SK152894A3 - N-substituted pyrazole derivatives, method of their production and herbicidal agents containing these derivatives - 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, process for their preparation and herbicidal compositions containing them

Technical field

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

BACKGROUND OF THE INVENTION

Okayima and Okada, J. Het. Chem., Volume 27, pages 567-574 describe the preparation of 4-N-phenylcarboxamido-5-methylthio-1,3-dimethylpyrazole. Japanese Patent Application No. 3119468 describes a process for the production of certain 5-mercaptopyrazoles. French patent no. 2337997, as well as Huppatz J. L., Aust. J. Chem., Vol. 36, p. 135-147 (1982) discloses certain fungicidally active pyrazole carboxamides. U.S. Pat. 4620865 and European patent no. 0151866 discloses certain pyrazole-4-carboxamides that exhibit herbicidal properties.

SUMMARY OF THE INVENTION

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

Y

Rl in which

R ¹ represents an alkyl group straight or branched having up to 6 carbon atoms, optionally substituted by one or more halogen atoms, cycloalkyl having 3 to 6 carbon atoms, optionally substituted by one or more groups R ^6, - (CH ) -Ar, where n

n is zero or one, and

Ar is phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, R ^G groups, a hydroxyl group, a group -OR®, -S (O) ^, and R ⁷ alkenyl or alkynyl, straight or branched a chain of up to 6 carbon atoms optionally substituted by one or more groups selected from the group consisting of halogen atoms, the groups R ^G and -OR ^G , or a group selected from the group consisting of -SO- _? NR ^GX R ^G2 -S0 _and R ' ^{7 t} and -CONR ^S1 R ^G2 ,

R ² represents -XR ^10,

R ³ represents a hydrogen or halogen atom, a straight or branched chain alkyl group having up to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group having 3 to 6 carbon atoms optionally substituted by one or more substituents selected from halogen atoms and the radicals R ^G, cyano or nitro, -S (O) R ^6, τη phenyl, optionally substituted by one or more groups selected from the group consisting of halogen, nitro, a group R ^6, -OR ⁶ a cyano group or a group -CO R ^6,

R ⁴ is phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, a group R ^6, -OR ^6, -S (O) R ^7, and -NR ⁵ R *, and m

pyridyl, optionally substituted by one or more groups selected from the group consisting of halogen, nitro, a group R ^6, -0R ^G, -S (O) _add R ^7, and -NR G R '.

^R is H or an alkyl group straight or branched having up to 6 carbon atoms,

Y represents an oxygen atom or a sulfur atom,

R ^y represents an alkyl group straight or branched having up to 6 carbon atoms, optionally substituted by one or more halogen atoms,

R @ ¹ and R @ ² , which are the same or different, are each a straight or branched chain alkyl group containing up to 6 carbon atoms, which is 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 having 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 atoms, nitro, R ⁶ groups , -0R ^G, ~ S (0) R ^7, and -NR R®,

HERE

R @ ⁹ and R @ ⁹ , which are the same or different, each represent a hydrogen atom or a straight or branched chain alkyl group containing up to 6 carbon atoms, which is optionally substituted by one or more halogen atoms,

R ¹⁰ represents a phenyl group, which is optionally substituted by one or more groups selected from halogen atoms, nitro, R °, -OR ®, -S (O) R ⁷ , -NHCOR ® and -NR ® R m;

a pyridyl group optionally substituted by one or more groups selected from the group consisting of halogen atoms, nitro, R ^e , -OR ^e , -S (O) R ⁷ , -NHCOR ^e and -NR ® R, or m

straight or branched chain alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, the chain optionally containing one or more oxygen or sulfur atoms or -NR ' ⁵ - groups optionally substituted by one or more groups selected from atoms halogens, -OR®, -S (O) ^ R®, -NR®R ⁹ , -CO ₂ R®, -OCOR®, -NHCOR®, -CONR®R °, R ¹² ,

-COR®, R ³³ and cyano,

X is O, -NR ¹¹ - or -S (O) -,

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

R ¹² represents a cycloalkyl group containing three to seven ring atoms, which may optionally contain one to three heteroatoms selected from oxygen, sulfur and -NR ⁵ -,

R ¹³ represents a cycloalkyl group having 3 to 6 carbon atoms which is substituted by one or more groups selected from halogen atoms, R ® and -OR ®, or a cycloalkenyl group containing 5 or 6 carbon atoms optionally substituted by one or more a number of groups selected from the group consisting of halogen atoms, R® and -OR®,

m is zero, one or two, P is zero one or two, and q is zero, one or two,

provided that when Y represents an oxygen atom, R ³ represents a methylthio or Nphenylamino group, R ¹ represents a phenyl group and R ⁵ represents a hydrogen atom, R ^x and R ³ do not simultaneously represent a methyl group, and their agriculturally acceptable salts which have valuable herbicidal features.

The term agriculturally acceptable salts refers to salts whose cations are known and used in the art to form salts for agricultural and horticultural use. Water-soluble salts are preferred. Suitable base salts include alkali metal salts (e.g., sodium and potassium), alkaline earth metals (e.g., calcium and magnesium), and ammonium and ammonium salts (e.g., diethanolamine, triethanolamine, octylamine, morpholine, and dioctylmethylamine). Suitable acid addition salts which form amino-containing compounds of formula I include salts with inorganic acids such as hydrochlorides, sulfates, phosphates and nitrates, and salts with organic acids such as acetic acid.

Some of the compounds of formula I have been found to have actually been synthesized without having been reported to have fungicidal properties. In another aspect the invention provides a compound of formula I, as defined above, excluding compounds of the formula I, wherein Y is oxygen, R ¹ is methyl, R ³ is trifluoromethyl, R ⁵ is H, ^{R, and} 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, 4-trifluoromethyl nitrophenyl, 2-bromo-4-nitrophenyl, 2-chloro-5-trifluoromethylphenyl, 2,5-dicloro-4-nitrophenyl, 2,3,4,5-tetrachlorophenyl, 2, 6-dibromo-4-trifluoromethoxyphenyl and pentafluorophenyl.

In one embodiment, the invention provides N-substituted pyrazole derivatives of formula (I) wherein:

R ¹ · is alkyl straight or branched chain containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms, cycloalkyl having 3 to 6 carbon atoms, optionally substituted by one or more groups E ^'5, or a group - (CH) -Ar, where n is zero or one, and

Ar is phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, a group R®, OH, -0R of ^e, -S (O) _m R ^7, and -NR G R '

R ³ represents a hydrogen or halogen atom, an alkyl group, straight or branched chain containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms, cycloalkyl having 3 to 6 carbon atoms, optionally substituted by one or more groups R ^G , CN, s (O) _m R ^a, phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, a group ^{R6, -OR6} and cyano, or -CO ₂ R ⁶ , θ represents a phenyl group optionally substituted by one or more groups selected from the group consisting of halogen, nitro, a group R ^6, -OR ^6, -S (0) _m R ^7, -NHCOR ⁶ and -NR ⁶ R ⁹ or a pyridyl group optionally substituted by one or more groups selected from the group consisting of halo atoms gene, a nitro group, a group R ^6, OR ^6, S (0) R ^7, -NHCOR ⁶ and -NR ^p R'- '.

LTT

In this embodiment, X preferably represents an oxygen or sulfur atom or an -NR ¹ · ^{1 group} .

According to a second embodiment, the invention provides N-substituted pyrazole derivatives of the general formula I in which:

R ¹ represents a straight or branched chain alkyl group having up to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group having 3 to 6 carbon atoms optionally substituted by one or more R ⁶ groups, or - ( CH) -Ar, where n is zero or one, and

Ar is phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, R ^e group, a hydroxyl group, a group -0R ^e, -S (O) ^ R ⁷ and -NR ^B R ^9,

R ³ represents a hydrogen or halogen atom, an alkyl group, straight or branched chain containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms, cycloalkyl having 3 to 6 carbon atoms, optionally substituted by one or more groups R ⁵ , cyano or nitro, -S (0) ^R, R is phenyl, which is optionally substituted by one or more groups selected from the group consisting of halogen, nitro, a group R ^G, -0R ^e, and cyano, or -CO R ⁶ ,

R ³ represents a straight-chain or branched alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, the chain optionally containing one or more oxygen or sulfur atoms or -NR ⁵ - optionally substituted by one or more groups selected from the group consisting of: halogen atoms, the group -0R ^B, -S (O) R ^a, -NR ^B R ^s>, -CO R ^63, -OCOR ^G, NHCOR ^e, -CONR ^B R ^$? , R ³ ' ² and cyano.

According to a third embodiment, the invention provides N-substituted pyrazole derivatives of the general formula I, wherein:

R ³ represents a hydrogen or halogen atom, an alkyl group, straight or branched chain containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms, cycloalkyl having 3 to 6 carbon atoms, optionally substituted by one or more groups R® , cyano or nitro, -S (O) R ^6, m

phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, a group R ^8, 0R ^with a cyano group or a group -CO R ^8,

R ¹⁰ represents a straight-chain or branched alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, the chain optionally containing one or more oxygen or sulfur atoms or -NR ⁵ - groups optionally substituted by one or more groups selected from the group consisting of halogen atoms, -OR ^8, -S (0) _q R ^c, -NR ⁸ R, -CO R ^8, -OCOR ^c, NHCOR ^{G, b} R ^-C0NR? R @ ^{1 is} -COR @ ⁸ , R @ ¹³ and cyano.

A preferred group of compounds of formula I includes those wherein Y is O.

To another group of preferred compounds of formula I include those wherein R ³ is methyl or ethyl.

Another preferred group of compounds of formula I include those wherein R ¹ is methyl.

Compounds, wherein R ³ is trifluoromethyl.

Also preferred are compounds wherein R ⁴ is 2,4-difluorophenyl.

Also preferred are compounds of formula I wherein R ⁴ is 2,4-difluorophenyl or 2,4,6-trifluorophenyl.

Hydrogen compounds are also preferred.

Another preferred group includes compounds wherein X is of formula I wherein X is preferred.

wherein ^R is selected from the compounds of the formula I is sulfur. Compounds means an oxygen atom are also

Another preferred group of compounds of formula I includes those wherein R ¹⁰ is a phenyl group substituted with at least one halogen atom, preferably a fluorine atom.

Another preferred group of compounds of formula I includes those wherein R ¹⁰ is 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 group of compounds of formula I includes those wherein R ² is -SR ¹⁰ , wherein R ¹⁰ is an alkenyl group containing up to 4 carbon atoms.

Another preferred group of compounds of formula I includes those wherein R ¹⁰ is a straight, branched, alkyl, alkenyl or alkynyl group containing up to 6, preferably up to 5, carbon atoms optionally substituted by one or more halogen atoms.

When R ¹⁰ is alkyl, is linear or branched, substituted with one or more groups R ¹² or R ^13, R ¹⁰ preferably represents -CH-CH or R ¹² R ^13th

Z 2

Another preferred group of compounds of formula I includes those wherein:

R ³ - represents an alkyl group having one or two carbon atoms, optionally substituted by one or more halogen atoms (preferably F), which are the same or different,

R ³ is alkyl having up to 3 carbon atoms optionally substituted with up to 5 halogen atoms (preferably F or Cl), which may be identical or different, or a group -SCH.

