Insecticidal compounds

Abstract

The present invention relates to novel triazole derivatives of formula (I) having insecticidal activity, to processes and intermediates for preparing them, to insecticidal, acaricidal, nematicidal or molluscicidal compositions comprising them and to methods of using them to combat and control insect, acarine, nematode or mollusc pests; wherein R.sup.1, R.sup.2, G.sup.1, G.sup.2, Q.sup.1 and Q.sup.2 are as defined in claim 1; or salts thereof. ##STR00001##

Claims

1. A compound of formula (I) ##STR00068## wherein Q.sup.1 is 4-cyano-phenyl; Q.sup.2 is a moiety of formula (II) ##STR00069## wherein Y.sup.1 and Y.sup.5 are each independently Cl, Br, I, methyl, trifluoromethyl, ethyl, methoxy, trifluoromethoxy, trifluoromethylthio or methoxymethyl, and Y.sup.3 is heptafluoroprop-2-yl; R.sup.1 is C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8alkynyl, C.sub.1-C.sub.8alkylcarbonyl, C.sub.1-C.sub.8alkoxycarbonyl, hydroxyl, C.sub.1-C.sub.8alkyloxy, or aminocarbonyl-C.sub.1-C.sub.4alkylene; R.sup.2 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8alkynyl, C.sub.1-C.sub.8alkylcarbonyl, C.sub.1-C.sub.8alkoxycarbonyl, hydroxyl, C.sub.1-C.sub.8alkyloxy, or aminocarbonyl-C.sub.1-C.sub.4alkylene; and G.sup.1 and G.sup.2 are both oxygen; or an agrochemically acceptable salt thereof.

2. A compound of formula (I) according to claim 1 characterized in that Q.sup.1 is 4-cyano-phenyl; Y.sup.1 is Cl, Br, I, methyl, trifluoromethyl, ethyl, methoxy, trifluoromethoxy, trifluoromethylthio or methoxymethyl; Y.sup.5 is Cl, Br, I, methyl, trifluoromethyl, ethyl, methoxy, trifluoromethoxy, trifluoromethylthio or methoxymethyl; Y.sup.3 is heptafluoroprop-2-yl; R.sup.1 is C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkenyl; R.sup.2 is hydrogen, C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.8alkenyl; and G.sup.1 and G.sup.2 are both oxygen.

3. A compound of formula (I) according to claim 1 characterized in that Q.sup.1 is 4-cyano-phenyl; Y.sup.1 is Cl, Br, I, methyl or ethyl; Y.sup.5 is Cl, Br, I, methyl or ethyl; Y.sup.3 is heptafluoroprop-2-yl; R.sup.1 is C.sub.2-C.sub.4alkyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4alkyl; and G.sup.1 and G.sup.2 are both oxygen.

4. A compound of formula (I) according to claim 1 characterized in that Q.sup.1 is 4-cyano-phenyl; Y.sup.1 is Cl, Br, methyl or ethyl; Y.sup.5 is Cl, Br, methyl or ethyl; Y.sup.3 is heptafluoroprop-2-yl; R.sup.1 is C.sub.2-C.sub.4alkyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4alkyl; and G.sup.1 and G.sup.2 are both oxygen.

5. A compound of formula (I) according to claim 4 characterized in that Q.sup.1 is 4-cyano-phenyl; Y.sup.1 is Cl, Br, methyl, ethyl; Y.sup.5 is Cl, Br, methyl, ethyl; Y.sup.3 is heptafluoroprop-2-yl; R.sup.1 is ethyl; R.sup.2 is hydrogen, methyl, ethyl; and G.sup.1 and G.sup.2 are both oxygen.

6. A method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1.

7. An insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1 together with an agrochemically acceptable diluent or carrier.

8. A composition according to claim 7 which further comprises one or more additional insecticidal, acaricidal, nematicidal or molluscicidal compounds.

9. A method of protecting plants from insects, acarines, nematodes or molluscs, comprising applying to said plants, to the locus thereof, or to plant propagation material thereof, an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula I of claim 1.

10. A compound of formula (I) according to claim 5 characterized in that Y.sup.1 is Cl or Br; Y.sup.5 is Cl or Br; and R.sup.2 is hydrogen.

