1- Aryl-3-thioalkyl pyrazoles, the synthesis thereof and the use thereof as insecticides

• US 6,518,266 B1
• Filed: 07/21/2000
• Issued: 02/11/2003
• Est. Priority Date: 07/22/1999
• Status: Expired due to Term

• Current Assignee: 3-Dimensional Pharmaceuticals, Inc. (Johnson & Johnson), Heska Corporation (Mars Incorporated)
• Original Assignee: 3-Dimensional Pharmaceuticals, Inc. (Johnson & Johnson), Heska Corporation (Mars Incorporated)
• Inventors: Soll, Richard M., Sha, Deyou, Dhanoa, Daljit S., Silver, Gary, Doller, Dario, Stinchcomb, Dan T., Meegalla, Sanath, Wisnewski, Nancy, Agrafiotis, Dimitris, Seward, R. Lee
• Primary Examiner(s): Berch, Mark L.
• Assistant Examiner(s): Habte, Kahsay
• Application Number:
  US09/621,456
• Time in Patent Office: 935 Days
• Field of Search: 548/371, 548/1, 548/369.2, 548/370.4, 548/377.1, 548/364.1, 548/202, 548/247, 548/124, 548/110, 544/66, 544/67, 544/333, 544/405, 514/404, 514/255.05, 514/229.2, 514/403, 546/275.4, 546/138, 546/144, 546/135
• US Class Current: 514/229.2
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: A01N 43/82 five-membered rings with three ring hetero atoms
• CPC Class Codes: A01N 55/00 Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing organo-phosphorus compounds A01N57/00
• CPC Class Codes: C07D 231/18 One oxygen or sulfur atom
• CPC Class Codes: C07D 231/20 One oxygen atom attached in position 3 or 5
• CPC Class Codes: C07D 231/44 Oxygen and nitrogen or sulfur and nitrogen atoms
• CPC Class Codes: C07D 231/52 Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
• CPC Class Codes: C07D 403/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C07D 409/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C07D 413/04 directly linked by a ring-member-to-ring-member bond

Abstract

The present invention is directed to novel pyrazole derivatives and their use as pesticidal agents. The pyrazole derivatives have Formula I:

or a salt thereof, where

R¹ represents R⁵O, R⁵SO₂, R⁵SO or R⁵S in which R⁵ is as defined herein;

X is halo, cyano, C_1-6 alkoxycarbonyl, C_2-6 alkynyl, optionally substituted C_6-14 aryl or an optionally substituted 5- to 7-membered heteroaromatic ring linked to thiazole via a carbon-carbon bond;

R² is hydrogen, amino, chloro, bromo, iodo, cyano, C_1-6 alkoxy, C_1-6 alkyl or C_6-10 aryl; and

R³-R⁷ each represent hydrogen, halogen, straight- or branched-chain C_1-4 alkyl or C_1-4 alkoxy, either of which is unsubstituted or substituted by one or more halogen atoms, straight- or branched-chain C_1-4 alkylthio or C_1-4 alkylsulphinyl, either of which is substituted by one or more halogen atoms, nitro, cyano, or straight- or branched-chain C_1-4 alkylsulphonyl group which is unsubstituted or substituted by one or more halogen atoms.

Claims

1. A method of inhibiting a arthropod GABA receptor, comprising contacting one or more arthropod GABA receptors with one or more compounds of Formula I:

or a salt thereof, where

R¹ represents R⁵O, R⁵SO₂, R⁵SO or R⁵S in which R⁵ is optionally halogen substituted C_1-6 alkyl, optionally halogen substituted C_2-6 alkenyl, optionally halogen substituted C_2-6 alkynyl, (C_3-7 cycloalkyl)methyl;

or benzyl, optionally substituted by halo, hydroxy, methoxy or ethoxy;