R * represents a phenyl group which is optionally substituted by one to three groups selected from halogen atoms, trifluoromethyl group and methoxy group,

R ⁵ represents a hydrogen atom or a methyl group,

Y represents an oxygen or sulfur atom,

X is O or -S (O) -,

R ¹⁰ is phenyl or pyridyl optionally substituted with halogen, methoxy, hydroxyl, -NHCOCH 4, amino, -CH ₃ , methyl and trifluoromethyl, C 3-6 cycloalkyl straight, branched or branched chain alkyl, alkenyl or alkynyl of up to 6 carbon atoms optionally substituted by one or more groups selected from halogen atoms, -COCH2CH3, cyano, cyclopropyl, methoxy and methoxy; -C0NHCH _3, and

p is zero or one.

Due to their herbicidal properties, important compounds include in particular the following compounds:

1. 4-N- (2,4-difluorophenyl) carboxainido-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-1- (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. 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chlorophenylthio) -1-methyl-3-trifluoromethylpyrazole; 4-N- (2,4-difluorophenyl) carboxamido-5- (4-trifluoromethylphenylthio) -1-methyl-3-trifluoromethylpyrazole; 4-N-phenylcarboxamido-5- (3-trifluoromethylphenylthio) -1,3-dimethylpyrazole,

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; 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; 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-trifluoromethylpyrazole;

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

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

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

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-trifluoromethylpyrazole;

38. 5-cyclohexylthio-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole;

39. 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (1-methylpropylthio) -3-trifluoromethylpyrazole;

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. 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-3-trifluoromethylpyrazole;

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

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-Ν- (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; 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methyl-2-propenylthio) -3-trifluoromethylpyrazole,

57. 5- (2-chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole,

58. 4-N- (2,4-difluorophenyl) carboxamido-5- (2-methoxyethyl) -1-methyl-3-trifluoromethylpyrazole;

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;

62. 5- (N-methylaminocarbonylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole,

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) carboxamido-1-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-trifluoromethylpyrazole;

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-methyl-3-trifluoromethylpyrazole,

69. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3- (n-propyl) pyrazole;

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-3-methylthiopyrazole; 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- [2- (2,4,5-trifluorophenyl) carboxamidopyrazole,

75. 4-N- (2-fluorophenyl) carboxamido-5- (2-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-trifluoromethylpyrazole;

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-trifluoromethylpyrazole,

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- [2- (2,3,4-trifluorophenyl) carboxamidopyrazole,

83. 4-N- (4-bromo-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-Ν-methyl-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole. 5- (4-chlorophenyl-) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole,

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

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

97. 3-Chlorodifluoromethyl-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropyloxy) pyrazole. 4-N- (2,4-difluorophenyl) carboxamido-1-ethyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole,

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

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

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

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

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

104. 4-Ν- (2,4,6-trifluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3-trifluoromethylpiperazole,

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

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

Numbers 1 to 106 are assigned to these compounds for reference and identification below.

The compounds of formula (I) may be prepared by the application or adaptation of known methods (i.e., methods previously used or described in the chemical literature), for example as described below.

In the following, where the symbols appearing in the general formulas are not specifically defined, they mean that they have the meaning defined above in accordance with the first definition of each symbol in the description.

It is to be understood that in the description of the following procedures, the individual steps may be carried out in a different order, and that appropriate protecting groups are required to obtain the desired compounds.

According to the invention, the compounds of formula (I) can be prepared by reacting a compound of formula (II)

(II) in which R ^x, R ^3, R ^4, R ⁵ and Y are as defined above and Z is a leaving group, with a compound of formula III

R ² - X ^x (III) wherein R ² is as defined above and X ¹ represents a hydrogen or alkali metal (for example sodium or potassium) atom. The reaction is generally carried out in an inert solvent such as acetonitrile, dioxane or tetrahydrofuran, optionally in the presence of a base, preferably potassium carbonate, at a temperature from room temperature to the reflux temperature of the solvent. The leaving group Z is preferably a halogen atom, for example a chlorine, bromine or fluorine atom.

According to another embodiment of the invention, compounds of formula I wherein Y is sulfur may be prepared by reacting a corresponding compound of formula I wherein Y is oxygen with a thionating agent, such as Lawesson's reagent (2,4-bis (4-methoxyphenyl)) (1,3-dithia-2,4-diphosphetane-2,4-disulfide) in an inert solvent, preferably toluene, at a temperature of from 50 ° C to the reflux temperature of the solvent.

The compounds of formula I, wherein ^R is alkyl straight or branched chain C 6 -to carbon atoms, can be prepared according to the invention by reaction of the corresponding compound of formula I, wherein R ^y is a hydrogen atom and an alkylating agent, preferably alkyl halide or dialkyl sulfate, in the presence of a base such as potassium hydroxide or potassium carbonate, in an inert solvent such as tetrahydrofuran at a temperature from room temperature to the reflux temperature of the solvent. This reaction is carried out optionally in the presence of a phase transfer catalyst such as tetrabutylammonium bromide, typically at a concentration of 0.01 - 0.1 mol%. Alternatively, the sodium or potassium salt of a compound of formula I may be prepared by reacting a compound of formula I wherein R ⁵ represents a hydrogen atom with a base, preferably sodium hydride, in an inert solvent, followed by reaction with an alkylating agent.

According to another embodiment of the invention, compounds of formula I wherein Y is O can be prepared by reacting a compound of formula IV

R wherein R ^1, R ^3, and R ³ are as defined above, with a halogenating agent to give an acid halide (which may optionally be isolated) followed by reaction with an amine of the formula V

Η-NH''R ^'5 (V) in which R ¹ and R · ^p as defined above. Preferably, the halogenating agent is a chlorinating agent, for example thionyl chloride, and the reaction to obtain the acid halide is optionally carried out in an inert solvent at a temperature from room temperature to reflux. The reaction between the acid halide and the amine of formula V is generally carried out in the presence of a base, preferably triethylamine, in an inert solvent such as tetrahydrofuran at a temperature of from 0 ° C to the reflux temperature of the solvent.

According to a further embodiment of the invention, the compounds of the formula I can also be prepared by reacting a compound of the formula IVa

(IVa) in which R ^x, R ^3, R, ^R, Y and X are as defined above, or a salt thereof with the compound R-L ^xo, where R ^xo is as defined above and L is a leaving group . Preferably L is halogen (preferably chloro or bromo), p-toluenesulfonyloxy or methanesulfonyloxy, and (where R ^o is an optionally substituted phenyl or pyridyl) nitro. The reaction is generally carried out in an inert solvent such as ethanol or methanol in the presence of a base (e.g. sodium hydride or sodium methoxide). When 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 another embodiment of the invention, compounds containing the group -XR ^XO in which R ^x0 represents a phenyl group or a pyridyl group substituted by a group -SR ' ⁷ can be produced by diazotization of the corresponding compounds wherein R ^x0 represents a phenyl group or a pyridyl group substituted by an amino group, and then reacting the product thus obtained by diazotization with a disulfide of the formula R ⁷ S-SR ⁷ , where R ^{7 is} as defined above. The reaction is generally carried out using a diazotizing agent such as an alkylnitrite (e.g. tert-butylnitrite) in an inert solvent (e.g. acetonitrile or dichloromethane) at a temperature from -20 ° C to reflux.

The intermediates used in the preparation of the compounds of formula I may be prepared by application or adaptation of known methods, for example those described below.

Compounds of formula II in which Y is oxygen and Z represents a leaving group, for example halogen, can be prepared from compounds of formula VI

HO (VI) in which Z represents a leaving group, for example a halogen atom, by conversion to an acid halide, preferably an acid chloride, for example by reaction with thionyl chloride optionally in the presence of an inert solvent at room temperature to reflux, followed by chloride reaction acid (which may optionally be isolated) with an amine in the presence of a base, preferably triethylamine in an inert solvent such as tetrahydrofuran, at a temperature from 0 C to ^{the CT} boiling point of the solvent used.

Compounds of formula II in which Y is a sulfur atom may be prepared by reacting the corresponding compound of formula II in which Y is oxygen with a thionating agent, for example Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3- dithia-2,4-diphosphetane-2,4-disulfide) in an inert solvent, preferably toluene, at a temperature of from 50 ° C to the reflux temperature of the solvent.

Compounds of formula III in which X ¹ represents an alkali metal atom, for example sodium or potassium, may be prepared by reacting the corresponding compound of formula III in which X ¹ represents a hydrogen atom with an alkali metal-containing base such as sodium hydride in an inert a solvent such as dioxane at a temperature of from 20 ° C to the reflux temperature of the solvent.

Compounds of formula III wherein R ² is -SR ¹⁰ and X ¹ is hydrogen can be prepared by reacting a compound of formula R ¹⁰ -Br with:

(a) sodium thioxide in ethanol,

(b) thiourea in ethanol, followed by reaction of the compound thus obtained R ¹⁰ SC (= NH) NH ₂ .HBr with sodium hydroxide in ethanol; or

C) potassium xanthate (CH _{3 CH?>} OC (S) S ^_ A ''') in ethanol, followed by hydrolysis of the resulting compound of the formula R ^XO SC (= S) OCH ₂ CH ₃ with NaOH in ethanol.

Compounds of formula III wherein R ² is -SR ¹ ° and X ¹ is hydrogen can also be prepared by reduction of a disulfide of the formula R 2 ^O -SR ¹⁰ , using, for example, sodium borohydride in ethanol.

Compounds of formula IV in which X represents a group other than -S (O) - in which p is zero or one may be prepared from compounds of formula VII

(VII) replacing the Z group with R ² (by the procedure described for the preparation of the compound of formula I from the compound of the formula II), followed by converting the formyl group to the carboxyl group (described below for preparing the compound of the formula VI from the compound of the formula VII).

Compounds of formula (IV) may also be prepared by hydrolysis of an ester of formula (VIIa)

R ¹ wherein R is an alkyl group. This may be accomplished using conventional procedures, for example by reaction with potassium carbonate in an ethanolic solvent.

Compounds of formula IV may also be prepared by reacting 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 salts thereof may be prepared by reacting a compound of formula II with a compound of formula HXX ^a .

Compounds of formula VI may be prepared by oxidizing the corresponding aldehyde of formula VII using an oxidizing agent, preferably potassium permanganate, using a base, preferably sodium hydroxide, in a solvent, preferably water, at a temperature of from room temperature to 100 ° C.

Compounds of formula (VII) may be prepared by reaction

5-hydroxypyrazole of formula VIII

HO

R ¹

^R3 (VIII) with formylating agent. Preferably, the formylating agent is a mixture of phosphorus oxychloride and N, N-dimethylformamide, wherein simultaneous chlorination is carried out to produce a compound of formula VII in which Z is chlorine. The reaction is generally carried out at a temperature of from 0 ° C to 150 ° C.

The 5-hydroxypyrazoles of formula VIII can be prepared by reacting the beta-keto ester of formula IX

R ³ C (O) CH CO A (IX) wherein A represents a lower alkyl group, with a hydrazine of formula X

R ^X NHNH

The reaction is generally carried out in a solvent, preferably water, at a temperature from room temperature to the reflux temperature. During this reaction, a mixture of isomeric products can be produced which can be separated by known methods. The preparation of the above-mentioned intermediates VI, VII and VIII is well described in the literature, for example, in L. F. Lee et al., J. Het. Chem., 27, 243 (1990).