11. A compound of formula (I) according to claim 10 characterized in that Y.sup.1 is Cl; and Y.sup.5 is Br.

Description

PREPARATION EXAMPLES

Examples

(1) The following abbreviations were used throughout this section: s=singlet; bs=broad singlet; d=doublet; dd=double doublet; dt=double triplet; t=triplet, tt=triple triplet, q=quartet, sept=septet; m=multiplet; Me=methyl; Et=ethyl; Pr=propyl; Bu=butyl; M.p.=melting point.

Example I 1.1: N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-fluoro-3-nitro-benzamide

(2) ##STR00036##

(3) To a suspension of 2-fluoro-3-nitrobenzoic acid (309 g, 1.67 mol) in dichloroethane (2090 ml) was added N,N-dimethylformamide (1.3 ml, 16.7 mmol) followed by slow addition of oxalyl chloride (150 ml, 1.69 mol) at ambient temperature. The reaction mixture was stirred and heated at 50° C. until a solution was formed. The reaction mixture was allowed to cool to ambient temperature and then added to a solution of 2-bromo-6-chloro-4-[1,1,1,2,3,3,3-heptafluoro-prop-2-yl]aniline (described in WO/10127926) (125 g, 334 mmol) in dichloroethane (477 ml) followed by addition of triethylamine (564 ml, 4.01 mol). The reaction mixture was stirred at reflux for 4 hours. The reaction was quenched by addition of saturated aqueous sodium hydrogen carbonate (500 ml). The layers were separated and the organic layer was washed with water (500 ml). The combined aqueous layers were extracted twice with dichloroethane (2×500 ml). The combined organic extracts were dried over sodium sulfate and concentrated. The crude residue was dissolved in THF and a 1N solution of sodium hydroxide (2 eq) was added. The mixture was stirred at room temperature until the diacylated product disappeared. Then ethyl acetate (1 L) and saturated aqueous sodium hydrogen carbonate (1 L) were added. The layers were separated and the aqueous layer was extracted with ethyl acetate (4×250 ml). The organic layer was concentrated, filtered through silica gel, and concentrated again. The residue (181 g) was used directly for the next step.

(4) .sup.1H NMR (CDCl.sub.3, 400 MHz): 8.39 (m, 1H), 8.21 (m, 1H), 8.09 (d, 1H), 7.78 (s, 1H), 7.67 (s, 1H), 7.43 (t, 1H).

Example I 2.1: N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-methoxy-3-nitro-benzamide

(5) ##STR00037##

(6) To a solution of N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-fluoro-3-nitro-benzamide (Example I 1.1) (181 g, 334 mmol) in methanol (2 L) was added potassium carbonate (233 g, 1.67 mol) at ambient temperature. The reaction mixture was stirred for 13.5 hours at ambient temperature. The reaction mixture was concentrated and the residue was dissolved in ethylacetate (1 L). Then saturated aqueous sodium hydrogen carbonate (500 ml) and water (500 ml) were added. The layers were separated and the aqueous layer was extracted with ethyl acetate (4×250 ml). The combined organic layers were concentrated. The residue was recrystallized from methanol-water to give N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-methoxy-3-nitro-benzamide (138 g, 75% yield). .sup.1H NMR (400 MHz, CDCl.sub.3): 9.21 (bs, 1H), 8.46 (d, 1H), 8.09 (d, 1H), 7.88 (s, 1H), 7.75 (s, 1H), 7.48 (t, 1H), 4.19 (s, 3H) ppm.

(7) The following compounds were made by the the same or similar procedures:

Example I 2.2: N-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-methoxy-3-nitrobenzamide

(8) ##STR00038##

(9) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.21 (bs, 1H), 8.42 (dd, 1H), 8.07 (dd, 1H), 7.68 (s, 2H), 7.44 (t, 1H), 4.14 (s, 3H) ppm.

Example I 2.3: N-[2,6-dimethyl-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-methoxy-3-nitrobenzamide

(10) ##STR00039##

(11) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.72 (bs, 1H), 8.34 (dd, 1H), 7.97 (dd, 1H), 7.47 (t, 1H), 7.31 (s, 2H), 4.03 (s, 3H), 2.30 (s, 6H) ppm.

Example I 2.4: N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-6-methyl-phenyl]-2-methoxy-3-nitrobenzamide

(12) ##STR00040##

(13) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.88 (bs, 1H), 8.46 (dd, 1H), 8.07 (dd, 1H), 7.45 (t, 1H), 7.42 (s, 2H), 4.13 (s, 3H), 2.73 (q, 2H), 2.39 (s, 3H), 1.26 (t, 3H) ppm.

