylpyrazole, 95. 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(n-propyloxy) -3-trifluoromethylpyrazole, 96. 4-N-(2,4-difluorophenyl)carboxarnido-1-methyl-5-(2-methylpropyloxy)-3-trifluoromethylpyrazole, 3597. 3-chlorodifluoromethyl-4-N-(2,4-difluorophenyl)-carboxamido-1-methyl-5-(2-methylpropyloxy)pyrazole, 98. 4-N-(2,4-difluorophenyl)carboxamido- 1-ethyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, WO 93/25535 2:l 3 7 6 8 9 pcr/Ep93/~66 99. 4-N-(2,4-difluorophenyl)carboxamido-1-ethyl-S-(2-propenylthio)-3-trifluoromethylpyrazole, 100. 4-N-(2,4,6-trifluorophenyl)carboxamido-1-ethyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, S 101. 4-N-(2,3-difluorophenyl)carboxarnido-1-methyl-S-(2-methylpropylthio)-3-trifluoromethylpyrazole, 102. 4-N-(2,6-difluorophenyl)carboxarnido-1-methyl-S-(2-methylpropylthio)-3-trifluoromethylpyrazole, 103. 4-N-(2,3,6-trifluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 104. 4-N-(2,4,6-trifluorophenyl)carbox~miclo-1-methyl-S-(2-methylpropylthio)-3-trifluoromethylpyrazole, 105. 4-N-(2,5-difluorophenyl)carboxamido- 1-methyl-S-(2-methylpropylthio)-3-trifluoromethylpyrazole, and 106. 4-N-(2,4-difluorophenyl)carboxarnido-1-methyl-S-(2-methypropylthio)-3-pentafluoroethylpyrazole.
The numbers 1 to 106 are assigned to these compounds for reference and identification hereinafter.
Thè compounds of formula I can be prepared by the application or adaptation of known methods (i.e. methods heretofore used or described in the chemical literature), for example as hereinafter described.
In the following description where symbols appearing in formulae are not specific~lly defined it is to be understood that ~hey are "as hereinbefore defined" in accordance with the first definition of each symbol in this specification.
It is to be understood that in the descriptions of the following processes, that the sequences may be performed in different orders and that suitable protecting groups may be required to achieve the compounds sought.
According to a feature of the present invention, compounds of formula I may be prepared by reacting a compound of formula II:
Y
J~ R3 R4R5~
''' :` ' ' ,, . . z/~,,N

II

~ WO 93/25S35 ~13 7 6 8 9 PCr/EP93/01466 wherein R1, R3, R4, R5 and Y are as hereinbefore defined and Z represents a leaving group, with a compound of formula III:
R2-xl III
wherein R2 is as hereinbefore defined and x1 represents S hydrogen or an alkali metal (e.g. sodium or pot~Ccillm). The reaction is generally performed in an inert solver~t such as acetonitrile, dioxan or tetrahydrofuran optionally in the presence of a base, e.g. sodium hydride, pot~ccillm t-butoxide or preferably pot~ccillm carbonate, at a temperature from ambient to the reflux temperature of the solvent. Preferably the leaving group Z is a halogen atom e.g. chlorine bromine or fluorine According to a further feature of the present invention, compounds of formula I wherein Y represent the sulphur atom may be prepared by reacting the corresponding compound of formula I in which Y represents the oxygen atom with a thionating compound, for example Lawesson's reagent [2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulphide] in an inert solvent, preferably toluene at a temperature from 50C to the reflux temperature of the solvent.
According to a feature of the present invention, compounds of formula I wherein R5 represents a straight- or branched- chain alkyl group cont~inin~ up to 6 carbon atoms may be prepared by re~ctin~
the corresponding compound of formula I in which RS represents hydrogen with an alkylating agent, preferably an alkyl halide or a dialkylsulphate, in the presence of a base, for example pot~ccillm hydroxide or pot~ccillm carbonate, in an inert solvent such as tetrahydrofuran at a temperature from ambient to the reflux temperature of the solvent. This reaction may be performed optionally in the presence of a phase transfer catalyst such as tetrabutylarnmonium bromide typically as 0.01-0.1 mole%.
Alternatively the sodium or po~c~cillm salt of compound I may be prepared by reacting a compound of formula I wherein R5 ~
represents hydrogen with a base preferably sodium hydride in an inert solvent followed by reaction with an alkylating agent.
According to a further feature of the present invention compounds of formula I in which Y represents oxygen may be prepared by the reaction of a compound of formula IV:

wo 93/2553~ 2~37~8~ Pcr/Ep93/~66 o HO J~ ~R
R2 ~N
R
IV
wherein R1, R2 and R3 are as hereinbefore defined, with a halogenating agent to give an acid halide (which may optionally be S isolated) followed by reaction with an amine of formula V

wherein R4 and R5 are as hereinbefore defined. Preferably the halogenating agent is a chlorinating agent, for example thionyl chloride and the reaction to give the acid halide is optionally performed in an inert solvent at a temperature from ambient to the reflux temperature. The reaction between the acid halide and the amine of formula V is generally perforrned in the presence of base, preferably triethyl~mine, in an inert solvent e.g. tetrahydrofuran at a temperature from 0C to the reflux temperature of the solvent.
According to a further feature of the present invention compounds of formula I may also be prepared by the reaction of a compound of formula IVa or a salt thereof:
y R4R5N~ ~R3 ~1 IVa wherein R1, R3, R4, R5, Y and X are as hereinbefore defined with a compound of formula R10-L wherein R10 is as hereinbefore defined and L is a leaving group. Preferably L represents a halogen atom (more preferably chlorine or bromine), para-tohlenes--lr)honyloxy or methylsulphonyloxy and (where R10 represents optionally substituted phenyl or pyridyl) nitro. The reaction is generally performed in an inert solvent such as ethanol or methanol in the presence of a base (e.g. sodium hydride or sodium methoxide). Where the reaction is performed with a salt of wo 93/25535 2~ ~7~8~ pcr/Ep93/ol466 a compound of formula (IVa) preferably the alkaline metal or alkaline earth metal salt is used (e.g. the sodium or potassium salt).
According to a further feature of the present invention compounds cont~ining a group XR10 in which R10 represents phenyl or pyridyl substituted by a group -SR7 may be prepared by the diazotisation of the corresponding compounds in which R10 represents phenyl or pyridyl substituted by -NH2 followed by the reaction of the diazotised product thus obtained with a disulphide of formula R7S-SR7 wherein R7 is as hereinbefore defined. The reaction is generally performed using an a diazotising reagent such as an alkyl nitrite (e.g. t-butyl nitrite in an inert solvent (e.g.
acetonitrile or dichloromethane) at a temperature from -20C to reflux temperature.
Intermediates used in the preparation of compounds of formula I may be prepared by tne application or adaptation of known methods, for example methods described hereinafter.
Compounds of forrnula II in which Y represents oxygen and Z
represents a leaving group, e.g. halogen may be-prepared from compounds of formula VI:
o J~,N
z ~1 VI
wherein Z represents a leaving group, e.g. halogen, via conversion to the acid halide, preferably the acid chloride, for example by re~ting with thionyl chloride optionally in the presence of an inert solvent at a temperature from ambient to the reflux temperature, and subsequent reaction of the acid chloride (which may optionally be isolated) with an amine of formula V in the presence of a base, preferably triethylamine in an inert solvent, eg tetrahydrofuran, at a temperature from 0C to the reflux temperature of the solvent.
Compounds of formula II wherein Y represents the sulphur atom may be prepared by re~cting the corresponding compound of formula II in which Y represents the oxygen atom with a thionating WO 93/2S535 ~ ~ ~ Ç 8 9 ` PCI/EP93/0~6 compound, for example Lawesson's reagent [2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulphide] in an inert solvent, preferably toluene at a temperature from 50C to the reflux temperature of the solvent.
Compounds of formula III in which xl represents an alkali metal e.g. sodium or pot~ccillm may be prepared by the reaction of the corresponding compound of formula III wheréin Xl represents hydrogen with an alkali metal-cont~inin~ base such as NaH in an inert solvent such as dioxan at a temperature from 20C to the reflux temperature of the solvent.
Compounds of formula III in which R2 represents -SR10 and x1 represents hydrogen may be prepared by the reaction of a compound of formula R10-Br with:
a) sodium thiol in ethanol; or b) thiourea in ethanol, followed by reaction of the compound of formula R10S-C(=NH)NH2.HBr thus obtained with sodium hydroxide in ethanol; or c) pot~s~illm x~nth~te [EtOC(=S)S-K+] in ethanol followed by hydrolysis of the compound of formula R10SC( = S)OEt thus obtained with sodium hydroxide in ethanol.
Compounds of formula III in which R2 represents -SR10 and xl represents hydrogen may also be prepared by the reduction of a disulphide of formula R10S-SR10, using for example sodium borohydride in ethanol.
Compounds of formula IV in which X represents a group other than -S(O)p~ wherein p is zero or one may be prepared from compounds of formula VII:
o J ~

VII
by the replacement of the group Z by a group R2 [by the procedure described for the preparation of a compound of formula I from a compound of formula II], followed by conversion of the formyl group to carboxy [by the procedure described below for the WO 93/25535 ~137 6 8 9 PCI/EP93/01466 preparation of a compound of formula VI from a compound of formula VII].
Compounds of formula IV may also be prepared by the hydrolysis of an ester of formula (VIIa):
RO2C ~ ,R3 R2 ~N~

(VIIa) wherein R represents an alkyl group. This may be achieved by conventional techniques, for example by reaction with pot~ m carbonate in a ethanolic solvent.
Compounds of formula IV may also be prepared by the reaction of an acid of formula (VI) with a compound of formula (III). The reaction is generally performed as described above for the reaction of a compound of formula (II) with a compound of formula (III).
Compounds of formula (IVa) or salts thereof may be prepared by the reaction of a compound of formula II with a compound of formula H-X-X1.
Compounds of formula VI may be prepared by the oxidation of the corresponding aldehyde of fGrmula VII using an oxidant, preferably pot~c~ m perm~ng~n~te in the presence of a base, preferably sodium hydroxide, in a solvent, ~refel~bly water at a temperature from ambient to 100C.
Compounds of formula VII may be prepared by the reaction of a 5-hydroxypyrazole of formula VIII:

HO /~N' ~1 VIII
with a formylating reagent. Preferably the forrnylating agent is a mixture of phosphorus oxychloride and N,N-dimethylformamide, when a ~imlllt~neous chlorination is effected to produce a compound of formula VII in which Z represents chlorine. The WO 93/2553~ 3 7 6 8 ~ PCr/EP93/~66 reaction is generally carried out at a temperature from 0C to 150C.
5-Hydroxypyrazoles of formula VIII may be prepared by the reaction of a beta-ketoester of formula IX:
S R3C(o)CH2Co2A IX
wherein A represents lower alkyl, with a hydrazine of formula X: ' RlNHNH2 X.
The reaction is generally performed in a solvent, preferably water, at a temperature from ambient to the refllLx temperature. A
mixture of isomeric products may be produced during this reaction which may be separated by methods well known in the art. The preparation of the above intermediates VI, VII and VIII are well described in the literature, for example J.Het.Chem 27, 243 (1990) L.F.Lee et al.
Compounds of formula VIII wherein R3 represents cyano may be prepared by dehydration of the corresponding compound of formula VIII in which R3 is replaced by -CONH2 using for example phosphoms oxychloride optionally in the presence of an inert solvent at a temperature from ambient to the reflux temperature or para-toluenesulphonyl chloride in pyridine at a temperature from 50C to the reflux temperature, followed by hydrolysis with sodium hydroxide in an alcohol at a temperature from 20 to 100C.
Compounds of forrnula VIII in which R3 is replaced by -CONH2 may be prepared by hydrolysis of the corresponding ester - of formula VIII, wherein R3 represents -C02R61 preferably using a solution of sodium or pot~ m hydroxide in a solvent, e.g. a~ueous alcohol at a temperature from 0C to the reflux temperature of the solvent, to give the corresponding carboxylic acid which is converted to the corresponding acid chloride, for example by reaction with thionyl chloride (optionally in an inert solvent) at a temperature from ambient to the reflux temperature which is treated with arnmonia optionally in the presence of a suitable solvent e.g.
aqueous alcohol, at a temperature from 0C to the reflux temperature to give the desired product.
Compounds of formula VIII in which R3 is replaced by -CONH2 may alternatively be prepared by ammonolysis of the WO 93/2S535 ~13 7 ~ 8 9 PCr/EPs3/01466 corresponding ester of formula VIII wherein R3 represents -CO2R6, preferably by treatment with ammonia in a sealed vessel at a temperature from 100 to 200C.
Beta-ketoester compounds of forrnula IX wherein R3 represents a straight- or branched- chain alkyl group cont~ining up to 6 carbon atoms optionally substituted by one or more halogen atoms; or a phenyl group optionally substituted by one or more groups selected from halogen, nitro, R6, oR6 and cyano; or a cycloalkyl group cont~ining from 3 to 6 carbon atoms optionally substitued by one or more groups R6; or nitro or -CO2R6 may be prepared by well known procedures e.g. Beilstein 10, 682 (J.C.S. 49, 447 Perkin, Bellenot), or Nippon K~g~h- Zasshi 82, 132 (1961) K.
Hattori & H. Nakano, or Bull Soc. Chim Fr. (1964), 5, 945 G Braar, M. Vilkas.
Compounds of formula VIII wherein R3 represents -C02R6 may also be prepared by the reaction of an acetylene-1,2-koxycarbonyl compound of formula XI:

with a hydrazine of formula X. This reaction is generally performed in an inert solvent, preferably an alcohol e.g. methanol at a temperature from 0C to reflux to give a compound of formula XII:
=~C02R6 R602C \NHNHR
XII
which is cyclised in basic conditions e.g. using sodium methoxide irl a suitable solvent e.g. methanol at a temperature from 0C to reflux. Optionally both of these stages may be performed in one step using the base and solvent combination.
Compounds of formula VI wherein Z represents halogen may be prepared from an ester of formula XIII:

wo 93/25535 ~1 ~ 7 6 8 9 pcr/Ep93/o~66 ~N

Rl .
XIII
wherein R represents an alkyl group and Z'represents halogen.
This reaction is performed in a base e.g. sodium hydroxide in a S solvent, preferably aqueous alcohol at a temperature from 0C to 100C.
Esters of formula XIII or esters of formula VI wherein R2 represents -SR10 may be prepared by diazotisation of an amine of formula XIV:
RO2C ~ ,R3 ~,N

XIV.
This reaction may be performed with sodium nitrite in a mineral acid, for example a mixture of concentrated sulphuric acid and acetic acid, at a temperature from 0C to 60C and subsequent reaction with:
(a) a copper halide (where an ester of formula XIII is desired) or a disulphide of formul R1OS-SR10 (where an ester of formula IV wherein R2 represents -SR10 is desired) and a mineral acid or with an aqueous solution of pot~ccil-m iodide at a temperature from 0C to 100C; or. The diazotisation may alternatively be performed using an alkyl nitrite e.g. tert-butyl nitrite in the presence of a suitable halogenating agent (where an ester of formula XIII is desired), preferably bromoform or iodine or anhydrous cupric chloride, or at a temperature from 0 to 100C
optionally in the presence of an inert solvent, preferably acetonitrile or chloroform.
Compounds of formula XIV wherein R3 is halogen, cyano or -SR6 may be prepared by the diazotisation of a compound of formula XV:

2~ 6 8 9 WO 93/25~35 ~ PCI/EP93/01466 ..

R02C ~ ~NH2 R

XV
wherein Rl are as hereinbefore defined. The reaction conditions for this reaction are as hereinbefore described for the S conversion of a compound of formula XIII to a compound of formula XIV where a cyanide reagent, e.g. copper cyanide may also be used in place of a halogenating agent; or using a diazotising reagent such as an alkyl nitrite (e.g. t-butyl nitrite in an inert solvent (e.g. acetor~itrile or dichloromethane) at a temperature from -20C
to reflux temperature followed by treating the diazotised intermediate with a disulphide of formula R6S-SR6. This reaction may be performed selectively to achieve diazotisation at the 3-position of the pyrazole ring.
Compounds of formula XIV may be prepared by reaction of a lS compound of formula XVI:
R02C >=<R3 NC
XVI
wherein B represents halogen (preferably chlorine), -oR6 or -SR6, with a hydrazine of formula X. When B represents oR6 or -SR6 this reaction is generally performed in an alcoholic solvent at a temperature from ambient to 200C. When B represents halogen, preferably chlorine, the reaction is generally performed in an inert solvent, preferably tetrahydrofuran, optionally in the presence of a base eg. triethylamine at a temperature from 0C to reflux temperature.
Compounds of formula XV may be prepared by reaction of a hydrazine of formula X with an alkali metal salt of an alkyldicyanoacetate of formula XVII:
R02C-CH(CN)2 XVII.
Preferably potassium ethyl dicyanoacetate is used. The reaction is generally performed in the presence of an acid, e.g.
hydrochloric acid, at ambient to reflux temperature.

WO 93/25~;35 ~13 ~ 6 8 9 PCI'/EP93/~66 Alkyldicyanoacetate potassium salts may be prepared by the reaction of an ap~ropliate alkylchloroformate with malononitrile in the presence of potassium hydroxide in an inert solvent, preferably tetrahydrofuran, at a temperature from 0 to 100C.
S Compounds cont~inin~ a group -S(O)mR6, -S(o)mR7, -S(O)p- or ~S(O)qR6 wherein m, p and q represent one or two may be prepared from the corresponding compound in which m, p and q represent zero or one by oxidation for example using meta-chloroperbenzoic acid in an inert solvent e.g. chloroform at a temperature from -20C to reflux temperature.
Compounds of formula (VIIa) in which Rl represents a group other than Ar and R2 represents -SR10 may be prepared by the reaction of a compound of formula XVIII:
RO2C ~ ,R3 H N'N
~1 XVIII
wherein Rl represents a group other than Ar, with an alkyl lithillm reagent, followed by treatment of the lithiated intermediate thus obtained with a compound of formula R1OS-SR10 or R10-S-Cl.
Preferably the alkyl lithillm reagent is lithillm di-isopropylamide.
The reaction is generally carried in an aprotic solvent (e.g.
tetrahydrofuran) at a temperature from -70C to 0C. Preferably R10 represents an optionally subtituted aLkyl or alkenyl group.
Compounds of formula XVIII may be prepared by the reaction of a compound of formula XIX:
RO2C ~ ,R3 H
H

XIX
with a compound of formula R1-X2, wherein R1 is a group other than Ar and X2 is a leaving group, in the presence of a base.
Preferably x2 represents for example a chlorine, bromine or iodine atom or a tosyl or mesyl group. Suitable bases include pot~sil-m wo 93/25~35 ~11 3 ~6 ~ 9 pcr/Ep93/ol466 carbonate, sodium hydride and caesium carbonate. The reaction is generally perfomed in a solvent (e.g. acetonitrile).
Compounds of formula XI, XVl XVII and XIX are well known in the literature or may be prepared by the application or S adaptation of known methods.
Agriculturally acceptable salts of the N-subs,tituted pyrazole derivatives of formula I may be prepared by known methods.
The following examples illustrate the preparation of compounds of formula I. In the present specification b.p. means boiling point, m.p. means melting point. Where the letters NMR
appear, the characteristics of the proton nuclear magnetic resonance spectrum follow. Unless otherwise specified the percentages are by weight.
Example 1 A mixture of 5-chloro-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (4.0 g), 4-chlorothiophenol (6 g) and pot~ccillm carbonate (2.4 g) was stirred in dry acetonitrile and heated at reflux for 3 hours. The solid was filtered, washed with acetonitrile, and the filtrate evaporated in vacuo to give a solid.
Purification by chromatography eluting with hexane/dichloromethane gave 4-N-(2,4-difluorophenyl)carboxamido-S-(4-chlorophenylthio)-1-methyl-3-trifluoromethylpyrazole (compound 1, 5.15 g) as a white solid, m.p.
172C-173C.
By proceeding in a similar manner the following compounds were also prepared from the al,~ro~liate starting materials wherein the various symbols are as defined in the following table:
y ~ NH/~

