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PESTICIDALLY ACTIVE THIOSEMICARBAZONE COMPOUNDS

20250197358 · 2025-06-19

    Inventors

    Cpc classification

    International classification

    Abstract

    The present invention relates to the compounds of formula (I), and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof wherein the variables are defined according to the description. The compounds of formula (I), as well as the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof, are useful for combating or controlling invertebrate pests, in particular arthropod pests and nematodes. The invention also relates to such compounds for use in a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural and a veterinary composition comprising said compounds.

    ##STR00001##

    Claims

    1. A compound of the formula I ##STR00176## wherein A is N or CR.sup.A; B.sup.1 is N or CR.sup.B1; B.sup.2 is N or CR.sup.B2; R.sup.A is H, halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, wherein the alkyl, alkoxy, alkynyl, cycloalkyl moieties are unsubstituted or substituted with halogen; R.sup.B1 and R.sup.B2 independently of each other are H, halogen, OH, CN, SCN, SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, wherein the alkyl, alkoxy, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C(O)OR.sup.a, NR.sup.bR.sup.c; Q is N(R.sup.2)C(O), N(R.sup.2)C(S), NC(X), or N(R.sup.2)C(NR), wherein Ar is bound to either side of Q; X is N(R.sup.3).sub.2; R is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, or C.sub.3-C.sub.6-cycloalkyl, wherein the alkyl, and cycloalkyl moieties are unsubstituted or substituted with halogen, R.sup.3 is H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl; C.sub.3-C.sub.6-cycloalkyl; R.sup.2 is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C(O)OR.sup.a; m is 0, 1, or 2; R.sup.6 is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, wherein the alkyl, alkynyl, and cycloalkyl moieties are unsubstituted or substituted with halogen, Ar is phenyl or 5- or 6-membered heteroaryl or 1,3-benzodioxole, which are unsubstituted or substituted with R.sup.Ar, wherein R.sup.Ar is halogen, OH, CN, SCN, SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C(O)OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, OC.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NHC.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(O)NR.sup.bR.sup.c, SO.sub.2NR.sup.bR.sup.c, or S(O).sub.mR.sup.e; R.sup.s is selected from (CR.sup.xR.sup.y).sub.nOCO(OC.sub.1-C.sub.6-alkyl).sub.p Y, (CR.sup.xR.sup.y).sub.nOCO(C.sub.2-C.sub.6-alkenyl).sub.q-Y, (CR.sup.xR.sup.y).sub.nOCONR.sup.jR.sup.k, n is 1 or 2; p is 0, 1, 2, 3, 4, or 5; q is 0, 1, or 2; Y is C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, 5- to 6-membered heterocyclic group, or phenyl, wherein the alkyl, heterocyclic and phenyl groups are unsubstituted or substituted with R.sup.f; R.sup.x and R.sup.y independently are selected from H or C.sub.1-C.sub.6-alkyl, wherein the alkyl group is unsubstituted or substituted with R.sup.1; R.sup.j and R.sup.k independently are selected from H or C.sub.1-C.sub.6-alkyl, wherein the alkyl group is unsubstituted or substituted with R.sup.1; R.sup.n H, C.sub.1-C.sub.6-alkyl, wherein the alkyl moiety is unsubstituted or substituted with halogen, C.sub.1-C.sub.6-alkylene-CN; R.sup.11 is C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkoxy, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, C(O)NR.sup.bR.sup.c, aryl, arylcarbonyl, aryl-C.sub.1-C.sub.4-alkyl, aryloxy-C.sub.1-C.sub.4-alkyl, heteroaryl, carbonylheteroaryl, heteroaryl-C.sub.1-C.sub.4-alkyl or heteroaryloxy-C.sub.1-C.sub.4-alkyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.g and wherein the heteroaryl is a 5- or 6-membered monocyclic heteroaryl or a 8-, 9- or 10-membered bicyclic heteroaryl; R.sup.a, R.sup.b, and R.sup.c are, identical or different, H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylC.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C.sub.1-C.sub.6-alkylene-CN, phenyl, or CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.1; R.sup.e is C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, wherein the alkyl, cycloalkyl moieties are unsubstituted or substituted with halogen; R.sup.f is halogen, N.sub.3, OH, CN, NO.sub.2, SCN, SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxyx-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C(O)OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, OC.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NHC.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(O)NR.sup.bR.sup.c, SO.sub.2NR.sup.bR.sup.c, or S(O).sub.mR.sup.e; R.sup.g is halogen, OH, CN, SCN, SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C(O)OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, OC.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NHC.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(O)NR.sup.bR.sup.c, SO.sub.2NR.sup.bR.sup.c, or S(O).sub.mR.sup.e; and the N-oxides, stereoisomers, tautomers, and agriculturally or veterinarily acceptable salts thereof.

