Insecticidal compounds

Abstract

The present invention relates to novel bisamide 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 ##STR00001##
wherein X.sub.0, X.sub.1, X.sub.2, Y.sub.1, Y.sub.2, R.sub.1, R.sub.2, G.sub.1 and G.sub.2, and Q are as described in formula 1 or salts and n-Oxides thereof.

Claims

1. A compound of formula (I) ##STR00102## wherein X.sub.0 is bromo, chloro or hydrogen; X.sub.1 is methoxy.[.;.]. .Iadd.and .Iaddend.X.sub.2 is hydrogen.[.;.]..Iadd., or X.sub.1 is hydrogen and X.sub.2 is cyano; .Iaddend. Y.sub.1 and Y.sub.2 are independently .Iadd.of each other .Iaddend.chloro, bromo, iodo, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, .[.and.]. .Iadd.or .Iaddend.C.sub.1-C.sub.4haloalkoxy; R.sub.1 and R.sub.2 are .[.independent.]. .Iadd.independently .Iaddend.of one another 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.8-alkyloxy, .[.and.]. .Iadd.or .Iaddend.aminocarbonyl-C.sub.1-C.sub.4alkylene; G.sub.1 and G.sub.2 are .[.independent.]. .Iadd.independently .Iaddend.of each other oxygen or sulfur; Q is a group selected from .Iadd.Q1, .Iaddend.Q2, Q3, Q4 and Q5, where .Iadd.Q1 is a group of formula (IIa) ##STR00103## where the substituents W1 are independently selected from halogen, cyano, and C.sub.1 alkyl, and n1 is 2, .Iaddend. Q2 is a group of formula (IIb) ##STR00104## where W.sub.2 is selected from.[.,.]. hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy or C.sub.1-C.sub.4 haloalkoxy, Q3 is a group of formula (IIc) ##STR00105## where W.sub.3 is selected from.[.,.]. hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy or C.sub.1-C.sub.4 haloalkoxy, Q4 is a group of formula (IId) ##STR00106## where W.sub.4 is selected.[.,.]. .Iadd.from .Iaddend.hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy or C.sub.1-C.sub.4 haloalkoxy, Q5 is a group of formula (IIe) ##STR00107## where W.sub.5 is selected from hydrogen, halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C4 alkoxy or C.sub.1-C.sub.4 haloalkoxy.

2. .[.A.]. .Iadd.The .Iaddend.compound of formula (I) according to claim 1 wherein Y.sub.1 and Y.sub.2 are selected from Cl, Br, I, methyl, ethyl, methoxy, difluoromethoxy, and trifluoromethoxy.[.,.]..Iadd.; .Iaddend. X.sub.0 is hydrogen .[.or Br.]..Iadd., bromo, .Iaddend.or .[.Cl.]. .Iadd.chloro; .Iaddend. R.sub.1 is selected from hydrogen or C.sub.1-C.sub.2alkyl; R.sub.2 is selected from hydrogen, C.sub.1-C.sub.2alkyl; and G.sup.1 and G.sup.2 are both oxygen.

3. A compound of formula (III) ##STR00108## wherein .[.X.sub.0, Y.sub.1, Y.sub.2, X.sub.1, X.sub.2, R.sub.1, and R.sub.2 are as defined in formula (I) of claim 1.]. .Iadd.X.sub.0 is bromo, chloro or hydrogen; X.sub.1 is methoxy and X.sub.2 is hydrogen, or X.sub.1 is hydrogen and X.sub.2 is cyano; Y.sub.1 and Y.sub.2 are independently of each other chloro, bromo, iodo, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, or C.sub.1-C.sub.4haloalkoxy; R.sub.1 and R.sub.2 are independently of one another 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.8-alkyloxy, or aminocarbonyl-C.sub.1-C.sub.4alkylene; and G.sub.2 is oxygen or sulfur.Iaddend..

4. 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.

5. 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.

6. A composition according to claim 5 which further comprises one or more additional insecticidal, acaricidal, nematicidal or molluscicidal compounds.

7. A method of protecting useful 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 in claim 1.

.Iadd.8. The compound of formula (I) according to claim 1 wherein Q is Q1..Iaddend.

.Iadd.9. The compound of formula (I) according to claim 8 wherein Q1 is a group of formula (IIa) ##STR00109## where the substituents W1 are independently selected from, cyano and C.sub.1 alkyl, and n1 is 2..Iaddend.