~A
Q~

WO 93/25535~ ~ i . PCr/EP93/Q1466 ~1376~ ~

Cpd. Rl R3 A Y P Q m.p.(C) 2 CH3 CF3 CH O2,4-diF 4-OMe 128-130 3 CH3 CF3 CH o2,4-diF 4-F 119-122 4 CH3 CF3 CH O2,4-diF 4-Br 170-171 CH3 CF3 CH O2,4-diF 4-OH 170-171 6 CH3 CF3 CH O2,4-diF 2-F 114-115 7 CH3 CF3 CH O2,4-diF 3-F 131-132 8 CH3 CF3 CH O2,4-diF H 131-133 9 CH3 CF3 CH O2,4-diF ~NHCOMe 197-199 CH3 CF3 CH O2,4-diF 4-CH3 131-133 12 CH3 CF3 CH o 4-OCH3 4-Cl 137-139 13 CH3 CF3 CH O2,4-diF 3-Cl 133-135 14 CH3 CF3 CH O2,4-diF 4-CF3 159-161 16 CH3 CH3 CH O 4-F 4-Cl 165-166 17 CH3 CH3 CH O2,4-diF 4-C1 166-168 18 CH3 CH3 CH O2,4-diF 3-Cl 136-138 63 CH3 CF3 CH S2,4-diF 4-F oil (a) 64 CH3 CF2Cl CH O2,4-diF 4-F 112-114 CH3 CF2Cl CH O2,4,6-triF 4-F 129-130 66 CH3 CF3 N O2,4-diF H 138-140 67 CH3 CF3 CH O2,4-diF 4-NH2 172-173 68 CH3 CF3 CH O2,4-diF 3-Cl-4-F 146-147 69 CH3 nPr CH O2,4-diF 4-F 126-127.5 CH2CF3 CF3 CH O2,4-diF 4-F 129- 130 Note: (a) NMR (CDCl3) dH 3.30(s,3H) 6.8-7.0(m,4H) 7.2-7.3(m,2H) 8.25-8.35(m,1H) 8.60(s,1H) ppm.
Example 2 S A suspension of sodium hydride in dry dioxan was stirred at room temperature under an inert atmosphere and a solution of 4-fluorophenol (1.2g) in dioxan was added. After 0.5 hours a solution of 5-chloro-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (2.47g) in dioxan (25ml) was added. The rnixture was then heated under reflux conditions for 20 hours, WO 93/2553~ ~13~7~8~9 pcr/Ep93/o1466 cooled and poured onto ice/water. This was extracted with dichloromethane and the extract washed with water, dried (anhydrous magnesium sulphate) and evaporated. The resultant yellow solid was purified by chromatography eluting with S ether/hexane and recrystallised from ethyl acetate to give 4-N-(2,4-difluorophenyl)carboxamido-5-(4-fluorophenoxy~- 1-methyl-3-trifluoromethylpyrazole (compound 19, 1.25g), m.p. 169C-170C.

Example 3 A mixture of 4-carboxylic acid chloride-1-methyl-5-(3-trifluoromethylphenoxy)-3-trifluoromethylpyrazole (2.1g), 4-fluoroaniline (0.62g) and triethylamine (0.8rnl) in tetrahydrofuran was stirred at room temperature for approx;m~tely 2 hours. The II~ixture was diluted with water and the resulting solid was filtered, dried and recrystallised to give 4-N-(4-fluorophenyl)carboxamido-5-(3-trifluoromethylphenoxy)-1-methyl-3-trifluoromethylpyrazole (compound 20, 2.1g), m.p. 171-172C.
By proceeding in a sirnilar manner 4-N-(2,4-difluorophenyl)-carboxamido-5-(3-chlorophenoxy)- 1-methyl-3-trifluoromethylpyrazole (compound 21) was prepared, m.p. 131-132C.

Example 4 4-Carboxylic acid chloride-5-(4-chlorophenoxy)-1,3-dimethylpyrazole was dissolved in tetrahydrorulan and added to a solution of aniline (0.6g) and triethyla~nine (0.9ml) in tetrahydrofuran. The reaction mixture was stirred for 2 hours, water was added and the resulting solid was filtered, dried and recrystallised from hexane/ethyl acetate to give 4-N-phenylcarboxamido-5-(4-chlorophenoxy)-1,3-dimethylpyrazole (compound 22, lg), m.p. 99-101C.
By proceeding in a similar manner 4-N-(4-fluorophenyl)carboxamido-5-(4-chlorophenoxy)-1,3-dimethylpyrazole (compound 23), m.p. 161-162C was prepared.
Example ~
A mixture of 5-chloro-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (4.0g), 4-chlorophenol (2.16g) and w0 93/25535 2~ 3 7 ~i 8 9 pcr/Eps3/~466 pot~csi-lm t-butoxide (2.16g) in t-butanol was refluxed for a~prox;",~tely 72 hours. Water was added and a solid was isolated and purified by chromatography eluting with hexane/ethyl acetate to give 4-N-(2,4-difluorophenyl)carboxamido-5-(4-chlorophenoxy)-1-methyl-3-trifluoromethylpyrazole (compound 24, 1.45g), m.p. 166-169C.

Example 6 Sodium thiomethoxide (1.63g) was added to a cooled solution of 5-chloro-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (4.0 g) in acetonitrile. The resulting suspension was stirred for two days, refluxed for one hour and filtered. The filtrate was concentrated and taken up into dichloromethane and water. The organic phase was dried (m~gneci~lm sulphate) and the solvent evaporated to give 4-N-(2,4-difluorophenyl)-carboxamido-5-methylthio-1-methyl-3-trifluoromethylpyrazole (compound 30) as a white solid (3.46 g), m.p. 130- 131C.

Example 7 A suspension of 5-chloro4-N-(2,4-difluorophenyl)carbo~miclo-1-methyl-3-trifluoromethylpyrazole (1.5 g) pot~ m carbonate (0.915 g) and 2,2,2-trifluoroethanol (1.5 ml) in acetonitrile was heated at reflux for six hours. The reaction was cooled and left to stand overnight. The reaction mixture was then ffltered and the solvent was removed from the ffltrate to leave a brown solid which was purified by colurnn chromatography to give 4-N-(2,4-difluorophenyl)carboxamido-5-(2,2,2-trifluoroethoxy)-1-methyl-3-trifluoromethylpyrazole (compound 31) as a white solid (0.84 g) m.p. 102 - 103C.
By proceeding in a similar manner the following compounds were prepared:
4-N-(2,4-difluorophenyl)carboxamido-5-(n-butylthio)-1-methyl-3-trifluoromethylpyrazole (compound 25), m.p. 69 - 70C;
4-N-(2,4-difluorophenyl)carboxamido-5-(2-propenylthio)- 1-methyl-3-trifluoromethylpyrazole (compound 26), m.p. 92 - 94C;
4-N-(2,4-difluorophenyl)carboxamido-5-isopropylthio-1-methyl-3-trifluoromethylpyrazole (compound 27), m.p. 106 - 107C;

~ WO 93/25535 ~13 7~8 9 PCr/EP93/01466 4-N-(2,4-difluorophenyl)carboxarnido-5-ethylthio- 1-methyl-3-trifluoromethylpyrazole (compound 28), m.p. 95 - 96.5C;
4-N-(2,4-difluorophenyl)carboxamido-5-(3-chloropropylthio)-1-methyl-3-trifluoromethylpyrazole (compound 29), m.p. 79 - 81C;
4-N-(2,4-difluorophenyl)carboxamido-5-(ethoxycarbonylmethylthio)- 1-methyl-3-trifluoro~ethylpyrazole (compound 32), m.p. 100 - 104C;
4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-5-(1-methylbutylthio)-3-trifluoromethylpyrazole (compound 33), m.p. 70 - 71C;
4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole (compound 34), m.p.
93 - 94C;
4-N-(2,4-difluorophenyl)carboxamido-5-(n-hexylthio)-1-methyl-3-trifluoromethylpyrazole (compound 35), m.p; 77 - 78C;
5-cyclopentylthio-4-N-(2,4-difluorophenyl)carbox~millo-1-methyl-3-trifluoromethylpyrazole (compound 36), m.p. 112 - 114C;
4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-5-(n-propylthio)-3-trifluoromethylpyrazole (compound 37), m.p. 89 -90C;
5-cyclohexylthio-4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-3-trifluoromethylpyrazole (compound 38), m.p. 92 - 94C;
4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-5-(1-methylpropylthio)-3-trifluoromethylpyrazole (compound 39), m.p.
98 - 99C;
4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(3-methylbutylthio)-3-trifluoromethylpyrazole (compound 40), m.p. 62 - 63C;
4-N-(2,4-difluorophenyl)carboxamido-5-(1,1-dimethylethylthio)- 1-methyl-3-trifluoromethylpyrazole (compound 41), m.p. 146 - 147C;
4-N-(2,4-difluorophenyl)carboxamido-5-ethoxy- 1-methyl-3-trifluoromethylpyrazole (compound 42), m.p. 108-109C;
5-(N-methylaminocarbonylmethylthio)-4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-3-trifluoromethylpyrazole (compound 62), m.p. 129 - 131C.

wO 93/25~35 ~ 3.7.6.~9 PCI/EP93/9~66 Example 8 3-Bromopropyne (0.61g) was added to a solution of sodium 4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-3-trifluoromethylpyrazole-S-thiolate (0.98g) in methanol and the S mixture stirred at room temperature for 3 hours. The solvent was then evaporated and the residue partitioned behyeen dichloromethane and water. The organic layer was dried and evaporated to give a white solid which was recrystallised from cyclohexane to give 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-propynylthio)-3-trifluoromethylpyrazole (compound 43) as off-white needles (0.77g), m.p. 136-137C.
By proceeding in a similar manner the following compounds were prepared:
5-(3-butenylthio)-4-N-(2,4-difluorophenyl)carbc x~mido- 1-methyl-3-trifluoromethylpyrazole (compound 44), m.p. 93-95C;
5-(2-bromo-2-propenylthio)-4-N-(2,4-difluorophenyl)-carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 45), m.p. 105-106C;
5-(3-bromo-2-propenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 46), m.p. 111-113C;
S-(cyanomethylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 47), m.p. 140-142C;
S -(3 -methyl-2-butenylthio)-4-N-(2,4-difluorophenyl)-carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 48), m.p. 122-123C;
- S-(cyclopropylmethylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 49), m.p. 99-101C;
5-(3-butynylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (compound S0), m.p.107-108C;
5-(2-chloropropylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 51), m.p. 75.5-76.5C;
4-N-(2,4-difluorophenyl)carboxamido-S-- (2,2-dimethoxyethylthio)-1-methyl-3-trifluoromethylpyrazole (compound 52), m.p. 118-119.5C;