X is halo, cyano, C_1-6 alkoxycarbonyl, C_2-6 alkynyl, optionally substituted C_6-14 aryl or an optionally substituted 5- to 7-membered heteroaromatic ring selected from the group consisting of pyridyl, thienyl, furanyl, isoxazolyl, thiazolyl, isothiazolyl, indolizinyl, isoindolyl, indolyl, indazolyl, quinolizinyl, quinolinyl, and isoquinolinyl, wherein said 5- to 7-membered heteroaromatic ring is linked via a ring carbon on said 5- to 7-membered heteroaromatic ring, and wherein said optional substituents are selected from the group consisting of C_1-4 alkyl, C_1-4 haloalkyl, halogen, C_1-4 alkoxy, C_1-4 haloalkoxy, C_1-4 alkoxycarbonyl, nitro, amino, cyano, C_1-4 alkylthio, C_1-4 alkylsulfinyl and C_1-4 alkylsulfonyl;

R² is hydrogen, amino, chloro, bromo, iodo, cyano, C_1-6 alkoxy, C_1-6 alkyl or C_6-10 aryl; and

R³-R⁷ each represent hydrogen, halogen, straight- or branched-chain C_1-4 alkyl or C_1-4 alkoxy, either of which is unsubstituted or substituted by one or more halogen atoms, straight- or branched-chain C_1-4 alkylthio or C_1-4 alkylsulphinyl, either of which is substituted by one or more halogen atoms, nitro, cyano, or straight- or branched-chain C_1-4 alkylsulphonyl group which is unsubstituted or substituted by one or more halogen atoms.

3. The method of claim 1 or claim 2, wherein R¹ is an C_1-4 alkylsulfonyl, C_1-4 alkylsulphinyl or C_1-4 alkylthio group, any of which is optionally halo-substituted.

4. The method of claim 1 or claim 2, wherein R¹ is —

SCH₃, —

SOCH₃, —

SO₂CH₃, —

SCH₂CH₃, —

SCH₂CH₂CH₃, —

SCH₂CF₃, cyclopropylmethylthio, 4-methoxybenzylthio, trifluoromethylthio or trifluoromethylsulfonyl.

5. The method of claim 4, wherein R¹ is —

SCH₃.

6. The method of claim 1 or claim 2, wherein X is cyano, chloro, iodo, C_1-4 alkoxycarbonyl or C_2-4 alkynyl.

7. The method of claim 1 or claim 2, wherein X is phenyl, naphthyl, pyridyl, thienyl, furanyl, isoxazolyl, thiazolyl, isothiazolyl, indolizinyl, isoindolyl, indolyl, indazolyl, quinolizinyl, quinolinyl, or isoquinolinyl, any of which is optionally substituted by one or more substituents selected from the group consisting of C_1-4 alkyl, C_1-4 haloalkyl, halogen, C_1-4 alkoxy, C_1-4 haloalkoxy, C_1-4 alkoxycarbonyl, nitro, amino, cyano, C_1-4 alkylthio, C_1-4 alkylsulfinyl and C_1-4 alkylsulfonyl.

8. The method of claim 7, wherein X is 3-methyloxadiazin-5-yl, thiophen-2-yl;

thiophen-3-yl, 5-methylthiophen-2-yl, 4-methylthiophen-2-yl, 5-chlorothiophen-2-yl, 4-chlorothiophen-2-yl, 5-methylcarbonylthiophen-2-yl, benzothiophen-2-yl, pyrimidin-6-yl, pyrazin-6-yl, phenyl, 2-methylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-cyanophenyl, 2-methoxyphenyl, 2-methylthiophenyl, 2,4-dimethoxyphenyl, 3-methylphenyl, 3-isopropylphenyl, 3-methoxyphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-cyanophenyl, 2-methoxyphenyl, 2-methylthiophenyl, 3,5-di(trifluoromethyl)phenyl, 3-chloro-4-fluorophenyl, 3,4-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, 1,3-benzodioxazol-5-yl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, biphenyl, 4-isopropylphenyl, 4-methoxyphenyl, or 4-methylthiophenyl.