    2. The compound of formula I according to claim 1, wherein A is CR.sup.A, B.sup.1 is CR.sup.B1, and B.sup.2 is CR.sup.B2.

    3. The compound of formula I according to claim 1, wherein A is N, B.sup.1 is CR.sup.B1, and B.sup.2 is CR.sup.B2.

    4. The compound of formula I according to claim 1, wherein Q is N(R.sup.2)C(O) or NC(X), R.sup.2 and X are as defined in claim 1 and wherein Ar is bound to either side of Q.

    5. The compound of formula I according to claim 1, wherein R.sup.s is (CR.sup.xR.sup.y).sub.nOCO(OC.sub.1-C.sub.6-alkyl).sub.p Y, R.sup.x, R.sup.y, Y, p and n are as defined in claim 1.

    6. The compound of formula I according to claim 1, wherein Ar is phenyl which is unsubstituted or substituted with R.sup.Ar.

    7. The compound of formula I according to claim 1, wherein R.sup.11 is phenyl which is unsubstituted or substituted with R.sup.g.

    8. A composition comprising at least one compound of formula I according to claim 1, an N-oxide, or an agriculturally acceptable salt thereof, and at least one liquid and/or solid carrier.

    9. A method for combating or controlling an invertebrate pest, comprising contacting said invertebrate pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound according to claim 1.

    10. A method for protecting growing plants from attack or infestation by an invertebrate pest, comprising contacting a plant, or soil or water wherein the plant is growing, with a pesticidally effective amount of at least one compound according to claim 1.

    11. A seed comprising a compound according to claim 1, the stereoisomer, or salts thereof in an amount of from 0.1 g to 10 kg per 100 kg of seed.

    12. (canceled)

    13. A non-therapeutical method for treating or protecting an animal from infestation or infection by an invertebrate pest comprising bringing the animal in contact with a pesticidally effective amount of at least one compound of the formula I according to claim 1, a stereoisomer thereof, and/or at least one veterinarily acceptable salt thereof.

    Description

    EXAMPLES

    [0660] With appropriate modification of the starting materials, the procedures as described in the preparation examples below were used to obtain further compounds of formula I. The compounds obtained in this manner are listed in the table C that follows, together with physical data.

    [0661] Compounds can be characterized e.g. by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), by .sup.1H-NMR and/or by their melting points.

    [0662] Analytical HPLCMethod 1: Agilent Eclipse Plus C18, 504.6 mm, ID 5 m; Elution: A=10 mM A mm. Formate (0.1% Formic Acid), B=Acetonitrile (0.1% Formic Acid), Flow=1.2 ml/min. at 30 C.; Gradient: 10% B to 100% B-3 min, hold for 1 min, 1 min-10% B. Run Time=5.01 min.

    [0663] Analytical HPLCMethod 2: Kinetex XB C18 1, 7 502.1 mm; A=Water+0.1% TFA, B=Acetonitrile, Flow=0.8 ml/min-1.0 ml/min in 1.5 min. at 60 C.; Gradient: 5% B to 100% B-1.5 min.

    [0664] .sup.1H-NMR: The signals are characterized by chemical shift (ppm, 6 [delta]) vs. tetramethylsilane respectively, CDCl.sub.3 for .sup.13C-NMR, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m=multiplet, q=quartet, t=triplet, d=doublet and s=singlet.