WO 93/25535 ~1 376 ~ 9 PCr/EPs3/01466 5-(2-butenylthio)-4-N-(2,4-difluorophenyl)carbox~miclo- 1-methyl-3-trifluoromethylpyrazole (compound 53), m.p. 95-97C, 4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-5-(n-pentylthio)-3-trifluoromethylpyrazole (compound 54), m.p. 87-89C;
4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-5-(2-methylbutylthio)-3-trifluoromethylpyrazole (compound 55), m.p. 83-85C;
4-N-(2,4-di~luorophenyl)carboxarnido-1-methyl-5-(2-methyl-2-propenylthio)-3-trifluoromethylpyrazole (compound 56), m.p. 107-109C;
5-(2-chloro-2-propenylthio)-4-N-(2,4-difluorophenyl)carbox~mi~lo-l-methyl-3-trifluoromethylpyrazole (compound 57), m.p. 93-95C;
4-N-(2,4-difluorophenyl)carboxarnido-5-(2-methoxyethyl)-1-methyl-3-trifluoromethylpyrazole (compound 58), m.p. 88-90C;
5-(3-chloro-2-propenylthio)-4-N-(2,4-difluorophenyl)-carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 59), m.p. 95-96C.
Example 9 Thionyl chloride (2.4 ml) was added to a solution of 5-ethylthio-1-ethyl-3-trifluoromethylpyræole-4-carboxylic acid (0.5 g) in toluene and the reaction reflll~ed for 3 hours. After cooling, the solvent and excess thionyl chloride were removed under reduced pressure. The residue was dissolved in dichloromethane and triethylamine (0.34 ml~ was added followed by 2,4-difluoroaniline (0.2 ml) with stirring at room temperature for 2 hours. The mixture was poured into water and the organic layer was separated, washed with HCl, saturated sodium carbonate and brine.The organic phase was then dried (MgSO4) and evaporated under reduced pressure to give 5-ethylthio-1-ethyl-4-N-(2,4-difluorophenyl)carbox~miclo-3-trifluoromethylpyrazole (compound 60) as a beige solid (0.54 g), m.p. 91-93C.
By proceeding in a similar manner 5-ethylthio-1-ethyl-4-N-(2,4,6-trifluorophenyl)carboxamido-3-trifluoromethylpyrazole (compound 61) was prepared as a beige solid, m.p. 94-96C.

wo 93/2553~ ~ 37 ~8 9 pcr/Eps3/~466 E;xample 10 A r~ixture of 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid (2.0 g) and thionyl chloride (13.9 g) was heated under reflux in dry toluene (30 ml) for 1.5 hours, and evaporated in vacuo to give 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid chloride as an oil. A solution of this in dry tetrahydrofuran (20 ml) was added to a stirred solution of aniline (0.64 g) in dry tetrahydrofuran (30 ml) cont~ining triethylamine (0.7 g). The mixture was stirred over~ight, and the solid filtered off and washed with ether (50 rnl). The combined f;ltrates were evaporated in vacuo to give a brown solid, which after recryst~ tion from toluene/hexane gave 5-(4-fluorophenylthio)- l-methyl-4-N-(phenyl)carboxaII~ide-3-trifluoromethylpyrazole, compound 91 (1.4 g) as a brown solid, m.p.

By proceeding in a sir~ilar manner the following compounds were prepared from the corresponding carboxylic acids, wherein the syrnbols are as defined in the following table:
o H~

Rl Q~ I

Cpd. R3 P Q m.p./C
71 SMe 2,4-F2 4-F 164-167 72 CF3 3-Cl-4-F 4-F 169-170 73 CF3 3,4-F2 4-F152.5-153.5 74 CF3 2,4,5-F3 4-F 125-126 CF3 2-F 4-F 133.5-13S
76 CF3 4-Cl 4-F 142-143 77 CF3 2-F-4-Cl 4-F130.5-131.5 78 CF3 2,4,6-F3 4-F 175-177 CF3 4-F 4-F 129.5-131 81 CF3 2,4-CI2 4-F148.5-150.5 ~ W0 93/25535 ~ 3~768 9 PCI'/EP93/01466 Cpd. R3 P Q m.p./C
82 CF3 2,3,4-F3 4-F 145-147 83 CF3 2-F-4Br 4-F 120.5-122.5 84 CF3 2-F-4-Me 4-F 127- 128 CF3 3-F 4-F 111.5-113.5 86 CF3 2,3-F2 4-F, 119-121 87 CF3 2,5-F2 4-F 104-105 88 CF3 2,6-F2 4-F 146- 147 89 CF3 3,5-F2 4-F 114-116 CF3 2,3,6-F3 4-F 156-158 Example 11 To a stirred suspension of 5-(4-aminophenylthio)4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole ~2.3 g) in dry dichloromethane (30 ml), was added dimethyldisulphide (1.0 g) followed by the dropwise addition of tert-butylnitrite (1.1 g) over S minlltes. The mixture was stirred at 50C
for 3 hours, then overnight at ambient temperature before pouring into water. The organic layer was separated and the aqueous solution extracted again with dichloromethane. The combined organics were dried over anhydrous magnesium sulphate and evaporated in vacuo to give an oil. Purification by chromatography or silica gel eluting with a mixture of dichloromethane and hexane gave 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(4-methylthiophenylthio)-3-trifluoromethylpyrazole, compound 92 (0.9 g) as a cream solid, m.p. 122-124C.

Example 12 A suspension of 4-N-(2,4-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole (2.0 g), iodomethane (0.29 ml), powdered pot~ m hydroxide (0.286 g) and tetrabutyl~mmonium bromide (0.3 g) in tetrahydrofuran~ (5 ml) was stirred at room temperature for 26 hours, and the solid filtered off. The filtrate was evaporated in vacuo giving a residue to which was added dichloromethane and water. The organic phase was washed with saturated brine solution, dried over anhydrous magnesium sulphate and evaporated in vacuo to give an oil.
Trituration with ether gave a solid which was purified by ~137689 WO 93/25S35 , ' , ` ~ PCI/EP93/9~,6 chromatography on silica gel eluting with ether/n-hexane (1:1) to furnish 5-(4-fluorophenylthio)-1-methyl-4-N-methyl-N-(2,4-difluorophenyl)carboxarnido-3-trifluoromethylpyrazole, compound 93 (1.48 g) m.p. 99-100C in the form of a white solid.
S
Example 13 To a stirred solution of 5-(4-chlorophenylthio)-4-N-(2,4-difluorophenyl)carboxarnido-1-methyl-3-trifluoromethyl pyræole (0.63 g) in trifluoroacetic acid (8 rnl), was added dropwise at 0C a solution of 30~o hydrogen peroxide (0.19 rnl). After 2 hours at 0C
the mixture was allowed to warm to room temperature over 2 hours, then poured onto ice/water (50 ml). The precipate was collected, washed with water and dried over phosphorous pentoxide in a desiccator, and then purified by chromatography on silica gel eluting with ether in hexane (1:1) to give 5-(4-chlorophenylsulphinyl)-4-N-(2,4-difluorophenyl)carbox~micle-1 methyl-3-trifluoromethylpyrazole, compound 94 (0.426 g) m.p. 178-179C as a white solid Reference Exam~le 1 A mixture of 4-carboxy-S-chloro-1-methyl-3-trifluoromethylpyrazole (20.54g) and thionyl chloride in dry toluene was heated and stirred for 2 hours at 80C, cooled and evaporated.
Hexane was added to the residue which was filtered and the filtrate concentrated to give the acid chloride (21.4g). This was dissolved in dry tetrahydrofuran and added to a stirred solution of 2,4-difluoroaniline (13.4g) and triethylamine (17.46rnl) in dry tetrahydrofuran. The ~ ule was stirred at room temperature for 18 hours, filtered and the solid washed with tetrahydrofuran. The evaporated filtrates were recrystallised from toluene to give 5-chloro-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (20.7g) as an off white solid, m.p. 138-140C.
By proceeding in a similar manner the following compounds were prepared from the appropriately substituted starting materials:

~ WO 93/2s535 ~13 7C 8 9 PCr/EPs3/01466 o P ~ R3 Cl/\N' Rl Rl R3 p m.p. (C) CH3 CH3 2,4-diF 159-161 CH3 CF2Cl 2,4-DiF
CH3 CF2Cl 2,4,6-TriF
CH3 n-Pr 2,4-DiF 115-118 CH2CF3 CF3 2,4-DiF

4-Carboxy-5-chloro-1-methyl-3-trifluoromethylpyræole is described by L.F. Lee, F.M. Schleppnik, R.W. Salineider and D.H.
Campbell in J. Het. Chem. 27, 243 (1990).

Reference Example 2 - A mixture of 5-chloro4-formyl-1,3-dimethylpyrazole (30g), pot~ m perm~ng~n~te (30g) and pot~c~ m hydroxide in water was stirred at 60C for 1 hour. The cooled mixture was filtered, the filtrate acidified (concentrated hydrochloric acid solution) and the resulting precipitate was filtered, washed with water and dried to give 4-carboxy-5-chloro-1,3-dimethylpyrazole m.p. 197-201C.
By proceeding in a similar manner the following compounds were prepared from the appropriately substituted starting materials:
4-carboxy-5-chloro-1-methyl-3-chlorodifluoromethylpyræole m.p.
153-155C;
4-carboxy-5-chloro-1-methyl-3-(n-propyl)pyræole m.p. 130-131C;
4-carboxy-5-chloro-1-(2,2,2-trifluoroethyl)-3-trifluoromethylpyrazole.

Reference Example 3 1,3-Dimethyl-5-hydroxypyræolè (60g) was added to a mixture of phosphorus oxychloride and N,N-dimethylformamide and the WO 93/25535 ~1 3 7 6 ~ 9 PCr/EP93/~,66 reslllsing mLxture was heated at 95-100C for 16 to 18 hours. The reaction n~xture was poured onto ice-water, made basic (with arnmonia solution) and the resulting precipitate isolated and washed with water. Recryst~llic~tion from hexane give S-chloro-4-S formyl-1,3-dimethylpyrazole m.p. 77-80C.

Reference Example 4 Methylhydrazine (25g) was added to a mixture of ethyl acetoacetate (70g) in water. The reaction mixture was heated at 70C for 0.5 hours then cooled, extracted (chloroform) and dried (anhydrous magnesium sulphate). Evaporation of the solvent left a solid which was recrystallised from hexane/ethyl acetate to give 1,3-dimethyl-S-hydroxypyræole, m.p. 123-124C.

~eference Exam~le S
A solution of 4-formyl-1-methyl-5-(3-trifluoromethylphenoxy)-3-trifluoromethylpyrazole (7g), pot~ccillm perrn~ng~n~te (3.1g) and pot~ccium hydroxide (a~roxi.-l~tely 0.3g) in water was heated at 60 to 80C for 2 hours. The resllltin~ solution was cooled, filtered and the filtrate ~ ified. The reslllting precipitate was filtered, washed - with water and dried. Recryst~llic~tion of the solid gave 4-carboxy-l-methyl-5-(3-trifluoromethylphenoxy)-3-trifluoromethylpyrazole which was refluxed with thionyl chloride in toluene for 40 minlltes.
The resulting solution was cooled and concentrated to give 4-carboxylic acid chloride-1-methyl-5-(3-trifluoromethylphenoxy)-3-trifluoromethylpyrazole as a colourless oil.
By procee-ling in a similar manner 4-carboxylic acid chloride-1-methyl-5-(3-chlorophenoxy)-3-trifluoromethylpyrazole and 4-carboxylic acid chloride-5-(4-chlorophenoxy)-1,3-dimethylpyrazole was prepared.