Example I 3.1: 3-Amino-N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide

(14) ##STR00041##

(15) N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-methoxy-3-nitro-benzamide (20 g, 36.1 mmol) was dissolved in THF (300 ml). Then NaOH (90 ml), tetrabutylammonium bromide (1.2 g, 3.6 mmol) and sodium dithionite (18.9 g, 108.4 mmol) were added. The mixture was heated under reflux for four hours and then cooled down to room temperature. The reaction mixture was diluted with ethyl acetate, water was added and the phases were separated. The organic phase was washed with aqueous solution of sodium hydrogen carbonate, dried over sodium sulfate, filtered and concentrated. Flashchromatography (eluent: acetone/heptane 20:80) gave 3-amino-N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide (10.9 g, 57.6% yield).

(16) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.55 (bs, 1H), 7.84 (s, 1H), 7.61 (dd, 1H), 7.12 (t, 1H), 7.03 (dd, 1H), 4.35 (bs, 2H), 4.02 (s, 3H), ppm.

(17) The following compounds were made by the same or similar procedure:

Example I 3.2: 3-Amino-N-[2,6-dimethyl-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-methoxy-benzamide

(18) ##STR00042##

(19) .sup.1H NMR (400 MHz, DMSO): 9.73 (s, 1H), 7.41 (s, 2H), 6.93 (t, 1H), 6.84 (dd, 1H), 6.78 (dd, 1H), 5.15 (bs, 2H), 3.72 (s, 3H), 2.32 (s, 6H) ppm.

Example I 3.3: 3-Amino-N-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-6-methyl-phenyl]-2-methoxy-benzamide

(20) ##STR00043##

(21) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.11 (s, 1H), 7.63 (d, 1H), 7.39 (s, 2H), 7.13 (t, 1H), 7.08 (d, 1H), 4.7 (bs, 2H), 3.99 (s, 3H), 2.73 (q, 2H), 2.38 (s, 3H), 1.24 (t, 3H) ppm.

Example I 3.4: 3-Amino-N-[2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)phenyl]-2-methoxy-benzamide

(22) ##STR00044##

(23) .sup.1H NMR (400 MHz, DMSO): 9.57 (s, 1H), 7.89 (s, 2H), 7.60 (dd, 1H), 7.12 (t, 1H), 7.0 (dd, 1H), 4.04 (s, 3H), 3.97 (bs, 2H) ppm.

Example I 4.1: 3-N-(ethylamino)-N′-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide

(24) ##STR00045##

(25) 3-amino-N-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide (1.00 g, 1.91 mmol) was dissolved in methanol (13.6 ml) and acetaldehyde (0.107 ml, 1.91 mmol) and acetic acid (0.12 ml, 2.10 mmol) were added. Then cyanoborohydride (0.132 g, 2.10 mmol) was added in small portions. The reaction mixture was stirred for 1 hour at room temperature. After evaporation of the solvent ethyl acetate and an aqueous solution of sodium hydroxide (0.1M) were added. The layers were separated and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and concentrated. The residue was purified by flash chromatography (eluent: cyclohexane/ethyl acetate 100:0=>60:40) to give 3-N-(ethylamino)-N′-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide (0.969 g, 92%).

(26) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.39 (bs, 1H), 7.73 (s, 1H), 7.62 (s, 1H), 7.40 (d, 1H), 7.09 (t, 1H), 6.83 (bd, 1H), 4.35 (bs, 1H), 3.79 (s, 3H), 3.15 (q, 2H), 1.25 (t, 3H) ppm.

(27) The following compounds were made by the same or similar procedure:

Example I 4.2: 3-N-(ethylamino)-N′-[2,6-dichloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide

(28) ##STR00046##

(29) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.46 (bs, 1H), 7.68 (s, 2H), 7.51 (bd, 1H), 7.20 (t, 1H), 6.98 (bs, 1H), 4.40 (bs, 1H), 4.00 (s, 3H), 3.28 (q, 2H), 1.36 (t, 3H) ppm.

Example I 4.3: 3-N-(ethylamino)-N′-[2-ethyl-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-6-methyl-phenyl]-2-methoxybenzamide

(30) ##STR00047##

(31) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.0 (bs, 1H), 7.55 (bd, 1H), 7.38-7.42 (m, 2H), 7.22 (t, 1H), 6.05 (bs, 1H), 4.40 (bs, 1H), 4.00 (s, 3H), 3.28 (q, 2H), 2.73 (q, 2H), 2.39 (s, 3H), 1.38 (t, 3H), 1.25 (t, 3H) ppm.