9. The method of claim 1 or claim 2, wherein R² is hydrogen.

10. The method of claim 1 or claim 2, wherein R² is NH₂.

11. The method of claim 1 or claim 2, wherein

R³ is halogen;

R⁴ is hydrogen;

R⁵ is hydrogen, C_1-6 alkyl optionally substituted by one or more halogen atoms, C_1-6 alkoxy, optionally substituted by one or more halogen atoms;

R₆ is hydrogen; and

R⁷ is halogen.

12. The method of claim 1 or claim 2, wherein

R³, R⁵ and R⁷ are chloro;

and R⁴ and R⁶ are hydrogen;

R³ is chloro;

R⁵ is trifluoromethyl; and

R⁴, R⁷, and R⁶ are hydrogen;

R³ is bromo;

R⁵ is trifluoromethyl; and

R⁴, R⁷, and R⁶ are hydrogen;

R³ is bromo;

R⁵ and R⁷ are trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

R³ and R⁷ are chloro;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

or

R³ and R⁷ are bromo;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen.

13. The method of claim 1 or claim 2, wherein

R³ and R⁷ are chloro;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

or

R³ and R⁷ are bromo;

R⁵ is trifluoromethoxy; and

R⁴ and R⁶ are hydrogen.

14. The method of claim 1 or claim 2, wherein said compound is selected from the group consisting of:

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-iodo-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-chloro-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-bromo-3-methylthiopyrazol-5-ylamine;

Methyl 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carboxylate;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carboxylic acid;

Ethyl 5-amino-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-3-methylthiopyrazole-4-carboxylate;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(4-methylphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-phenyl-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-phenyl-3-methylthiopyrazole;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2-methylphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-[2-(trifluoromethyl)phenyl]pyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2,4-dimethoxyphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-ethynyl-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2-trimethylsilylethynyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-pyrazin-2-ylpyrazol-5-ylamine;

1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-pyrazin-2-ylpyrazole;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(5-chlorothien-2-yl)pyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(5-methoxycarbonylthien-2-yl)pyrazol-5-ylamine; and

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(3-methyl-1,2,4-oxadiazin-5-yl)-2-ylpyrazol-5-ylamine;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carbonitrile;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carbonitrile;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-ethylthiopyrazole-4-carbonitrile;

5-Amino-3-methylthio-1-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]pyrazole-4-carbonitrile;

5-Amino-3-methylthio-1-[4-(trifluoromethyl)phenyl]pyrazole-4-carbonitrile;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfinyl)pyrazole-4-carbonitrile;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfonyl)pyrazole-4-carbonitrile;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfonyl)pyrazole-4-carbonitrile;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfinyl)pyrazole-4-carbonitrile;

5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-[(4-methoxyphenyl)methylthio]pyrazole-4-carbonitrile;

and pesticidally acceptable salts thereof.

2. A method for controlling arthropods, comprising contacting an animal, plant or object with a composition comprising

(a) a pesticidally effective amount of at least one compound of Formula I:

or a salt thereof, where

R¹ represents R⁵O, R⁵SO₂, R⁵SO or R⁵S in which R⁵ is optionally halogen substituted C_1-6 alkyl, optionally halogen substituted C_2-6 alkenyl, optionally halogen substituted C_2-6 alkynyl, (C_3-7 cycloalkyl)methyl;

or benzyl, optionally substituted by halo, hydroxy, methoxy or ethoxy;