Reference Example 6 3-Trifluoromethylphenol (6.9ml) was added to a warm solution of pot~ccillm t-blltoxide in t-butanol. The resulting Ir~ixture was stirred for 0.5 hours and 5-chloro4-forrnyl-1-methyl-3-trifluoromethylpyrazole (12g) was added. The rnLxture was heated at reflux for 3 hours then cooled, diluted with water and the resulting solid was isolated and dried. Recryst~llic~tion from ~ W093/25535 2~37~ PCr/EPs3/01466 hexane gave 4-formyl-1-methyl-5-(3-trifluoromethylphenoxy)-3-trifluoromethylpyrazole (9.2g), m.p. 81-82C.
By proceeding in a similar manner 4-formyl-1-methyl-5-(3-chlorophenoxy)-3-trifluoromethylpyrazole, m.p. 61-63C and 4-S formyl-1,3-dimethyl-5-(4-chlorophenoxy)pyrazole, m.p. 74-75C
were prepared.

Reference Example 7 5-Chloro-4-N-(2,4-difluorophenyl)carboxamido- 1-methyl-3-trifluoromethylpyrazole (29.7g) was added to a rI~ixture of sodium sulphide monohydrate (42g) and sulphur (5.6g) in isopropanol. The mLxture was heated at reflux under an inert atmosphere for 1.75 hours. The cooled solution was decanted, treated with charcoal and ffltered to give a brilliant yellow solution which was concentrated, filtered and then evaporated to dryness to give sodium 1-methyl-4-N-(2,4-difluorophenyl)carbox~ miclo-3-trifluoromethylpyrazole-5-thiolate (31.68 g) as a solid, m.p.311 - 313C.

Reference Example 8 Ethyl 3-(trifluoromethyl)pyrazole-4-carboxylate (S g), pot~cci~m carbonate (3.48 g) and ethyl iodide (2.3 ml) in acetonitrile were heated at reflux overnight. After cooling, ethyl acetate and water were added and the organic phase separated. The aqueous layer was extracted with ethyl acetate and the combined organic extracts were dried (m~gnesit~m sulphate) and evaporated under reduced pressure to give a yellow oil which was purified by cryst~llic~ti-~n in hexane to produce 4-ethoxycarbonyl-1-ethyl-3-trifluoromethylpyrazole as white crystals (3.65 g), ~ H (CDCl3) 1.25 (3H,t), 1.45 (3H,t), 4.10 (2H,q), 4.20 (2H,q), 7.90(1H,s) ppm.
Reference Example 9 n-Butyllithi~lm (2.5M, 3.5 ml) was added to a solution of diisopropylamine (1.25 ml) in tetrahydrofuran under an inert atmosphere at 0C. The solution was stirred lror 45 min at 0C and transfered to a solution of 4-ethoxycarbonyl-1-ethyl-3-trifluoromethane pyrazole (1.76 g) in tetrahydrofuran at -78C
under an inert atmosphere. The deep orange solution was stirred at -78C for 3.5 hours after which ethyl disulphide (1.1 ml) was added.

WO 93/25~;3~ ~1 37.B 8~ PCI`/EP93/~,66 The solution was allowed to warm to room temperature overnight with stirring. The precipitate was diluted with ether and the organic layer washed with 2M HCI solution. The aqueous layer was extracted once more with ether. The combined organic extracts were dried (MgS04) and evaporated under reduced pressure to give ethyl 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylate as a yellow oil (2 g). ~ H (CDC13) 1.25 (3H,t), 1.40 (6H,m), 3.0 (2H,q), 4.40 (4H,m) ppm.

Reference Example 10 Ethyl 5-ethylthio--1-ethyl-3-trifluoromethylpyrazole-4-carboxylate (2 g) was dissolved in ethanol and potassium hydroxide (1 g) in water was added. The reaction was stirred at room temperature overnight. Water and ethyl acetate were added and the lS organic layer was separated from the aqueous layer. The latter was acidified with concentrated HCl and extracted with ethyl acetate .
The combined organic extracts were dried (MgS04) and evaporated under reduced pressure to give 5-ethylthio-1-ethyl-3-trifluoromethyl pyrazole-4-carboxylic acid as a beige solid (1.42 g), ~H (CDCI3) 1.25 (3H,t), 1.45 (3H,t), 3.05 (2H,q), 4.45 (2H,q), 6.5 (lH, br s) ppm.

Reference Example 11 Lawesson's reagent [2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulphide], 2.14 g) was added to a solution o~ 5-chloro-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole (3.0 g) in dry toluene (110 ml), and the rnixture heated at 80-85C for 2 hours, and then at reflux for 1.50 hours. Additional Lawessonls reagent (3.57 g) was added, with heating under reflux conditions for a further 9 hours. The solvent was evaporated in vacuo and the residue purified by chromatography on silica gel, eluting with dichloromethane/hexane (1:1) to furnish 5-chloro-4-N-(2,4-difluorophenyl)thiocarboxamido-l-methyl-3-trifluoromethylpyrazole (2.49 g) as a yellow oil.

Reference Example 12 Methyl 5-(4-fluorophenylthio)-1-methyl-3-methylthiopyrazole-4-carboxylate (1.0 g) wa~ heated under reflux for 2.5 hours with a solution of pot~csillm hydroxide (0.4 g), water (3 ml) and methanol.

~WO 93/25535 21 37 ~ 8 9 PCr/EP93/01466 After evaporation in vacuo the residue was dissolved in water, filtered, and the filtrate acidified to pH 1 ~vith hydrochloric acid.
The precipated solid was filtered and dried over phosphorus pentoxide in a desiccator, yielding 5-(4-fluoro-phenylthio)-1-methyl-3-methylthiopyrozole-4-carboxylic acid (1.0 g).

Reference Example 13 To a stirred solution of methyl 5-amino-1-methyl-3-methylthiopyrazole-4-carboxylate (2.0 g) in dichloromethane, was added 4-fluorophenyldisulphide (5.1 g). A solution of tert-butyl nitrite (2.0 g) in dichloromethane (5 ml) was added portionwise during 20 minutes, and the mixture stirred overnight. After evaporation in vacuo the residue was chromatographed on silica gel eluting with dichloromethane/hexane (1:1) to give methyl 5-(4-fluorophenylthio)-1-methyl-3-methylthiopyrazole-4-carboxylate methyl (1.2 g) m.p. 92-94C, after recryst~llic~tinn from cyclohexane.

Reference Example 14 To a solution of 2-cyano-3,3-bismethylthio propenoic acid methyl ester (10.1 g) in methanol was added acetic acid (20 ml), followed by methylhydrazine (2.3 g) in one portion. The mixture was stirred overnight and evaporated in vacuo. The residue was triturated with water and the solid filtered off, and purified by chromatography on silica gel eluting with dichloromethane to give methyl 5-amino-1-methyl-3-methylthiopyrazole-4-carboxylate (1.5 g) as a white solid.

Reference Example 15 A mixture of S-chloro-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid (2.0 g), 4-fluorothiophenol (1.66 g) and anhydrous pot~sillm carbonate (3.26 g) was heated under reflux in acetonitrile with stirring for 4 hours. After filtration the filtrate was evaporated, acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined extract was dried (anhydrous m~gnesillm sulphate)j filtered and evaporated in vacuo. Recryst~ tion from ether/hexane gave 5-(4-fluorophenylthio)-1-methyl-3-Wo 93/2553~ ~1 3 76 ~ 9 PCI'/EP93/~66 trifluoromethylpyrazole-4-carboxvlic acid (0.98 g), m.p. 190-193.7C
as a white solid.