Example I 4.5: 3-N-(ethylamino)-N′-[2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide

(32) ##STR00048##

(33) .sup.1H NMR (400 MHz, CDCl.sub.3): 9.50 (bs, 1H), 7.88 (s, 2H), 7.52 (d, 1H), 7.19 (t, 1H), 6.94 (bd, 1H), 4.40 (bs, 1H), 4.00 (s, 3H), 3.25 (m, 2H), 1.36 (t, 3H) ppm.

Example II 1.1: Methyl 3-(ethylamino)-2-methoxy-benzoate

(34) ##STR00049##

(35) A pressure vial was charged with Pd/C (10%, 0.021 g) and 2-propanol (3.4 ml). A solution of ammonium formiate (0.452 g, 7.10 mmol) in water (0.35 ml) was added and the resulting mixture was stirred for 5 min. Methyl 2-methoxy-3-nitro-benzoate (0.100 g, 0.473 mmol) was added and the reaction media was cooled to 0 C. Acetaldehyde (0.105 g, 2.37 mmol) was added and the reaction media was stirred for 16 h at ambient temperature. The reaction mixture was filtered through a short pad of celite and filtrate was evaporated under reduced pressure. The residue was dissolved in dichloromethane and washed with brine. Organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was further purified by column chromatography on silica gel (eluent: 0-30% EtOAc in cyclohexane) to give methyl 3-(ethylamino)-2-methoxy-benzoate (0.0839 g, 85%) as a beige oil. .sup.1H NMR (400 MHz, CDCl.sub.3): 7.09 (dd, 1H), 7.01 (t, 1H), 6.77 (dd, 1H), 4.30 (bs, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 3.16 (q, 2H), 1.27 (t, 3H) ppm.

Example II 2.1: Methyl 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoate

(36) ##STR00050##

(37) To a solution of methyl 3-(ethylamino)-2-methoxy-benzoate (0.158 g, 0.754 mmol) in dichloromethane (2.6 ml) was added triethylamine (0.233 ml, 1.66 mmol) followed by 4-cyanobenzoyl chloride (0.140 g, 0.829 mmol). After stirring at ambient temperature for 16 h the reaction was quenched by addition of saturated aqueous NH.sub.4Cl. The mixture was extracted with dichloromethane (2×) and organic layers were washed with brine, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The residue was further purified by column chromatography on silica gel (eluent: 0-40% EtOAc in cyclohexane) to give methyl 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoate (0.207 g, 81%) as a beige gum.

(38) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.77-7.58 (m, 1H), 7.55-7.35 (m, 4H), 7.32-7.20 (m, 1H), 7.12-6.99 (m, 1H), 4.20 (bs, 1H), 3.88 (s, 3H), 3.83 (s, 3H), 3.73-3.61 (m, 1H), 1.33-1.21 (m, 3H) ppm

Example II 2.2: Methyl 3-[(4-cyanobenzoyl)amino]-2-methoxy-benzoate

(39) ##STR00051##

(40) To a solution of methyl 3-amino-2-methoxy-benzoate (0.750 g, 4.14 mmol) in dichloromethane (14 ml) was added triethylamine (1.28 ml, 9.11 mmol) followed by 4-cyanobenzoyl chloride (0.769 g, 4.55 mmol). The reaction mixture was stirred at 40 C for 3 h before being quenched by addition of aqueous saturated NH.sub.4Cl. Aqueous phase was extracted with dichloromethane (2×), combined organic phases were dried over anhydrous Na.sub.z SO.sub.4 and evaporated under reduced pressure. The residue was further purified by column chromatography on silica gel (eluent: 0-30% EtOAc in cyclohexane) to give methyl 3-[(4-cyanobenzoyl)amino]-2-methoxy-benzoate (0.862 g, 67%) as a white solid.

(41) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.71-8.65 (m, 2H), 8.01-7.97 (m, 2H), 7.84-7.81 (m, 2H), 7.64 (dd, 1H), 7.23 (t, 1H), 3.95 (s, 3H), 3.95 (s, 3H) ppm

Example II 2.3: Methyl 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoate

(42) ##STR00052##

(43) To a solution of methyl 3-[(4-cyanobenzoyl)amino]-2-methoxy-benzoate (0.0752 g, 0.242 mmol) in DMF (0.85 ml) was added K.sub.2CO.sub.3 (0.152 g, 1.09 mmol) followed by ethyl bromide (0.0804 ml, 1.07 mmol) and catalytic amount of tetrabutylamonium iodide. The resulting mixture was stirred at 75 C for 48 h. The reaction was quenched by addition of aqueous saturated NH.sub.4Cl. The mixture was extracted with dichloromethane, combined organic layers were washed with brine, dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure. The residue was further purified by column chromatography on silica gel (eluent: 0-40% EtOAc in cyclohexane) to give methyl 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoate (0.0686 g, 84%) as a beige gum.