.Iadd.10. The compound of formula (I) according to claim 9 wherein X.sub.1 is hydrogen and X.sub.2 is cyano..Iaddend.

.Iadd.11. The compound of formula (I) according to claim 8 wherein X.sub.1 is hydrogen and X.sub.2 is cyano..Iaddend.

.Iadd.12. The compound of formula (I) according to claim 1 wherein Q is Q2..Iaddend.

.Iadd.13. The compound of formula (I) according to claim 1 wherein Q is Q3..Iaddend.

.Iadd.14. The compound of formula (I) according to claim 1 wherein Q is Q4..Iaddend.

.Iadd.15. The compound of formula (I) according to claim 1 wherein Q is Q5..Iaddend.

.Iadd.16. The compound of formula (I) according to claim 1 wherein Y.sub.1 and Y.sub.2 are selected from chloro, bromo, ethyl, methoxy and difluoromethoxy..Iaddend.

.Iadd.17. The compound of formula (I) according to claim 1 wherein X.sub.0 is bromo or chloro..Iaddend.

.Iadd.18. The compound of formula (I) according to claim 1 wherein X.sub.0 is bromo..Iaddend.

.Iadd.19. A compound selected from ##STR00110## ##STR00111## .Iaddend.

.Iadd.20. The compound of claim 19, wherein the compound is ##STR00112## .Iaddend.

.Iadd.21. The compound of claim 19, wherein the compound is ##STR00113## .Iaddend.

.Iadd.22. The compound of claim 19, wherein the compound is ##STR00114## .Iaddend.

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; EtOAc=Ethyl acetate; TBME=tert-butyl methyl ether

Example P1: N-[3-[[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]carbamoyl]-2-methoxy-phenyl]pyridine-4-carboxamide (Entry 3 of Table B)

(2) ##STR00030##

Step 1: 4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]aniline

(3) ##STR00031##

(4) Aniline (40 g, 425 mmol) was dissolved in 670 ml TBME and 470 ml water. and treated with sodium dithionite (102 g, 510 mmol), tetrabutylammonium hydrogen sulphate (11.6 g, 34 mmol), and Sodium bicarbonate (42.9 g, 510 mmol, 1.2 eq.). The yellow emulsion was treated drop wise with 1,2-Dibromo-1,1,2,3,3,3-hexafluoro-propane (72.9 ml, 510 mmol, prepared as described in Eur. Pat. Appl., 1418163) keeping the temperature below 250° C. during vigorous stirring. After the addition the reaction was allowed to stir for a further 3 hr, the organic phase separated and the water phase back extracted with (×3) with tert-butyl methyl ether. The combined organic phases were washed with brine, dried over anhydrous MgSO.sub.4, filtrated and concentrated in vacuo to give 46 g (33%) of the title compound as dark brownish oil that was used in the next step without further purification.

(5) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 7.36-7.43 (d, J=8.4 Hz, 1H); 6.78 (d, J=8.4 Hz, 1H); 4.14 (br. s., 2H)

Step 2: 2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]aniline

(6) ##STR00032##

(7) 4-[1-[Bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]aniline (46.0 g, 136 mmol) was dissolved in DMF (370 ml) and treated portion wise with N-bromosuccinimide (25.1 g, 138 mmol) whilst keeping the reaction temperature below 30° C. The mixture was allowed to stir at rt until TLC analysis after 3 hr showed reaction completion. The reaction mixture was diluted with TBME and water, the organic phase separated, and the aqueous phase back extracted with 2×100 ml tert-butyl methyl ether. The combined organic phases were washed with water, brine, dried over Na.sub.2SO.sub.4, filtrated and concentrated in vacuo. This gave 62 g of the title compound (containing a small amount of DMF) as a brown oil that was used in the next step without further purification.

(8) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 7.64 (s, 1H); 7.32 (d, J=8.4 Hz, 1H); 6.81 (d, J=8.4 Hz, 1H); 3.36 (br s. 2H).

Step 3: 2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-aniline

(9) ##STR00033##

(10) A solution of 2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]aniline (62 g, 139 mmol) in DMF (450 ml) was treated with N-chlorosuccinimide (19.9 g, 146 mmol) and the mixture was heated to 70° C. LCMS after 2 hr showed reaction completion. The reaction mixture was diluted with TBME and water, the organic phase separated, and the aqueous phase back extracted with 2×100 ml TBME. The combined organic phases were washed with water, brine, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo to give 59.2 g of a brown oil that was purified over a silica gel cartridge (Torrent) eluting with 100:0.fwdarw.50:50 heptane/EtOAc. This gave the title compound (46 g, 76%) as a pale brown oil.