Reference Example 16 5-Chloro-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid (15.3g,), 2-methylpropanethiol (19.2 ml,), and anhydrous pot~ m carbonate (40.5g) were heated in acetonitrile at reflux for 68 hours under an inert atmosphere. The reaction mLxture was filtered hot and then evaporated to give a cream solid which was then suspended in 2M hydrochloric acid and extracted with dichloromethane. The extracts were combined, dried over anhydrous m~gnesillm sulphate, filtered and evaporated. The resulting cream solid was then triturated with hexane to give 1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole~-carboxylic acid (6.4g) as a white solid m.p.183-184 C.
By proceeding in a similar manner 1-methyl-5-(2-methylpropylthio)-3-pentafluoroethylpyrazole-4-carboxylic acid was prepared, ~H (DMSO d6) 0.96 (d,6H), 1.68 (m,lH), 2.85 (d,2H), 4.00(s,3H), 13.20 (s,1H) ppm.
According to a feature of the present invention, there is provided a method for controlling the growth of weeds (i.e.
undesired vegetation) at a locus which comprises applying to the locus a herbicidally effective amount of at least one N-substituted pyrazole derivative of formula I or an agriculturally acceptable salt thereof. For this purpose, the N-substituted pyrazole derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers and/or surface active agents suitable for use in herbicidal compositions), for example as hereinafter described.
The compounds of formula I show herbicidal activity against dicotyledonous (i.e. broad-leafed) and monocotyledonous (e.g.
grass) weeds by pre- and/or post-emergence application.
By the term "pre-emergence application" is meant application to the soil in which the weed seeds or seedlings are present before . emergence of the weeds above the surface of the soil. By the term "post-emergence application" is meant application to the aerial or exposed portions of the weeds which have emerged above the ~ wO 93/25535 213 76~ 9 ~ PCr/EP93/01466 surface of the soil. For example, the compounds of formula I may be used to control the growth of:
broad-leafed weeds, for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Ipomoea spp. e.g. Ipomoea purpurea, Sesbania eY~lt~t~, Sinapis arvensis, Solanum nigrum and X~nthillm strumarium, and grass weeds, for example Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Eleusine indica and Setaria spp, e.g. Setaria faberii or Setaria viridis, and sedges, for example, Cyperus esculentus.
The amounts of compounds of formula I applied vary with the nature of the weeds, the compositions used, the time of application, the climatic and edaphic conditions and (when used to control the growth of weeds in crop-growing areas) the nature of the crops.
When applied to a crop-growing area, the rate of application should be sufficient to control the growth of weeds without c~ ing substantial permanent damage to the crop. In general, taking these factors into account, application rates between G.Olkg and Skg of active material per hectare give good results. However, it is to be understood that higher or lower application rates may be used, depending upon the particular problem of weed control encountered.
The compounds of formula I may be used to control selectively the growth of weeds, for example to control the growth of those species hereinbefore mentioned, by pre- or post-emergence application in a directional or non-directional fashion, e.g. by directional or non-directional spraying, to a locus of weed infestation which is an area used, or to be used, for growing crops, for example cereals, e.g. wheat, barley, oats, maize and rice, soya beans, field and dwarf beans, peas, lucerne, cotton, pe~n~-t~, flax, onions, carrots, cabbage, oilseed rape, sunflower, sugar beet, and permanent or sown gr~c~l~n~l before or after sowing of the crop or before or after emergence of the crop. For the selective control of weeds at a locus of weed infestation which is an area used, or to be used, for growing of crops, e.g. the crops hereinbefore mentioned, app~ication rates between 0.01kg and 4.0kg, and preferably between Wo93/25535 21 S7~89 pcr/Ep93/~66 0.01kg and 2.0kg, of active material per hectare are particularly suitable.
The compounds of formula I may also be used to control the growth of weeds, especially those indicated above, by pre- or post-S emergence application in established orchards and other tree-growing areas, for example forests, woods and parks, and plantations, e.g. sugar cane, oil palm and rubber plantations. For this purpose they may be applied in a directional or non- directional fashion (e.g. by directional or non-directional spraying) to the weeds or to the soil in which they are expected to appear, before or after planting of the trees or plantations at application rates between 0.25kg and S.Okg, and preferably between 0.5kg and 4.0kg of active material per hectare.
The compounds of formula I may also be used to control the growth of weeds, especially those indicated above, at loci which are not crop-growing areas but in which the control of weeds is nevertheless desirable.
Examples of such non-crop-growing areas include airfields, industriàl sites, railways, roadside verges, the verges of rivers, irrigation and other waterways, scrublands and fallow or uncultivated land, in particular where it is desired to control the growth of weeds in order to reduce fire risks. When used for such purposes in which a total herbicidal effect is frequently desired, the active compounds are normally applied at dosage rates higher than those used in crop-growing areas as hereinbefore described. The precise dosage will depend upon the nature of the vegetation treated and the effect sought.
Pre- or post-emergence application, and preferably pre-emergence application, in a directional or non-directional fashion (e.g. by directional or non-directional spraying) at application rates between 1.0kg and 20.0kg, and preferably between S.0 and 10.0kg, of active material per hectare are particularly suitable for this purpose.
When used to control the growth of weeds by pre-emergence application, the compounds of formula I may be incorporated into the soil in which the weeds are expected to emerge. It will be appreciated that when the compounds of formula I are used to control the growth of weeds by post-emergence application, i.e. by ~ W O 93/25535 21 3 7 6 8 9 PC~r/EP93/01466 application to the aerial or exposed portions of emerged weeds, the compounds of formula I will also normally come into contact with the soil and may also then exercise a pre-emergence control on later-germin~ting weeds in the soil.
Where especially prolonged weed control is required, the application of the compounds of formula I may be repeated if required.
According to a further feature of the present invention, there are provided compositions suitable for herbicidal use comprising one or more of the N-substituted pyrazole derivatives of formula I or an agriculturally acceptable salt thereof, in association with, and preferably homogeneously dispersed in, one or more compatible agriculturally- acceptable diluents or carriers and/or surface active agents [i.e. diluents or carriers and/or surface active agents of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula I]. The term "homogeneously dispersed" is used to include compositions in which the compounds of formula I are dissolved in other components. The term "herbicidal compositions"
is used in a broad sense to inclntle not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use. Preferably, the compositions contain from 0.05 to 90~o by weight of one or more compounds of formula I.
The herbicidal compositions may contain both a diluent or carrier and surface-active (e.g. wetting, dispersing, or emulsifying) agent. Surface-active agents which may be present in herbicidal compositions of the present invention may be of the ionic or non-ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g. nonyl- or octyl-phenols, or carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by con~enc~tion with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyl- and dioctyl-sodium sulphonosucçin~tes and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates.

WO93/25535 21 3~t6~9 . PCI/EP93/~66 Suitably, the herbicidal compositions according to the present invention may comprise up to lO~o by weight, e.g. from 0.05% to 10% by weight, of surface-active agent but, if desired, herbicidal compositions according to the present invention may comprise higher proportions of surface-active agent, for example up to lS~o by weight in liquid em~ ble suspension concentrates and up to 25% by weight in liquid water soluble concentrates.
Examples of suitable solid diluents or carr~ers are ~hlminillm silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent carbon black and clays such as kaolin and bentonite. The solid compositions (which may take the form of dusts, granules or wettable powders) are preferably prepared by grinding the compounds of formula I with solid diluents or by impregn~ting the solid diluents or carriers with solutions of the compounds of formula I in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders. Granular formulations may be prepared by absorbing the compounds of formula I (dissolved in suitable solvents, which may, if desired, be volatile) onto the solid diluents or carriers in granular form and, if desired, evaporating the solvents, or by gr~n~ ting compositions in powder form obtained as described above. Solid herbicidal compositions, particularly wettable powders and granules, may contain wetting or dispersing agents (for example of the types described above), which may also, when solid, serve as diluents or carriers.
Liquid compositions according to the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may incorporate a surface-active agent.
Suitable liquid diluents for incorporation in the liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal and vegetable oils and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents). Surface-active agents, which may be present in the liquid compositions, may be ionic or non-ionic (for example of the types described above) and may, when liquid, also serve as diluents or carriers.
Powders, dispersible granules and liquid compositions in the form of concentrates may be diluted with water or other suitable ~ W 0 93/25S35 ~1376-~ PC~r/~P93/01466 diluents, for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
When desired, liquid compositions of the compound of formula I
may be used in the form of self-emulsifying concentrates Cont~ining the active substances dissolved in the emulsifying agents or in solvents cont~inin~ emulsifying agents compatible with the active substances, the simple addition of water to such concentrates producing compositions ready for use.
Liquid concentrates in which the diluent or carrier is an oil may be used without further dilution using the electrostatic spray technique.
Herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, stabilisers, sequestering agents, anti-caking agents, colouring agents and corrosion inhibitors. These adjuvants may also serve as carriers or diluents.
Unless otherwise specified, the following percenta~es are by weight. Preferred herbicidal compositions according to the present invention are aqueous suspension concentrates which comprise from 10 to 70% of one or more compounds of formula I, from 2 to 10% of surface-active agent, from 0.1 to 5% of thickener and from 15 to 87.9% of water;
wettable powders which comprise from 10 to 90% of one or more compounds of formula I, from 2 to 10% of surface-active agent and from 8 to 88% of solid diluent or carrier;
water soluble or water dispersible powders which comprise from 10 to 90% of one or more compounds of formula I, from 2 to 40% of sodium carbonate and from 0 to 88% of solid diluent;
liquid water soluble concentrates which comprise from S to 50%, e.g. 10 to 30%, of one or more compounds of formula I, from 5 to 25~o of surface-active agent and from 25 to 90%, e.g. 45 to 85%, of water miscible solvent, e.g. dimethylformamide, or a mixture of waLer-miscible solvent and water;
liquid em~ ifi~hle suspension concentrates which comprise from 10 to 70% of one or more compounds of formula I, from 5 to WO 93/25535 ~31`B ~ Pcr/EP93/~466 15~o of surface-active agent, from 0.1 to 5% of thickener and from 10 to 84.9~c of organic solvent;
granules which comprise from 1 to 90~o, e.g. 2 to 10% of one or more compounds of formula I, from 0.5 to 7~c, e.g. 0.5 to 2~o, of surface-active agent and from 3 to 98.5~o, e.g. 88 to 97.5~o, of granular carrier and em1l1cifi~ble concentrates which comprise 0.05 to 90~o, and preferably from 1 to 60~ of one or more compounds of formula I;
from 0.01 to 10%, and preferably from 1 to 10%, of surface-active agent and from 9.99 to 99.94%, and preferably from 39 to 98.99~o, of organic solvent.
Herbicidal compositions according to the present invention may also comprise the compounds of formula I in association with, and preferably homogeneously dispersed in~ one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described.
Examples of other pesticidally active compounds which may be included in, or used in conjunction with, the herbicidal compositions of the present invention include herbicides, for example to increase the range of weed species controlled for example alachlor [2-chloro-2,6'-diethyl-N-(methoxy-methyl)-acetanilide], atrazine [2-chloro-4-ethylamino-6-isoplo~ylamino-1,3,5-triazine], bromoxynil [3,5-dibromo-4-hydroxybenzonitrile], chlortoluron [N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea], cy~n~7ine [2-chloro-4-(1-cyano-1- methylethylamino)-6-ethylamino-1,3,5-triazine], 2,4-D [2,4-dichlorophenoxy-acetic acid], dicamba [3,6-dichloro-2-methoxybenzoic acid], difenzoquat [1,2- dimethyl-3,5-diphenyl-pyrazolium salts], fla~ opl,lethyl [methyl N-2-(N- benzoyl-3-chloro-4-fluoroanilino)-propionate], fluometuron [N'-(3-trifluoro-methylphenyl)-N,N-dimethylurea], isoproturon [N'-(4-isopropylphenyl)-N,N-dimethylurea], insecticides, e.g. synthetic pyrethroids, e.g. permethrin and cypermethrin, and fungicides, e.g.
carb~m~tec, e.g. methyl N-(1-butyl-carbamoyl- benzimidazol-2-yl)carbamate, and triazoles e.g. 1-(4-chloro-phenoxy)-3,3- dimethyl-- 1-(1,2,4-triazol-1-yl)-butan-2-one.
Pesticidally active compounds and other biologically active materials which may be included in, or used in conjunction with, the WO 93/25535 ~ 8.~ PCr/EPs3/01466 herbicidal compositions of the present invention, for example those hereinbefore mentioned, and which are acids, may, if desired, be utilized in the form of conventional derivatives, for example alkali metal and amine salts and esters.
S According to a further feature of the present invention there isprovided an article of m~n1-f~ct11re comprising at least one of the N-substituted pyrazole derivatives of formula I or, as is preferred, a herbicidal composition as hereinbefore described, and preferably a herbicidal concentrate which must be diluted before use, comprising at least one of the N-substituted pyrazole derivatives of formula I
within a container for the aforesaid derivative or derivatives of formula I, or a said herbicidal composition, and instructions physically associated with the aforesaid container setting out the manner in which the aforesaid derivative or derivatives of forrnula I
or herbicidal composition contained therein is to be used to control the growth of weeds. The containers will norrnally be of the types convention~11y used for the storage of chemical substances which are solid at normal ambient temperatures and herbicidal compositions particularly in the form of concentrates, for example cans and drurns of metal, which may be internally lacquered, and plastics materials, bottles or glass and plastics materials and, when the contents of the container is a solid, for example granular, herbicidal compositions, boxes, for example of cardboard, plastics materials and metal, or sacks. The containers will normally be of sufficient capacity to contain amounts of the N-substituted pyrazole derivative or herbicidal compositions sufficient to treat at least one acre of ground to control the growth of weeds therein but will not exceed a size which is convenient for conventional methods of handling. The instructions will be physically associated with the container, for example by being printed directly thereon or on a label or tag affixed thereto. The directions will normally indicate that the contents of the container, after dilution if necessary, are to be applied to control the growth of weeds at rates of application between 0.01kg and 20kg of active material per hectare in the manner and for the purposes hereinbefore described.
The following Exam~?les illustrate herbicidal compositions according to the present invention:

WO 93/25535 ~13 7 ~ PCI/EP93~466 EXAMPLE Cl A soluble concentrate is formed from:
Active ingredient (compound 1) 20% w/v Potassiumhydroxide solution 33~o w/v 10% v/v Tetrahydrofurfuryl alcohol (THFA) lO~o v/v Water , to 100 volumes.
by stirring THFA, active ingredient (compound 1) and 90% volume of water and slowly adding the pot~c~ m hydroxide solution until a steady pH 7-8 iS obtained then m~king up to volume with water.
Similar soluble concentrates may be prepared as described above by replacing the N-substituted pyrazole (compound 1) with other compounds of formula I.

