SI9300317A - N-substituted derivatives of pyrazole - Google Patents

Abstract

N-substituted pyrazole derivatives of formula (I) wherein R<1> represents optionally substituted alkyl or cycloalkyl; optionally substituted phenyl or benzyl; optionally substituted alkenyl or alkynyl; or a group selected from -SO2NR<61>R<62>, -SO2R<71> and -CONR<61>R<62>; R<2> represents -X-R<10>; R<3> represents hydrogen, halogen, optionally substituted alkyl or cycloalkyl, cyano, nitro, -S(O)mR<6>, optionally substituted phenyl or -CO2R<6>; R<4> represents optionally substituted phenyl or pyridyl; R<5> represents hydrogen or alkyl; Y represents oxygen or sulphur; R<6> represents alkyl or haloalkyl; R<61> and R<62> independently represent alkyl or haloalkyl; R<7> represents alkyl or haloalkyl; R<71> represents alkyl, haloalkyl or optionally substituted phenyl; R<8> and R<9> independently represent hydrogen, alkyl or haloalkyl; R<10> represents optionally substituted phenyl or pyridyl; or optionally substituted alkyl, alkenyl or alkynyl; X represents oxygen atom, -NR<11>- or -S(O)p-; R<11> represents hydrogen, alkyl or haloalkyl; m and p independently represent 0, 1 or 2; and their herbicidal properties are described.

Description

N-substituted pyrazole derivatives

The present invention relates to N-substituted pyrazole derivatives, processes for their preparation, compositions containing and their use as herbicides.

Okajima and Okada, J. Het. Chem., Vol. 27 p. 567-574 describe the preparation of 4-Nphenylcarboxamido-5-methylthio-1,3-dimethylpyrazole. Japanese patent application no. 3119468 lists the process for the preparation of certain 5-mercapto pyrazole compounds. French patent no. No. 2,337,997 describes certain fungicidal pyrazole-carboxamide derivatives such as e.g. Huppatz J. L., Aust. J. Chem Vol. 36, p. 135-147 (1982). U.S. Pat. No. 4,620,865 and European Pat. 0151866 show certain pyrazole-4carboxamide derivatives with herbicidal properties.

The present invention provides N-substituted pyrazole derivatives of formula I Y

And where:

R ¹ 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 R ⁶ groups;

a group - (CH ₂ ) _n -Ar, where n is 0 or 1 and Ar represents a phenyl group optionally substituted by one or more halogen selected groups, nitro, R ⁶ , -OH, -OR ⁶ , -S ( O) _m R ⁷ and -NR ⁸ R ⁹ ;

a straight or branched chain alkynyl or alkynyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen, R ⁶ and -OR ⁶ groups; or a group selected from -SO ₂ NR ⁶¹ R ⁶² , -SO ₂ R ⁷¹ and -CONR ⁶¹ R ⁶² ;

R ² represents:

the group -XR ¹⁰ ;

R ³ 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 R ⁶ groups; a cyano or nitro group;

a group -S (O) _m R ⁶ ;

phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ and cyano; or a group -CO ₂ R ⁶ ;

R ⁴ represents:

phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ ; or pyridyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ ;

R ⁵ represents a hydrogen atom or a straight or branched chain alkyl group containing up to 6 carbon atoms;

Y represents an oxygen or sulfur atom;

R ⁶ represents a straight or branched chain alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms;

R ⁶¹ and R ⁶² , which may be the same or different, each represent a straight- or branched-chain alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms;

R ⁷ represents a straight or branched chain alkyl group containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms;

R ⁷¹ 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, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ ;

R ⁸ and R ⁹ , which may be the same or different, each represent a straight or branched hydrogen or alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms;

R ¹⁰ represents:

phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁸ , -S (O) _m R ⁷ , -NHCOR ⁶ and -NR ⁸ R ⁹ ;

pyridyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ , -NHCOR ⁶ and -NR ⁸ R ⁹ ;

a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, wherein the chain may optionally comprise one or more oxygen or sulfur atoms or -NR ⁵ groups, optionally substituted by one or several groups selected from halogen, -OR ⁸ , -S (O) q R ⁶ , -NR ⁸ R ⁹ , -CO ² R ⁸ , -OCOR ⁶ , -NHCOR ⁶ , -CONR ⁸ R ⁹ , R ¹² , -COR ⁸ , R ¹³ and cyano;

X represents an oxygen atom, NR ¹¹ - or -S (O) _p -,

R ¹¹ represents a straight or branched chain hydrogen or alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms;

R ¹² represents a cycloalkyl group containing from 3 to 7 ring atoms which may optionally contain from 1 to 3 ring heteroatoms selected from oxygen, sulfur and -NR ⁵ -;

R ¹³ represents:

a cycloalkyl group containing from 3 to 6 carbon atoms which is substituted by one or more groups selected from halogen, R ⁸ and -OR ⁸ ; or a cycloalkenyl group containing 5 or 6 carbon atoms, optionally substituted by one or more groups selected from halogen, R ⁸ and -OR ⁸ ;

m is 0.1 or 2; p is 0.1 or 2; q is 0.1 or 2;

with the proviso that if Y represents oxygen, R ² represents methylthio or N-phenylamino, R ⁴ represents phenyl and R ⁵ represents hydrogen, R ¹ and R ³ do not simultaneously represent methyl; and their agriculturally acceptable salts having valuable herbicidal properties.

The term agriculturally acceptable salts means salts whose cations are known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably, these salts are water soluble. Suitable bases include alkali metal (eg sodium and potassium), alkaline earth metal (eg calcium and magnesium), ammonium and amine (eg diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts. Suitable acid addition salts formed with compounds of formula I containing an amino group include salts with inorganic acids, e.g. hydrochlorides, sulfates, phosphates and nitrates and salts with organic acids, e.g. acetic acid.

Certain compounds of formula I are shown without any indication that they have actually been synthesized as having fungicidal properties. According to a further aspect of the present invention there are provided compounds of formula I as previously defined, except for compounds of formula I wherein Y represents oxygen, R ¹ represents methyl, R ³ represents trifluoromethyl, R ⁵ represents hydrogen, R ² represents a group, ; selected from methoxy, 2,2,2-trifluoroethoxy, ethylthio, n-propylamino and methanesulfonyl and R ⁴ represents a group selected from 2-trifluoromethylphenyl, 2-chloro-4-nitrophenyl, 2-trifluoromethyl-4-nitrophenyl, 2-bromo -4-nitrophenyl, 2-chloro-5-trifluoromethylphenyl, 2,5-dichloro-4-nitrophenyl, 2,3,4,5-tetrachlorophenyl, 2,6-dibromo-4-trifluoromethoxyphenyl and pentafluorophenyl.

In one embodiment, the present invention provides N-substituted pyrazole derivatives of formula I in which:

R ¹ 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 R ⁶ groups; or a group - (CH ₂ ) _n -Ar, where n is 0 or 1 and Ar represents phenyl, optionally substituted by one or more groups selected from halogen, nitro R ⁶ , -OH, -OR ⁶ , -S ( O) _m R ⁷ and -NR ⁸ R ⁹ ;

R ³ 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 3 to 6 carbon atoms, optionally substituted by one or more R ⁶ groups; cyano group; a group -S (O) _m R ⁶ ;

phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ and cyano; or a group -CO ₂ R ⁶ ;

R ¹⁰ represents:

phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁸ , -S (O) mR ⁷ -NHCOR ⁶ and -NR ⁸ R ⁹ ; or pyridyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) mR ⁷ -NHCOR ⁶ and -NR ⁸ R ⁹ .

In this embodiment, X preferably represents an oxygen or sulfur atom or a group -NR ¹¹ . _;

In another embodiment, the present invention provides N-substituted pyrazole derivatives of formula I in which:

R ¹ 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 R ⁶ groups;

or a group - (CH ₂ ) _n -Ar, where n is 0 or 1 and Ar represents phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OH, -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ :

R ³ 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 R ⁶ groups; a cyano or nitro group; a group -S (O) _m R ⁶ ;

phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , OR ⁶ and cyano; or a group -CO ₂ R ⁶ ;

R ¹⁰ represents:

a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, wherein the chain may optionally comprise one or more oxygen or sulfur atoms or -NR ⁵ groups optionally substituted by one or more groups, selected from halogen, -OR ⁸ , -S (O) q R ⁶ , -NR ⁸ R ⁹ , CO2R ⁸ , -OCOR ⁶ , -NHCOR ⁶ , -CONR ⁸ R ⁹ , R ¹² and cyano.

In the third embodiment, the present invention provides N-pyrazole derivatives of formula I, in which:

R ³ 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 3 to 6 carbon atoms, optionally substituted by one or more R ⁶ groups; a cyano or nitro group; a group -S (O) _m R ⁶ ;

phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ and cyano; or a group -CO ₂ R ⁶ ;

R ¹⁰ represents a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, wherein the chain may optionally comprise one or more oxygen or sulfur atoms or -NR ⁵ groups optionally substituted by one or more groups selected from halogen, -OR ⁸ , -S (O) q R ⁶ , -NR ⁸ R ⁹ , CO2R ⁸ , -OCOR ⁶ , -NHCOR ⁶ , -CONR ⁸ R ⁹ , R ¹² , -COR ⁸ , R ¹³ and cyano.

A preferred type of compounds of formula I is one where Y represents an oxygen atom.

A further preferred type of compounds of formula I is one where R ¹ represents methyl or ethyl.

A further preferred type of compounds of formula I is one where R ¹ represents methyl.

Compounds in which R ³ represents trifluoromethyl are also preferred.

Compounds in which R ⁴ represents 2,4-difluorophenyl are also preferred.

Compounds of formula I in which R ⁴ represents 2,4-difluorophenyl or 2,4,6-trifluorophenyl are also preferred.

Compounds in which R ⁵ represents a hydrogen atom are also preferred.

A further preferred type of compounds of formula I is one where X represents a sulfur atom. Compounds of formula I wherein X represents an oxygen atom are also preferred.

A further preferred type of compounds of formula I is one where R ¹⁰ represents phenyl substituted by at least one halogen atom, preferably fluorine.

A further preferred type of compounds of formula I is one where R ¹⁰ represents a straight or branched chain alkyl or alkenyl group containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms.

A further preferred type of compounds of formula I is one in which R ² represents -SR ¹⁰ , where R ¹⁰ represents an alkenyl group containing up to 4 carbon atoms.

A further preferred type of compounds of formula I is one in which R ¹⁰ represents an alkyl, alkenyl or alkynyl group having a straight or branched chain containing up to 6, preferably up to 5 carbon atoms, optionally substituted by one or more halogen atoms.

Where R ¹⁰ represents a straight or branched chain alkyl group which is substituted by one or more groups R ¹² or R ¹³ , preferably R ¹⁰ , represents a group -CH ² R ¹² or -cit 2r ¹³ .

A further preferred type of compounds of formula I is one where:

R ¹ represents an acyl group containing one or two carbon atoms, optionally substituted by one or more halogen atoms (preferably fluorine), which may be the same or different;

R ³ represents:

an alkyl group containing up to 3 carbon atoms, optionally substituted by up to 5 halogen atoms (preferably fluorine or chlorine), which may be the same or different; or a group -SMe;

R ⁴ represents phenyl optionally substituted by one or three groups selected from halogen, trifluoromethyl and methoxy;

R ⁵ represents a hydrogen atom or a methyl group;

Y represents an oxygen or sulfur atom;

X represents an oxygen atom or a group -S (O) _p -;

R ¹⁰ represents:

phenyl or pyridyl optionally substituted by a group selected from halogen, methoxy, hydroxy, -NHCOMe, -NH ₂ , -SMe, methyl and trifluoromethyl; a cycloalkyl group containing from 3 to 6 carbon atoms;

a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms, optionally substituted by one or more groups selected from halogen, -CO ₂ Et, cyano, cyclopropyl, methoxy and -CONHMe;

and is p Oali 1.