X is halo, cyano, C_1-6 alkoxycarbonyl, C_2-6 alkynyl, optionally substituted C_6-14 aryl or an optionally substituted 5- to 7-membered heteroaromatic ring selected from the group consisting of pyridyl, thienyl, furanyl, isoxazolyl, thiazolyl, isothiazolyl, indolizinyl, isoindolyl, indolyl, indazolyl, quinolizinyl, quinolinyl, and isoquinolinyl, wherein said 5- to 7-membered heteroaromatic ring is linked via a ring carbon on said 5- to 7-membered heteroaromatic ring, and wherein said optional substituents are selected from the group consisting of C_1-4 alkyl, C_1-4 haloalkyl, halogen, C_1-4 alkoxy, C_1-4 haloalkoxy, C_1-4 alkoxycarbonyl, nitro, amino, cyano, C_1-4 alkylthio, C_1-4 alkylsulfinyl and C_1-4 alkylsulfonyl;

R² is hydrogen, amino, chloro, bromo, iodo, cyano, C_1-6 alkoxy, C_1-6 alkyl or C_6-10 aryl; and

R³-R⁷ each represent hydrogen, halogen, straight- or branched-chain C_1-4 alkyl or C_1-4 alkoxy, either of which is unsubstituted or substituted by one or more halogen atoms, straight- or branched-chain C_1-4 alkylthio or C_1-4 alkylsulphinyl, either of which is substituted by one or more halogen atoms, nitro, cyano, or straight- or branched-chain C_1-4 alkylsulphonyl group which is unsubstituted or substituted by one or more halogen atoms; and

(b) one or more pesticidally-acceptable diluents or carriers.

15. A pesticidal composition comprising:

(a) a pesticidally effective amount of at least one compound of Formula I;

or a salt thereof, where

R¹ represents R⁵O, R⁵SO₂, R⁵SO or R⁵S in which R⁵ is optionally halogen substituted C_1-6 alkyl, optionally halogen substituted C_2-6 alkenyl, optionally halogen substituted C_2-6 alkynyl, (C_3-7 cycloalkyl)methyl;

or benzyl, optionally substituted by halo, hydroxy, methoxy or ethoxy;

X is halo, cyano, C_1-6 alkoxycarbonyl, C_2-6 alkynyl, optionally substituted C_6-14 aryl or an optionally substituted 5- to 7-membered heteroaromatic ring selected from the group consisting of pyridyl, thienyl, furanyl, isoxazolyl, thiazolyl, isothiazolyl, indolizinyl, isoindolyl, indolyl, indazolyl, quinolizinyl, quinolinyl, and isoquinolinyl, wherein said 5- to 7-membered heteroaromatic ring is linked via a ring carbon on said 5- to 7-membered heteroaromatic ring, and wherein said optional substituents are selected from the group consisting of C_1-4 alkyl, C_1-4 haloalkyl, halogen, C_1-4 alkoxy, C_1-4 haloalkoxy, C_1-4 alkoxycarbonyl, nitro, amino, cyano, C_1-4 alkylthio, C_1-4 alkylsulfinyl and C_1-4 alkylsulfonyl;

R² is hydrogen, amino, chloro, bromo, iodo, cyano, C_1-6 alkoxy, C_1-6 alkyl or C_6-10 aryl; and

R³-R⁷ each represent hydrogen, halogen, straight- or branched-chain C_1-4 alkyl or C_1-4 alkoxy, either of which is unsubstituted or substituted by one or more halogen atoms, straight- or branched-chain C_1-4 alkylthio or C_1-4 alkylsulphinyl, either of which is substituted by one or more halogen atoms, nitro, cyano, or straight- or branched-chain C_1-4 alkylsulphonyl group which is unsubstituted or substituted by one or more halogen atoms; and

(b) one or more pesticidally-acceptable diluents or carriers.

16. The composition of claim 15, wherein R¹ is an C_1-4 alkylsulfonyl, C_1-4 alkylsulphinyl or C_1-4 alkylthio group, any of which is optionally halo-substituted.

17. The composition of claim 15, wherein R¹ is —

SCH₃, —

SOCH₃, —

SO₂CH₃, —

SCH₂CH₃, —

SCH₂CH₂CH₃, —

SCH₂CF₃, cyclopropylmethylthio, 4-methoxybenzylthio, trifluoromethylthio or trifluoromethylsulfonyl.