(11) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 7.60 (s, 1H); 7.46 (s, 1H); 4.78 (br. s., 2H).

Step 4: N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-2-fluoro-3-nitro-benzamide

(12) ##STR00034##

(13) A solution of 2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-aniline (46 g, 104 mmol) and potassium iodide (4.3 g, 25.9 mmol) were dissolved in acetonitrile (460 ml). To this solution was added 2-fluoro-3-nitro-benzoyl chloride (45.8 g, 207 mmol, prepared as described in J. Amer. Chem. Soc, 135(26), 9675, 2013) and the mixture heated to 82° C. over night. LCMS after this time showed reaction completion. The mixture was diluted with 400 ml dichloromethane, quenched with NaHSO.sub.3 sol. and extracted with 2×250 ml dichloromethane. The combined organic layers were washed with brine, dried over Na.sub.2SO.sub.4, filtrated and evaporated to give 86 g of crude product as a yellow resin. Purification over silica gel cartridge (Torrent) eluting with Heptane/EtOAc 100:0.fwdarw.50:50 gave 62 g (100%) of the title compound as pale yellow crystals.

(14) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.44-8.54 (m, 1H); 8.28 (td, J=7.7, 1.8 Hz, 1H), 8.14 (d, J=12.1 Hz, 1H); 7.86 (s, 1H), 7.74 (s, 1H), 7.53 (t, J=8.1 Hz, 1H).

(15) LCMS: (Method ZDQ13): 599, 601 (M+H), 603, retention time 1.17 min.

Step 5: N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-2-methoxy-3-nitro-benzamide

(16) ##STR00035##

(17) A solution of N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-2-fluoro-3-nitro-benzamide (62 g, 102 mmol) was dissolved in MeOH (450 ml) and treated with a solution of sodium methoxide in methanol (5.4 mol/L, 29 ml, 158 mmol) at rt. The mixture was allowed to stir at rt until LCMS/TLC showed reaction completion. The reaction mixture was diluted with 100 ml of water and stirred for 6 hr at rt. Then the mixture was evaporated, the residue was dissolved in EtOAc, and the EtOAc solution washed with brine, the organic layer dried over Na.sub.2SO.sub.4, filtered, and concentrated in vacuo. The crude product was used in the next step without further purification.

(18) .sup.1H NMR (CDCl.sub.3, 400 MHz): δ (ppm) 9.22 (s, 1H); 8.45 (dd, J=7.7, 1.8 Hz, 1H); 8.08 (dd, J=8.1, 1.8 Hz, 1H); 7.86 (s, 1H); 7.74 (s, 1H); 7.45 (t, J=8.1 Hz, 1H); 7.27 (s, 1H); 4.12 (s, 3H).

(19) LCMS: (Method ZDQ13): 611, 613 (M+H), 615, retention time 1.18 min.

Step 6: 3-amino-N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-2-methoxy-benzamide

(20) ##STR00036##

(21) N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-2-methoxy-3-nitro-benzamide (5.6 g, 8.4 mmol) dissolved in iso-propanol (120 ml) was treated with anhydrous tin chloride (5.7 g, 30 mmol) and then dropwise with concentrated hydrochloric acid (8 ml) at rt. The mixture was then heated to 90° C. for 1 hr after which LCMS/TLC showed reaction completion. The mixture was poured on water, adjusted to pH10 with 2N NaOH and extracted with 3×100 ml EtOAc. The combined organic layers were washed with brine, dried over MgSO.sub.4, filtrated and concentrated in vacuo. Purification by over a silica gel cartridge (Rf200) eluting with Cyclohexane/EtOAc 95:5.fwdarw.60:40 gave the title compound (4.6 g, 94%) as a brownish resin:

(22) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.53 (s, 1H); 7.84 (s, 1H); 7.72 (s, 1H), 7.59 (dd, J=7.7, 1.8 Hz, 1H); 7.12 (t, J=7.7 Hz, 1H); 7.01 (dd, J=7.9, 1.7 Hz, 1H); 4.18 (br. s., 2H); 4.01 (s, 3H).

(23) LCMS: (Method ZDQ13): 583, 585 (M+H), 587, retention time 1.14 min.