Particularly important compounds due to their herbicidal properties include the following:

1. 4-N- (2,4-difluorophenyl) carboxamido-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-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

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,

6. 4-N- (2,4-difluorophenyl) carboxamido-5- (2-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

7. 4-N- (2,4-difluorophenyl) carboxamido-5- (3-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

8. 4-N- (2,4-difluorophenyl) carboxamido-5-phenylthio-1-methyl-3-trifluoromethylpyrazole,

9. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-acetamidophenylthio) -1-methyl-3-trifluoromethylpyrazole,

10. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-methylphenylthio) -1-methyl-3-trifluoromethylpyrazole,

11. 4-N- (3-Trifluoromethylphenyl) carboxamido-5- (4-methylphenylthio) -1-methyl-3-trifluoromethylpyrazole,

12. 4-N- (4-methoxyphenyl) carboxamido-5- (4-chlorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

13. 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chlorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

14. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-trifluoromethylphenylthio) -1-methyl-3trifluoromethylpyrazole,

15. 4-N-phenylcarboxamido-5- (3-trifluoromethylphenylthio) -1,3-dimethylpyrazole,

16. 4-N- (4-fluorophenyl) carboxamido-5- (4-chlorophenylthio) -1,3-dimethylpyrazole,

17. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-chlorophenylthio) -1,3-dimethylpyrazole,

18. 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chlorophenylthio) -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,

21. 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chlorophenoxy) -1-methyl-3-trifluoromethylpyrazole,

22. 4-N-phenylcarboxamido-5- (4-chlorophenoxy) -1,3-dimethylpyrazole,

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,

25. 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-chloropropylthio) -1-methyl-3-trifluoromethylpyrazole,

30. 4-N- (2,4-difluorophenyl) carboxamido-5-methylthio-1-methyl-3-trifluoromethylpyrazole,

31. 4-N- (2,4-difluorophenyl) carboxamido-5- (2,2,2-trifluoroethoxy) -1-methyl-3-trifluoro methylpyrazole,

32. 4-N- (2,4-difluorophenyl) carboxamido-5- (ethoxycarbonylmethylthio) -1-methyl-3trifluoromethylpyrazole,

33. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (1-methylbutylthio) -3trifluoromethylpyrazole,

34. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole,

35. 4-N- (2,4-difluorophenyl) carboxamido-5- (n-hexylthio) -1-methyl-3-trifluoromethylpyrazole,

36. 5-cyclopentylthio-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole,

37. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (n-propylthio) -3-trifluoro 'methylpyrazole,

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-trifluoro] methylpyrazole,

40. 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,

42. 4-N- (2,4-difluorophenyl) carboxamido-5-ethoxy-1-methyl-3-trifluoromethylpyrazole,

43. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-propynylthio) -3-trifluoromethylpyrazole,

44. 5- (3-Butenylthio) -4-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) carboxamido-1-methyl-3-trifluoromethylpyrazole,

47. 5- (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-3trifluoromethylpyrazole,

49. 5- (cyclopropylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole,

50. 5- (3-Butynylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole,

51. 5- (2-Chloropropylthio) -4-N- (2 _> 4-difluorophenyl) carboxamido-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-methyl-3-trifluoromethylpyrazole,

54. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (n-pentylthio) -3-trifluoromethylpyrazole,

55. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylbutylthio) '- 3-trifluoromethylpyrazole,

56. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methyl-2-propenylthio) -3trifluoromethylpyrazole,

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,

59. 5- (3-Chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole,

60. 5-ethylthio-1-ethyl-4-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole,

61. 5-ethylthio-1-ethyl-4-N- (2,4,6-trifluorophenyl) carboxamido-3-trifluoromethylpyrazole,

2

5- (N-methylaminocarbonylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole,

63. 4-N- (2,4-difluorophenyl) -5- (4-fluorophenylthio) -thiocarboxamido-1-methyl-3-trifluoromethylpyrazole,

64. 3-chlorodifluoromethyl-5- (4-fluorophenylthio) -4-N- (2,4-difluorophenyl) carboxamido1-methylpyrazole,

65. 3-chlorodifluoromethyl-5- (4-fluorophenylthio) -1-methyl-4-N- (2,4,6-trifluorophenyl) carboxamidopyrazole,

66. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-pyridylthio) -3-trifluoromethyl pyrazole,

67. 5- (4-Aminophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole,

68. 5- (3-Chloro-4-fluorophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyltrifluoromethylpyrazole,

69. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1- (2,2,2-trifluoroethyl) -3trifluoromethylpyrazole,

70. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1- (2,2,2-trifluoroethyl) 3-trifluoromethylpyrazole,

71. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3methylthiopyrazole,

72. 4-N- (3-chloro-4-fluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

73. 4-N- (3,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

74. 5- (4-Fluorophenylthio) -1-methyl-3-trifluoromethyl-4-N- (2,4,5-trifluorophenyl) carboxamidopyrazole,

75. 4-N- (2-fluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

76. 4-N- (4-chlorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

77. 4-N- (4-chloro-2-fluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoro methylpyrazole,

78. 5- (4-Fluorophenylthio) -1-methyl-3-trifluoromethyl-4-N- (2,4,6-trifluorophenyl) carboxamidopyrazole,

79. 4-N- (2-chloro-4-fluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoro methylpyrazole,

80. 4-N- (4-fluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

81. 4-N- (2,4-dichlorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

82. 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-methylphenyl) carboxamido-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,

87. 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-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole,

90. 5- (4-Fluorophenylthio) -1-methyl-3-trifluoromethyl-4-N- (2,3,6-trifluorophenyl) carboxamidopyrazole,

91. 5- (4-Fluorophenylthio) -1-methyl-4-N- (phenyl) carboxamido-3-trifluoromethylpyrazole,

92. 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-3trifluoromethylpyrazole,

94. 5- (4-Chlorophenylsulfinyl) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole,

95. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (n-propyloxy) -3trifluoromethylpyrazole,

96. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropyloxy) -3trifluoromethylpyrazole,

97. 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) -3trifluoromethylpyrazole,

99. 4-N- (2,4-difluorophenyl) carboxamido-1-ethyl-5- (2-propenylthio) -3trifluoromethylpyrazole,

100. 4-N- (2,4,6-Trifluorophenyl) carboxamido-1-ethyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole,

101. 4-N- (2,3-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole,

102. 4-N- (2,6-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole,

103. 4-N- (2,3,6-trifluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole,

104. 4-N- (2,4,6-Trifluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole,

105. 4-N- (2,5-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, and

106. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3pentafluoroethylpyrazole.

Nos. 1 to 106 are assigned to these compounds for reference and identification thereafter.

The compounds of formula I may be prepared by the use or adaptation of known methods (i.e., methods so far used or described in the chemical literature), e.g. as they are described behind this.

In the following description, it should be borne in mind that symbols in formulas where they are not specifically defined have the same meaning as previously defined according to the first definition of each symbol in this description.

It is understood that in the descriptions of the following procedures, the sequences may be arranged differently and that protecting groups may be required to obtain the compounds sought.

According to an aspect of the present invention, a compound of formula I can be prepared by reacting a compound of formula II

wherein R ¹ , R ³ , R ⁴ , R ⁵ and Y are as previously defined and Z represents a leaving group, with a compound of formula III

R ² -X ^x III wherein R ² is as previously defined and X ¹ represents hydrogen or an alkali metal (eg sodium or potassium). The reaction is generally carried out in an inert solvent, such as e.g. acetonitrile, dioxane or tetrahydrofuran, optionally in the presence of a base, e.g. sodium hydride, potassium t-butoxide, or preferably potassium carbonate, at room temperature 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 aspect of the present invention, compounds of formula I wherein Y represents a sulfur atom can be prepared by the reaction of a corresponding compound of formula I in which

V represents an oxygen atom with a thionylation compound, e.g. Lawesson's reagent [2,4bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphethane-2,4-disulfide] in an inert solvent, preferably toluene at a temperature of 50 ° C to the reflux temperature of the solvent.

According to an aspect of the present invention compounds of formula I wherein R ⁵ represents a straight or branched chain alkyl group containing up to 6 carbon atoms can be prepared by reacting a compound of formula I wherein R ⁵ represents hydrogen, with an alkylating agent, preferably alkyl halide or dialkyl sulfate in the presence of a base, e.g. potassium hydroxide or potassium carbonate in an inert solvent, such as e.g. tetrahydrofuran, at room temperature to the reflux temperature of the solvent. This reaction can be carried out optionally in the presence of a phase transfer catalyst, such as e.g. tetrabutylammonium bromide, typically in an amount of 0.01-0.1 mol

%.

Alternatively, the sodium or potassium salt of compound I may be prepared by reaction of a compound of formula I, wherein R ⁵ represents hydrogen, with a base, preferably sodium hydride, in an inert solvent, followed by reaction with an alkyl agent.

According to a further aspect of the present invention, a compound of formula I in which Y represents oxygen can be prepared by reacting a compound of formula IV

IV wherein R ¹ , R ² and R ³ are as previously defined, with a halogenated agent, to obtain an acid halide (which may be isolated), followed by reaction with an amine of formula V

H-NR ⁴ R ⁵ V where R ⁴ and R ^{5 are} as previously defined. Preferably, the halogenating agent is a chlorinating agent, e.g. thionyl chloride, and the reaction to obtain the acid halide is optionally carried out in an inert solvent at room temperature to reflux. The reaction between an acid halide and an amine of formula V is generally carried out in the presence of a base, preferably triethylamine, in an inert solvent, e.g. tetrahydrofuran at a temperature of 0 ° C to the reflux temperature of the solvent.

According to a further aspect of the present invention, compounds of formula I can be prepared by reaction of a compound of formula IVa or a salt thereof

wherein R ¹ , R ³ , R ⁴ , R ⁵ , Y and X are as previously defined, with a compound of formula R ¹⁰ -L, wherein R ¹⁰ is as previously defined and L is a leaving group. Preferably L represents a halogen atom (more preferably chlorine or bromine), para-toluenesulfonyloxy or methylsulfonyloxy and (where R ¹⁰ represents optionally substituted phenyl or pyridyl) nitro. The reaction is generally carried out in an inert solvent such as e.g. ethanol or methanol in the presence of a base (eg sodium hydride or sodium methoxide). Where the reaction is carried out with a salt of a compound of formula (IVa), an alkali metal or alkaline earth metal salt (e.g., sodium or potassium salt) is preferably used.

According to a further aspect of the present invention, compounds containing the group -XR ¹⁰ in which R ¹⁰ represents phenyl or pyridyl substituted with the group -SR ⁷ can be prepared by diazotizing the corresponding compounds wherein R ¹⁰ represents phenyl or pyridyl substituted with - NH ₂ , followed by the reaction of the diazotized product thus obtained with a disulfide of formula R ⁷ S-SR ⁷ , wherein R ⁷ is as previously defined. The reaction is generally carried out using a diazotime reagent, such as e.g. alkylnitrite (e.g., t-butylnitrite) in an inert solvent (e.g., acetonitrile or dichloromethane) at a temperature of -20 ° C to reflux.

The intermediates used in the preparation of compounds of formula I can be prepared by the use or adaptation of known methods, e.g. the procedures described thereafter.

A compound of formula II wherein Y represents oxygen and Z represents a leaving group, e.g. halogen can be prepared from compounds of formula VI

where Z represents a leaving group, e.g. halogen, by conversion of an acid halide, preferably an acid chloride, e.g. by reaction with thionyl chloride, optionally in the presence of an inert solvent at room temperature to reflux temperature, and the subsequent reaction of acid chloride (which may be isolated), with an amine of formula V in a base, preferably triethylamine, in an inert solvent, e.g. tetrahydrofuran at a temperature of 0 ° C to the reflux temperature of the solvent.