Compounds of formula VIII in which R ³ is cyano can be prepared by dehydrating the corresponding compound of formula VIII in which R ^{3 is} replaced by -CONH 4 using, for example, phosphorus oxychloride optionally in the presence of an inert solvent at a temperature from room temperature to room temperature refluxing, or para-toluenesulfonyl chloride in pyridine at a temperature of from 50 ° C to reflux, followed by hydrolysis with sodium hydroxide in alcohol at a temperature of from 20 to 100 ° C.

Compounds of formula VIII in which R ³ is replaced by a group -CONH ^, may be prepared by hydrolysis of the corresponding ester of formula VIII, wherein R ³ is -CO ₂ R ^a, preferably using a solution of sodium or potassium in a solvent, e.g. in aqueous alcohol, at a temperature of from 0 ° C to the reflux temperature of the solvent to give the corresponding carboxylic acid, which is converted to the corresponding acid chloride, for example by reaction with thionyl chloride (optionally to reflux, to which is added ammonia optionally in the presence of a suitable solvent, for example an aqueous alcohol, at a temperature of from 0 ° C to the reflux temperature to give the desired product.

Compounds of formula VIII in which R ^{3 is} replaced by -CONH 4 may alternatively be prepared by ammonolysis of the corresponding ester of formula VIII in which R ³ is -CO 4 R ⁶ , preferably by the addition of ammonia in a sealed vessel at a temperature of from 100 to 200 ° C.

Beta-keto esters of formula IX, where R ³ is alkyl straight or branched chain 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 including halogen atoms, nitro, R ⁶ , -OR ⁶ and cyano, or C 3 -C 6 cycloalkyl optionally substituted by one or more R ⁶ , or nitro or -CO ₂ R ⁶ may be prepared by known methods, for example as described by Perkin, Bellenot, Beilstein 10, 682 (JCS 49, 447), or by K. Hattori and H. Nakano, Nippon Kagaku Zasshi 82, 132 (1961), or by G. Braar, M.

Vilkas, Bull Soc. Chim Fr. (1964), 5, 946.

Compounds of formula VIII wherein R ³ is -CO R ® may also be prepared by reacting an acetylene-1,2-dialkoxycarbonyl compound of formula XI

R ⁶ O ₂ CC C-CO ₂ R ^{g of} (XI) with a hydrazine of formula X. This reaction is generally performed in an inert solvent, preferably an alcohol, for example methanol, at a temperature from 0 DEG C. to reflux to provide the compound of the formula XII ^ ⁶ CCBR

R 4 OriC NHNHR ¹ which is cyclized under basic conditions, for example using sodium methoxide in a suitable solvent, for example methanol, at a temperature from 0 ° C to reflux. Both of these steps can be performed in one step using a combination of bases and solvents.

Compounds of formula VI in which Z represents a halogen atom may be prepared from an ester of formula XIII ^R 2 ^C / R ³ • N (XIII)

R ¹ in which R is alkyl, and Z is halogen. The reaction is carried out in principle, for example, sodium hydroxide, in a solvent, preferably aqueous alcohol;

at a temperature of from 0 ° C to 100 ° C. f i

J

Esters of formula (XIII) or esters of formula (VI) wherein R ² is -SR ¹⁰ may be prepared by diazotization of an amine of formula (XIV):

This reaction may be carried out with sodium nitrite in a mineral acid, for example a mixture of concentrated sulfuric acid and acetic acid, at a temperature of from 0 ° C to 60 ° C, followed by reaction with:

(a) copper halide (when ester of formula XIII is required) or disulfide of formula R ¹⁰ S-SR ¹⁰ (when ester of formula IV in which R ² is -SR ^XO is desired) and mineral acid or aqueous solution potassium iodide at a temperature of from 0 ° C to 100 ° C. The diazotization may alternatively be carried out using an alkyl nitrite, for example tert-butyl nitrite, in the presence of a suitable halogenating agent (when an ester of formula XIII is desired), preferably bromoform or iodine or anhydrous cupric chloride, or at 0 to 100 ° C optionally in the presence of inert. a solvent, preferably acetonitrile or chloroform.

Compounds of formula XIV wherein R ³ is halogen, cyano or -SR ^e may be prepared by diazotization of a compound of formula XV

RO ₂ C / _ NH ₂

R ¹ (XV) wherein R ^{1 is} as defined above. The reaction conditions for this reaction are as described above for the conversion of a compound of formula XIII to a compound of formula XIV, where cyanide, for example copper cyanide, may also be used as a reagent instead of a halogenating agent; or using a diazotising reagent such as an alkyl nitrite (e.g. tert. butyl nitrite) in an inert solvent (e.g. acetonitrile or dichloromethane) at from -20 DEG C. to reflux, followed by reaction of the diazotised intermediate with a disulphide of formula R ^G S -SR ^G. This reaction can be performed selectively to achieve diazotization at the 3-position of the pyrazole ring.

Compounds of formula XIV may be prepared by reacting a compound of formula XVI

NC (XVI) wherein B is a halogen (preferably a chlorine atom), -OR ⁶ or -SR ^G, with a hydrazine of formula X. When B represents a group ^G or -0R -SR ^6, the reaction is carried out generally in an alcohol solvent at room temperature to 200 ° C. When B represents a halogen atom, preferably chlorine, this reaction is generally carried out in an inert solvent, preferably tetrahydrofuran, optionally in the presence of a base, for example triethylamine, at a temperature from 0 ° C to reflux.

Compounds of formula XV may be prepared by reacting a hydrazine of formula X with an alkali metal salt of an alkyldicyanoacetate of formula XVII

RO ₂ C-CH (CN)

Preferably, potassium ethyldicyanoacetate is used. The reaction is generally carried out in the presence of an acid, for example hydrochloric acid, at a temperature from room temperature to the reflux temperature. The alkyl salts of alkyldicyanoacetates 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 from 0 ° C to 100 ° C.

Compounds containing a group -5 (0) ^ ^Π σ ', -S (O) _m R ^7, S (0) and S (0) ^R6, wherein m, p and q have a value of one or two may be prepared from corresponding compounds in which m, p and q have a value of zero or one by oxidation using, for example, meta-chloroperbenzoic acid in an inert solvent such as chloroform at a temperature of from -20 ° C to reflux.

Compounds of formula VIIa in which R ¹ is other than Ar and R ³ is -SR ^XO may be prepared by reacting a compound of formula XVIII

(XVIII)

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

Compounds of formula XVIII may be prepared by reacting a compound of formula XIX

RO ₂ C

^R3 (XIX) with a compound of formula R ² X, wherein R ^x is other than Ar and ^X is a leaving group, in the presence of a base. Preferably X 1 is, for example, a chlorine, bromine or iodine atom, a tosyl or a mesyl group. Suitable bases include potassium carbonate, sodium hydride and cesium carbonate. The reaction is generally carried out in a solvent (e.g. acetonitrile).

Compounds of formulas XI, XVI, XVII and XIX are well known in the literature or can be prepared by application or adaptation of known methods.

Agriculturally acceptable salts of the N-substituted pyrazole derivatives of formula (I) may be prepared by known methods.

The following Examples illustrate the preparation of compounds of Formula I. The abbreviation NMR shows the characteristics of the proton nuclear magnetic resonance spectrum. Unless otherwise indicated, percentages are by weight.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

A mixture of 4.0 g of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 6 g of 4-chlorothiophenol and 2.4 g of potassium carbonate is stirred in dry acetonitrile and heated to under reflux for 3 hours. The solid was filtered off, washed with acetonitrile, and the filtrate was evaporated in vacuo to give a solid. Chromatographic purification using hexane / dichloromethane as eluent gave 5.15 g of 4-N- (2,4-difluorophenyl) carboxamido-5- (4-chlorophenylthio) -1-methyl-3-trifluoromethylpyrazole (compound 1) in a white colored solid, m.p. 172 ° C - 173 ^{θ Ο.}

In a similar manner, the following compounds are also prepared from the respective starting materials, in which each symbol has the meaning defined in the following table:

P

Y

R ³

Zlúče- nina R ¹ R ² A Y P Q melting point (° C) 2 CH 3 CF 3 CH 0 2,4-difluoro 4-OCH 3 128-130 3 CH 3 CF 3 CH 0 2,4-difluoro 4-F 119-122 4 CH 3 CF 3 CH 0 2,4-difluoro 4-Br 170-171 5 CH 3 CF 3 CH 0 2,4-difluoro 4-OH 170-171 6 CH 3 CF 3 CH 0 2,4-difluoro 2-F 114-115 7 CH 3 C F 3 CH 0 2,4-difluoro 3-F 131-132 8 CH 3 CF 3 CH 0 2,4-difluoro H 131-133 9 CH 3 CF 3 CH 0 2,4-difluoro 4-NHCOCH_ 197-199 l 10 CH 3 CF 3 CH 0 2,4-difluoro 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-difluoro 3-C1 133-135 14 CH 3 C F 3 CH 0 2,4-difluoro 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-difluoro 4-C1 166-168 18 CH 3 CH 3 CH 0 2,4-difluoro 3-C1 136-138 63 CH 3 CF 3 CH WITH 2,4-difluoro 4-F oily substance (s) 64 CH 3 CF Cl 2 CH 0 2,4-difluoro 4-F 112-114 65 CH 3 CF Cl 2 CH 0 2,4,6-trifluoro 4-F 129-130 66 CH 3 CF 3 N 0 2,4-difluoro H 138-140 67 CH 3 CF 3 CH 0 2,4-difluoro 4-NH 2 172-173 68 CH 3 CF CH 0 2,4-difluoro 3-C1-4-F 146-147 69 CH 3 riC H 3 V CH 0 2,4-difluoro 4-F 126 to 127.5 70 CM CF 2 3 CF 3 CH 0 2,4-difluoro 4-F 129-130

Table legend:

(a) NMR (CDCl3), ppm: 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).

Example 3

The suspension of sodium hydride in dry dioxane is stirred at room temperature under an inert atmosphere and the solution is added

1.2 g of 4-fluorophenol in dioxane. After 0.5 h, a solution of 2.47 g of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole in 25 mL of dioxane was added. The mixture was then heated to reflux for 20 hours, cooled and poured into ice-water. Extraction with dichloromethane is then carried out, the extract is washed with water, dried (anhydrous magnesium sulphate) and evaporated. The resulting yellow solid was chromatographed using ether / hexane as the eluent and recrystallized from ethyl acetate to give 1.25 g of 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenoxy) 1-methyl-3-trifluoromethylpyrazole (compound 19), m.p. 169-170 ° C.

Example 3

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

Similarly prepared 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chlorophenoxy) -1-methyl-3-trifluoromethylpyrazole (132 ° C).

37) 21) with melting point 131 Example 4

5- (4-Chlorophenoxy) -1,3-dimethylpyrazole-4-carboxylic acid chloride was dissolved in tetrahydrofuran and added to a solution of 0.6 g of aniline and 0.9 ml of triethylamine 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 1 g of 4-N-phenylcarboxamido-5- (4-chlorophenoxy) -1,3 -dimethylpyrazole (compound 22), m.p. 99-101 ° C.

Similarly prepared 4-N- (4-fluorophenyl) carboxamido-5- (4-chlorophenoxy) -1,3-dimethylpyrazole (compound 23), m.p. 161-162 ° C.