Example II 3.1: 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoic acid

(44) ##STR00053##

(45) To a solution of 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoate (0.120 g, 0.354 mmol) in MeOH (1.2 ml) was added 5M NaOH (0.142 ml, 0.707 mmol). The reaction mixture was stirred for 1.5 h at ambient temperature before being quenched by addition of aqueous saturated NH.sub.4Cl. The mixture was extracted with dichloromethane (3×), combined organic layers were washed with brine, dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure to obtain 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoic acid (0.0827 g, 72%) as a white solid sufficiently pure for further chemistry.

(46) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.98-7-78 (m, 1H), 7.68-7.29 (m, 5H), 7.25-7.10 (m, 1H), 4.30 (bs, 1H), 3.91 (s, 3H), 3.71-3.57 (m, 1H), 1.42-1.19 (m, 3H) ppm

Example P1.1: N-[2-bromo-6-chloro-4-[1,1,1,2,3,3,3-heptafluoro-prop-2-yl]phenyl]-3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzamide (Compound No. 1 of Table A)

(47) ##STR00054##

(48) 3-N-(ethylamino)-N′-[2-bromo-6-chloro-4-(1,1,1,2,3,3,3-heptafluoro-prop-2-yl)-phenyl]-2-methoxybenzamide (Example I 4.1) (150 mg, 0.272 mmol) was dissolved in tetrahydrofuran (2 ml). Pyridine (0.066 ml, 0.816 mmol) and 4-cyanobenzoyl chloride (90 mg, 0.544 mmol) were added and the reaction mixture was stirred at ambient temperature for 1.5 hours. The reaction mixture was poured into aqueous sodium hydrogen carbonate, the phases were separated and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered and concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 0/100=>50:50). The fractions containing the desired product were combined and the solvents were evaporated. The residue was further purified by column chromatography on silica gel (eluent: CH.sub.2Cl.sub.2/Methyltbutylether 95:5). The fractions containing the desired product were combined and the solvents were evaporated to gave pure Compound No. 1 of Table A (148 mg, 80% yield). .sup.1H NMR (400 MHz, CDCl.sub.3): 8.78 (bs, 1H), 8.04 (d, 1H), 7.81 (s, 1H), 7.70 (s, 1H), 7.55 (d, 1H), 7.40-7.55 (m, 4H), 7.43 (t, 1H), 4.34-4.48 (m, 1H), 3.96 (s, 3H), 3.67-3.80 (m, 1H), 1.48 (t, 3H) ppm.

Example P1.2: N-[2-bromo-6-chloro-4-[1,1,1,2,3,3,3-heptafluoro-prop-2-yl]phenyl]-3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzamide (Compound No. 1 of Table A)

(49) ##STR00055##

(50) To a solution of 3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzoic acid (0.150 g, 0.462 mmol) in dichloroethane (0.92 ml) was added one drop of DMF followed by a slow addition of oxalyl chloride (0.0409 ml, 0.467 mmol). The reaction mixture was stirred at room temperature for 2 h before addition of a solution of 2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline (0.150 g, 0.400 mmol) in dichloroethane (0.80 ml). Triethylamine (0.140 ml. 1.00 mmol) was added and the reaction mixture was stirred at 75 C for 16 h. The reaction was quenched by addition of saturated aqueous NaHCO.sub.3, the aqueous layer was extracted with CH.sub.2Cl.sub.2 (2×), the combined organic layers were dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure. The residue was further purified by column chromatography on silica gel (eluent: 10-50% EtOAc in cyclohexane) to give N-[2-bromo-6-chloro-4-[1,1,1,2,3,3,3-heptafluoro-prop-2-yl]phenyl]-3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzamide (0.019 g, 7%) as a white solid.