Step 7: N-[3-[[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]carbamoyl]-2-methoxy-phenyl]pyridine-4-carboxamide

(24) ##STR00037##

(25) To a solution of 3-amino-N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-2-methoxy-benzamide (83 mg, 0.14 mmol) and Pyridine (45 μl, 0.55 mmol) in THF (4 ml) was added pyridine-4-carbonyl chloride hydrochloride (28 mg, 0.15 mmol) The mixture was stirred at rt and monitored by TLC/LCMS. After 23 hr, there was still about 20% of starting material present and thus, additional pyridine-4-carbonyl chloride hydrochloride (25 mg, 0.14 mmol) was added. Upon reaction completion, the mixture was quenched with water and sat. NaHCO.sub.3-sol, and extracted with 2×20 ml EtOAc. The combined organic layers was washed with brine, dried over Na.sub.2SO.sub.4, filtrated and concentrated in vacuo.

(26) The crude product was purified over silica gel cartridge (Rf200) eluting with Cyclohexane/EtOAc 10:90.fwdarw.0:100 to give the title compound (87 mg, 93%) as a pale yellow resin.

(27) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.03 (s, 1H); 8.89 (d, J=4.9 Hz, 2H); 8.69 (dd, J=8.1, 1.5 Hz, 1H); 8.51 (s, 1H); 7.96 (dd, J=7.9, 1.7 Hz, 1H); 7.86 (s, 1H); 7.74-7.81 (m, 3H); 7.41 (t, J=8.1 Hz, 1H); 4.09 (s, 3H).

(28) LCMS: (Method ZDQ13): 688, 690 (M+H), 692, retention time 1.10 min.

Example P2: Step 2: N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzamide (Entry 1 of Table B)

Step 1: N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-3-(ethylamino)-2-methoxy-benzamide

(29) ##STR00038##

(30) A solution of N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-2-methoxy-3-nitro-benzamide (5.0 g, 8.1 mmol, step 6, Example P1), acetaldehyde (0.61 ml, 10.6 mmol), and acetic aid (0.61 ml, 10.6 mmol) in MeOH (100 ml), was treated with sodium cyanoborohydride (699 mg, 10.6 mmol) at rt. The resulting mixture was stirred at rt and after 4 hr LCMS shows full conversion. The mixture was concentrated in vacuo, and the residue was quenched with 25 ml water and extracted 3×50 ml of dichloromethane. The combined organic layers was washed with water, brine, dried over Na.sub.2SO.sub.4, filtrated concentrated in vacuo. Purification over a silica gel cartridge (Rf200) eluting with dichloromethane/MeOH gave the title compound (4.8 g, 96%) as off white crystals.

(31) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.49 (s, 1H); 7.84 (s, 1H); 7.72 (s, 1H); 7.48 (dd, J=7.7, 1.5 Hz, 1H); 7.18 (t, J=7.9 Hz, 1H); 6.89 (dd, J=8.1, 1.5 Hz, 1H); 4.17 (br. s., 1H), 3.97 (s, 3H); 3.24 (q, J=7.0 Hz, 2H); 1.35 (t, J=7.2 Hz, 3H).

(32) LCMS: (Method ZDQ13): 611, 613 (M+H), 615, retention time 1.27 min

Step 2: N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-3-[(4-cyanobenzoyl)-ethyl-amino]-2-methoxy-benzamide

(33) ##STR00039##

(34) 4-cyanobenzoyl chloride (105 mg, 0.615 mmol) was added to a solution of N-[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]-3-(ethylamino)-2-methoxy-benzamide (353 mg, 0.559 mmol) and Pyridine (1831, 2.24 mmol) in THF (15 ml). The mixture was stirred at rt and monitored by TLC/LCMS. Upon reaction completion, the reaction mixture was quenched with water and sat. NaHCO.sub.3-sol, and extracted with 2×20 ml EtOAc. The combined organic layers were washed with brine, dried over Na.sub.2SO.sub.4, filtrated and evaporated.

(35) Purification over a silica gel cartridge (Rf200) eluting with Cyclohexane/EtOAc 100:0.fwdarw.60:40, gave the title compound (368 mg, 89%) as a white foam.

(36) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): Selected signals, rotamer mixture: 8.05 (d, J=7.7 Hz); 7.81 (s), 7.70 (s); 7.38-7.63 (m), 3.52-4.57 (m); 1.11-1.69 (m).