Example 5

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

Example 6

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

Example 7

A suspension of 1.5 g of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 0.915 g of potassium carbonate and 1.5 ml of 2,2,2-trifluoroethanol in acetonitrile is heated. to reflux for 6 hours. The reaction mixture was cooled and allowed to stand overnight. Then the reaction mixture was filtered and the solvent was removed from the filtrate to give a brown colored solid which was purified by column chromatography to give 0.84 g of 4-N- (2,4-difluorophenyl) carboxamido-5- (2). 2,2-trifluoroethoxy) -1-methyl-3-trifluoromethylpyrazole (compound 31) as a white colored solid, m.p. 102-103 ^° C.

The following compounds are produced 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.

- 96,5 ° C,

4-Ν- (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-difluorophenylphenyl) 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-trifluoromethylpyrazole (compound 40), m.p. 62-63 ° C;

4-Ν- (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, and

5- (N-metylaminokarbonylmetyltio) -4-N- (2,4-difluorophenyl) carboxamido-l-methyl-3-trifluoromethylpyrazole (compound 62), melting point: 129-131 ^C ° C

Example 8

To a solution of 0.98 g of sodium 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole-5-thioxide in methanol is added 0.61 g of 3-bromopropine and the mixture is stirred at room temperature for 3 hours. The solvent was then evaporated and the residue partitioned between dichloromethane and water. The organic layer was dried and evaporated to give a white colored solid which was recrystallized from cyclohexane to give 0.77 g of 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-propynylthio). -3-Trifluoromethylpyrazole (Compound 43) as off-white needle crystals, m.p. 136-137 ° C.

The following compounds were prepared in a similar manner:

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. 111-111 ° C,

5- (cyanomethylthio) -4-(- (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-trifluoromethylpyrazole (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-trifluoromethylpyrazole (compound 56), m.p. 107-109 ° C;

5- (2-chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (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, and

5- (3-chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 59), m.p. 95-96 ° C.

Example 9

To a solution of 0.5 g of 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylic acid in toluene was added 2.4 ml of thionyl chloride and the reaction mixture was heated under reflux for 3 hours. After cooling, excess thionyl chloride was removed by solvent under reduced pressure. The residue was dissolved in dichloromethane and 0.34 ml of triethylamine was added followed by 0.2 ml of 2,4-difluoroaniline, and the mixture was stirred at room temperature for 2 hours. The mixture was washed with hydrochloric acid, saturated sodium carbonate solution and brine. The organic phase was then dried over magnesium sulphate and evaporated under reduced pressure to give 0.54 g of 5-ethylthietylethyl-4-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole (compound 60) as a beige colored mp 91-93 ° C.

In a similar manner 5-ethylthio-1-ethyl-4-N- (2,4,6-trifluorophenyl) carboxamido-3-trifluoromethylpyrazole (compound 61) was prepared as a beige colored solid, m.p. 94-96 ° C.

Example 10

A mixture of 2.0 g of 5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid and 13.9 g of thionyl chloride is heated to reflux in 30 ml of dry toluene for 1.5 hours, and then evaporated in vacuo to give 5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid chloride as an oil. A solution of this material in 20 mL of dry tetrahydrofuran was added to a stirred solution of 0.64 g of aniline in 30 mL of tetrahydrofuran containing 0.7 g of triethylamine. The mixture was stirred overnight, the solid was filtered off and washed with 50 ml of ether. The combined filtrates were evaporated in vacuo to give a brown colored solid which, after recrystallization from toluene / hexene, gave 1.4 g of 5- (4-fluorophenylthio) -1-methyl-4-N- (phenyl) carboxamido -3-Trifluoromethylpyrazole (Compound 91) as a brown colored solid, m.p. 146-148 ° C.

In a similar manner, the following compounds are prepared from the corresponding carboxylic acids in which each symbol is as defined in the following table:

compound R ³ P Q melting point (° C) 71 S CH 3 2.4 "F 4-F 164-167 72 CF 3 3-Cl-4-F 4-F 169-170 73 CF 3 3,4-F 4-F 152.5 to 153.5 74 CF 3 2,4,5-F _a 4-F 125-126 75 CF 3 2-F 4-F 133.5 to 135

compound _R a P Q melting point (° C) 76 CF 3 4-C1 4-F 142-143 77 CF 3 2-F-4-C1 4-F 130.5 to 131, 5 78 CF 2,4,6-F 4-F 175-177 3 79 C F 3 2-C1-4-F . 4-F 118-119 80 CF 3 4-F 4-F 129.5 to 131 81 C F 2,4-C1 4-F 148.5 to 150, 5 3 82 CF 3 2,3,4-F 3 4-F 145-147 83 CF 3 2-F-4-Br 4-F 120.5 to 122, 5 84 CF 2-F-4-CH 4-F 127-128 3 3 85 CF 3 3-F 4-F 111.5 to 113, 5 86 CF 2,3-F 4-F 119-121 3 87 CF 3 2,5-F 4-F 104-105 88 CF 3 2,6-F 4-F 146-147 89 C F 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 2.3 g of 5- (4-aminophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole in 30 ml of dry dichloromethane was added 1.0 g of dimethyldisulfide, followed by stirring 5 g of t-butyl nitrite are added dropwise over 5 minutes. The mixture was stirred at 50 ° C for 3 hours, then at room temperature overnight, and then poured into water. The organic layer was separated and the aqueous solution was extracted again with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate and evaporated in vacuo to give an oil. Chromatographic purification on silica gel using dichloromethane / hexane as eluent afforded 0.9 g of 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (445 methylthiophenylthio) -3-trifluoromethylpyrazole (compound 92) in the form of a cream colored solid, m.p. 122 124 ° C.

Example 12

A suspension of 2.0 g of 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 0.29 ml of iodomethane, 0.286 g of powdered potassium hydroxide and 0.3 g tetrabutylammonium bromide in 5 mL tetrahydrofuran was stirred at room temperature for 26 hours, and the solid was filtered off. The filtrate was evaporated in vacuo, and dichloromethane and water were added. The organic phase is washed with saturated sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated in vacuo to give an oily substance. Trituration with ether gives a solid which is chromatographed on silica gel using ether / n-hexane (1: 1). 1 as eluent to give 1.48 g of 5- (4-fluoro-phenylthio) -1-methyl-4-N-methyl-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole (compound 93) as white colorless solid, m.p. 99-100 ° C.

Example 13

To a stirred solution of 0.63 g of 5- (4-chlorophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole in 8 ml of trifluoroacetic acid is added dropwise at temperature 0 ° C 30% hydrogen peroxide solution (0.19 mL). After 2 h at 0 ° C, the mixture was warmed to room temperature for 2 hO 7 days and then poured into 50 mL ice / water. The precipitate is collected, washed with water and dried over phosphorus pentoxide in a desiccator, and then purified by chromatography on silica gel using ether in hexane (1: 1) as eluent to give 0.426 g of 5- (4-chlorophenylsulfinyl) -4- N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole (compound 94) as a white colored solid, m.p. 178-179 ° C.

- 46 Reference Example 1

A mixture of 20.54 g of 4-carboxy-5-chloro-1-methyl-3-trifluoromethylpyrazole and thionyl chloride in dry toluene is stirred and heated to 80 ° C for 2 hours, then cooled and evaporated. Hexane is added to the residue, the mixture is filtered and the filtrate is concentrated to give 21.4 g of the acid chloride, which is dissolved in dry tetrahydrofuran and added to a stirred solution of 13.4 g of 2,4-difluoroaniline and 17.46 ml. triethylamine 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 20.7 g of 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole as an off-white solid, mp 138-140 ° C.

In a similar manner, the following compounds were prepared from appropriately substituted starting materials:

R ¹ R ³ P melting point (° C) CH CH 3 4-F 158-160 CH CH 2,4-difluoro 159-161 3 3 CH CF 3-CF 139-141 3 3 3 CH CF 4-OCH 169-171 3 3 3 CH CF Cl 2,4-difluoro 3 2

R ³ R ³ P melting point (° C) CH CF Cl 2,4,6-trifluoro 3 2 CH nC H 2,4-difluoro 115-118 3 3 Ύ CH CF CF 2,4-difluoro - Z 3 3

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

Reference example 2

A mixture of 30 g of 5-chloro-4-formyl-1,3-dimethylpyrazole, 30 g of potassium permanganate and potassium hydroxide in water is stirred at 60 ° C for 1 hour. The cooled mixture was filtered, the filtrate was acidified (with concentrated hydrochloric acid), the resulting precipitate was filtered off, washed with water and dried to give 4-carboxy-5-chloro-1,3-dimethylpyrazole, mp 197-201 ° C.

In a similar manner, the following compounds are prepared from appropriately substituted starting materials:

4-carboxy-5-chloro-1-methyl-3-chlorodifluoromethylpyrazole, m.p. 153-155 ° C;

4-carboxy-5-chloro-1-methyl-3- (n-propyl) pyrazole, m.p. 130-131 ° C, and

4-carboxy-5-chloro-1- (2,2,2-trifluoroethyl) -3-trifluoromethylpyrazole.

Reference example 3

To a mixture of phosphorus oxychloride and Ν, Ν-dimethylformamide was added 60 g of 1,3-dimethyl-5-hydroxypyrazole and the resulting mixture was heated at 95-100 ° C for 16-18 hours. The reaction mixture was poured into ice-water, basified with ammonium hydroxide solution and the resulting precipitate collected and washed with water. Recrystallization from hexane gave 5-chloro-4-formyl-1,3-dimethylpyrazole, m.p. 77-80 ° C.

Reference example 4

To a mixture of 70 g of ethyl acetoacetate in water is added 25 g of methylhydrazine. The reaction mixture was heated at 70 ° C for 0.5 h, then cooled, extracted with chloroform and dried over anhydrous magnesium sulfate. Evaporation of the solvent gave a solid which was recrystallized from hexane-ethyl acetate to give 1,3-dimethyl-5-hydroxypyrazole, mp 123-124 ° C.

Reference example 5

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

Similarly, 1-methyl-5- (3-chlorophenyl) -3-trifluoromethylpyrazole-4-carboxylic acid chloride and 5- (4-chlorophenoxy) -1,3-dimethylpyrazole-4-carboxylic acid chloride are prepared.

- 49 Reference example 6

To a warm solution of potassium tert-butoxide in tert-butanol was added 6.9 mL of 3-trifluoromethylphenol. The resulting mixture was stirred for 0.5 h and 12 g of 5-chloro-4-formyl-1-methyl-3-trifluoromethylloyrazole was added. The mixture was heated at reflux for 3 hours and then cooled, diluted with water and the resulting solid collected and dried. Recrystallization from hexane gave 9.2 g of 4-formyl-1-methyl-5- (3-trifluoromethylphenoxy) -3-trifluoromethylpyrazole, m.p. 81-82 ° C.

Similarly, 4-formyl-1-methyl-5- (3-chlorophenoxy) -3-trifluoromethylpyrazole with a melting point of 61-63 ° C and 4-formyl-1,3-dimethyl-5- (4-chlorophenoxy) pyrazole was prepared with m.p. mp 74-75 ° C.