Compounds of formula II wherein Y represents a sulfur atom can be prepared by reacting a corresponding compound of formula II in which Y represents an oxygen atom with a thionyl compound such as e.g. Lawesson's reagent [2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphethane2,4-disulfide] in an inert solvent, preferably toluene, at a temperature of 50 ° C to the reflux temperature of the solvent.

Compounds of formula III in which X ¹ represents an alkali metal, e.g. sodium or potassium may be prepared by reaction of a corresponding compound of formula III, wherein X ¹ represents hydrogen, with a base containing an alkali metal, e.g. as NaH in an inert solvent, such as e.g. dioxane, at a temperature of 20 ° C to the reflux temperature of the solvent.

A compound of formula III in which R ² represents -SR ¹⁰ and X ¹ represents hydrogen can be prepared by reaction of a compound of formula R ¹⁰ -Br with:

a) sodium thiol in ethanol; or

b) thiourea in ethanol, followed by the reaction of the compound of formula

R ¹⁰ SC (= NH) NH ₂ .HBr thus obtained with sodium hydroxide in ethanol; or

c) potassium xanthate [EtOC (= S) S'K ⁺ ] in ethanol, followed by hydrolysis of a compound of formula R ¹⁰ SC (= S) OEt, thus obtained with sodium hydroxide in ethanol.

Compounds of formula III in which R ² represents -SR ¹⁰ and X ¹ represents hydrogen can also be prepared by reduction of a disulfide of formula R ¹⁰ S-SR ¹⁰ using e.g. of sodium borohydride in ethanol.

Compounds of formula IV in which X represents a group other than -S (O) _p - wherein p is 0 or 1 can be prepared from compounds of formula VII

Oh

vn by replacing group Z with group R ² [by the process described for the preparation of a compound of formula I from a compound of formula II], followed by the conversion of a formyl group to carboxy [by the procedure described below for the preparation of compounds of formula VI from a compound of formula VII],

Compounds of formula IV can also be prepared by hydrolysis of an ester of formula Vila

(Villa) wherein R represents an alkyl group. This can be achieved by conventional techniques e.g. by reaction with potassium carbonate in an ethanol solvent.

The compound of formula IV can also be prepared by reaction of an acid of formula (VI) with a compound of formula (III). The reaction is generally carried out as described above for the reaction of a compound of formula (II) with a compound of formula (III).

Compounds of formula (IVa) or their salts can be prepared by reacting a compound of formula II with a compound of formula Η-Χ-Χ ¹ .

The compounds of formula VI can be prepared by oxidizing the corresponding aldehyde of formula VII using an oxidant, preferably potassium permanganate, in the presence of a base, preferably sodium hydroxide, in a solvent, preferably water, at room temperature to 100 ° C.

Compounds of formula VII can be prepared by the reaction of 5-hydroxypyrazole of formula VIII

VIII with formylating reagent. Preferably, the formylable agent is a mixture of phosphorus oxychloride and Ν, Ν-dimethylformamide, when simultaneous chlorination is induced to produce a compound of formula VII in which Z represents chlorine. The reaction is generally carried out at a temperature from 0 ° C to 150 ° C.

The 5-hydroxypyrazoles of formula VIII can be prepared by the reaction of the 3-ketoester of formula IX

R ³ C (O) CH ₂ CO ₂ A IX where A represents lower alkyl, with hydrazine of formula X

R ¹ NHNH ₂ X.

The reaction is generally carried out in a solvent, preferably water, at room temperature to reflux temperature. During this reaction, a mixture of isomeric products can be produced, which can be separated by methods well known in the art. The preparation of the above and21 topics VI, VII and VIII is described in the literature, e.g. J. Het. Chem 27, 243 (1990) LF.Lee et al.

Compounds of formula VIII wherein R ³ is cyano can be prepared by dehydration of a corresponding compound of formula VIII wherein R ^{3 is} replaced by -CONH ₂ using e.g. phosphorus oxychloride, optionally in the presence of an inert solvent, at room temperature to reflux temperature, or para-toluenesulfonyl chloride in pyridine, at a temperature of 50 ° C to reflux temperature, followed by hydrolysis with sodium hydroxide in alcohol at a temperature of 20 to 100 ° C.

Compounds of formula VIII in which R ^{3 is} substituted with -CONH 2 can be prepared by hydrolysis of a corresponding ester of formula VIII, wherein R ³ represents -CO ₂ R ⁶ , preferably using a solution of sodium or potassium hydroxide in a solvent, e.g. aqueous alcohol, at a temperature from 0 ° C to the reflux temperature of the solvent, to obtain the corresponding carboxylic acid, which is converted to the corresponding acid chloride, e.g. by reaction with thionyl chloride (optionally in an inert solvent), at room temperature to reflux temperature treated with ammonia, optionally in the presence of a suitable solvent, e.g. aqueous alcohol, at a temperature from 0 ° C to reflux temperature, to give the desired product.

Compounds of formula VIII in which R ^{3 is} replaced by -CONH2 can alternatively be prepared by ammonolysis of a corresponding ester of formula VIII, wherein R ³ represents -CO ² R ⁶ , preferably by treatment with ammonia in a hermetically sealed container at a temperature of 100 to 200 ° C.

(3) ketoester of compounds of formula IX, wherein R ³ represents a straight or branched chain alkyl group containing 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, R ⁶ , -OR ⁶ and cyano; or a cycloalkyl group containing 3 to 6 carbon atoms optionally substituted by one or more groups R ⁶ or nitro or -CO ₂ R ⁶ can be prepared by well-known methods, e.g. Beilstein 10, 682 (JCS 49, 447 Perkin, Bellenot), or Nippon Kagaku Zasshi 82,132 (1961) by K. Hattori & H. Nakano, or Buli Soc. Chim Fr. (1964), 5, 945 G. Braar, M. Vilkas.

Compounds of formula VIII wherein R ³ is -CO ₂ R ⁶ can also be prepared by reaction of acetylene-1,2-dialkoxycarbonyl compounds of formula XI r ⁶ o ₂ c - c = c - co ₂ r ⁶ XI with hydrazine of formula X. This reaction is generally carried out in an inert solvent, preferably an alcohol, e.g. methanol, at a temperature from 0 ° C to reflux, to give the compound of formula XII,

- ^ CO ₂ R ^{6 r6} ° 2 ^C NHNHR ¹

XII which is cyclized under basic conditions, e.g. using sodium methoxide, in a suitable solvent, e.g. methanol, at a temperature from 0 ° C to reflux. In the given case, these two steps can be carried out in a single one using a combination of base and solvent.

Compounds of formula VI wherein Z represents a halogen can be prepared from an ester of formula XIII,

ii

XIII wherein R represents an alkyl group and Z represents halogen.

This reaction is carried out at the base, e.g. sodium hydroxide, in a solvent, preferably aqueous alcohol, at a temperature of 0 ° C to 100 ° C.

Esters of formula XIII or esters of formula VI, wherein R ² represents -SR ¹⁰ , can be prepared by diazotizing an amine of formula XIV

RO ₂ (K_ / R3 h ₂ n ^/ i < ^N

L

R ¹

XIV.

This reaction can be carried out with sodium nitrite in a mineral acid, e.g. mixtures of concentrated sulfuric acid and acetic acid, at a temperature from 0 ° C to 60 ° C and the following reaction by:

(a) Copper halide (where an ester of formula XIII is desired) or a disulfide of formula R ¹⁰ S-SR ¹⁰ (where an ester of formula IV is desired, where R ² represents -SR ¹⁰ ) and a mineral acid or with an aqueous solution of potassium iodide at temperature 0 ° C to 100 ° C; diazotization may alternatively be carried out using alkyl nitrite, e.g. tert.butyl nitrite, in the presence of a suitable halogen agent (where an ester of formula XIII is desired), preferably bromoform or iodine or anhydrous copper chloride, or at a temperature of from 0 to 100 ° C, optionally in the presence of an inert solvent, preferably acetonitrile or chloroform.

Compounds of formula XIV wherein R ^{3 is} halogen, cyano or -SR ⁶ can be prepared by diazotizing a compound of formula XV,

RO ₂ (X _ .NH ₂

I H

L ₂ Ν ^Χ Ν ^ ² L

R ¹

XV where R ¹ is as previously described. The reaction conditions for this reaction are those described previously for the conversion of a compound of formula XIII to a compound of formula XIV, wherein the cyanide reagent, e.g. copper cyanide may also be used in place of the halogenated agent; or using a diazotime reagent, such as e.g. alkylnitrite (e.g. t-butyl nitrite) in an inert solvent (e.g. acetonitrile or dichloromethane) at a temperature of -20 ° C to reflux temperature, followed by treatment of the diazotized disulfide intermediate of formula R ⁶ S-SR ⁶ . This reaction can be carried out selectively to achieve diazotization in position 3 of the pyrazole ring.

The compound of formula XIV can be prepared by reaction of a compound of formula XVI,

RO ₂ C,

- /

R ³

NC ' ^B XVI where B represents halogen (preferably chlorine), -OR ⁶ or -SR ⁶ , with hydrazine of formula X. If B represents -OR ⁶ or -SR ⁶ , this reaction is generally carried out in an alcoholic solvent at room temperature to 200 ° C. If B represents halogen, preferably chlorine, the reaction is generally carried out in an inert solvent, preferably tetrahydrofuran, optionally in the presence of a base, e.g. triethylamine, at a temperature from 0 ° C to reflux temperature.

The compounds of formula XV can be prepared by the reaction of hydrazine of formula X with an alkali metal salt of alkyldiciano acetate of formula XVII

RO ₂ C-CH (CN) ₂ XVII.

Preferably, potassium ethyldicianoacetate is used. The reaction is generally carried out in the presence of an acid, e.g. hydrochloric acid, at room temperature to reflux.

The potassium alkyldicyanoacetate salts can be prepared by reacting the corresponding alkyl chloroformate with malononitrile in the presence of potassium hydroxide in an inert solvent, preferably tetrahydrofuran, at a temperature of 0 ° C to 100 ° C.

Compounds containing the group -S (O) _m R ⁶ , -S (O) mR ⁷ , -S (O) p- or -S (O) _q R ⁶ , wherein m, p and q may be 1 or 2 , can be prepared from the corresponding compound in which m, p and q are 0 or 1, by oxidation, e.g. using meta-chloroperbenzoic acid in an inert solvent, e.g.

chloroform, at -20 ° C to reflux temperature.

Compounds of formula (Vila) in which R ¹ represents a group other than Ar and R ² represents -SR ¹⁰ can be prepared by reaction of a compound of formula XVIII,

XVIII where R ¹ represents a group other than Ar with an alkyllithium reagent, followed by treatment of the lithium intermediate thus obtained with a compound of formula R ¹⁰ S-SR ¹⁰ or R ¹⁰ -S-C 1. A preferred alkyllithium reagent is lithium diisopropylamide. The reaction is generally carried out in an aprotic solvent (e.g. tetrahydrofuran) at a temperature of -70 ° C to 0 ° C. Preferably R ¹⁰ represents an optionally substituted alkyl or alkenyl group.

Compounds of formula XVIII can be prepared by reaction of a compound of formula XIX ro ₂ c _x

R3 η ^λ 7 '

I

H

XIX with a compound of formula R ¹ -X ² wherein R ^{1 is a} group other than Ar and X ^{2 is a} leaving group in the presence of a base. Preferably X ² represents, e.g. chlorine, bromine or iodine atom or tosyl or mesyl group. Suitable bases include potassium carbonate, sodium hydride and cesium carbonate. The reaction is generally carried out in a solvent (eg acetonitrile).