18. The composition of claim 15, wherein R¹ is —

SCH₃.

19. The composition of claim 15, wherein X is cyano, chloro, iodo, C_1-4 alkoxycarbonyl or C_2-4 alkynyl.

20. The composition of claim 15, wherein X is phenyl, naphthyl, pyridyl, thienyl, furanyl, isoxazolyl, thiazolyl, isothiazolyl, indolizinyl, isoindolyl, indolyl, indazolyl, quinolizinyl, quinolinyl, or isoquinolinyl, any of which is optionally substituted by one or more substituents selected from the group consisting of C_1-4 alkyl, C_1-4 haloalkyl, halogen, C_1-4 alkoxy, C_1-4 haloalkoxy, C_1-4 alkoxycarbonyl, nitro, amino, cyano, C_1-4 alkylthio, C_1-4 alkylsulfinyl and C_1-4 alkylsulfonyl.

21. The composition of claim 15, wherein X is 3-methyloxadiazin-5-yl, thiophen-2-yl;

thiophen-3-yl, 5-methylthiophen-2-yl, 4-methylthiophen-2-yl, 5-chlorothiophen-2-yl, 4-chlorothiophen-2-yl, 5-methylcarbonylthiophen-2-yl, benzothiophen-2-yl, pyrimidin-6-yl, pyrazin-6-yl, phenyl, 2-methylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-cyanophenyl, 2-methoxyphenyl, 2-methylthiophenyl, 2,4-dimethoxyphenyl, 3-methylphenyl, 3-isopropylphenyl, 3-methoxyphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-cyanophenyl, 2-methoxyphenyl, 2-methylthiophenyl, 3,5-di(trifluoromethyl)phenyl, 3-chloro-4-fluorophenyl, 3,4-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, 1,3-benzodioxazol-5-yl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, biphenyl, 4-isopropylphenyl, 4-methoxyphenyl, or 4-methylthiophenyl.

22. The composition of claim 15, wherein R² is hydrogen.

23. The composition of claim 15, wherein R² is NH₂.

24. The composition of claim 15, wherein

R³ is halogen;

R⁴ is hydrogen;

R⁵ is hydrogen, C_1-6 alkyl optionally substituted by one or more halogen atoms, C_1-6 alkoxy, optionally substituted by one or more halogen atoms;

R₆ is hydrogen; and

R⁷ is halogen.

25. The composition of claim 15, wherein

R³ R⁵ and R⁷ are chloro;

and R⁴ and R⁶ are hydrogen;

R³ is chloro;

R⁵ is trifluoromethyl; and

R⁴, R⁷, and R⁶ are hydrogen;

R³ is bromo;

R⁵ is trifluoromethyl; and

R⁴, R⁷, and R⁶ are hydrogen;

R³ is bromo;

R⁵ and R⁷ are trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

R³ and R⁷ are chloro;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

or

R³ and R⁷ are bromo;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen.

26. The composition of claim 15, wherein

R³ and R⁷ are chloro;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

or R³ and R⁷ are bromo;

R⁵ is trifluoromethoxy; and

R⁴ and R⁶ are hydrogen.

27. The composition of claim 15, wherein said compound is selected from the group consisting of:

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-iodo-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-chloro-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-bromo-3-methylthiopyrazol-5-ylamine;

Methyl 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carboxylate;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carboxylic acid;

Ethyl 5-amino-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-3-methylthiopyrazole-4-carboxylate;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(4-methylphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-phenyl-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-phenyl-3-methylthiopyrazole;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2-methylphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-[2-(trifluoromethyl)phenyl]pyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2,4-dimethoxyphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-ethynyl-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2-trimethylsilylethynyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-pyrazin-2-ylpyrazol-5-ylamine;