Reference example 7

To a mixture of 42 g of sodium sulfide monohydrate and 5.6 g of sulfur in isopropanol was added 29.7 g of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole. The mixture was refluxed under an inert atmosphere for 2.75 hours. The cooled solution was decanted, charcoal was added and the mixture was filtered to give a bright yellow solution which was concentrated, filtered and then evaporated to dryness to give 31.68 g of sodium 1-methyl-4-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole-5-thiolate as a solid, m.p. 311-313 ° C.

Reference Example 8 g of ethyl 3- (trifluoromethyl) pyrazole-4-carboxylate, 3.48 g of potassium carbonate, and 2.3 ml of ethyl iodide in acetonitrile are heated at reflux overnight. After cooling, ethyl acetate and water are added and the organic phase is separated. The aqueous layer was extracted with ethyl acetate, the combined organic extracts were dried over magnesium sulfate and evaporated under reduced pressure to give a yellow colored oil which was purified by crystallization from hexane to give 3.65 g of 4-ethoxycarbonyl-1-ethyl-3. -trifluoromethylpyrazole as white colored crystals.

NMR (CDCl3), ppm: 1.25 (t, 3H), 1.45 (t, 3H), 4.10 (q, 2H), 4.20 (q, 2H), 7.90 (s , 1H).

Reference example 9

To a solution of 1.25 ml of diisopropylamine in tetrahydrofuran under an inert atmosphere at 0 ^C, c, 3.5 ml of 2.5 M n-butyl lithium. The solution was stirred at 0 ° C for 45 minutes and transferred at -78 ° C under an inert atmosphere to a solution of 1.76 g of 4-ethoxycarbonyl-1-ethyl-3-trifluoromethylpyrazole in tetrahydrofuran. The dark orange solution was stirred at -78 ° C for 3.5 hours, and then 1.1 mL of ethyl disulfide was added. The solution was allowed to warm to room temperature with stirring overnight. The precipitate was diluted with ether and the organic layer was washed with 2M hydrochloric acid solution. The aqueous layer was extracted once more with ether. The combined organic extracts were dried over magnesium sulphate and evaporated under reduced pressure to give 2 g of ethyl 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylate as a yellow colored oil.

NMR (CDCl), the value of _h in ppm: 1.25 (t, 3H), 1.40 (m, 6H), 3.0 (q, 2H), 4.40 (m, 4 H).

Reference Example 10 g of ethyl 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylate are dissolved in ethanol and 1 g of potassium hydroxide in water is added. The reaction mixture was stirred overnight at room temperature. Water and ethyl acetate were added and the organic layer was separated from the aqueous layer. The aqueous layer was acidified with concentrated hydrochloric acid and extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulfate and evaporated under reduced pressure to give 1.42 g of 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carboxylic acid as a beige colored solid.

NMR (CDCl3), ppm: 1.25 (t, 3H), 1.45 (t, 3H), 3.05 (q, 2H), 4.45 (q, 2H), 6.5 (broad) s, 1H).

Reference example 11

To a solution of 3.0 g of 5-chloro-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole in 110 ml of dry toluene is added 2.14 g of Lawesson's reagent (2,4-bis ( 4-methoxyphenyl) -1,

3-dithia-2,4-diphosphetane-2,4-disulfide) and the mixture is heated at 80-85 ° C for 2 hours and then refluxed for 1.50 hours. An additional 3.57 g of Lawesson's reagent was added, and the mixture was refluxed for an additional 9 hours. The solvent was evaporated in vacuo and the residue purified by chromatography on silica gel using dichloromethane / hexane 1: 1 as eluent to give 2.49 g of 5-chloro-4-N- (2,4-difluorophenyl) thiocarboxamido -1-methyl-3-trifluoromethylpyrazole as a yellow colored oily substance.

Reference Example 12

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

Reference example 13

To a stirred solution of methyl 5-amino-1-methyl-3-methylthiopyrazole-4-carboxylate (2.0 g) in dichloromethane was added 4-fluorophenyldisulfide (5.1 g). A solution of 2.0 g of t-butylnitrile in 5 ml of dichloromethane was added portionwise over 20 minutes, and the mixture was stirred overnight. After evaporation in vacuo, the residue is chromatographed on silica gel using dichloromethane / hexane 1: 1 as the eluent to give 1.2 g of methyl 5- (4-fluorophenylthio) -1-methyl-3 after recrystallization from cyclohexane. methyl thiopyrazole-4-carboxylate, m.p. 92-94 ° C.

Reference example 14

To a solution of 10.1 g of 2-cyano-3,3-bismethylthiopropenoic acid methyl ester in methanol was added 20 ml of acetic acid followed by 2.3 g of methylhydrazine in one portion. The mixture was stirred overnight and then evaporated in vacuo. The residue was triturated with water, the solid was filtered off, and chromatographed on silica gel using dichloromethane as eluent to give 1.5 g of methyl 5-amino-1-methyl-3-methylthiopyrazole-4-carboxylate as white colored solid.

Reference example 15

A mixture of 2.0 g of 5-chloro-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid, 1.66 g of 4-fluorothiophenol and 3.26 g of anhydrous potassium carbonate is heated to reflux in acetonitrile with stirring for 4 hours. hours. The mixture was filtered, then the filtrate was evaporated, acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and evaporated in vacuo. Recrystallization from ether / hexane gave 0.98 g of 5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid as a white colored solid, m.p. 190-193.7 ° C.

Reference example 16

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

Similarly, 1-methyl-5- (2-methylpropylthio) -3-pentafluoroethylpyrazole-4-carboxylic acid was prepared.

NMR (Perdeuterodimethylsulfoxide), _h -ppm: 0.96 (d,

6H), 1.68 (m, 1H), 2.85 (d, 2H), 4.00 (S, 3H), 13.20 (s,

1H).

The invention further provides a method for controlling the growth of weeds (i.e., undesirable vegetation) at a site by applying to said site a herbicidally effective amount of at least one N-substituted pyrazole derivative of formula I or an agriculturally acceptable salt thereof. N-substituted pyrazole derivatives are generally used for this purpose in the form of herbicidal compositions (i.e., in combination with compatible diluents or carriers and / or surfactants suitable for use in the herbicidal compositions), for example as described below.

The compounds of formula (I) exhibit herbicidal activity against dicotyledonous (i.e. broadleaf) weeds and monocotyledonous weeds (e.g. grasses) in pre-reergent and / or post-emergence application.

The term pre-emergence application ”refers to application to soil in which weed seeds or germinate plants are present.

- 54 before weeds reach the surface of the soil. The term post-emergence application refers to application to above-ground parts of weeds or to parts of weeds exposed to herbicide that have emerged above the soil surface. The compounds of the formula I can be used, for example, for controlling growth:

broadleaf weeds such as

Abutilon theophrasti (abutilon),

Amaranthus retroflexus,

Bidens pilosa,

Chenopodium album,

Gallium aparine,

Ipomoea spec., Such as Ipomoea purpurea,

Sesbania exaltata,

Sinapis arvensis (Field Mustard),

Solanum nigrum, and Xanthium strumarium (grass aphid), grass weeds such as

Alopecurus myosuroides,

Avena fatua (deaf oats),

Digitaria sanguinalis,

Echinochloa crus-galli,

Eleusine indica (eleuzine), a

Setaria spec., Such as Setaria faberii or Setaria viridis (green bar), and chess, such as

Cyperus esculentus.

The application rates of the compounds of the formula I vary depending on the nature of the weeds, the compositions used, the time of application, the climatic and soil conditions and the nature of the crop plant when used to control the growth of weeds on the areas under cultivation. useful plants. When applied to areas where crops are or will be cultivated, the amount applied should be sufficient to control the growth of weeds but do not cause significant permanent damage to the crops. In general, taking into account these factors, good results are obtained at application rates of between 0.01 kg and 5 kg of active ingredient per hectare. It will be appreciated that higher or lower application rates may be used, depending on the particular solution to the weed control problem.

The compounds of formula (I) may be used to selectively control weed growth, for example, to control the growth of the aforementioned weed species, by pre-emergence or post-emergence, directed or non-directed application, for example by directed or non-directed spraying. or will be used for the cultivation of crops such as cereals such as wheat, barley, oats, maize and rice, soybeans, field beans, peas, lanterns, cotton, peanuts, flax, onions, carrots, cabbages, tusks, cauliflower, oilseed rape, sunflower, sugar beet and permanent or sown meadows before or after sowing the crop before or after emergence of the crop. For the selective control of weeds at a site infested with weeds, which is the area to be used or will be used for the cultivation of the useful plants, for example those mentioned above, application rates between 0.01 kg and 4.0 kg, preferably between 0,01 kg and 2,0 kg of active substance per hectare.

The compounds of the formula I can also be used for controlling the growth of weeds, in particular the abovementioned weeds, by pre-emergence or post-emergence application in orchards and other areas where trees are grown, for example in forests, groves and parks, and plantations, for example sugar cane plantations, oil palm trees and rubber trees. For this purpose, these substances may be applied by a directed discount in a non-directional manner (for example by directed or non-directional spraying) to weeds or soil on which they are expected to occur, before or after planting trees or plantations, at application rates between 0,25 kg and 5.0 kg, preferably between 0.5 kg and 4.0 kg of active substance per hectare.

The compounds of the formula I can also be used for controlling the growth of weeds, in particular the weeds mentioned above, in places where the crops are not grown, but where control of weeds is necessary.

Examples of such areas where crops are not grown include airports, open areas of industrial plants, railways, roadsides, river banks, irrigation canals and other waterways, shrubs, eels and uncultivated land. These are particularly areas where weeds need to be controlled to reduce the risk of fire. When used for this purpose, where a total herbicidal effect is often desired, the active compounds are usually applied at higher doses than are used to treat cropped areas as described above. The exact dosage depends on the nature of the vegetation treated and the desired effect.

Preemergent or post-emergence application, preferably pre-emergence application, carried out in a directional or non-directional manner (e.g. by directional or non-directional spraying), using rates of application between 1.0 kg and 20.0 kg, preferably between 5.0, is particularly suitable for this purpose. kg and 10.0 kg of active substance per hectare.

When used to control weed growth by pre-emergence application, the compounds of formula (I) may be incorporated into the soil on which weeds are expected to emerge. It will be understood that when compounds of formula I are used to control weed growth by post-emergence application, i. application to aerial parts or parts exposed to herbicide-emerging weeds, the compounds of formula I normally also come into contact with the soil, where they may show a pre-emergence effect on the later germinating weeds found in the soil.

Where particularly prolonged weed control is desired, the application of the compounds of formula I may be repeated if necessary.

In accordance with another embodiment, the invention provides compositions suitable for herbicidal use comprising one or more N-substituted pyrazole derivatives of Formula I or agriculturally acceptable salts thereof, in combination (and preferably homogeneously dispersed) with one or more compatible agriculturally acceptable diluents or carriers. and / or surfactants, (i.e., diluents or carriers, and / or surfactants which are generally considered in the art to be useful in herbicidal compositions and which are compatible with the compounds of Formula I). The term "homogeneously dispersed" includes compositions in which the compounds of formula I are dissolved in the other ingredients. The term herbicidal compositions is used in a broad sense and includes not only compositions which are ready for immediate use as herbicides, but also concentrates to be diluted for use. These compositions preferably contain from 0.05 to 90% by weight of one or more compounds of formula (I).