(37) LCMS: (Method ZDQ13): 740, 742 (M+H), 744, retention time 1.20 min

Example P3: N-[3-[[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]carbamoyl]-2-methoxy-phenyl]-N-ethyl-1-oxido-pyridin-1-ium-4-carboxamide (Entry 44 of the table B)

(38) ##STR00040##

(39) A colourless solution of N-[3-[[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]carbamoyl]-2-methoxy-phenyl]-N-ethyl-pyridine-4-carboxamide (Entry 36 of the table B) (0.095 g) in dichloromethane (3.0 ml) was treated with 0.040 g of 70% meta-chloroperbenzoic acid. After 16 hours stirring at 20° C., full conversion was observed by LC-MS and TLC analyses. The reaction mixture was washed with an aqueous solution of sodium sulfite, and then twice with an aqueous solution of sodium bicarbonate. The organic phase was dried over sodium sulfate and evaporated to yield the title compound as a white powder with a melting range of 109-228° C.

(40) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.60 (br.s, 1H), 8.05 (d, J=8.1 Hz, 1H), 7.97 (br. d, 2H), 7.78 (s, 1H), 7.53 (d, J=8.1 Hz, 1H), 7.49 (s, 1H), 7.8 (t, J=8.1 Hz, 1H), 7.20 (br. d, 2H), 6.61 (t, J=73 Hz, 1H), 4.30 (br. m, 1H), 3.91 (s, 3H), 3.75 (br. m, 1H), 1.41 (br. t, 3H).

Example P4: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-pyridine-4-carboxamide (Entry 36 of the table B)

(41) ##STR00041##

Step 1: 4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-2-(difluoromethoxy)aniline

(42) ##STR00042##

(43) A solution of 2-difluoromethoxyaniline (4.5 g) in a mixture of 2-methoxy-2-methyl-propane (41 ml) and water (41 ml) was stirred at 20° C. Sodium hydrosulfite (6.8 g), sodium bicarbonate (2.8 g) and tetrabutylammonium hydrogensulfate (0.69 g) followed by 1-chloro-1,1,2,3,3,3-hexafluoro-2-iodo-propane (preparation described in Patent FR 1337264) (10.0 g) were added. Gas evolution was observed during the first 4 hours. The mixture was stirred for 3 days, after which time the phases were separated. The aqueous phase was extracted twice with 2-methoxy-2-methyl-propane and the combined organic phases were washed twice with 1 molar aqueous hydrochloric acid (100 ml) followed by two washing with water (100 ml), then brine (100 ml). The organic phase was dried over sodium sulfate and the solvent removed under reduced pressure to yield 4-[1-[chloro (difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-2-(difluoromethoxy)aniline as orange oil that was used in the following step without further purification.

(44) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 7.29 (m, 2H), 6.84 (d, J=8.1 Hz, 1H), 6.49 (t, J=73 Hz, 1H), 4.15 (br. s, 2H).

Step 2: 2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)aniline

(45) ##STR00043##

(46) To an orange solution of 4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-2-(difluoromethoxy)aniline (3.88 g) (preparation described in step 1) in dichloromethane (24 ml) was added portion wise N-bromosuccinimid (2.41 g) under stirring at 20° C. The reaction mixture became dark brown. The reaction was complete after 1 hour (LC-MS analysis). To the reaction mixture was added, under stirring, an aqueous solution of sodium hydroxide (100 ml, 1 mole/l). After separation of the phases, the organic phase was washed with another 100 ml portion of 0.1 M sodium hydroxide. The combined aqueous phases were extracted twice with 100 ml dichloromethane. The organic layers were joined, dried over sodium sulfate and the solvent removed under reduced pressure, leaving 2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)aniline as brown oil that was used in the following step without further purification.

(47) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 7.55 (s, 1H), 7.25 (s, 1H), 6.60 (t, J=72.7 Hz, 1H), 4.60 (br. s, 2H).

Step 3: N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-2-fluoro-3-nitro-benzamide

(48) ##STR00044##

(49) A solution of 2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)aniline (4.38 g) (preparation described in step 2) in acetonitrile (25 ml) was treated with powdered potassium iodide (0.172 g) followed by a solution of 2-fluoro-3-nitro-benzoyl chloride (2.53 g) in acetonitrile (20 ml). The resulting mixture was stirred under reflux for 20 hours. The reaction mixture was evaporated to dryness and the residue partitioned between dichloromethane and aqueous saturated sodium bicarbonate. The aqueous phase was extracted twice with dichloromethane and the combined organic phases were dried over sodium sulfate and evaporated. The residue was purified by flash chromatography over silica gel eluting with a mixture of ethyl acetate and heptanes. N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-2-fluoro-3-nitro-benzamide was isolated as solid melting at 125-127° C.