1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-pyrazin-2-ylpyrazole;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(5-chlorothien-2-yl)pyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(5-methoxycarbonylthien-2-yl)pyrazol-5-ylamine; and

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(3-methyl-1,2,4-oxadiazin-5-yl)-2-ylpyrazol-5-ylamine;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carbonitrile;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carbonitrile;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-ethylthiopyrazole-4-carbonitrile;

5-Amino-3-methylthio-1-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]pyrazole-4-carbonitrile;

5-Amino-3-methylthio-1-[4-(trifluoromethyl)phenyl]pyrazole-4-carbonitrile;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfinyl)pyrazole-4-carbonitrile;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfonyl)pyrazole-4-carbonitrile;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfonyl)pyrazole-4-carbonitrile;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-(methylsulfinyl)pyrazole-4-carbonitrile;

5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-[(4-methoxyphenyl)methylthio]pyrazole-4-carbonitrile;

and pesticidally acceptable salts thereof.

39. The composition of claim 15, wherein

R³ R⁵ and R⁷ are chloro;

and R⁴ and R⁶ are hydrogen;

R³ is chloro;

R⁵ is trifluoromethyl; and

R⁴, R⁷, and R⁶ are hydrogen;

R³ is bromo;

R⁵ is trifluoromethyl; and

R⁴, R⁷, and R⁶ are hydrogen;

R³ is bromo;

R⁵ and R⁷ are trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

R³ and R⁷ are chloro;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

or

R³ and R⁷ are bromo;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen.

40. The composition of claim 15, wherein

R³ and R⁷ are chloro;

R⁵ is trifluoromethyl; and

R⁴ and R⁶ are hydrogen;

or

R³ and R⁷ are bromo;

R⁵ is trifluoromethoxy; and

R⁴ and R⁶ are hydrogen.

41. The composition of claim 15, wherein said compound is selected from the group consisting of:

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-iodo-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-chloro-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-bromo-3-methylthiopyrazol-5-ylamine;

Methyl 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carboxylate;

5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthiopyrazole-4-carboxylic acid;

Ethyl 5-amino-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-3-methylthiopyrazole-4-carboxylate;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(4-methylphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-phenyl-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-phenyl-3-methylthiopyrazole;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2-methylphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-[2-(trifluoromethyl)phenyl]pyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2,4-dimethoxyphenyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-ethynyl-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(2-trimethylsilylethynyl)-3-methylthiopyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-pyrazin-2-ylpyrazol-5-ylamine;

1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-pyrazin-2-ylpyrazole;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(5-chlorothien-2-yl)pyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(5-methoxycarbonylthien-2-yl)pyrazol-5-ylamine;

1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-3-methylthio-4-(3-methyl-1,2,4-oxadiazin-5-yl)-2-ylpyrazol-5-ylamine;

and pesticidally acceptable salts thereof.

28. A compound of Formula I:

or a salt thereof, where

R¹ represents R⁵O, R⁵SO₂, R⁵SO or R⁵S in which R⁵ is optionally halogen substituted C_1-6 alkyl, optionally halogen substituted C_2-6 alkenyl, optionally halogen substituted C_2-6 alkynyl, (C_3-7 cycloalkyl)methyl;

or benzyl, optionally substituted by halo, hydroxy, methoxy or ethoxy;

X is halo, C_1-6 alkoxycarbonyl, C_2-6 alkynyl, optionally substituted C_6-14 aryl or an optionally substituted 5- to 7-membered heteroaromatic ring selected from the group consisting of pyridyl, thienyl, furanyl, isoxazolyl, thiazolyl, isothiazolyl, indolizinyl, isoindolyl, indolyl, indazolyl, quinolizinyl, quinolinyl, and isoquinolinyl, wherein said 5- to 7-membered heteroaromatic ring is linked via a ring carbon on said 5- to 7-membered heteroaromatic ring, and wherein said optional substituents are selected from the group consisting of C_1-4 alkyl, C_1-4 haloalkyl, halogen, C_1-4 alkoxy, C_1-4 haloalkoxy, C_1-4 alkoxycarbonyl, nitro, amino, cyano, C_1-4 alkylthio, C_1-4 alkylsulfinyl and C_1-4 alkylsulfonyl;