    [0665] Abbreviations used are: d for day(s), h for hour(s), min for minute(s), r.t./room temperature for 20-25 C., Rt for retention time; DMSO for dimethyl sulfoxide, OAc for acetate, EtOAc for ethyl acetate, THF for tetrahydrofuran, DMF for N,N-dimethylformamide, ACN for acetonitrile, DCM for dichloromethane, TEA for triethylamine and t-BuOH for tert-butanol. [0666] Compound: C-7: Synthesis of [(Z)N-[(E)-[4-[4-cyano-1-methyl-5-[[4-(trifluoromethoxy)benzoyl]amino]pyrazol-3-yl]phenyl]methyleneamino]-N-(2-isopropyl-5-methylphenyl)carbamimidoyl]sulfanylmethyl acetate

    Step 1: Synthesis of 3,5-dibromo-1H-pyrazole-4-carbonitrile

    [0667] To a stirred mixture of 1H-pyrazole-4-carbonitrile (20.0 g) in Ethanol (250 mL) and Water (350 mL) was added Sodium acetate (123.36 g) portion wise at ambient temperature. The mixture was cooled to 10 C. and was added bromine (22.1 mL) drop wise in 25 min at 10 C. The mixture was stirred for 2 h at ambient temperature. The mixture was extracted with dichloromethane and the organic extracts washed with 10% aq. sodium thiosulphate solution. The organic extracts dried over anhydrous sodium sulphate and evaporated invacuo to obtain the title compound as a off-white solid (49 g). HPLC/MS (Method 1): Rt: 1.69 min; m/z=250.1 (M1).sup..

    Step 2: Synthesis of 3,5-dibromo-1-methyl-pyrazole-4-carbonitrile

    [0668] To a stirred mixture of 3,5-dibromo-1H-pyrazole-4-carbonitrile (49 g) in N,N-dimethylformamide (250 mL) were added Iodomethane (18.24 mL) drop wise and cesium carbonate (95.45 g) portion wise at ambient temperature. The mixture was stirred for 17 h at ambient temperature. To a mixture water was subsequently added and the white product was precipitated out. The precipitated product was filtered under suction filter, washed with water and dried in vacuo to obtain the title compound as a white solid (50 g). HPLC/MS (Method 1): Rt: 1.84 min; m/z=261.4 (M2).sup.+; .sup.1H NMR (300 MHz, DMSO-d.sub.6) 3.89 (s, 3H)

    Step 3: Synthesis of 5-amino-3-bromo-1-methyl-pyrazole-4-carbonitrile

    [0669] To a stirred mixture of 3,5-dibromo-1-methyl-pyrazole-4-carbonitrile (8 g) in 1-methyl-2-pyrrolidinone (8 mL) was added 2,4-dimethoxybenzylamine (10.1 mL) at ambient temperature. The mixture was stirred at 180 C. for 2 h. The mixture was cooled to 10 C. and 4N HCl (30 mL) was added to mixture at 10 C. The mixture was stirred for 1 h at ambient temperature and then the mixture was extracted with EtOAc. The organic extracts dried over anhydrous sodium sulphate and evaporated in vacuo. The residue obtained was subjected to flash chromatography, eluting with a gradient of EtOAc and heptane to obtain the title compound as a pale yellow solid (4.7 g). HPLC/MS (Method 1): Rt: 1.27 min; m/z=201.2 (M).sup.+; .sup.1H NMR (500 MHz, DMSO-d.sub.6) 6.93 (s, 2H), 3.51-3.47 (m, 3H).

    Step 4: Synthesis of N-(5-bromo-4-cyano-2-methyl-pyrazol-3-yl)-4-(trifluoromethoxy)benzamide

    [0670] To a stirred mixture of 5-amino-3-bromo-1-methyl-pyrazole-4-carbonitrile (4.7 g) in dichlormethane (60 mL) were added pyridine (9.45 mL) and 4-(trifluromethoxy)benzoyl chloride (4.5 mL) drop wise at 0 C. The mixture was stirred at ambient temperature for 6 h and 1N HCl (50 mL) was subsequently added to the mixture. The mixture was extracted with dichloromethane (100 mL2) and the organic extracts washed with saturated sodium bicarbonate solution. The organic extracts dried over anhydrous sodium sulphate and evaporated in vacuo. The residue obtained was subjected to flash chromatography, eluting with a gradient of EtOAc and heptane to obtain the title compound as a white solid (5.8 g). HPLC/MS (Method 1): Rt: 2.02 min; m/z=389.4 (M).sup.+; .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.16 (s, 1H), 8.07 (dd, J=8.7, 1.9 Hz, 2H), 7.54 (d, J=8.3 Hz, 2H), 3.71 (d, J=1.8 Hz, 3H).