The compounds of formula XI, XVI, XVII and XIX are well known in the literature or can be prepared by the use or adaptation of known methods.

The agriculturally acceptable salts of the N-substituted pyrazole derivatives of formula I can be prepared by known methods.

The following examples illustrate the preparation of compounds of formula I. In the foregoing description, boiling. means the boiling point, the ground. means the melting point. The NMR label is followed by the characteristics of the proton nuclear magnetic resonance spectrum. Unless otherwise stated, 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 potassium carbonate (2.4 g) was stirred in dry acetonitrile and reflux for 3 hours. The solid was filtered, washed with acetonitrile and the filtrate was evaporated in vacuo to give a solid.

Purification by chromatography eluting with hexane / dichloromethane gave 4-N- (2,4-difluorophenyl) carboxamido-5- (4-chlorophenylthio) -1-methyl-3-trifluoromethylpyrazole (compound 1, 5.15 g) as white solid, m.p. 172-173 ° C.

By acting in a similar manner, the following compounds are prepared from the appropriate starting materials, with different symbols being defined in the following table:

Compound- R ¹ R ³ A Y P Q Tal. (° C) 2 ch ₃ cf ₃ CH 0 2,4-diF 4-OMe 128-130 3 ch ₃ cf ₃ CH 0 2,4-diF 4-F 119-122 4 ch ₃ cf ₃ CH 0 2,4-diF 4-Nr 170-171 5 ch ₃ cf ₃ CH 0 2,4-diF 4-OH 170-171 6 ch ₃ cf ₃ CH 0 2,4-diF 2-F 114-115 7 ch ₃ cf ₃ CH 0 2,4-diF 3-F 131-132 8 ch ₃ cf ₃ CH 0 2,4-diF H 131-133 9 ch ₃ cf ₃ CH 0 2,4-diF 4-NHCOMe 197-199 10 ch ₃ cf ₃ CH 0 2,4-diF 4-CH ₃ 131-133 11 ch ₃ cf ₃ CH 0 3-CF ₃ 4-CH ₃ 117-119 12 ch ₃ cf ₃ CH 0 4-OCH ₃ 4-C1 137-139 13 ch ₃ cf ₃ CH 0 2,4-diF 3-CI 133-135 14 ch ₃ cf ₃ CH 0 2,4-diF 4-CF ₃ 159-161 15 ch ₃ ch ₃ CH 0 H 3-CF ₃ 115-116 16 ch ₃ ch ₃ CH 0 4-F 4-C1 165-166 17 ch ₃ ch ₃ CH 0 2,4-diF 4-C1 166-168 18 ch ₃ ch ₃ CH 0 2,4-diF 3-CI 136-138 63 ch ₃ cf ₃ CH s 2,4-diF 4-F oil (s) 64 ch ₃ cf ₂ ci CH 0 2,4-diF 4-F 112-114 65 ch ₃ cf ₂ ci CH 0 2,4,6-triF 4-F 129-130 66 ch ₃ cf ₃ N 0 2,4-diF H 138-140 67 ch ₃ cf ₃ CH 0 2,4-diF 4.NH ₂ 172-173 68 ch ₃ cf ₃ CH 0 2,4-diF 3-C1-4-F 146-147 69 ch ₃ nPr CH 0 2,4-diF 4-F 126-127.5 70 ch ₂ cf ₃ cf ₃ CH 0 2,4-diF 4-F 129-130

Note: (a) NMR (CDCl3) d _H 3.80 (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

The suspension of sodium hydride in dry dioxane was stirred at room temperature under an inert atmosphere and a solution of 4-fluorophenol (1.2 g) in dioxane was added. After 0.5 hours, a solution of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (2.47 g) in dioxane (25 ml) was added. The mixture was then heated under reflux for 20 hours, cooled and poured onto ice / water. It is extracted with dichloromethane and the extract is washed with water, dried (anhydrous magnesium sulfate) and evaporated. The resulting yellow solid was purified by chromatography eluting with ether / hexane and recrystallized from ethyl acetate to give 4-N- (2,4-difluorophenyl) carboxamido-5 (4-fluorophenoxy) -1-methyl-3-trifluoromethylpyrazole (compound 19 , 1.25 g), m.p. Mp 169-170 ° C.

Example 3

A mixture of 1-methyl-5- (3-trifluoromethylphenoxy) -3-trifluoromethylpyrazole-4-carboxylic acid chloride (2.1 g), 4-fluoroaniline (0.62 g) and triethylamine (0.8 ml) in tetrahydrofuran is stirred at room temperature for about 2 hours. The mixture was diluted with water and the resulting solid filtered, dried and recrystallized to give 4-N- (4-fluorophenyl) carboxamido-5- (3-trifluoromethylphenoxy) -1-methyl-3-trifluoromethylpyrazole (compound 20, 2.1 g ), m.p. 171-172 ° C.

By acting in a similar manner, 4-N- (2,4-difluoro-phenyl) carboxamido-5 (3-chlorophenoxy) -1-methyl-3-trifluoromethylpyrazole (compound 21), m.p. 131-132 ° C.

Example 4

Chloride-5- (4-chlorophenoxy) -1,3-dimethylpyrazole-4-carboxylic acid was dissolved in tetrahydrofuran and added to a solution of aniline (0.6 g) and triethylamine (0.9 ml) in tetrahydrofuran. The reaction mixture was stirred for 2 hours, water was added and the resulting solid was filtered, dried and recrystallized from hexane / ethyl acetate to give 4-N-phenylcarboxamido-5- (4-chlorophenoxy) -1,3-dimethylpyrazole (compound 22.1 g), m.p. 99101 ° C.

By acting in a similar manner, 4-N- (4-fluorophenyl) carboxamido-5- (4-chlorophenoxy) -1,3-dimethylpyrazole (compound 23), m.p. 161-162 ° C.

Example 5

A mixture of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (4.0 g), 4-chlorophenol (2.16 g) and potassium t-butoxide (2.16 g) reflux in t-butanol for about 72 hours. Water was added and the solid was isolated and purified by chromatography eluting with hexane / ethyl acetate to give 4-N- (2,4difluorophenyl) carboxamido-5- (4-chlorophenoxy) -1-methyl-3-trifluoromethylpyrazole (compound 24, 1.45 g), m.p. Mp 166-169 ° C.

Example 6

Sodium thiomethoxide (1.63 g) was added to a cooled solution of 5-chloro-4-N- (2,4difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (4.0 g) in acetonitrile. The resulting suspension was stirred for 2 days, refluxed for 1 hour and filtered. The filtrate was concentrated and taken up in dichloromethane and water. The organic phase was dried (magnesium sulfate) and the solvent was evaporated to give 4-N- (2,4-difluorophenyl) carboxamido5-methylthio-1-methyl-3-trifluoromethylpyrazole (compound 30) as a white solid (3.46 g). m.p. 130-131 ° C.

Example 7

Suspension of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (1.5 g) potassium carbonate (0.915 g) and 2,2,2-trifluoroethanol (1.5 ml) ) in acetonitrile was heated at reflux for 6 hours. The reaction mixture was cooled and allowed to stand overnight. The reaction mixture was then filtered and the solvent removed from the filtrate to leave a solid which was purified by column 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. 102-103 C.

The following compounds are prepared in a similar manner:

4-N- (2,4-difluorophenyl) carboxamido-5- (n-butylthio) -1-methyl-3-trifluoromethylpyrazole (compound 25), m.p. 69-70 ° C;

4-N- (2,4-difluorophenyl) carboxamido-5- (2-propenylthio) -1-methyl-3-trifluoromethylpyrazole (compound 26), m.p. 92-94 ° C;

4-N- (2,4-difluorophenyl) carboxamido-5-isopropylthio-1-methyl-3-trifluoromethylpyrazole (Compound 27), m.p. 106-107 ° C;

4-N- (2,4-difluorophenyl) carboxamido-5-ethylthio-1-methyl-3-trifluoromethylpyrazole (Compound 28), m.p. 95-96 ° C;

4-N- (2,4-difluorophenyl) carboxamido-5- (3-chloropropylthio) -1-methyl-3-trifluoromethylpyrazole (Compound 29), m.p. 79-81 C;

4-N- (2,4-difluorophenyl) carboxamido-5- (ethoxycarbonylmethylthio) -1-methyl-3-trifluoromethylpyrazole (compound 32), m.p. 100-104 ° C;

4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (1-methylbutylthio) -3-trifluoromethylpyrazole (compound 33), m.p. 70-71 ° C;

4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole (compound 34), m.p. 93-94 ° C;

4- N- (2,4-difluorophenyl) carboxamido-5- (n-hexylthio) -1-methyl-3-trifluoromethylpyrazole (compound 35), m.p. 77-78 ° C;

5- Cyclopentylthio-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (Compound 36), m.p. 112-114 ° C;

4- N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (n-propylthio) -3-trifluoromethylpyrazole (Compound 37), m.p. 89-90 ° C;

5- Cyclohexylthio-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (Compound 38), m.p. 92-94 ° C;

4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (1-methylpropylthio) -3-trifluoromethylpyrazole (compound 39), m.p. 98-99 ° C;

4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (3-methylbutylthio) -3-trifluoro32 methylpyrazole (compound 40), m.p. 62-63 ° C;

4-N- (2,4-difluorophenyl) carboxamido-5- (1,1-dimethylethylthio) -1-methyl-3-trifluoromethylpyrazole (compound 41), m.p. 146-147 ° C;

4- N- (2,4-difluorophenyl) carboxamido-5-ethoxy-1-methyl-3-trifluoromethylpyrazole (compound 42), m.p. 108-109 ° C;

5- (N-methylaminocarbonylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole (compound 62), m.p. Mp 129-131 ° C.

Example 8

3-Bromopropine (0.61 g) was added to a solution of sodium 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole-5-thiolate (0.98 g) in methanol and the mixture was stirred at room temperature. temperature for 3 hours. The solvent was evaporated and the residue partitioned between dichloromethane and water. The organic layer was dried and evaporated to give a white solid, which was recrystallized from cyclohexane to give 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-propynylthio) -3-trifluoromethylpyrazole (compound 43) as needles in gray-white (0.77 g), m.p. Mp 136-137 ° C.

By acting in a similar manner, the following compounds are prepared:

5- (3-Butenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 44), m.p. 93-95 ° C;

5- (2-Bromo-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 45), m.p. 105-106 ° C;

5- (3-Bromo-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (Compound 46), m.p. 111-113 ° C;

5- (cyanomethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 47), m.p. 140-142 ° C;

5- (3-methyl-2-butenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoro33 methylpyrazole (compound 48), m.p. 122-123 ° C;

5- (cyclopropylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (Compound 49), m.p. 99-101 ° C;

5- (3-Butynylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 50), m.p. 107-108 ° C;

5- (2-chloropropylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 51), m.p. 75.5-76.5 ° C;

4- N- (2,4-difluorophenyl) carboxamido-5- (2,2-dimethoxyethylthio) -1-methyl-3-trifluoromethylpyrazole (compound 52), m.p. 118-119.5 ° C;

5- (2-Butenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 53), m.p. 95-97 ° C;

4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (n-pentylthio) -3-trifluoromethylpyrazole (compound 54), m.p. 87-89 ° C;

4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylbutylthio) -3-trifluoromethylpyrazole (compound 55), m.p. 83-85 ° C;

4- N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methyl-2-propenylthio) -3-trifluoro methylpyrazole (Compound 56), m.p. 107-109 ° C;

5- (2-Chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoro methylpyrazole (Compound 57), m.p. 93-95 ° C;

4- N- (2,4-difluorophenyl) carboxamido-5- (2-methoxyethyl) -1-methyl-3-trifluoromethylpyrazole (compound 58), m.p. 88-90 ° C;

5- (3-Chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoro methylpyrazole (compound 59), m.p. 95-96 ° C;

Example 9

Thionyl chloride (2.4 ml) was added to a solution of 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4 carboxylic acid (0.5 g) in toluene and the reaction mixture was refluxed for 3 hours. After cooling, the solvent and excess thionyl chloride are removed under reduced pressure. The residue was taken up in dichloromethane and triethylamine (0.34 ml) was added followed by the addition of 2,4-difluoroaniline (0.2 ml) while stirring at room temperature for 2 hours. The mixture was poured into water and the organic layer separated, washed with HCl, saturated sodium carbonate and brine. The organic phase was then dried (MgSO ₄ ) and evaporated under reduced pressure to give 5-ethylthio-1-ethyl-4-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole (compound 60) as a grayish Java solid (0.54 g), m.p. 91-93 ° C.