EX~MPLE C2 A wettable powder is formed from:
Active ingredient (compound 1) 50~o w/w Sodium dodecylberlzene sulphonate 3% W/W
Sodium lignosulphate 5% w/w Sodium formaldehyde alkylnaphthalene sulphonate 2% w/w Microfine silicon dioxide 3% w/w and China clay 37% w/w by blending the above ingredients together and grinding the mixture in an air jet mill.
Similar wettable powders may be prepared as described above by 25 replacing the N-substituted pyrazole (compound 1) with other compounds of formula I.

A water soluble powder is formed from:
Activeingredient (compound 1) 50% w/w Sodium dodecylbenzenesulphonate 1% w/w Microfine silicon dioxide 2% w/w Sodium bicarbonate 47% w/w by mixing the above ingredients and grinding the above mLxture in a h~mmer 35 mill.
- Similar water soluble powders may be prepared as described above by replacing the N-substituted pyrazole (compound 1) with other compbunds of formula I.

~ W O 93/2553~ 2~ 3 ~ ff 8 g PC~r/EP93/01466 .

Representative compounds of formula I have been used in herbicidal applications according to the following procedures.

- METHOD OF USE OF HERBICID~L COMPOUNDS:
s a) General Appropriate quantities of the compounds used to treat the plants were dissolved in acetone to give solutions equivalent to application rates of up to 4000g test compound per hectare (g/ha). These solutions were applied from a 10 standard laboratory herbicide sprayer delivering the equivalent of 290 litres of spray fluid per hectare.

b) Weed control: Pre-emergence The seeds were sown in 70 mm square, 75 mm deep plastic pots in non-sterile soil . The quantities of seed per pot were as follows:-Weed speciesApprox number of seeds/pot 1) Broad-leafedweeds Abutilon theophrasti 10 AmaraIlthus retroflexus 20 Galium aparine 10 Ipomoea purpurea 10 Sinapis arvensis 15 X~n~hillm strumarium 2.

2) Grass weeds Alopecurus myosuroides 15 Avena fatua 10 Echinochloa crus-galli 15 Setaria viridis 20.

3) Sedges Cyperus esculentus 3.

Crop 1) Broad-leafed Cotton 3 Soya 3.

2) Grass Maize 2 Rice 6 Wheat 6.

WO 93/25535 PCI/EP93/OI,~L66 ~37~8~ ~
- so The compounds of the invention were applied to the soil surface, cont~inin~ the seeds, as described in (a). A single pot of each crop and each weed was allocated to each treatment, with unsprayed controls and controls 5 sprayed with acetone alone.
After treatment the pots were placed on capillar~ m~tting kept in a glass house, and watered overhead . Visual ~csessment of crop damage was made 20-24 days after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the plants in the 10 control pots.

c) Weed control: Post-emergence The weeds and crops were sown directly into John Innes potting compost in 75 mrn deep, 70 mm square pots except for 15 ` Arnaranthus which was pricked out at the see~llin~ stage and transferred to the pots one week before spraying. The plants were then grown in the greenhouse until ready for spraying with the compounds used to treat the plants. The number of plants per pot were as follows :-1) Broad leafed weeds Weed species Number of plants per pot Growth stage Abutilon theophrasti 3 1-2 leaves Amaranthus retrofiexus 4 1-2 leaves Galium aparine 3 1st whorl Ipomoea purpurea 3 1-2 leaves Sinapisarvensis 4 21eaves X~nthinm strumarium 1 2-3 leaves.

2) Grass weeds Weed species Number of plants per p~t Growth sta~e Alopecurus myosuroides 8-12 1-2 leaves Avena fatua 12-18 1-2 leaves Echinochloacrus-galli 4 2-3 leaves Setaria viridis 15-25 1-2 leaves.
, ~ wo 93/2s535 ~13 7689 pcr/Ep93/ol466 3) Sed~es Weed species Number of plants per pot Growth stage - Cyperus esculentus 3 3 leaves.
s 1) Broad leafed C~rops ~umber of plants per pot Growth stage Cotton 2 1 leaf Soya 2 2 leaves.

2) Grass Crops Number of plants per pot Growth stage Maize 2 2-3 leaves Rice 4 2-3 leaves Wheat 5 2-3 leaves.
The compounds used to treat the plants were applied to the plants as described in (a). A single pot of each crop and weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.

After treatment the pots were placed on capillary m~tting in a glass house, and watered overhead once after 24 hours and then by controlled sub-irrigation. Visual ~c~escment of crop damage and weed control was made 20-24 days after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the plants in the control pots.
The compounds of the invention, used at 4kg/ha or less, have shown an excellent level of herbicidal activity together with crop tolerance on the weeds used in the foregoing experiments.
When applied either pre- or post emergence at 4000g/ha or less compounds 1 to 106 gave at least 70~o reduction in growth of one or more of the weed species; the compounds also showed selectivity against at least one crop species.
. . . ,, , ' .

Claims (25)

1. An N-substituted pyrazole derivative of formula I:

wherein:
R1 represents:-a straight or branched chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group containing from 3 to 6 carbon atoms optionally substituted by one or more groups R6;
a group -(CH2)n-Ar wherein n represents zero or one and Ar represents a phenyl group optionally substituted by one or more groups selected from halogen, nitro, R6, -OH, -OR6, -S(O)mR7 and -NR8R9;
a straight or branched chain alkenyl or alkynyl group containing up to 6 carbon atoms optionally substituted by one or more groups selected from halogen, R6 and -OR6; or a group selected from -SO2NR61R62, -SO2R71 and -CONR61R62;
R2 represents:-a group -X-R10;
R3 represents:-a hydrogen or halogen atom;
a straight or branched chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group containing from 3 to 6 carbon atoms optionally substituted by one or more halogen atoms or groups R6;
a cyano or nitro group;
a group -S(O)mR6;

phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR6 and cyano; or a group -CO2R6;
R4 represents:
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR6, -S(O)mR7 and -NR8R9; or pyridyl optionally substituted by one or more groups selected from halogen, nitro, R6, OR6, -S(O)mR7 and -NR8R9;
R5 represents the hydrogen atom or a straight- or branched-chain alkyl group containing up to 6 carbon atoms;
Y represents the oxygen or sulphur atom;
R6 represents a straight- or branched- chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R61 and R62, which may be the same or different, each represents a straight- or branched- chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R7 represents a straight- or branched- chain alkyl group containing up to 4 carbon atoms optionally substituted by one or more halogen atoms;
R71 represents:-a straight- or branched- chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms; or phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR6, -S(O)mR7 and -NR8R9;
R8 and R9, which may be the same or different, each represents hydrogen or a straight or branched chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R10 represents:-phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR8, -S(O)mR7, -NHCOR6 and -NR8R9;
pyridyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR6, -S(O)mR7, -NHCOR6 and -NR8R9;
a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to ten carbon atoms wherein the chain may optionally comprise one or more oxygen or sulphur atoms or -NR5-groups, optionally substituted by one or more groups selected from halogen, -OR8, -S(O)qR6, -NR8R9, -CO2R8, -QCOR6, -NHCOR6, -CONR8R9, R12, -COR8, R13 and cyano;
X represents an oxygen atom, -NR11- or -S(O)p-, R11 represents hydrogen or a straight or branched chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
R12 represents a cycloalkyl group containing from three to seven ring atoms, which may optionally contain from one to three heteroatoms in the ring selected from oxygen, sulphur and -NR5-;
R13 represents:
a cycloalkyl group containing from 3 to 6 carbon atoms which is substituted by one or more groups selected from halogen, R8 and -OR8; or a cycloalkenyl group containing 5 or 6 carbon atoms optionally substituted by one or more groups selected from halogen, R8 and -OR8;
m represents zero, one or two; p represents zero, one or two;
q represents zero, one or two;
with the proviso that when Y represents oxygen, R2 represents methylthio or N-phenylamino, R4 represents phenyl and R5 represents hydrogen, R1 and R3 do not simultaneously represent methyl;
and agriculturally acceptable salts thereof.

2. A compound according to claim 1 wherein:
R1 represents:-a straight or branched chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group containing from 3 to 6 carbon atoms optionally substituted by one or more groups R6; or a group -(CH2)n-Ar wherein n represents zero or one and Ar represents phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OH, -OR6, -S(O)mR7 and -NR8R9;
R3 represents:-a hydrogen or halogen atom;
a straight or branched chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group containing from 3 to 6 carbon atoms optionally substitued by one or more groups R6;
a cyano group;
a group -S(O)mR6;
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR6 and cyano; or a group -CO2R6;
R10 represents:-phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR8, -S(O)mR7, -NHCOR6 and -NR8R9; or pyridyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR6, -S(O)mR7, -NHCOR6 and -NR8R9.

3. A compound according to claim 2 wherein X
represents an oxygen or sulphur atom or a group -NR11.

4. A compound according to claim 1 wherein:
R1 represents:-a straight or branched chain alkyl group containing up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group containing from 3 to 6 carbon atoms optionally substituted by one or more groups R6; or a group -(CH2)n-Ar wherein n represents zero or one and Ar represents phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OH, -OR6, -S(O)mR7 and -NR8R9;

R3 represents:-a hydrogen or halogen atom;
a straight or branched chain alkyl group containing Up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group containing from 3 to 6 carbon atoms optionally substituted by one or more groups R6;
a cyano or nitro group;
a group -S(O)mR6;
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6,-OR6 and cyano; or a group -CO2R6;
R10 represents:-straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to ten carbon atoms wherein the chain may optionally comprise one or more oxygen or sulphur atoms or -NR5-groups, optionally substituted by one or more groups selected from halogen, -OR8, -S(O)qR6, -NR8R9, -CO2R8, -OCOR6, -NHCOR6, -CONR8R9, R12 and cyano.