The herbicidal compositions may contain both a diluent or carrier and a surfactant (for example, a spreading agent, a dispersant or an emulsifier). The surfactants present in the herbicidal compositions of the invention may be of the ionogenic or nonionic type, for example sulphoricinoleate, quaternary ammonium derivatives, ethylene oxide condensate products with alkyl and polyarylphenols, for example nonylphenol or octylphenol acid, or carboxylic acid esters, whose solubility was ensured by etherification of free hydroxyl groups by condensation with ethylene oxide, alkali metal and alkaline earth metal salts of sulfuric and sulfonic acid esters such as dinonyl and dioctyl sodium sulfonosuccinates, and alkali metal and alkali metal salts of high molecular weight sulfonic acid derivatives such as sodium and calcium lignosulfonate and sodium and calcium alkylbenzene sulfonates.

The herbicidal compositions according to the invention may suitably contain up to 10% by weight, for example from 0.05 to 10% by weight. surfactant, however, if necessary, the herbicidal compositions of the invention may also contain a higher proportion of surfactant, for example up to 15% by weight. in the case of liquid emulsifiable suspension concentrates and up to 25% by weight. in the case of liquid water-soluble concentrates.

Examples of suitable solid diluents or carriers include aluminum silicate, talc, magnesium oxide, diatomaceous earth, tertiary calcium phosphate, powdered cork, adsorbing carbon black and clays such as kaolin and bentonite. Solid compositions in the form of dusts, granules or wettable powders are preferably prepared by grinding the compounds of formula I with solid diluents or impregnating the solid diluents or carriers with solutions of the compounds of formula I in volatile solvents, evaporating solvents and, if necessary, milling the products to obtain powders. Granular compositions can be prepared by dissolving the compounds of formula I in suitable solvents which are volatile, if necessary, adsorbed to solid diluents or carriers in granular form, and then evaporating the solvents, if necessary, or by granulating the powdered formulations obtained as described above. Solid herbicidal compositions, in particular wetting powders and granules, may contain wetting agents or dispersing agents, for example the types described above, which may also, if solid, serve as diluents or carriers.

The liquid compositions of the invention may be in the form of aqueous, organic or aqueous organic solutions, suspensions and emulsions which may contain a surfactant. Suitable liquid diluents for incorporation into liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal and vegetable oils and light aromatic and naphthenic petroleum fractions, and mixtures of these diluents. The surfactants present in the liquid compositions are ionic or non-ionic, for example they may be surfactants of the types described above and may also serve as diluents or carriers when liquid.

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

If desired, liquid compositions containing a compound of formula I can be used in the form of self-emulsifiable concentrates containing the active ingredients dissolved in emulsifiers or solvents containing emulsifiers compatible with the active ingredients. Addition of water to such concentrates alone results in ready-to-use compositions.

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

The herbicidal compositions of the invention may also contain, if necessary, conventional adjuvants such as adhesives, protective colloids, thickeners, penetration agents, stabilizers, complexing agents, anti-caking agents, colorants and corrosion inhibitors. These excipients may also serve as diluents or carriers.

Unless otherwise indicated, the percentages below are by weight. Preferred herbicidal compositions of the invention are:

aqueous suspension concentrates containing 10 to 70% of one or more compounds of formula (I), 2 to 10% of a surfactant, 0.1 to 5% of a thickener and 15 to 20% of a thickener;

87.9% water, ι

soaking powders containing 10 to 90% of one or more compounds of Formula I, 2 to 10% surfactant and 8 to 88% solid diluent or carrier, water-soluble or water dispersible powders containing 10 to 90% of one or more compounds of the general formula of formula I, 2 to 40% sodium carbonate and 0 to 88% solid diluent, liquid water-soluble concentrates containing 5 to 50%, for example 10 to 30%, of one or more compounds of formula I, 5 to 25% of a surfactant; 25 to 90%, for example 45 to 85%, a water-miscible solvent, for example dimethylformamide, or a mixture of a water-miscible solvent, liquid emulsifiable suspension concentrates containing 10 to 70% of one or more compounds of formula I, 5 to 15% active agent, 0.1-5% thickener and 10-84.9% organic solvent juices, water-dispersible granules containing 1 to 90%, for example 2 to 10%, of one or more compounds of the formula I, 0.5 to 7%, for example 0.5 to 2%, of a surfactant and 3 to 98.5 %, for example 88 to 97.5%, of a granular carrier, and emulsifiable concentrates containing 0.05 to 90%, preferably 1 to 60%, of one or more compounds of formula I, 0.01 to 10%, preferably 1 to 10% , a surfactant and 9.99 to 99.54%, preferably 39 to 98.99% organic solvent.

The herbicidal compositions of the invention may also contain compounds of formula I in combination (and preferably homogeneously dispersed) with one or more other pesticidally active compounds and, if necessary, one or more compatible pesticidally acceptable diluents or carriers, surfactants and conventional auxiliary agents. substances as described above. Examples of other pesticidally active compounds which are included in the herbicidal compositions of the invention or which may be used in combination with the herbicidal compositions of the invention include, for example, herbicides to extend the spectrum of weed control activity, such as:

alachlor [2-chloro-2,6'-diethyl-N- (methoxymethyl) acetanilide], atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine], bromoxynil [3,5-dibromo] -4-hydroxybenzonitrile], chlortoluron [N '- (3-chloro-4-methylphenyl) -N, N-dimethylurea], cyanazine [2-chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino- l, 35, triazine],

2,4-D [2,4-dichlorophenoxyacetic acid], dicamba [3,6-dichloro-2-methoxybenzoic acid], difenzoquat [1,2-dimethyl-3,5-diphenylpyrazolium salt], and 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 such as synthetic pyrethroids such as permethrin and cypermethrin, and fungicides such as carbamates such as methyl N- (1-butylcarbamoylbenzimidazol-2-yl) carbamate and triazoles such as 1- (4- chloro-phenoxy) -3,3-dimethyl-l- (1,2,4-triazol-l-yl) butan-2-one.

The pesticidal active compounds and other biologically active materials which are contained in the herbicidal compositions of the invention or which can be used in combination with the herbicidal compositions of the invention, for example the aforementioned substances, can be used in the form of an acidic character and, if necessary, customary derivatives, for example alkali metal salts and amines and esters.

According to a further embodiment, the invention also includes products comprising at least one of the N-substituted pyrazole derivatives of the formula I, or preferably the herbicidal composition described above, in particular a herbicidal concentrate to be diluted before use, comprising at least one of the N-substituted pyrazole derivatives of the formula I a package for the aforementioned derivative (s) of formula (I), or said herbicidal composition, the package comprising instructions describing how to use the aforementioned derivative (s) of formula (I) or the herbicidal composition for controlling weed growth.

These containers are commonly used types of containers for storing chemicals which are solid at ambient temperature and herbicidal compositions, in particular in the form of concentrates, such as cans and metal drums containing an inner coating, and plastic containers, glass bottles and bottle bottles. and, in the case of granular herbicidal compositions, a box, for example a cardboard box, a plastic box and a metal box, or bags. These packages should normally be large enough to accommodate an amount of N-substituted pyrazole derivatives or herbicidal compositions that are sufficient to treat at least about 40 acres of weeds to control the growth of weeds on that plot, but should not exceed a suitable size for common handling methods. For example, the instructions that are attached to the package may be directly printed on the package, or the package may include a label or tag with such instructions. Said guides usually state that the contents of the package, if necessary after dilution, are applied to control weed growth at application rates between 0.01 kg and 20 kg of active ingredient per hectare, in the manner and for the purposes described above.

The following examples illustrate the herbicidal compositions of the invention.

Example C1

A soluble concentrate is prepared from the following ingredients:

active ingredient (compound 1)% (w / v) potassium hydroxide solution tetrahydrofurfuryl alcohol water% (w / v)% (v / v)% (v / v) up to 100 parts by mixing tetrahydrofurfuryl alcohol, active ingredient (compound 1) and 90% by volume of water, if sodium hydroxide solution is slowly added to this mixture until a constant pH of 7-8 is reached, and then the volume is made up with water.

Similar soluble concentrates may be prepared as described above except that the N-substituted pyrazole (compound 1) is replaced by other compounds of formula I.

Example C2

A soaking powder is prepared from the ingredients listed below:

Active ingredient (Compound 1) 50% (w / w) Sodium dodecylbenzenesulfonate 3% (w / w) Sodium formaldehyde alkylnaphthalenesulfonate 2% (w / w) Ultra-fine silica 3% (w / w) Kaolin 37% (w / w) by mixing the components and grinding in an air mill.

Similar wetting powders may be prepared as described above except that the N-substituted pyrazole (compound 1) is replaced by other compounds of formula I.

Example C3

Of the powder ingredients listed below:

active ingredient (Compound 1) sodium dodecylbenzenesulfonate ultra-fine silica sodium bicarbonate by grinding the above in a hammer mill.

water-soluble% (w / w)% (w / w)% (w / w)% (w / w) ingredients are mixed and mixed

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

Representative compounds of formula I were used for herbicidal application according to the following procedure.

<Methodology for the use of herbicidal compounds

(a) General instructions

An appropriate amount of the compounds used to treat plants is dissolved in acetone to give solutions corresponding to application rates of up to 4000 g test compound per hectare. These solutions are applied using a standard laboratory herbicide sprayer at doses equivalent to 290 liters of spray liquid per hectare.

b) Weed control - pre-emergence application

The seeds are sown in non-sterile soil in 70 mm square plastic dishes with a depth of 75 mm. Each dish contains the following number of seeds:

the approximate number of seeds

Weeds in a bowl

1) Broadleaf weeds

Abutilon theophrasti Amaranthus retroflexus Gallium aparine Ipomoea purpurea Sinapis arvensis Xanthiura strumarium

Weeds approximate the number of seeds in a bowl

2) Grass weeds

Alopecurus myosuroides 15 Avena fatua 10 Echi.nochloa crus-galli 15 Setaria viridis 20 3) Šáchory Cyperus esculentus 3

Utility plants

1) Broadleaves cotton 3 soy 3

2) Grass corn rice wheat

The compounds of the invention are applied to the surface of the seed-containing soil as described in a). For each treatment, one dish of each species of crop and weed species is used. Untreated dishes and plates treated with acetone alone serve as controls.

After treatment, the dishes are placed on a capillary support in a greenhouse and irrigated from above. A visual assessment of plant damage is made 10-24 days after spraying. Results are expressed as a percentage of reduction in growth or damage to useful plants or weeds as compared to plants in control dishes.

c) Weed control - post-emergence application

Weeds and crops are planted directly into John Innes compost in 70 mm square dishes with a depth of 75 mm, except for Amaranthus, which is pricked into the dishes a week before spraying at the wedge stage. The plants are then grown in a greenhouse until they need to be sprayed with the compounds used to treat the plants. Each dish contains the following number of plants:

number of plants in the bowl growth stage

1) Broadleaf weeds

Abutilon theophrasti Amaranthus retroflexus Gallius aparine

1-2 leaves 1-2 leaves 1. sow

number of plants growth stage in dish Ipomoea purpurea 3 1-2-lists Sinapis arvensis 4 2 sheets Xanthium strumarium 1 2-3 sheets Grass weeds Alopecurus myosuroides 8 - 12 1-2-lists Avena fatua 12 - 18 1-2 sheets Echinochloa crus-galli 4 2-3 sheets Setaria viridis 15 - 25 1-2 sheets sedge Cyperus esculentus 3 3 sheets

Broadleaf useful plants cotton 2 1 sheet soy 2 2 sheets Grass plants à sweet corn 2 2-3 sheets rice 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). One dish from each species of crop and weed species is used for each treatment. Untreated plates and plates treated with acetone alone are used as controls.