(51) The compounds in tables A were prepared in the same or a similar way as described above:

(52) TABLE-US-00003 TABLE A [M + H] LC-MS No. STRUCTURE RT (min) (measured) Method MP ° C.  1 94-96  2 97-99  3 86-87  4 187-189  5 0 97-99  6 188-189  7 84-86  8  97-107  9 72-76 10  84-100 11 1.16 616, 618 ZDQ13 12 1.19 630, 632 ZDQ13
LC-MS Method: ZDQ13

(53) ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

(54) Instrument Parameter: Ionization method: Electrospray Polarity: positive and negative ions Capillary: 3.00 kV Cone: 30 V Extractor: 2.00 V Source Temperature: 150° C., Desolvation Temperature: 350 C Cone Gas Flow: 50 L/Hr Desolvation Gas Flow: 400 L/Hr Mass range: 100 to 900 Da
Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μM, 30×2.1 mm, Temp: 60° C. DAD Wavelength range (nm): 210 to 500 Solvent Gradient: A=H2O+5% MeOH+0.05% HCOOH B=Acetonitril+0.05% HCOOH

(55) TABLE-US-00004 Time A % B % Flow (ml/min) 0.00 90 10 0.85 1.20 0 100.0 0.85 1.50 0 100.0 0.85

BIOLOGICAL EXAMPLES

(56) These Examples illustrate the insecticidal and acaricidal properties of the compounds of formula (I). The tests were performed as follows:

(57) Spodoptera littoralis (Egyptian Cotton Leafworm):

(58) Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with 5 L1 larvae. The samples were checked for mortality, feeding behavior, and growth regulation 3 days after treatment (DAT).

(59) The following compound gave at least 80% control of Spodoptera littoralis: 1, 2, 3, 4, 5, 6, 7, 9, 10, 11, 12.

(60) Heliothis virescens (Tobacco Budworm):

(61) Eggs (0-24 h old) were placed in 24-well microtiter plate on artificial diet and treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After an incubation period of 4 days, samples were checked for egg mortality, larval mortality, and growth regulation.

(62) The following compound gave at least 80% control of Heliothis virescens: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

(63) Plutella xylostella (Diamond Back Moth):

(64) 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After drying, the MTP's were infested with L2 larvae (7-12 per well). After an incubation period of 6 days, samples were checked for larval mortality and growth regulation.

(65) The following compound gave at least 80% control of Plutella xylostella: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

(66) Diabrotica balteata (Corn Root Worm):

(67) A 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After drying, the MTP's were infested with L2 larvae (6-10 per well). After an incubation period of 5 days, samples were checked for larval mortality and growth regulation.

(68) The following compound gave at least 80% control of Diabrotica balteata: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

(69) Thrips tabaci (Onion Thrips):

(70) Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 7 days, samples were checked for mortality.

(71) The following compounds gave at least 80% control of Thrips tabaci: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

(72) Tetranychus urticae (Two-Spotted Spider Mite):

(73) Bean leaf discs on agar in 24-well microtiter plates were sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality.

(74) The following compounds gave at least 80% control of Tetranychus urticae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

(75) Myzus persicae (Green Peach Aphid):

(76) Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 6 DAT, samples were checked for mortality.

(77) The following compounds gave at least 80% control of Myzus persicae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

(78) Aedes aegypti (Yellow Fever Mosquito):

(79) Test solutions, at an application rate of 200 ppm in ethanol, were applied to 12 well tissue culture plates. Once the deposits were dry, five, two to five day old adult female Aedes aegypti were added to each well, and sustained with a 10% sucrose solution in a cotton wool plug. Assessment of knockdown was made one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction.

(80) None of the prepared examples described in the table showed knockdown activity after one hour. The following compounds gave at least 80% control of Aedes aegypti after 48 h and/or 24 h: 1, 2, 3, 4, 5, 6, 7. The compounds 8 to 12 were not tested against Aedes aegypti (Yellow fever mosquito).

(81) Anopheles stephensi (Indian Malaria Mosquito):

(82) Test solutions, at an application rate of 200 ppm in ethanol, were applied to 12 well tissue culture plates. Once the deposits were dry, five, two to five day old adult female Anopheles stephensi were added to each well, and sustained with a 10% sucrose solution in a cotton wool plug. Assessment of knockdown was made one hour after introduction, and mortality was assessed at 24 and 48 hours after introduction.

(83) None of the prepared examples described in the table showed knockdown activity after one hour. The following compounds gave at least 80% control of Anopheles stephensi after 48 h and/or 24 h: 1, 2, 4, 5, 6, 7. The compounds 8 to 12 were not tested against Anopheles stephensi (Indian malaria mosquito).