By acting in a similar manner, 5-ethylthio-1-ethyl-4-N- (2,4,6-trifluorophenyl) carboxamido-3-trifluoromethylpyrazole (compound 61) is prepared as a grayish brown solid, m.p. 94-96 ° C.

Example 10

A mixture of 5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid (2.0 g) and thionyl chloride (13.9 g) was refluxed 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 mixed solution of aniline (0.64 g) in dry tetrahydrofuran (30 ml) containing triethylamine (0.7 g). The mixture was stirred overnight and the solid was filtered off and washed with ether (50 ml). The combined filtrates were evaporated in vacuo to give a brown solid, which was then recrystallized from toluene / hexane to give 5- (4-fluorophenylthio) -1-methyl-4-N- (phenyl) carboxamide-3-trifluoromethylpyrazole compound 91, (1.4 g) as a brown solid, m.p. Mp 146-148 ° C.

By acting in a similar manner, the following compounds are prepared from the corresponding carboxylic acids, the symbols being as defined in the following table:

Compound. R3 P Q M.p. (° C) 71 SMe 2,4-F ₂ 4-F 164-167 72 cf ₃ 3-CI-4-F 4-F 169-170 73 cf ₃ 3,4-F2 4-F 1525-1535 74 cf ₃ 2,4,5-F ₃ 4-F 125-126 75 cf ₃ 2-F 4-F 133.5-135 76 cf ₃ 4-C1 4-F 142-143 77 cf ₃ 2-F-4-CI 4-F 130.5-131.5 78 cf ₃ 2,4,6-F ₃ 4-F 175-177 79 CF ₃ 2-C1-4-F 4-F 118-119 80 cf ₃ 4-F 4-F 129.5-131 81 cf ₃ 2,4-Cl ₂ 4-F 1485-1505 82 cf ₃ 2,3,4-F ₃ 4-F 145-147 83 cf ₃ 2-F-4No. 4-F 120.5-1225 84 cf ₃ 2-F-4-Me 4-F 127-128 85 cf ₃ 3-F 4-F 1115-1135 86 cf ₃ 2,3-F ₂ 4-F 119-121 87 cf ₃ 2.5-F ₂ 4-F 104-105 88 cf ₃ 2,6-F ₂ 4-F 146-147 89 cf ₃ 3,5-F ₂ 4-F 114-116 90 cf ₃ 2,3,6-F ₃ 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 dimethyldisulfide (1.0 g ), followed by dropwise addition of tert.butyl nitrite (1.1 g) over 5 minutes. The mixture was stirred at 50 ° C for 3 hours then overnight at room temperature before being poured into water. The organic layer was separated and the aqueous solution was extracted again with dichloromethane. The combined organic extracts were dried over anhydrous magnesium sulfate 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 solid, cloudy yellow in color, soil. 122124 ° C.

Example 12

Suspension of 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3trifluoromethylpyrazole (2.0 g), iodomethane (0.29 ml), powdered potassium hydroxide (0.286 g), and of tetrabutylammonium bromide (0.3 g) in tetrahydrofuran (5 ml) was stirred at room temperature for 26 hours and the solid was filtered off. The filtrate was evaporated in vacuo to give a residue to which dichloromethane and water were added. The organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated in vacuo to give an oil. Trituration with ether gave a solid which was purified by chromatography on silica gel eluting with ether / hexane (1: 1) to give 5- (4-fluorophenylthio) -1-methyl-4-N-methyl-N- (2 , 4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole, compound 93 (1.48 g), m.p. 99-100 ° C as a white solid.

Example 13

To a stirred solution of 5- (4-chlorophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (0.63 g) in trifluoroacetic acid (8 ml) was added dropwise at 0 ° C. solution of 30% hydrogen peroxide (0.19 ml). After 2 hours at 0 ° C, the mixture was allowed to warm to room temperature for 2 hours, then poured onto ice / water (50 ml). The precipitate was collected, washed with water and dried over phosphorus

3?

pentoxide in a desiccator and then purified by chromatography on silica gel eluting with ether in hexane (1: 1) to give 5- (4-chlorophenylsulfinyl) -4-N- (2,4-difluorophenyl) carboxamide-1-methyl-3 -trifluoromethylpyrazole, compound 94 (0.426 g), m.p. 178-179 ° C as a white solid.

Reference case 1

A mixture of 4-carboxy-5-chloro-1-methyl-3-trifluoromethylpyrazole (20.54 g) and thionyl chloride in dry toluene was heated and stirred for 2 hours at 80 ° C, cooled and evaporated. Hexane was added to the residue, which was filtered and the filtrate concentrated to give acid chloride (21.4 g). This was dissolved in dry tetrahydrofuran and added to a mixed solution of 2,4-difluoroaniline (13.4 g) and triethylamine (17.46 ml) in dry tetrahydrofuran. The mixture was stirred at room temperature for 18 hours, filtered and the solid was washed with tetrahydrofuran. The evaporated filtrates were recrystallized from toluene to give 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (20.7 g) as a gray-white solid, m.p. Mp 138-140 ° C.

By acting in a similar manner, the following compounds are prepared from the corresponding substituted starting materials:

Oh

R ¹ r3 P M.p. (° C) CH ₃ ch ₃ 4-F 158-160 ch ₃ ch ₃ 2,4-diF 159-161 ch ₃ cf ₃ 3-CF ₃ 139-141 ch ₃ cf ₃ 4-OCH ₃ 169-171

4-Carboxy-5-chloro-1-methyl-3-trifluoromethylpyrazole is described by L.F. Lee, F. M. Schleppnik, R.W. Salineider and D.H. Campbell v J. Het. Chem. No. 27,243 (1990).

Reference case 2

A mixture of 5-chloro-4-formyl-1,3-dimethylpyrazole (30 g), potassium permanganate (30 g) and potassium hydroxide in water was stirred at 60 ° C 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-l, 3dimethylpyrazole, m.p. 197-201 ° C.

Reference Example 3 l, 3-dimethyl-5-hydroxypyrazole (60 g) was added to a mixture of phosphorus oxychloride and Ν, dimethylformamide and the resulting mixture heated at 95-100 ° C for 16 to 18 hours. The reaction mixture was poured onto ice-water, adjusted to alkaline (with ammonia solution) and the resulting precipitate was isolated and washed with water. Recrystallization from hexane gave 5-chloro 4-formyl-1,3-dimethylpyrazole, m.p. 77-80 ° C.

Reference case 4

Methylhydrazine (25 g) was added to a mixture of ethyl acetoacetate (70 g) in water. The reaction mixture was heated at 70 ° C for 0.5 h, then cooled, extracted (chloroform) and dried (anhydrous magnesium sulfate). Solvent evaporation left a solid which was recrystallized from hexane / ethyl acetate to give 1,3-dimethyl-5-hydroxypyrazole, m.p. 123124 ° C.

Reference case 5

A solution of 4-formyl-1-methyl-5- (3-trifluoromethylphenoxy) -3-trifluoromethylpyrazole (7 g), potassium permanganate (3.1 g) and potassium hydroxide (approximately 0.3 g) in water is heated to 60 to 80 ° C for 2 hours. The resulting solution was cooled, filtered and the filtrate acidified. The resulting precipitate was filtered, washed with water and dried. Recrystallization of the solid gave 4-carboxy-1-methyl-5- (3-trifluoromethylphenoxy) -3-trifluoromethylpyrazole, which was refluxed with thionyl chloride in toluene for 40 minutes. The resulting solution was cooled and concentrated to give chloride-1-methyl-5- (3-trifluoromethylphenoxy) -3-trifluoromethylpyrazole-4-carboxylic acid as a colorless oil.

By acting in a similar manner, 1-methyl-5- (3-chlorophenoxy) -3trifluoromethylpyrazole-4-carboxylic acid chloride and 5- (4-chlorophenoxy) -1, 3dimethylpyrazole-4-carboxylic acid chloride are prepared.

Reference case 6

3-Trifluoromethylphenol (6.9 ml) was added to a warm solution of potassium t-butoxide in t-butanol. The resulting mixture was stirred for 0.5 h and 5-chloro-4-formyl-1-methyl-3trifluoromethylpyrazole (12 g) was added. The mixture was refluxed for 3 hours, then cooled, diluted with water, and the resulting solid was isolated and dried. Recrystallization from hexane gave 4-formyl-1-methyl-5- (3-trifluoromethylphenoxy) -3-trifluoromethylpyrazole (9.2 g), m.p. 81-82 ° C.

By acting in a similar manner, 4-formyl-1-methyl-5- (3-chlorophenoxy) -3trifluoromethylpyrazole, m.p. 61-63 ° C and 4-formyl-1,3-dimethyl-5- (4-chlorophenoxy) pyrazole, m.p. 74-75 ° C.

Reference case 7

5-Chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (29.7 g) was added to a mixture of sodium sulfide monohydrate (42 g) and sulfur (5.6 g) in isopropanol . The mixture was refluxed under an inert atmosphere for 1.75 hours. The cooled solution was decanted, treated with charcoal and filtered to give a pale yellow solution, which was concentrated, filtered and then evaporated to dryness to give sodium l-methyl-4-N- (2,4-difluorophenyl) carboxamido-3- trifluoromethylpyrazole 5-thiolate (31.68 g) as a solid, m.p. 311-313 ° C.

Reference case 8

Ethyl 3- (trifluoromethyl) pyrazole-4-carboxylate (5 g), potassium carbonate (3.48 g) and ethyl iodide (2.3 ml) in acetonitrile were heated at reflux overnight. After cooling, ethyl acetate was added and water and the organic phase separated. The aqueous layer was extracted with ethyl acetate and the combined organic extracts were dried (magnesium sulfate) and evaporated under reduced pressure to give a yellow oil which was purified by crystallization in hexane to give

4-ethoxycarbonyl-1-ethyl-3-trifluoromethylpyrazole as white crystals (3.65 g), δ _Η (CDCl ₃ 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-Butyllithium (2.5 M, 3.5 ml) was added to a solution of diisopropylamine (1.25 ml) in tetrahydrofuran under an inert atmosphere at 0 ° C. The solution was stirred for 45 minutes at 0 ° C and transferred to a solution of 4-ethoxycarbonyl-1-ethyl-3-trifluoromethanespyrazole (1.76 g) in tetrahydrofuran at -78 ° C under an inert atmosphere. The dark orange solution was stirred at -78 ° C for 3.5 hours then ethyl ethyl disulfide (1.1 ml) was added.

The solution was allowed to warm to room temperature overnight while stirring. The precipitate was diluted with ether and the organic layer was washed with a 2 M HCl solution. The aqueous layer was extracted once again with ether. The combined organic extracts were dried (MgSO ₄ ) and evaporated under reduced pressure to give ethyl 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylate as a yellow oil (2 g), δ _Η (CDC1 ₃ ) 1.25 (3H, t), 1.40 (6H, m), 3.0 (2H, q), 4.40 (4H, m) ppm.