After treatment, the dishes are placed on a capillary mat in a greenhouse, after 24 hours they are irrigated once from above and then irrigated in a controlled manner from below. A visual assessment of crop damage and weed control is performed 20-24 days after spraying. Results are expressed as percent reduction in growth or damage to useful plants or weeds, as compared to plants in control dishes.

The compound of the invention, used at a rate of 4 kg / ha or less, exhibits an excellent level of herbicidal activity on weeds used in the above experiments and at the same time the useful plants are very tolerant to them.

At pre-emergence or post-emergence application at 4000 g / hectare or less, compounds 1 to 106 inhibit the growth of one or more weed species by at least 70%. The compounds also show selectivity to at least one species of useful plant.

Claims (25)

PATENT CLAIMS An N-substituted pyrazole derivative of the general formula I Y Rl in which R ³ represents a straight or branched chain alkyl group having up to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group having 3 to 6 carbon atoms optionally substituted by one or more R 6 groups, - ( CH 1 = Ar, where n 'is zero or one, and Ar is phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, R® group, a hydroxyl group, a group -OR®, -S (O) _m R ⁷ and -NR®R®, alkenyl or a straight or branched chain alkynyl group containing up to 6 carbon atoms optionally substituted by one or more groups selected from the group consisting of halogen atoms, R® and -OR®, or a group selected from -SO NR ^G 1 R ^{G 2} , -SO R ⁷³ 'and -CONR ^s ' R ^ea , R ² represents -XR ^10, R ³ represents a hydrogen or halogen atom, a straight or branched chain alkyl group having up to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group having 3 to 6 carbon atoms optionally substituted by one or more substituents selected from halogen atoms and the groups R ^6, cyano or nitro, a group S (O) _m R ^G, phenyl which is optionally substituted by one or more groups selected from the group consisting of halogen, nitro, a group R ^6, -OR ⁶ a cyano group or a group -CO R ^6, R ¹ represents a phenyl group, which is optionally substituted by one or more groups selected from halogen atoms, nitro, R ⁶ , -OR ⁶ , -S (O) R ' ⁷ and -NR'^;, R ®, or pyridyl; a group optionally substituted by one or more groups selected from halogen atoms, nitro, R ^G , -OR ⁶ , -S (O) R ^7, and -NR ⁷ -R ⁸ , m ^R is H or an alkyl group straight or branched having up to 6 carbon atoms, Y represents an oxygen atom or a 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 ^G1 and R ^e2 are the same or different, are an alkyl group, straight or branched chain 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 having 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 atoms, nitro, R groups ^{6, the} -0R, -S (0) R ⁷ and -NR ^s R®, m R * and R®, which are the same or different, each represent a hydrogen atom or a straight or branched chain alkyl group containing up to 6 carbon atoms, which is optionally substituted by one or more halogen atoms, R ³ represents a phenyl group optionally substituted by one or more groups selected from halogen atoms, nitro, R ^G , -OR ®, -StO 4 R ⁷ , -NHCOR ® and -NR ^e R ®, pyridyl , optionally substituted with one or more groups selected from the group consisting of halogen, nitro, a group R®, -OR®, -S (O) _m R ^7, and -NR -NHCOR® ⁿ R ^p, or an alkyl, alkenyl or a straight or branched chain alkynyl group containing up to 10 carbon atoms, the chain optionally containing one or more oxygen or sulfur atoms or -NR ⁵ - groups optionally substituted by one or more groups selected from halogen atoms, -OR groups ®, -S (O) 2 R ^G -NR ® R ®, -CO ₂ R ⁵ , -OCOR ⁵ , -NHCOR ⁵ , -CONR ® R ®, R ¹² , -COR®, R ^13, and CN, X is O, -NR ¹¹ - or -S (0) R ¹¹ represents a hydrogen atom or a straight or branched chain alkyl group of up to 6 carbon atoms optionally substituted by one or more halogen atoms, R ¹² represents a cycloalkyl group having three to seven ring atoms, which may optionally contain one to three heteroatoms selected from the group consisting of oxygen, sulfur and -NR ⁵ -, R ¹³ represents a cycloalkyl group having 3 to 6 carbon atoms which is substituted by one or more groups selected from halogen atoms, R ® and -OR ⁸ , or a cycloalkenyl group containing 5 or 6 carbon atoms optionally substituted by one or more a plurality of groups selected from the group consisting of halogen atoms, R® and -OR®, m is zero, one or two, p is zero, one or two, and q is zero, one or two, provided that if Y is is O, ^R2 is methylthio or N-phenylamino, R ¹ is phenyl and R ^p is H, R ¹ and R ² are not simultaneously a methyl group, and an agriculturally acceptable salt thereof. The N-substituted pyrazole derivative according to claim 1, wherein R ¹ represents a straight or branched chain alkyl group having up to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group having 3 to 6 carbon atoms optionally substituted by one or more R 6 groups, or - ( CH) _n -Ar, where n is zero or one, and Ar represents a phenyl group optionally substituted by one or more groups selected from the group consisting of halogen atoms, nitro, R ⁶ , hydroxyl, -OR ®, -S (O) _m R ^7, and -NR ^O R 7 -, R ³ represents a hydrogen or halogen atom, an alkyl group, straight or branched chain containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms, cycloalkyl having 3 to 6 carbon atoms, optionally substituted by one or more groups R® , cyano, -S (O) _m R ⁶ , a phenyl group optionally substituted by one or more of halogen, nitro, R ®, -OR ® and cyano, or -CO 4 R ® . R represents a phenyl group optionally substituted by one or more groups selected from halogen atoms, nitro, R ®, -OR ®, -S (O) _m R ⁷ , -NHCOR ® and -NR ® R ®, or a pyridyl group optionally substituted by one or more groups selected from the group consisting of halogen atoms, nitro, R ⁶ , OR ⁶ , -S (O) R ⁷ , -NHCOR ⁶ and -NR ⁹ R ⁹ , m and the remaining symbols are as in claim 1. The N-substituted pyrazole derivative according to claim 2, wherein X represents an oxygen or sulfur atom or the group -NR ¹¹ , and the remaining symbols have the meanings as in claim 2. The N-substituted pyrazole derivative according to claim 1, wherein R ¹ represents a straight or branched chain alkyl group having up to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group having 3 to 6 carbon atoms optionally substituted by one or more R ⁶ groups, or - ( CH) -Ar, where n is zero or one, and Ar represents a phenyl group optionally substituted by one or more groups selected from the group consisting of halogen atoms, nitro, R ⁶ , hydroxyl, -OR ⁶ , -S (O) _m R ⁷ and -NR ^e R ⁹ , R ³ represents a hydrogen or halogen atom, a straight- or branched-.reťazcom containing up to 6 carbon atoms, optionally substituted by one or more halogen atoms, cycloalkyl having 3 to 6 carbon atoms, optionally substituted by one or more - 75 groups. R ^e, cyano or nitro, -SfO ^ R ^6, phenyl optionally substituted with one or more groups selected from the group consisting of halogen, nitro, a group R ^e, -0R ^with a cyano group or a group -CO R ⁶ , R ¹⁰ represents a straight-chain or branched alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, the chain optionally containing one or more oxygen or sulfur atoms or -NR ^S - groups optionally substituted by one or more groups selected from the group consisting of: halogen atoms, -OR, -SfOJ ^ R ^{6, -ΝΚ} Θ Η Θ, -CO ₌ R, -OCOR ^6, NHCOR ^S, -C0NRR '% R ^{X 2} and cyano, and the other groups are as defined in claim 1 . The N-substituted pyrazole derivative according to claim 1, wherein R ^: represents a hydrogen or halogen atom, a straight or branched chain alkyl group having up to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group having 3 to 6 carbon atoms optionally substituted by one or more R groups ^e, cyano or nitro, -S (O) R ^6, m a phenyl group which is optionally substituted by one or more groups selected from halogen atoms, nitro, R ⁶ , OR ⁶ cyano, or -CO ₂ R ^e , R ¹⁰ represents a straight-chain or branched alkyl, alkenyl or alkynyl group containing up to 10 carbon atoms, the chain optionally containing one or more oxygen or sulfur atoms or -NR ^S - groups optionally substituted by one or more groups selected from the group consisting of: including halogen atoms, -OR ®, -S (O) R ^e , -NR ^B R ^e , -CO R ⁸ , -OCOR ^e , NHCOR * ³ , -CONR ^B R ^S ', R ³ -COR ^e , R ¹³ and cyano, and the remaining symbols are as in claim 1. The N-substituted pyrazole derivative according to claim 1, 2 or 3, wherein R ¹⁰ represents a phenyl group substituted with at least one halogen atom, and the remaining symbols are as defined in claim 1, 2 or 3. The N-substituted pyrazole derivative according to claim 1, 4 or 5, wherein R ^{; 'O} is an alkyl or alkenyl straight or branched chain containing up to four carbon atoms optionally substituted by one or more halogen atoms, and the other groups are defined as in Claim 1, 4 or 5th The N-substituted pyrazole derivative according to claim 1, 4 or 5, wherein R represents ^a group ^-SR,, DEG, wherein R ¹⁰ is an alkenyl group containing up to four carbon atoms and the other groups are defined as in Claim 1, 4 or 5th The N-substituted pyrazole derivative according to claim 1, 4 or 5, wherein R ¹⁰ represents an alkyl, alkenyl or alkynyl group of straight or branched chain containing up to 6 carbon atoms optionally substituted by one or more halogen atoms, and the remaining symbols are as defined in claim 1, 4 or 5. The N-substituted pyrazole derivative according to claim 1 or 5, wherein R ³ is -CH 2 R ¹² or -CH 2 R ¹³ , and the remaining symbols are as in claim 1 or 5. The N-substituted pyrazole derivative according to claims 1 to 10, wherein Y is an oxygen atom, and the remaining symbols are as in claims 1 to 10. The N-substituted pyrazole derivative according to claims 1 to 11, wherein R ¹ represents a methyl or ethyl group, and the remaining symbols are as in claims 1 to 11. The N-substituted pyrazole derivative according to claims 1 to 12, wherein R ³ is trifluoromethyl, and the remaining symbols are as in claims 1 to 12. The N-substituted pyrazole derivative according to claims 1 to 13, wherein R ¹ represents 2,4-difluorophenyl or 2,4,6-trifluorophenyl, and the remaining symbols are as in claims 1 to 13. The N-substituted pyrazole derivative according to claims 1 to 14, wherein R ^p is H, and the other groups are defined as in claims 1 to 14. The N-substituted pyrazole derivative according to claims 1 to 15, wherein X represents a sulfur atom, and the remaining symbols are as in claims 1 to 15. The N-substituted pyrazole derivative according to claims 1 to 16, wherein X is an oxygen atom, and the remaining symbols are as in claims 1 to 16. The N-substituted pyrazole derivative according to claim 1 wherein, R ^x represents an alkyl group containing one or two carbon atoms optionally substituted by one or more halogen atoms which are the same or different, R ³ represents an alkyl group having up to 3 carbon atoms optionally substituted by up to 5 halogen atoms which are the same or different, or -SCH _a , R ⁴ represents a phenyl group optionally substituted by one to three groups selected from the group consisting of halogen atoms, trifluoromethyl and methoxy, ^R is H or methyl; Y represents an oxygen or sulfur atom, X is O or -S (O) R ¹⁰ is phenyl or pyridyl optionally substituted with halogen, methoxy, hydroxyl, -NHCOCH, amino,-SCH ₃ , methyl and trifluoromethyl, C 3-6 cycloalkyl straight, branched or branched chain alkyl, alkenyl or alkynyl of up to 6 carbon atoms optionally substituted by one or more groups selected from halogen atoms, -CO (CH 2 CH 4), cyano, cyclopropyl, methoxy and methoxy -CONHCH3, a p is zero or one and the remaining symbols are as in claim 1. The N-substituted pyrazole derivative according to claim 1 which is 4-N- (2,4-difluorophenyl) carboxamido-5- (4-chlorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-methoxyphenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-bromophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-hydroxyphenylthio) -l-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (2-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4 ^ difluorophenyl) carboxamido-5- (3-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5-phenylthio-l-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-acetamidophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-methylphenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (3-trifluoromethylphenyl) carboxamido-5- (4-methylphenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (4-methoxyphenyl) carboxamido-5- (4-chlorophenylthio) -l-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) -l-methyl-3-trifluoromethylpyrazole, 4-N-phenylcarboxamido-5- (3-trifluoromethylphenylthio) -1,3-dimethylpyrazole. 