R² is hydrogen, amino, chloro, bromo, iodo, cyano, C_1-6 alkoxy, C_1-6 alkyl or C_6-10 aryl; and

R³-R⁷ each represent hydrogen, halogen, straight- or branched-chain C_1-4 alkyl or C_1-4 alkoxy, either of which is unsubstituted or substituted by one or more halogen atoms, straight- or branched-chain C_1-4 alkylthio or C_1-4 alkylsulphinyl, either of which is substituted by one or more halogen atoms, nitro, cyano, or straight- or branched-chain C_1-4 alkylsulphonyl group which is unsubstituted or substituted by one or more halogen atoms.

29. The compound of claim 28, wherein R¹ is an C_1-4 alkylsulfonyl, C_1-4 alkylsulphinyl or C_1-4 alkylthio group, any of which is optionally halo-substituted.

30. The compound of claim 28, wherein R¹ is —

SCH₃, —

SOCH₃, —

SO₂CH₃, —

SCH₂CH₃, —

SCH₂CH₂CH₃, —

SCH₂CF₃, cyclopropylmethylthio, 4-methoxybenzylthio, trifluoromethylthio or trifluoromethylsulfonyl.

31. The compound of claim 28, wherein R¹ is —

SCH₃.

32. The compound of claim 28, wherein X is chloro or iodo.

33. The compound of claim 28, wherein X is C_1-4 alkoxycarbonyl or C_2-4 alkynyl.

34. The compound of claim 28, wherein X is phenyl, naphthyl, pyridyl, thienyl, furanyl, isoxazolyl, thiazolyl, isothiazolyl, indolizinyl, isoindolyl, indolyl, indazolyl, quinolizinyl, quinolinyl, or isoquinolinyl, any of which is optionally substituted by one or more substituents selected from the group consisting of C_1-4 alkyl, C_1-4 haloalkyl, halogen, C_1-4 alkoxy, C_1-4 haloalkoxy, C_1-4 alkoxycarbonyl, nitro, amino, cyano, C_1-4 alkylthio, C_1-4 alkylsulfinyl and C_1-4 alkylsulfonyl.

35. The compound of claim 28, wherein X is 3-methyloxadiazin-5-yl, thiophen-2-yl;

thiophen-3-yl, 5-methylthiophen-2-yl, 4-methylthiophen-2-yl, 5-chlorothiophen-2-yl, 4-chlorothiophen-2-yl, 5-methylcarbonylthiophen2-yl, benzothiophen-2-yl, pyrimidin-6-yl, pyrazin-6-yl, phenyl, 2-methylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-cyanophenyl, 2-methoxyphenyl, 2-methylthiophenyl, 2,4-dimethoxyphenyl, 3-methylphenyl, 3-isopropylphenyl, 3-methoxyphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethylphenyl, 2-cyanophenyl, 2-methoxyphenyl, 2-methylthiophenyl, 3,5-di(trifluoromethyl)phenyl, 3-chloro-4-fluorophenyl, 3,4-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, 1,3-benzodioxazol-5-yl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, biphenyl, 4-isopropylphenyl, 4-methoxyphenyl, or 4-methylthiophenyl.

36. The compound of claim 28, wherein R² is hydrogen.

37. The compound of claim 28, wherein R² is NH₂.

38. The compound of claim 28, wherein:

R³ is halogen;

R⁴ is hydrogen;

R⁵ is hydrogen, C_1-6 alkyl optionally substituted by one or more halogen atoms, C_1-6 alkoxy, optionally substituted by one or more halogen atoms;

R₆ is hydrogen; and

R⁷ is halogen, especially chloro.