Reference case 10

Ethyl 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylate (2 g) was dissolved in ethanol and potassium hydroxide (1 g) was added to water. The reaction mixture was stirred at room temperature overnight. Water and ethyl acetate were added and the organic layer was separated from the aqueous. The latter was acidified with concentrated HCl and extracted with ethyl acetate. The combined organic extracts were dried (MgSO ₄ ) and evaporated under reduced pressure to give 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylic acid as a gray-brown solid (1.42 g), δ _Η (CDC1 ₃ ) 1.25 (3H, t), 1.45 (3H, t), 3.05 (2H, q), 4.45 (2H, q), 6.5 (1H, br s) ppm.

Reference case 11

Lawesson's reagent [2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphethane-2,4-disulfide, 2.14 g) was added to a solution of 5-chloro-4-N- (2 , 4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole (3.0 g) in dry toluene (110 ml), and the mixture was heated at 8085 ° C for 2 hours and then refluxed for 1.5 hours. Additional Lawesson's reagent (3.57 g) was added with reflux for a further 9 hours. The solvent was evaporated in vacuo and the residue was purified by chromatography on silica gel eluting with dichloromethane / hexane (1: 1) to give 5-chloro-4-N- (2,4-difluorophenyl) thiocarboxamido-1-methyl-3-trifluoromethylpyrazole ( 2.49 g) as a yellow oil.

Reference case 12

Methyl 5- (4-fluorophenylthio) -1-methyl-3-methylthiopyrazole-4-carboxylate (1.0 g) was refluxed for 2.5 hours with potassium hydroxide solution (0.4 g), water (3 ml) and methanol. After evaporation in vacuo, the residue is dissolved in water, filtered and the filtrate acidified to pH 1 with hydrochloric acid. The precipitated solid was filtered and dried over phosphorus pentoxide in a desiccator to give 5- (4-fluorophenylthio) -1-methyl-3-methylthiopyrazole-4-carboxylic acid (1.0 g).

Reference Case 13

To a stirred solution of methyl 5-amino-1-methyl-3-methylthiopyrazole-4-carboxylate (2.0 g) in dichloromethane was added 4-fluorophenyldisulfide (5.1 g). A solution of tert.butyl nitrite (2.0 g) in dichloromethane (5 ml) was added portionwise over 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. 92-94 ° C, after recrystallization from cyclohexane.

Reference Case 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 the addition of methyl hydrazine (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 case 15

A mixture of 5-chloro-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid (2.0 g), 4-fluorothiophenol (1.66 g) and anhydrous potassium carbonate (3.26 g) was refluxed in acetonitrile while stirring 4 hours. After filtration, the filtrate was evaporated, acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined extract was dried (anhydrous magnesium sulfate), filtered and evaporated in vacuo. Recrystallization from ether / hexane gave 5- (4-fluorophenylthio) -1-methyl-3-trifluoro42 methylpyrazole-4-carboxylic acid (0.98 g), m.p. 190-193.7 ° C as a white solid.

Reference Case 16

5-Chloro-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid (15.3 g), 2-methylpropanethiol (19.2 ml) and anhydrous potassium carbonate (40.5 g) were refluxed at reflux for 68 hours at inert atmosphere. The reaction mixture was hot filtered and then evaporated to give a tan solid which was then suspended in 2 M hydrochloric acid and extracted with dichloromethane. The extracts were combined, dried over anhydrous magnesium sulfate, filtered and evaporated. The resulting turbid yellow solid was triturated with hexane to give 1-methyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole-4-carboxylic acid (6.4 g) as a white solid, m.p. 183-184 ° C.

By acting in a similar fashion, l-methyl-5- (2-methylpropylthio) -3-pentafluoroethylpyrazole-4-carboxylic acid δ _Η (DMSO d ₆ ) 0.96 (d, 6H), 1.68 (m, 1H) is prepared , 2.85 (d, 2H), 4.00 (s, 3H), 13.20 (s, 1H) ppm.

According to an aspect of the present invention, there is provided a method of controlling weed growth (i.e., unwanted vegetation) at a site comprising applying to it a herbicidally effective amount of at least one N-substituted pyrazole derivative of Formula I or an agriculturally acceptable salt thereof. For this purpose, N-substituted pyrazole derivatives are typically used in the form of herbicidal compositions (i.e., in conjunction with compatible diluents or carriers and / or surfactants suitable for use in herbicidal compositions) e.g. as described behind this.

The compounds of formula I have herbicidal efficacy against dicotyledonous (i.e. broadleaf) and monocotyledonous (i.e. grass) weeds with pre- and / or post-emergence application.

The term pre-emergence application means an application on the soil in which weed seeds or seedlings are present before the emergence of weeds above the surface of the soil. The term application by emergence means application to aerial or exposed parts of weeds that have arisen above the surface of the soil. E.g. compounds of formula I can be used to suppress growth:

broadleaf weeds, e.g. Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Ipomoea spp. e.g. Ipomoea purpurea,

Sesbania exaltata, Sinapis arvensis, Solar nigrum and Xanthium strumarium, and grass weeds, e.g. Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Eleusine indica and Setaria spp, e.g. Setaria faberii or Setaria viridis, and sedges, e.g. Cyperus esculentus.

The amounts of the compounds of formula I that are applied vary from the nature of the weeds, the compositions used, the application time, the climatic and edaphic conditions and (if used to suppress the growth of the weeds on the crop growing areas) the nature of the crops.

When applied to areas where the crop grows, the amount applied will be sufficient to suppress weed growth without causing significant permanent damage to the crop. In general, considering these factors, applications between 0.01 kg and 5 kg of effective substance per hectare give good results. However, it should be understood that higher or lower amounts can be used, depending on the particular problem we encounter in weed control.

The compounds of formula I can be used to selectively suppress weed growth, e.g. for the suppression of the growth of those species mentioned before by application before and after emergence in a direct or indirect way, e.g. by direct or indirect spraying into a weed-infested area where the surface is or is to be used for crop growth, e.g. cereals such as wheat, barley, oats, maize, and rice, soybeans, field and low beans, peas, clovers, cotton, groundnuts, flax, onions, carrots, cabbage, oilseed rape, sunflowers, beetroot, and durable or grassed area before or after sowing the crop or before or after the crop emerges. For selective weed control at a weed-infested site where the surface is or is to be used for crop growth, i.e. of the aforementioned crops, application quantities of between 0.01 kg and 4.0 kg and preferably between 0.01 kg and 2.0 kg of the active substance per hectare are particularly suitable.

The compounds of formula I can also be used to suppress weed growth / especially those mentioned above with pre- and post-emergence applications in landscaped orchards and other areas where trees grow, e.g. forests and parks and plantations, e.g. sugar cane, oil palm trees and rubber plantations. For this purpose, they can be applied directly or indirectly (ie by direct or indirect spray) to weeds or to the soil where they are expected to appear, before or after tree planting, in application quantities between 0.25 kg and 5, 0 kg and preferably between 0.5 kg and 4.0 kg of the active substance per hectare.

The compounds of formula I can also be used to suppress weed growth, especially those listed above at sites that are areas where crops do not grow, but nonetheless weed control is desirable.

Examples of areas where crops do not grow include airports, industrial sites, railways, grasslands along paths and rivers, irrigation and other waterways, areas with shrubs and clearings or uncultivated land, and especially where we want to suppress weed growth to reduce the risk of fires . When used for these purposes, for which the full herbicidal effect is often desired, the effective compounds are usually administered in dosage amounts higher than those used on the crop growing surfaces as previously described. The exact dosage depends on the nature of the vegetation we are cultivating and the effect we are trying to achieve.

Application before and after emergence and preferably application before emergence in direct or indirect way (ie with direct or indirect spray) in application quantities between 1,0 kg and 20,0 kg, and preferably between 5,0 and 10,0 kg of effective substance per acre is particularly suitable for this purpose.

If compounds of formula I are used to suppress weed growth for pre-emergence application, the compounds of formula I can be introduced into the soil in which weeds are expected to emerge. It should be borne in mind that when the compounds of formula I are used to suppress weed growth by sprouting application, i.e. for application to aerial or exposed portions of emergent weeds, the compounds of Formula I also typically come into contact with the soil and may then cause suppression before emergence in weeds that later germinate in the soil.

Where special prolonged weed control is required, the administration of the compounds of Formula I may be repeated if necessary.

In accordance with a further aspect of the present invention, compositions suitable for herbicidal use comprising one or more N-substituted pyrazole derivatives of formula I or their agriculturally acceptable salts, combined with and preferably homogeneously dispersed in one or more compatible agriculturally acceptable diluents or carriers and / or surfactants (i.e., diluents or carriers and / or surfactants of a type generally accepted in the art as suitable for use in herbicidal compositions and compatible with the compounds of formula I). The term homogeneously dispersed is used to include compositions wherein the compounds of formula I are dissolved in other components. The term herbicidal compositions is used in a broad sense to include not only compositions ready for use as herbicides, but also concentrates that must be diluted before use. Preferably, the compositions contain from 0.05 to 90 wt. % of one or more compounds of formula I.

Herbicidal compositions may contain both a diluent or carrier as well as a surface acitic agent (i.e., a wetting, dispersing or emulsifying agent). The surfactants that may be present in the herbicidal compositions of the invention may be of ionic or non-ionic type, e.g. sulforicinoleates, quaternary ammonium derivatives, products based on ethylene oxide condensates with alkyl and polyaryl phenols, e.g. nonyl or octylphenols or carboxylic acid anhydrosorbitol esters which become soluble by the etherification of free hydroxyl groups by condensation with ethylene oxide, alkali metal and alkaline earth metal esters of sulfuric acid and sulfonic acids, such as e.g. Dinonyl- and dioctyl-sodium sulfonosuccinate alkali and alkaline earth metal salts of high molecular weight sulfonic acid derivatives such as e.g. sodium and calcium lignosulfonates and sodium and calcium alkylbenzenesulfonates.

Suitable herbicidal compositions according to the present invention may comprise up to 10 wt. % e.g. of 0.05 wt. % to 10 wt. % surfactant, however, if desired, the herbicidal compositions according to the present invention may comprise higher proportions of the surfactant, e.g. up to 15 wt. % in liquid suspension soluble concentrates and up to 25 wt. % in liquid water-soluble concentrates.

Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesium, diatomaceous earth, tricalcium phosphate, powdered cork, adsorbent carbon black and clays, such as e.g. kaolin and bentonite. Solid compositions, which may be in the form of powders, granules or wettable powders) are preferably prepared by grinding compounds of formula I, with solid diluents or by impregnating solid diluents or carriers with solutions of compounds of formula I in volatile solvents, evaporating solvents and, if it is necessary to grind the products to obtain powders. Granular formulations can be prepared by absorbing compounds of formula I (dissolved in suitable solvents, which may be volatile if desired) to solid diluents or carriers in granular form and, if desired, by evaporation of solvents, or by granulating compositions in powder form obtained as is described above. Solid herbicidal compositions, in particular wettable powders and granules, may contain wetting and dispersing agents, (e.g., the types described above), which may serve as solid as diluents or carriers.

Liquid compositions according to the present invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions, which may include a surfactant. Suitable liquid diluents for incorporation into liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isofuron, toluene, xylene, mineral, animal and vegetable oils, and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents). The surfactants which may be present in the liquid compositions may be ionic or non-ionic (e.g., of the types described above) and, if liquid, may serve as diluents or carriers.

Powders, dispersible granules and concentrate liquid compositions may be diluted with water or other suitable diluents, e.g. mineral or vegetable oils, especially in the case of liquid concentrates in which the diluent or carrier is an oil, to obtain ready-to-use compositions.