    Step 5: Synthesis of N-[4-cyano-5-(4-formylphenyl)-2-methyl-pyrazol-3-yl]-4-(trifluoromethoxy)benzamide

    [0671] To a stirred mixture of N-(5-bromo-4-cyano-2-methyl-pyrazol-3-yl)-4-(trifluoromethoxy)benzamide (2.2 g) in 1,4-dioxane (25 mL) and water (3 mL) were added (4-formylphenyl)boronic acid (1.01 g) and potassium carbonate (1.56 g) at ambient temperature. The mixture was stirred at ambient temperature under inner gas purging for 10 min and was added Pd(dppf)Cl.sub.2 (0.414 g) at ambient temperature. The mixture was stirred at 100 C. for 7 h. The mixture was cooled to ambient temperature and Water was subsequently added. The mixture was extracted with EtOAc (50 mL2). The organic extracts dried over anhydrous sodium sulphate and evaporated in vacuo. The residue obtained was subjected to flash chromatography, eluting with a gradient of EtOAc and Heptane to obtain the title compound as a solid (1.55 g). HPLC/MS (Method 1): Rt: 2.02 min; m/z=415.5 (M+1).sup.+; .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.23 (s, 1H), 10.08 (d, J=1.9 Hz, 1H), 8.22-8.14 (m, 2H), 8.10 (dt, J=9.2, 7.1 Hz, 4H), 7.63 (d, J=8.3 Hz, 2H), 3.87 (d, J=1.9 Hz, 3H).

    Step 6: Synthesis of N-[4-cyano-5-[4-[(E)-[(2-isopropyl-5-methyl-phenyl)carbamothioyl hydrazono]methyl]phenyl]-2-methyl-pyrazol-3-yl]-4-(trifluoromethoxy)benzamide

    [0672] To a stirred mixture of N-[4-cyano-5-(4-formylphenyl)-2-methyl-pyrazol-3-yl]-4-(trifluoromethoxy) benzamide (0.250 g) in acetic acid (3 mL) was added 1-amino-3-(2-isopropyl-5-methyl-phenyl)thiourea (0.135 g) at 0 C. The mixture was stirred at ambient temperature for 4 h. Water was subsequently added and the mixture was extracted with EtOAc (20 mL2). The organic extracts dried over anhydrous Sodium sulphate and evaporated invacuo to obtain the title compound as a solid (0.310 g). HPLC/MS (Method 1): Rt: 1.312 min; m/z=621 (M+1).sup.+; .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.86 (s, 1H), 11.18 (s, 1H), 10.01 (s, 1H), 8.18 (dd, J=6.2, 2.5 Hz, 3H), 8.08 (d, J=7.9 Hz, 2H), 7.93 (d, J=8.0 Hz, 2H), 7.63 (d, J=8.3 Hz, 2H), 7.24 (d, J=8.0 Hz, 1H), 7.12 (d, J=8.0 Hz, 1H), 7.01 (s, 1H), 3.85 (d, J=2.0 Hz, 3H), 3.09 (p, J=7.5 Hz, 1H), 2.30 (s, 3H), 1.17 (d, J=6.8 Hz, 6H).

    Step 7: Synthesis of [(Z)N-[(E)-[4-[4-cyano-1-methyl-5-[[4-(trifluoromethoxy)benzoyl]amino]pyrazol-3-yl]phenyl]methyleneamino]-N-(2-isopropyl-5-methyl phenyl)carbamimidoyl]sulfanylmethyl acetate