4-N- (4-fluorophenyl) carboxamido-5- (4-chlorophenylthio) -1,3-dimethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-chlorophenylthio) -1,3-dimethylpyrazole. 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chlorophenylthio) -1,3-dimethylpyrazole. 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenoxy) -l-methyl-3-trifluoromethylpyrazole, 4-N- (4-fluorophenyl) carboxamido-5- (3-trifluoromethylphenoxy) -1-trifluoromethyl-mety1-3, 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chlorophenoxy) -1-methyl-3-trifluoromethylpyrazole, 4-N-phenylcarboxamido-5- (4-chlorophenoxy) -1,3-dimethylpyrazole, 4-N- (4-fluorophenyl) carboxamido-5- (4-chlorophenoxy) -1,3-dimethylpyrazole, or 4-N- (2,4-difluorophenyl) carboxamido-5- (4-chlorophenoxy) -1-methyl-3-trifluoromethylpyrazole, or an agriculturally acceptable salt thereof. The N-substituted pyrazole derivative according to claim 1 which is 4-N- (2,4-difluorophenyl) carboxamido-5- (n-butylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (2-propenylthio) -l-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5-isopropylthio-l-methyl -3-Trifluoromethylpyrazole 4-N- (2,4-difluorophenyl) carboxamido-5-ethylthio-l-methyl-3trifluórmetylpyrazol, 4-N- (2,4-difluorophenyl) carboxamido-5- (3-chloropropylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5-methylthio-1-methyl-3-trifluoromethylpyrazole, or 4-N- (2,4-difluorophenyl) carboxamido-5- (2,2,2-trifluoroethoxy) -1-methyl-3-trifluoromethylpyrazole, or an agriculturally acceptable salt thereof. A N-substituted pyrazole derivative according to claim 1 which is 4-N- (2,4-difluorophenyl) carboxamido-5- (ethoxycarbonylmethylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (1-methylbutylthio) -3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, 4- N- (2,4-Difluorophenyl) carboxamido-5- (n-hexylthio) -1-methyl-3-trifluoromethylpyrazole, 5-cyclopentylthio-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 4- N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (n-propylthio) -3-trifluoromethylpyrazole, 5-cyclohexylthio-4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-Ν- (2,4-difluorophenyl) carboxamido-l-methyl-5- (1-methylpropylthio) -3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-l-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-l-methyl-3-trifluoromethylpyrazole, 4- N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-propynylthio) -3-trifluoromethylpyrazole, 5- (3-Butenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 5- (2-bromo-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 5- (3-bromo-2-propenylthio) -4-N- (2,4-difluorophenyl) carboxamido-l-methyl-3-trifluoromethylpyrazole, 5- [4- (cyanomethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 5- (3-methyl-2-butenyltio) -4-N- (2,4-difluorophenyl) carboxamido-l-methyl-3-trifluoromethylpyrazole, 5- (cyclopropylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 5- (3-butinyltio) -4-N- (2,4-difluorophenyl) carboxamido-l-methyl-3-trifluoromethylpyrazole, 5- (2-chloropropylthio) -4-N- (2,4-difluorophenyl) carboxamido-1H-methyl-3-trifluoromethylpyrazole, 4- Ν- (2,4-difluorophenyl) carboxamido-5- (2,2-dimethoxyethylthio) -1-methyl-3-trifluoromethylpyrazole, 5- (2-Butenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-l-methyl-5- (n-pentylthio) -3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-l-methyl-5- (2-methylbutylthio) -3-trifluoromethylpyrazole, 4- N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methyl-2-propenylthio) -3-trifluoromethylpyrazole, 5- (2-chloro-2-propenylthio) -4-N- (2,4-difluorophenyl) caboxamido-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-3-trifluoromethylpyrazole, 5-ethylthio-l-ethyl-4-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole, 5-ethylthio-1-ethyl-4-N- (2,4,6-trifluorophenyl) carboxamido-3-trifluoromethylpyrazole, or 5- (N-methylaminocarbonylmethylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methyl-3-trifluoromethylpyrazole, or an agriculturally acceptable salt thereof. N-substituted pyrazole derivatives according to claim 1 which is 4-N- (2,4-difluorophenyl) -5- (4-fluorophenylthio) -thiocarbox85 amido-1-methyl-3-trifluoromethylpyrazole, 3-chlorodifluoromethyl-5- (4-fluorophenylthio) -4-N- (2,4-difluorophenyl) carboxamido-1-methylpyrazole, 3-chlorodifluoromethyl-5- (4-fluorophenylthio) -1-methyl-4-Ν- (2,4,6-trifluorophenyl) carboxamidopyrazole, 4- N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-pyridylthio) -3-trifluoromethylpyrazole, 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-methyl-3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1-methyl-3- (n-propyl) pyrazole, 4-N- (2,4-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -1- (2,2,2-trifluoroethyl) -3-trifluoromethyl, 4-N- (2,4-difluorophenyl) carboxamido-5- (4fluorophenylthio) -1-methyl-3-methylthio, 4-N- (3-chloro-4-fluorophenyl) carboxamido-5- (4-fluorophenylthio) -l-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- (2-fluorophenylthio) -l-methyl-3-trifluoromethylpyrazole, 4-N- (4-chlorophenyl) carboxamido-5- (4fluorophenylthio) -186 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) carboxamidopyrazole, 4-N- (2-chloro-4-fluorophenyl) carboxamido-5- (4fluorophenylthio) -1-trifluoromethyl-mety1-3, 4-N- (4-fluorophenyl) carboxamido-5- (4fluorophenylthio) -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-bromofluorophenyl) 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- (4fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,3-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -l-methyl-3-trifluoromethylpyrazole, 4-N- (2,5-difluorophenyl) carboxamido-5- (4fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 4-N- (2,6-difluorophenyl) carboxamido-5- (4-fluorophenylthio) -l-methyl-3-trifluoromethylpyrazole, 4-N- (3,5-difluorophenyl) carboxamido-5- (4fluorophenylthio) -? 87 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, λ 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (4-methylthio) , phenylthio) -3-trifluoromethylpyrazole, 5- (4-fluorophenylthio) -1-methyl-4-N-methyl-N- (2,4-difluorophenyl) carboxamido-3-trifluoromethylpyrazole, 5- (4-chlorophenyl-) -4-N- (2,4-difluorophenyl) carboxamido-l-methyl-3-trifluoromethylpyrazole, 4- [N- (2,4-difluorophenyl) carboxamido-1-methyl] -5- (n-propyloxy) -3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-l-methyl-5- (2-methylpropyloxy) -3-trifluoromethyl, 3-Chlorodifluoromethyl-4- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropyloxy) pyrazole 4- N- (2,4-difluorophenyl) carboxamido-1-ethyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, 4-N- (2,4-difluorophenyl) carboxamido-1-ethyl-5- (2-propenylthio) -3-trifluoromethylpyrazole, 4-N- (2,4,6-trifluorophenyl) carboxamido-l-ethyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, 4-N- (2,3-difluorophenyl) carboxamido-1-mety1-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, 4-N- (2,6-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, 4-N- (2,3,6-trifluorophenyl) carboxamido-l-methyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, 4-N- (2,4,6-trifluorophenyl) carboxamido-l-methyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, 4-N- (2,5-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3-trifluoromethylpyrazole, or 4-N- (2,4-difluorophenyl) carboxamido-1-methyl-5- (2-methylpropylthio) -3-pentafluoroethylpyrazole, or an agriculturally acceptable salt thereof. 23. A process for the preparation of an N-substituted pyrazole derivative of the formula I as defined in claim 1, which process comprises: a) a compound of formula II (II) wherein Z is a leaving group and the remaining symbols are as in claim 1, is reacted with a compound of formula III R ² -X ¹ (III) wherein R ³ is as defined in claim 1 and X ¹ is hydrogen or an alkali metal, or (b) for the preparation of an N-substituted pyrazole derivative in which Y represents a sulfur atom, reacting the corresponding N-substituted pyrazole derivative of the formula I in which Y represents an oxygen atom with a thionating compound, or c) for the preparation of a N-substituted pyrazole, wherein ^R is alkyl straight or rozvetvenýcm chain containing up to 6 carbon atoms, is subjected to the corresponding derivatives of N-substituted pyrazoles of formula I, wherein ^R is H by reaction with an alkylating agent or that is d) for the preparation of an N-substituted pyrazole derivative in which Y represents an oxygen atom, a compound of the formula IV i R ¹ , wherein each symbol is as defined in claim 1, is reacted with a halogenating agent to give an acid halide which is subsequently reacted with an amine of formula V H-NR ⁵ R (V) wherein the symbols R ⁴ and R ^s are as defined in Claim 1, or in that e) a compound of formula IVa X * w. (IVa) wherein the symbols are as defined in Claim 1, or a salt thereof, with a compound of formula R-L ^xo, where R ^xo is as defined in claim 1 and L is a leaving group, or in that f) to produce an N-substituted pyrazole derivative in which R · ¹ ° represents a phenyl or pyridyl group substituted with -SR ⁷ , diazotizes the corresponding N-substituted derivative. of a pyrazole of the formula I in which R ¹⁰ is an amino-substituted phenyl or pyridyl group and the diazotized product thus obtained is subsequently reacted with a disulfide of the formula R ⁷ -S-SR ⁷ , Wherein R ^{7 is} as defined in claim 1, J subsequently the N-substituted pyrazole derivative thus obtained is converted into its agriculturally acceptable salt. | 24. A herbicidal composition, characterized in that? as an active ingredient contains a herbicidally effective amount of a derivative? The N-substituted pyrazole of formula I as defined in claim 1, or an agriculturally acceptable salt thereof, in combination with an agriculturally acceptable diluent or carrier and / or surfactant. ii 25. A method for controlling weed growth at a particular site, comprising applying to said site an herbicidally effective amount of an N-substituted pyrazole derivative of the formula I as defined in claim 1, or an agriculturally acceptable salt thereof.