If desired, the liquid compositions of the compound of Formula I can be used in the form of self-emulsifying concentrates containing active substances dissolved in emulsifiable agents or in solvents containing emulsifiable agents compatible with the effective substances, with the simple addition of water to such concentrates to produce ready-made compositions for use.

Liquid concentrates in which the diluent or carrier is oil can be used without further dilution using electrostatic spray techniques.

The herbicidal compositions of the present invention may also contain (if desired) conventional adjuvants such as e.g. adhesives, protective colloids, thickeners, penetrating agents, stabilizers, sequesters, anti-caking agents, colorants and corrosion inhibitors. Adjuvants can also serve as carriers or diluents.

Unless otherwise stated, the following percentages are by weight. Preferred herbicidal compositions according to the present invention are:

aqueous suspension concentrates comprising from 10 to 70% of one or more compounds of formula I, from 2 to 10% of surfactant, from 0.1 to 5% of thickener and from 15 to 87,9% of water;

wettable powders comprising 10 to 90% of one or more compounds of formula I, 2 to 10% of surfactant and 8 to 88% of a solid diluent or carrier;

water-soluble or water-dispersible powders comprising 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 a solid diluent;

liquid water-soluble concentrates comprising from 5 to 50%, e.g. 10 to 30% of one or more compounds of formula I, 5 to 25% of surfactant and 25 to 90%, e.g. 45 to 85% water miscible solvent, e.g. dimethylformamide or a mixture of water and water miscible solvents;

liquid emulsifiable suspension concentrates comprising from 10 to 70% of one or more compounds of formula I from 5 to 15% of surfactant, from 0.1 to 5% of thickener and from 10 to 84,9% of organic solvent;

granules comprising from 1 to 90%, e.g. 2 to 10% of one or more compounds of formula I, from 0.5 to 7%, e.g. 0.5 to 2% surfactant and 3 to 98.5%, e.g. 88 to 97.5% of granular carrier and emulsifiable concentrates comprising 0.05 to 90%, 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 the surfactant and from 9.99 to 99.94%, and preferably 39 to 98.99, of the organic solvent.

The herbicidal compositions of the present invention may also comprise compounds of formula I combined with and preferably homogeneously dispersed in one or more other pesticidally effective compounds and, if desired, by one or more compatible pesticidally acceptable diluents or carriers, surfactants and conventional adjuvants such as described earlier. Examples of other pesticidally effective compounds that may be included in or used in connection with the herbicidal compositions of the present invention include herbicides, e.g. to increase weed control area e.g. alachlor [2-chloro-2,6'-diethyl-N- (methoxy-methyl) -acetanilide], atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine], bromoxynil [3 , 5dibromo-4-hydroxy-benzonitrile], chlortoluron [N '- (3-chloro-4-methylphenyl) Ν, Ν-dimethylurea], cyanazine [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-248 methoxybenzoic acid], difenzoquate [1,2-dimethyl-3,5 -diphenylpyrazolium salts], flampropmethyl [methyl N-2- (N-benzoyl-3-chloro-4-fluoroanilino) -propionate], fluometuron [N '- (3-trifluoromethylphenyl) -N, N-dimethylurea], isoproturon [N '- (4-isopropylphenyl) -N, N-dimethylurea], insecticides, e.g. synthetic pyrethroids, e.g. permethrin and cypermethrin, and fungicides, e.g. carbamates, e.g. methyl N- (1-butylcarbamoyl-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 effective compounds and other bioactive substances that may be included in, or used in connection with, the herbicidal compositions of the present invention, e.g. those mentioned before and which are acids, can be used in the form of conventional derivatives, e.g. esters and salts of alkali metals and amines.

In accordance with a further aspect of the present invention, an industrial product is provided comprising at least one of the N-substituted pyrazole derivatives of formula I, or as preferably a herbicidal composition as previously described and preferably a herbicidal concentrate, which must be diluted before use, which comprises at least one N-substituted pyrazole derivative of Formula I in a container for the aforementioned derivative or derivatives of Formula I or said herbicidal composition, and instructions physically associated with the aforementioned container indicating the manner in which said derivative or derivatives of Formula I or a herbicidal composition contained therein is used to suppress weed growth. Containers are normally of the type commonly used to store chemical substances that are solid at normal room temperature and herbicidal compositions, especially in the form of concentrates, e.g. containers and casks, of metal, which may be lacquered internally, and of plastic, bottle or glass or plastic, and if the contents of the container are solid, e.g. granular, herbicidal compositions, boxes, e.g. of cardboard, plastics and metal, or sacks. Containers typically have a suitable volume so that they contain quantities of N-substituted pyrazole derivative or herbicidal compositions sufficient to treat the soil with a surface of at least 4047 m ² to suppress weed growth therein, but not exceeding a size favorable to conventional methods of handling . The instructions are physically merged with the container, e.g. so that they are printed directly on it or on a label or tablet attached to it. The instructions usually indicate that the contents of the container after dilution, if necessary, are applied to suppress weed growth in application quantities between 0.01 kg and 20 kg of the active substance per acre, in the manner and for the purposes described previously.

The following examples illustrate the herbicidal compositions according to the present invention:

EXAMPLE Cl The soluble concentrate is formed from: an effective ingredient (compound 1) 20% w / v potassium hydroxide solution 33% w / v 10% tungsten tetrahydrofurfuryl alcohol (THFA) 10% vol / vol water to 100 vol.

by mixing THFA, the effective ingredient (compound 1), and 90% by volume of water, and slowly adding the potassium hydroxide solution until a constant pH of 7-8 is obtained, then supplemented with water to a total volume of 100.

Similar soluble concentrates can be prepared as described above by replacing the N-substituted pyrazole (compound 1) with other compounds of formula I.

EXAMPLE C2

The wettable powder is formed from:

effective ingredients (compound 1) of sodium dodecylbenzene sulfonate sodium lignosulfate sodium formaldehyde alkylnaphthalene sulfonate silica with a microfinance of kaolin% w / w 3% w / w 5% w / w% w / w% w / w and 37% by mixing of the above ingredients together and grinding the mixture in an air jet mill.

Similar wetting powders can be prepared as described above by replacing the N-substituted pyrazole (compound 1) with other compounds of formula I.

EXAMPLE C3

The water-soluble powder is formed from: the active ingredient (compound 1) of sodium dodecylbenzenesulfonate sodium silica with the microfinity of sodium bicarbonate% w / w% w / w% w / w 47% w / w by mixing the above ingredients and grinding the above mixture in a hammer mill.

Similar water-soluble powders can be prepared as described above by replacing the N-substituted pyrazole (compound 1) with other compounds of formula I.

The present compounds of formula I can be used in herbicidal applications according to the following procedures.

PROCEDURE FOR THE USE OF HERBICID COMPOUNDS:

a) General

The appropriate amounts of the compounds used for the treatment of the plants are dissolved in acetone to give solutions equivalent to application amounts of up to 4000 g of test compound per hectare (g / ha). These solutions are applied with a standard laboratory herbicide sprayer, which applies the equivalent of 2901 spray fluid per acre.

b) Weed control: before emergence

The seeds are sown in 70 mm ² plastic pots and 75 mm deep, in a non-sterile soil. The quantities of seeds per pot are as follows:

Weed types Approximate number of seeds / pot

1) Broad leafy weeds

Abutilon theophrasti 10 Amaranthus retroflexus 20 Galium aparine 10 Ipomoea purpurea 10 Sinapis arvensis 15 Xanthium strumarium 2

2) Grass weeds

Alopecurus myosuroides Avena fatua Echinochloa crus-galli

Setaria viridis

3) Shashi

Cyperus esculentus

Yield

1) Broad leaf soybean cotton

2) Corn grass nz wheat

The compounds of the present invention are applied to the soil surface containing the seeds as described in (a). Individual pots of each crop and each weed are assigned to each treatment with non-sprayed controls and controls sprayed with acetone alone.

After treatment, the crucible is placed on a capillary mat, which is maintained in the greenhouse and filled with water from the top. Visual assessment of crop damage is done 20-24 days after spraying. The results are expressed as a percentage reduction in the growth or damage of the crop or weeds compared to the plants in the control pots.

c) Weed control: After emergence

Weeds and crops are sown directly in pot compost from John Innes, in pots with an area of 75 mm ² and a depth of 75 mm except Amaranthus, which are planted in the seedling stage and transferred to pots 1 week before spraying. The plants then grow in the greenhouse until they are ready to be sprayed with the compounds used to treat the plants. The number of plants per pot is as follows:

1) Broad leafy weeds Types of weed Number of rattles per pot Stages to grow Abutilon theophrasti 3 1-2 list Amaranthus retroflexus 4 1-2 list Galium aparine 3 1. vertebrae Ipomoea purpurea 3 1-2 list Sinapis arvensis 4 2 sheets Xanthium strumarium 1 2-3 sheets 2) Grass weeds Types of weed Number of plants per pot Stages to grow Alopecurus myosuroides 8-12 1-2 list Avena fatua 12-18 1-2 list Echinochloa crus-galli 4 2-3 sheets Setaria viridis 15-25 1-2 list 3) Shashi Types of weed Number of plants per pot Stages to grow Cyperus esculentus 3 3 sheets T) Broadly leafy Crops Number of plants per pot Stages to grow cotton 2 1 sheet soybeans 2 2 sheets 2) Grasses Crops Number of plants per pot Stages to grow corn 2 2-3 sheets • v ΠΖ 4 2-3 sheets wheat 5 2-3 sheets

The compounds used to treat the plants are applied to the plants as described in (a). Each pot of each crop and weed is assigned to each treatment with non-sprayed controls and controls sprayed with acetone only.

After treatment, the crucible is placed on the capillary mat in the greenhouse and poured from the top with water once every 24 hours and then with controlled sub-navigation. Visual assessment of crop damage and weed control is done 20-24 days after spraying. The results are expressed as a percentage reduction in crop growth or damage or weed damage compared to the plants in the control pots.

The compounds of the invention used in an amount of 4 kg / ha or less have an excellent degree of herbicidal efficacy along with the crop tolerance of weeds used in the previous experiments.

Whether applied before or after emergence in an amount of 4000 g / ha or less, compounds 1 to 106 give at least a 70% reduction in the growth of one or more weed species; the compounds are also selective against at least one crop type.