5. A compound according to claim 1 wherein:
R3 represents:-a hydrogen or halogen atom;
a straight or branched chain alkyl group containing Up to 6 carbon atoms optionally substituted by one or more halogen atoms;
a cycloalkyl group containing from 3 to 6 carbon atoms optionally substituted by one or more groups R6;
a cyano or nitro group;
a group -S(O)mR6;
phenyl optionally substituted by one or more groups selected from halogen, nitro, R6, -OR6 and cyano; or a group -CO2R6;
R10 represents a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to ten carbon atoms wherein the chain may optionally comprise one or more oxygen or sulphur atoms or -NR5- groups, optionally substituted by one or more groups selected from halogen, -OR8, -S(O)qR6, -NR8R9, -CO2R8, -OCOR6, -NHCOR6, -CONR8R9, R12, -COR8, R13 and cyano.

6. A compound according to claim 1, 2 or 3 wherein R10 represents phenyl substituted by at least one halogen atom.

7. A compound according to claim 1, 4 or 5 wherein R10 represents a straight- or branched- chain alkyl or alkenyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms.

8. A compound according to claim 1, 4 or 5 wherein R2 represents -SR10, wherein R10 represents an alkenyl group containing up to four carbon atoms.

9. A compound according to claim 1, 4 or 5 wherein R10 represents a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms.

10. A compound according to claim 1 or 5 wherein R10 represents a group -CH2R12 or -CH2R13.

11. A compound according to any one of the preceding claims wherein Y represents an oxygen atom.

12. A compound according to any one of the preceding claims wherein R1 represents methyl or ethyl.

13. A compound according to any one of the preceding claims wherein R3 represents trifluoromethyl.

14. A compound according to any one of the preceding claims wherein R4 represents 2,4-difluorophenyl or 2,4,6-trifluorophenyl.

15. A compound according to any one of the preceding claims wherein R5 represents the hydrogen atom.

16. A compound according to any one of the preceding claims wherein X represents a sulphur atom.

17. A compound according to any one of the preceding claims wherein X represents an oxygen atom.

18. A compound according to claim 1 wherein:
R1 represents an alkyl group containing one or two carbon atoms optionally substituted by one or more halogen atoms which may be the same or different;
R3 represents:
an alkyl group containing up to three carbon atoms optionally substituted by up to five halogen atoms which may be the same or different; or a group -SMe;
R4 represents phenyl optionally substituted by from one to three groups selected from halogen, trifluoromethyl and methoxy;
R5 represents the hydrogen atom or a methyl group;
Y represents an oxygen or sulphur atom;
X represents an oxygen atom or a group -S(O)p-;
R10 represents:
phenyl or pyridyl optionally substituted by a group selected from halogen, methoxy, hydroxy, -NHCOMe, -NH2, -SMe, methyl and trifluoromethyl;
a cycloalkyl group containing from 3 to 6 carbon atoms;
a straight- or branch- chained alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more groups selected from from halogen, -CO2Et, cyano, cyclopropyl, methoxy, and-CONHMe;
and p represents zero or one.

19. A compound according to claim 1 which is:
4-N-(2,4-difluorophenyl)carboxamido-5-(4-chlorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-methoxyphenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-bromophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-hydroxyphenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(2-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(3-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-phenylthio-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-acetamidophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-methylphenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(3-trifluoromethylphenyl)carboxamido-5-(4-methylphenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-methoxyphenyl)carboxamido-5-(4-chlorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(3-chlorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-trifluoromethylphenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-phenylcarboxamido-5-(3-trifluoromethylphenylthio)-1,3-dimethylpyrazole, 4-N-(4-fluorophenyl)carboxamido-5-(4-chlorophenylthio)-1,3-dimethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-chlorophenylthio)-1,3-dimethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(3-chlorophenylthio)-1,3-dimethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-fluorophenoxy)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-fluorophenyl)carboxamido-5-(3-trifluoromethylphenoxy)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(3-chlorophenoxy)-1-methyl-3-trifluoromethylpyrazole, 4-N-phenylcarboxamido-5-(4-chlorophenoxy)-1,3-dimethylpyrazole, 4-N-(4-fluorophenyl)carboxamido-5-(4-chlorophenoxy)-1,3-dimethylpyrazole, or 4-N-(2,4-difluorophenyl)carboxamido-5-(4-chlorophenoxy)-1-methyl-3-trifluoromethylpyrazole, or an agriculturally accepable salt thereof.

20. A compound according to claim 1 which is:
4-N-(2,4-difluorophenyl)carboxamido-5-(n-butylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(2-propenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-isopropylthio-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-ethylthio-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(3-chloropropylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-methylthio-1-methyl-3-trifluoromethylpyrazole, or 4-N-(2,4-difluorophenyl)carboxamido-5-(2,2,2-trifluoroethoxy)-1-methyl-3-trifluoromethylpyrazole or an agriculturally accepable salt thereof.

21. A compound according to claim 1 which is 4-N-(2,4-difluorophenyl)carboxamido-5-(ethoxycarbonylmethylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(1-methylbutylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(n-hexylthio)-1-methyl-3-trifluoromethylpyrazole, 5-cyclopentylthio-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(n-propylthio)-3-trifluoromethylpyrazole, 5-cyclohexylthio-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(1-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(3-methylbutylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(1,1-dimethylethylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-ethoxy-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-propynylthio)-3-trifluoromethylpyrazole, 5-(3-butenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(2-bromo-2-propenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(3-bromo-2-propenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(cyanomethylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(3-methyl-2-butenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(cyclopropylmethylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(3-butynylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(2-chloropropylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(2,2-dimethoxyethylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(2-butenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(n-pentylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methylbutylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methyl-2-propenylthio)-3-trifluoromethylpyrazole, 5-(2-chloro-2-propenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(2-methoxyethyl)-1-methy1-3-trifluoromethylpyrazole, 5-(3-chloro-2-propenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-ethylthio-1-ethyl-4-N-(2,4-difluorophenyl)carboxamido-3-trifluoromethyl pyrazole, 5-ethylthio-1-ethyl-4-N-(2,4,6-trifluorophenyl)carboxamido-3-trifluoromethylpyrazole, or 5-(N-methylaminocarbonylmethylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, or an agriculturally accepable salt thereof.

22. A compound according to claim 1 which is:
4-N-(2,4-difluorophenyl)-5-(4-fluorophenylthio)-thiocarboxamido-1-methyl-3-trifluoromethylpyrazole, 3-chlorodifluoromethyl-5-(4 fluorophenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methylpyrazole, 3-chlorodifluoromethyl-5-(4-fluorophenylthio)-1-methyl-4-N-(2,4,6-trifluorophenyl)carboxamidopyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-pyridylthio)-3-trifluoromethylpyrazole, 5-(4-aminophenylthio)-4-N-(2,4difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 5-(3-chloro-4-fluorophenylthio)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-trifluoromethylpyrazole, 4-N-(2,4 difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-(n-propyl)pyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-(2,2,2-trifluoroethyl)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-methylthiopyrazole.
4-N(3-chloro-4-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(3,4-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4-N-(2,4,5-trifluorophenyl)carboxamidopyrazole, 4-N-(2-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-chlorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-chloro-2-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4-N-(2,4,6-trifluorphenyl)carboxamidopyrazole, 4-N-(2-chloro-4-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-dichlorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4-N-(2,3,4-trifluorophenyl)carboxamidopyrazole, 4-N-(4-bromo-2-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-4-N-(2-fluoro-4-methylphenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N-(3-fluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,3-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,5-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,6-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(3,5-difluorophenyl)carboxamido-5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpylazole, 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4-N-(2,3,6-trifluorophenyl)carboxamidopyrazole, 5-(4-fluorophenylthio)-1-methyl-4-N-(phenyl)carboxamido-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(4-methylthiophenylthio)-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-4-N-methyl-N-(2,4-difluorophenyl)carboxamido-3-trifluoromethylpyrazole, 5-(4-chlorophenylsulphinyl)-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(n-propyloxy)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropyloxy)-3-trifluoromethylpyrazole, 3-chlorodifluoromethyl-4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropyloxy)pyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-ethyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamido-1-ethyl-5-(2-propenylthio)-3-trifluoromethylpyrazole, 4-N-(2,4,6-trifluorophenyl)carboxamido-1-ethyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,3-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,6-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,3,6-trifluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4,6-trifluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,5-difluorophenyl)carboxamido-1-methyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, or 4-N-(2,4-difluorophenyl)carboxamido-1-methyl-5-(2-methypropylthio)-3-pentafluoroethylpyrazole.

or an agriculturally accepable salt thereof.

23. A process for the preparation of an N-substituted pyrazole derivative of formula I as defined in claim 1 which comprises:
a) the reaction of a compound of formula II:

wherein Z is a leaving group and the other symbols are as defined in claim 1, with a compound of general formula III:

wherein R2 is as defined in claim 1 and X1 represents hydrogen or an alkali metal;
b) where Y represents the sulphur atom, the reaction of the corresponding compound of formula I in which Y
represents the oxygen atom with a thionating compound;
c) where R5 represents a straight- or branched-chain alkyl group containing up to 6 carbon atoms, the reaction of the corresponding compound of formula I in which R5 represents hydrogen with an alkylating agent;
d) where Y represents oxygen, the reaction of a compound of formula IV:

IV
wherein the various symbols are as defined in claim 1,with a halogenating agent to give an acid halide followed by reaction with an amine of formula V

wherein R4 and R5 are as defined in claim 1;
e) the reaction of a compound of formula IVa or a salt thereof:

IVa wherein the various symbols are as defined in claim 1, with a compound of formula R10-L wherein R10 is as defined in claim 1 and L is a leaving group;
f) where R10 represents phenyl or pyridyl substituted by a group -SR7,the diazotisation of the corresponding compound of formula (I) in which R10 represents phenyl or pyridyl substituted by -NH2 followed by the reaction of the diazotised product thus obtained with a disulphide of formula R7S-SR7 wherein R7 is as defined in claim 1;
optionally followed by the conversion of an N-substituted pyrazole derivative thus obtained into an agriculturally acceptable salt thereof.

24. A herbicidal composition which comprises as active ingredient a herbicidally effective amount of an N-substituted pyrazole derivative of formula I as defined in claim 1 or an agriculturally acceptable salt thereof in association with an agriculturally acceptable diluent or carrier and/or surface active agent.

25. A method for controlling the growth of weeds at a locus which comprises applying to the locus a herbicidally effective amount of an N-substituted pyrazole derivative of formula I as defined in claim 1 or an agriculturally acceptable salt thereof.