    [0673] To a stirred mixture of N-[4-cyano-5-[4-[(E)-[(2-isopropyl-5-methyl-phenyl) carbamothioylhydrazono]methyl]phenyl]-2-methyl-pyrazol-3-yl]-4-(trifluoromethoxy) benzamide (0.300 g) in acetone (6 mL) were added bromomethyl acetate (0.111 g), sodium iodide (0.007 g) and N,N-diisopropyl ethylamine (0.125 g) at ambient temperature. The mixture was stirred at 70 C. for 4 h. The mixture was cooled to ambient temperature and stirred for 18 h at ambient temperature. Water was subsequently added and the mixture was extracted with EtOAc (20 ml2). The organic extracts dried over anhydrous sodium sulphate and evaporated in vacuo. The residue obtained was subjected to preperative HPLC purification, eluting with a gradient of MeCN and water to obtain the title compound as a solid (0.125 g). HPLC/MS (Method 1): Rt: 1.579 min; m/z=693 (M+1).sup.+; .sup.1H NMR (300 MHz, DMSO-d.sub.6) 11.19 (s, 1H), 9.24 (s, 1H), 8.43 (s, 1H), 8.19 (d, J=8.5 Hz, 2H), 8.12 (d, J=8.2 Hz, 2H), 8.02-7.86 (m, 2H), 7.63 (d, J=8.3 Hz, 2H), 7.26 (d, J=8.0 Hz, 1H), 7.16 (d, J=7.9 Hz, 1H), 6.99 (s, 1H), 5.65 (d, J=8.8 Hz, 2H), 3.85 (d, J=2.1 Hz, 3H), 3.24-3.04 (m, 1H), 2.29 (s, 3H), 2.03 (s, 3H), 1.16 (d, J=6.8 Hz, 6H).

    [0674] Compound: C-8: Synthesis of [(Z)N-[(E)-[4-[4-cyano-1-methyl-5-[[4-(trifluoromethoxy)benzoyl]amino]pyrazol-3-yl]phenyl]methyleneamino]-N-(2-isopropyl-5-methyl phenyl)carbamimidoyl]sulfanylmethyl 2-methylpropanoate was achieved following Step-7 of compound C-7 as mentioned previously.

    [0675] HPLC/MS (Method 1): Rt: 1.931 min; m/z=719 (M1).sup.; .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.23 (s, 1H), 9.27 (s, 1H), 8.48 (s, 1H), 8.23 (t, J=7.5 Hz, 2H), 8.17 (d, J=8.0 Hz, 1H), 7.98 (t, J=8.6 Hz, 2H), 7.75-7.85 (d, J=8.3 Hz, 1H), 7.68 (d, J=8.3 Hz, 2H), 7.30 (t, J=9.2 Hz, 1H), 7.21 (d, J=8.3 Hz, 1H), 7.03 (s, 1H), 5.72 (s, 2H), 3.90 (d, J=3.6 Hz, 3H), 3.27-3.15 (m, 1H), 2.7-2.8 (m, 1H), 2.34 (s, 3H), 1.28-1.03 (m, 12H).

    ##STR00125##

    TABLE-US-00006 TABLE C wherein i-Pr is isopropyl group. No Ar-Q [00126]embedded image [00127]embedded image HPLC/ MS Rt (min) C-1 [00128]embedded image [00129]embedded image [00130]embedded image 695 (Meth- od 1) 2.318 C-2 [00131]embedded image [00132]embedded image [00133]embedded image 698 (Meth- od 2) 1.425 C-3 [00134]embedded image [00135]embedded image [00136]embedded image 696 (Meth- od 2) 1.452 C-4 [00137]embedded image [00138]embedded image [00139]embedded image 668 (Meth- od 2) 1.374 C-5 [00140]embedded image [00141]embedded image [00142]embedded image 710 (Meth- od 2) 1.50 C-6 [00143]embedded image [00144]embedded image [00145]embedded image 724 (Meth- od 2) 1.525 C-7 [00146]embedded image [00147]embedded image [00148]embedded image 693 (Meth- od 1) 1.579 C-8 [00149]embedded image [00150]embedded image [00151]embedded image 719 (Meth- od 1) 1.931 C- 10 [00152]embedded image [00153]embedded image [00154]embedded image 730 (Meth- od 1) 2.005 C- 11 [00155]embedded image [00156]embedded image [00157]embedded image 737 (Meth- od 1) 2.176 C- 12 [00158]embedded image [00159]embedded image [00160]embedded image 744 (Meth- od 2) 1.509 C- 13 [00161]embedded image [00162]embedded image [00163]embedded image 714 (Meth- od 2) 1.512 C- 14 [00164]embedded image [00165]embedded image [00166]embedded image 716 (Meth- od 2) 1.475 C- 15 [00167]embedded image [00168]embedded image [00169]embedded image 686 (Meth- od 2) 1.416 C- 16 [00170]embedded image [00171]embedded image [00172]embedded image 736 (Meth- od 1) 2.55 C- 17 [00173]embedded image [00174]embedded image [00175]embedded image 723 (Meth- od 1) 2.59