Claims (25)

PATENT APPLICATIONS An N-substituted pyrazole derivative of formula I R ⁴ R ⁵ N, R ³ A ¹ where: R ¹ 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 R ⁶ groups; a group - (CH ₂ ) _n -Ar, where n is 0 or 1 and Ar represents a phenyl group optionally substituted by one or more halogen selected groups, nitro, R ⁶ , -OH, -OR ⁶ , -S ( O) _m R ⁷ and -NR ⁸ R ⁹ ; 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, R ⁶ and -OR ⁶ ; or a group selected from -SO ₂ NR ⁶¹ R ⁶² , -SO ₂ R ⁷¹ and -CONR ⁶¹ R ⁶² ; R ² represents: the group -XR ¹⁰ ; R ³ 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 R ⁶ groups; a cyano or nitro group; a group -S (O) _ffl R ⁶ ; phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ and cyano; or a group -CO ₂ R ⁶ ; R ⁴ represents: phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ ; or pyridyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ ; R ⁵ represents a hydrogen atom or a straight or branched chain alkyl group containing up to 6 carbon atoms; Y represents an oxygen or sulfur atom; R ⁶ represents a straight or branched chain alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms; R ⁶¹ and R ⁶² , which may be the same or different, each represent a straight- or branched-chain alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms; R ⁷ represents a straight or branched chain alkyl group containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms; R ⁷¹ 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, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ and-NR ⁸ R ⁹ ; R ⁸ and R ⁹ , which may be the same or different, each represent a straight or branched hydrogen or alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms; R ¹⁰ represents: phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁸ , -S (O) _m R ⁷ , -NHCOR ⁶ and -NR ⁸ R ⁹ ; pyridyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) _m R ⁷ , -NHCOR ⁶ and -NR ⁸ R ⁹ ; a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, wherein the chain may optionally comprise one or more oxygen or sulfur atoms or -NR ⁵ groups optionally substituted by one or more groups selected from halogen, -OR ⁸ , -S (O) qR ⁶ , -NR ⁸ R ⁹ , -CO2R ⁸ , -OCOR ⁶ , -NHCOR ⁶ , -CONR ⁸ R ⁹ , R ¹² , -COR ⁸ , R ¹³ in cyano; X represents an oxygen atom, NR ¹¹ - or -s (O) _p -, R ¹¹ represents a straight or branched chain hydrogen or alkyl group containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms; R ¹² represents a cycloalkyl group containing from 3 to 7 ring atoms which may optionally contain from 1 to 3 ring heteroatoms selected from oxygen, sulfur and -NR ⁵ -; R ¹³ represents: a cycloalkyl group containing from 3 to 6 carbon atoms which is substituted by one or more groups selected from halogen, R ⁸ and -OR ⁸ ; or a cycloalkenyl group containing 5 or 6 carbon atoms, optionally substituted by one or more groups selected from halogen, R ⁸ and -OR ⁸ ; m is 0.1 or 2; p is 0.1 or 2; q is 0.1 or 2; with the proviso that if Y represents oxygen, R ² represents methylthio or N-phenylamino, R ⁴ represents phenyl and R ⁵ represents hydrogen, R ¹ and R ³ do not simultaneously represent methyl; and their agriculturally acceptable salts. A compound according to claim 1, characterized in that: R ¹ 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 R ⁶ groups; or a group - (CH ₂ ) _n -Ar, where n is 0 or 1 and Ar represents phenyl, optionally substituted by one or more halogen selected groups, nitro R ⁶ , -OH, -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ ; R ³ 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 3 to 6 carbon atoms, optionally substituted by one or more R ⁶ groups; cyano group; a group -S (O) _m R ⁶ ; phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ and cyano; or a group -CO ₂ R ⁶ ; R ¹⁰ represents: phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁸ , -S (O) mR ⁷ -NHCOR ⁶ and -NR ⁸ R ⁹ ; or pyridyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ , -S (O) mR ⁷ -NHCOR ⁶ and -NR ⁸ R ⁹ . Compound according to claim 2, characterized in that X represents an oxygen or sulfur atom or a group -NR ¹¹ . Compound according to claim 1, characterized in that: R ¹ 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 R ⁶ groups; or a group - (CH ₂ ) _n -Ar, where n is 0 or 1 and Ar represents phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OH, -OR ⁶ , -S (O) _m R ⁷ and -NR ⁸ R ⁹ : R ³ 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 R ⁶ groups; a cyano or nitro group; a group -S (O) _ffl R ⁶ ; phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , OR ⁶ and cyano; or a group -CO ₂ R ⁶ ; R ¹⁰ represents: a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, wherein the chain may optionally comprise one or more oxygen or sulfur atoms or -NR ⁵ groups optionally substituted by one or more groups, selected from halogen, -OR ⁸ , -S (O) q R ⁶ , -NR ⁸ R ⁹ , CO2R ⁸ , -OCOR ⁶ , -NHCOR ⁶ , -CONR ⁸ R ⁹ , R ¹² and cyano. Compound according to claim 1, characterized in that: R ³ 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 3 to 6 carbon atoms, optionally substituted by one or more R ⁶ groups; a cyano or nitro group; a group -S (O) _m R ⁶ ; phenyl optionally substituted by one or more groups selected from halogen, nitro, R ⁶ , -OR ⁶ and cyano; or a group -CO ₂ R ⁶ ; R ¹⁰ represents a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, wherein the chain may optionally comprise one or more oxygen or sulfur atoms or -NR ⁵ groups optionally substituted by one or more groups selected from halogen, -OR ⁸ , -S (O) q R ⁶ , -NR ⁸ R ⁹ , CO2R ⁸ , -OCOR ⁶ , -NHCOR ⁶ , -CONR ⁸ R ⁹ , R ¹² , -COR ⁸ , R ¹³ and cyano. Compound according to claim 1, 2 or 3, characterized in that R ¹⁰ represents phenyl substituted by at least one halogen atom. A compound according to claim 1,4 or 5, characterized in that R ¹⁰ represents straight or branched chain alkyl or an alkenyl group containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms. A compound according to claim 1, 4 or 5, wherein R ² represents -SR ¹⁰ , wherein R ¹⁰ represents an alkenyl group containing up to 4 carbon atoms. Compound according to claim 1, 4 or 5, characterized in that R ¹⁰ represents an alkyl, alkenyl or alkynyl group having a straight or branched chain containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms. A compound according to claim 1 or 5, characterized in that R ¹⁰ represents a group -CH ₂ or -CH ₂ R ¹³ . A compound according to any one of the preceding claims, wherein Y represents an oxygen atom. A compound according to any one of the preceding claims, characterized in that R ¹ represents methyl or ethyl. A compound according to any one of the preceding claims, wherein R ³ represents trifluoromethyl. A compound according to any one of the preceding claims, wherein R ⁴ represents 2,4-difluorophenyl or 2,4,6-trifluorophenyl. A compound according to any one of the preceding claims, wherein R ⁵ represents a hydrogen atom. A compound according to any one of the preceding claims, characterized in that X represents a sulfur atom. A compound according to any one of the preceding claims, characterized in that X represents an oxygen atom. A compound according to claim 1, characterized in that: R ¹ represents an acyl group containing one or two carbon atoms, optionally substituted by one or more halogen atoms (preferably fluorine), which may be the same or different; R ^{3 is} : an alkyl group containing up to 3 carbon atoms, optionally substituted by up to 5 halogen atoms (preferably fluorine or chlorine), which may be the same or different; or a SMe group; R ⁴ represents phenyl optionally substituted by one or three groups selected from halogen, trifluoromethyl and methoxy; R ⁵ represents a hydrogen atom or a methyl group; Y represents an oxygen or sulfur atom; X represents an oxygen atom or a group -S (O) _p -; R ¹⁰ represents: phenyl or pyridyl optionally substituted by a group selected from halogen, methoxy, hydroxy, -NHCOMe, -NH ₂ , -SMe, methyl and trifluoromethyl; a cycloalkyl group containing from 3 to 6 carbon atoms; a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms, optionally substituted by one or more groups selected from halogen, -CO ₂ Et, cyano, cyclopropyl, methoxy and -CONHMe; and p is 0 or 1. A compound according to claim 1, characterized in that: 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-trifluoro61 methylpyrazole, 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-trifluoro methylpyrazole, 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-3trifluoromethylpyrazole, 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-trifluoro methylpyrazole, 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, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-chlorophenoxy) -1-methyl-3-trifluoromethylpyrazole, or an agriculturally acceptable salt thereof. 20. A compound according to claim 1, wherein: 4-N- (2,4-difluorophenyl) carboxamido-5- (n-butylthio) -1-methyl-3-trifluoro62 methylpyrazole, 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, 4-N- (2,4-difluorophenyl) carboxamido-5- (2,2,2-trifluoroethoxy) -1-methyl-3-trifluoro methylpyrazole, or an agriculturally acceptable salt thereof. 21. A compound according to claim 1, characterized in that: 4-N- (2,4-difluorophenyl) carboxamido-5- (ethoxycarbonylmethylthio) -1-methyl-3trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (1-methylbutylthio) -3trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, 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-trifluoro63 methylpyrazole, 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-3trifluoromethylpyrazole, 5- (3-bromo-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole, 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-3trifluoromethylpyrazole, 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-trifluoro methylpyrazole, 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) -3trifluoromethylpyrazole, 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-methyl-3-trifluoromethylpyrazole, 5- (3-chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole, 5-ethylthio-1-ethyl-4-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole, 5-ethylthio-1-ethyl-4-N- (2,4,6-trifluorophenyl) carboxamido-3-trifluoromethylpyrazole, 5- (N-methylaminocarbonylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl3-trifluoromethylpyrazole, or an agriculturally acceptable salt thereof. A compound according to claim 1, characterized in that: 4- N- (2,4-difluorophenyl) -5- (4-fluorophenylthio) -thiocarboxamido-1-methyl-3trifluoromethylpyrazole, 3-chlorodifluoromethyl-5- (4-fluorophenylthio) -4-N- (2,4-difluorophenyl) carboxamido1-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-trifluoromethyl-pyrazole, 5- (4-aminophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 5- (3-chloro-4-fluorophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyltrifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1- (2,2,2-trifluoroethyl) -3trifluoromethylpyrazole, 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-3methylthiopyrazole, 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-trifluorophenyl) carboxy65 midopyrazole, 4-N- (2-chloro-4-fluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoro methylpyrazole, 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-trifluoromethylpyrazole, 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-3trifluoromethylpyrazole, 5- (4-chlorophenylsulfinyl) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (n-propyloxy) -3trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropyloxy) -3trifluoromethylpyrazole, 3-chlorodifluoromethyl-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methyl66 propyloxy) pyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-ethyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-ethyl-5- (2-propenylthio) -3trifluoromethylpyrazole, 4-N- (2,4,6-trifluorophenyl) carboxamido-1-ethyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, 4-N- (2,3-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, 4-N- (2,6-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, 4-N- (2,3,6-trifluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, 4-N- (2,4,6-trifluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, 4-N- (2,5-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3trifluoromethylpyrazole, and 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3pentafluoroethylpyrazole. or an agriculturally acceptable salt thereof. A process for the preparation of an N-substituted pyrazole derivative of formula I as defined in claim 1, characterized in that it comprises: a) reacting a compound of formula II wherein Z is a leaving group and are other symbols as defined in claim 1 with a compound of general formula III R ² -X ' III wherein R ^{2 is} as defined in claim 1 and X ¹ represents hydrogen or an alkali metal; b) wherein Y represents a sulfur atom, the reaction of a corresponding compound of formula I in which Y represents an oxygen atom with a thionyl compound; c) wherein R ⁵ represents a straight or branched chain alkyl group containing up to 6 carbon atoms, the reaction of a corresponding compound of formula I in which R ⁵ represents hydrogen, with an alkylating agent; d) where Y represents oxygen, the reaction of a compound of formula IV O .R ³ HO R ¹ IV wherein the various symbols as defined in claim 1 are halogenated to give an acid halide followed by reaction with an amine of formula V H-NR ⁴ R ⁵ V wherein R ⁴ and R ^{5 are} as defined in claim 1; e) 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 R ¹⁰ -L, wherein R ^{10 is} as defined in claim 1 and L is a leaving group; f) wherein R ¹⁰ represents phenyl or pyridyl substituted with the group -SR ⁷ , diazotizing the corresponding compound of formula (I) in which R ¹⁰ represents phenyl or pyridyl substituted with -NH ₂ , followed by the reaction of the diazotized product thus obtained with a disulfide of formula R ⁷ S-SR ⁷ , wherein R ^{7 is} as defined in claim 1; followed by conversion of the N-substituted pyrazole derivative thus obtained to its agriculturally acceptable salt. A herbicidal composition comprising, as an effective ingredient, a herbicidally effective amount of an N-substituted pyrazole derivative of formula I as defined in claim 1 or its agriculturally acceptable salts in connection with an agriculturally acceptable diluent or carrier and / or surfactant . A method of controlling weed growth in a site, characterized in that it comprises applying to the site a herbicidally effective amount of an N-substituted pyrazole derivative of formula I as defined in claim 1 or its agriculturally acceptable salts.