    BIOLOGICAL EXAMPLES

    Example B1: Action on Yellow Fever Mosquito (Aedes aegypti)

    [0676] For evaluating control of yellow fever mosquito (Aedes aegypti) the test unit consisted of 96-well-microtiter plates containing 200 l of tap water per well and 5-15 freshly hatched A. aegypti larvae.

    [0677] The active compounds or mixtures were formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 l, using a custom built micro atomizer, at two replications. For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

    [0678] After application, microtiter plates were incubated at 281 C., 805% RH for 2 days. Larval mortality was then visually assessed.

    [0679] In this test, compounds C-1, C-2, C-3, C-4, C-7, C-8, C-9, C-12, C-13, C-15, C-16 at 800 ppm showed at least 50% mortality in comparison with untreated controls.

    Example B2: Action on Orchid Thrips (Dichromothrips corbetti)

    [0680] Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1:1 mixture of acetone:water (vol:vol), plus Kinetic HV at a rate of 0.01% v/v.

    [0681] Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual re-sealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28 C. for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment.

    [0682] In this test, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-12, C-13, C-14, C-15, C16, C-17 at 500 ppm showed at least 75% mortality in comparison with untreated controls.

    Example B3: Action on Boll Weevil (Anthonomus grandis)

    [0683] For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-wellmicrotiter plates containing an insect diet and 5-10 A. grandis eggs.

    [0684] The compounds were formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 l, using a custom built micro atomizer, at two replications.

    [0685] After application, microtiter plates were incubated at about 25+1 C. and about 75+5% relative humidity for 5 days. Egg and larval mortality were then visually assessed.

    [0686] In this test, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-12, C-13, C-14, C15, C-16, C-17 at 800 ppm showed at least 75% mortality in comparison with untreated controls.

    Example B4: Action on Silverleaf Whitefly (Bemisia argentifolii) (Adults)

    [0687] The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions 50 were made by the Tecan in 50% acetone:50% water (v/v) into 5 or 10 ml glass vials. A non-ionic surfactant (Kinetic) was included in the solution at a volume of 0.01% (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.

    [0688] Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and about 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and a nontoxic Tygon tubing connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid. Test plants were maintained in a growth room at about 25 C. and about 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.

    [0689] In this test, compounds C-1, C-2, C-3, C-4, C-5 at 300 ppm showed at least 75% mortality in comparison with untreated controls.

    Example B5: Action on Tobacco Budworm (Heliothis virescens)

    [0690] For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

    [0691] The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 l, using a custom-built micro atomizer, at two replications.

    [0692] After application, microtiter plates were incubated at about 28+1 C. and about 80+5% relative humidity for 5 days. Egg and larval mortality were then visually assessed.

    [0693] In this test, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11, C-12, C-13, C14, C-15, C-16, C-17 at 800 ppm showed at least 75% mortality in comparison with untreated controls.

    Example B6: Action on Diamond Back Moth (Plutella xylostella)

    [0694] The active compound is dissolved at the desired concentration in a mixture of 1:1 (v/v) distilled water:acetone. Surfactant (Kinetic HV) is added at a rate of 0.01% (v/v). The test solution is prepared at the day of use.

    [0695] Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0-100%.

    [0696] In this test, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-12, C-13, C-14, C15, C-16, C-17 at 500 ppm showed at least 75% mortality in comparison with untreated controls.

    Example B7: Action on Southern Armyworm (Spodoptera eridania), 2nd Instar Larvae

    [0697] The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 10 or 20 ml glass vials. A nonionic surfactant (Kinetic) was included in the solution at a volume of 0.01% (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.

    [0698] Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. About 10 to 11 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25 C. and about 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.

    [0699] In this test, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-11, C-12, C-13, C14, C-15, C-16, C-17 at 300 ppm showed at least 75% mortality in comparison with untreated controls.