Step 4: N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-2-methoxy-3-nitro-benzamide

(50) ##STR00045##

(51) To a pale brown solution of N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-2-fluoro-3-nitro-benzamide (2.23 g) (preparation described in step 3) in methyl alcohol (35.6 ml) was added potassium carbonate (1.10 g) and the resulting suspension was heated to 50° C. under stirring for 4 hours. The reaction was complete and the reaction mixture was filtered. The filtrate was evaporated and the residue was partitioned between dichloromethane and water. The aqueous phase was extracted with dichloromethane and the organic solution was dried over sodium sulfate and evaporated to yield the desired compound as brown oil. It was used without further purification in the next step.

(52) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.09 (s, 1H), 8.37 (dd, J=8.2 Hz, J=2 Hz, 1H), 8.05 (dd, J=8.2 Hz, J=2 Hz, 1H), 7.82 (s, 1H), 7.52 (s, 1H), 7.43 (t, J=8.2 Hz, 1H), 6.60 (t, J=73.5 Hz, 1H), 4.14 (s, 3H).

Step 5: 3-amino-N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-2-methoxy-benzamide

(53) ##STR00046##

(54) To a mixture of 2.306 g N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-2-methoxy-3-nitro-benzamide (preparation described in step 4), iron powder (0.535 g), ethyl alcohol (31 ml) and water (6 ml), was added 0.016 ml concentrated aqueous hydrochloric acid. The pale green suspension was heated to reflux temperature and became quickly brown. After stirring for two hours the reaction was complete (LC-MS and TLC analyses). The reaction mixture was filtered through a pad of celite and the solid residue washed with dichloromethane. The filtrate was evaporated and taken up in dichloromethane. The organic phase was dried over sodium sulfate and evaporated to yield the crude title compound as brown thick oil. This compound was used without further purification in the following step.

(55) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 9.42 (br. s, 1H), 7.81 (s, 1H), 7.50 (m, 2H), 7.10 (t, J=8.2 Hz, 1H), 6.97 (d, J=8.2 Hz, 1H), 6.61 (t, J=73.5 Hz, 1H), 3.98 (s, 3H), 3.95 (s, broad, 2H).

Step 6: N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-3-(ethylamino)-2-methoxy-benzamide

(56) ##STR00047##

(57) To a solution of 1.411 g of 3-amino-N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-2-methoxy-benzamide (preparation described in step 5) in 20 ml methanol, 0.156 ml acetic acid and 0.109 g acetaldehyde were added, followed by 0.180 g of sodium cyanoborohydride. Gas evolution was observed. The reaction mixture was stirred at 20° C. for 17 hours. Then the solvent was evaporated and the residue was partitioned between dichloromethane and water. The aqueous phase was extracted twice with dichloromethane and the combined organic phases were dried over sodium sulfate and evaporated. The crude product was flash-chromatographed over silica gel using a gradient from 10% ethyl acetate in cyclohexane to 20% ethyl acetate in cyclohexane. The desired product was isolated as a colorless solid with a melting point of 121-123° C.

Step 7: N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-pyridine-4-carboxamide (Entry 36 of the table B)

(58) ##STR00048##

(59) To a colorless solution of 0.300 g N-[2-bromo-4-[1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-(difluoromethoxy)phenyl]-3-(ethylamino)-2-methoxy-benzamide (preparation described in step 6) in 5.0 ml of tetrahydrofuran was added 138 mg of isonicotinoyl chloride hydrochloride. The suspension was heated to 70° C. for 1 hour. The reaction was complete, as shown by LC-MS and TLC analyses. The reaction mixture was concentrated under reduced pressure and the residue was dissolved in dichloromethane. The organic phase was washed with saturated aqueous sodium bicarbonate. The aqueous phase was back extracted twice with dichloromethane. The organic phases were combined and dried over sodium sulfate and evaporated. The crude product was chromatographed over silica gel eluting with a mixture of 50% ethyl acetate and 50% cyclohexane. After removal of the solvent, N-[3-[[2-bromo-6-(difluoromethoxy)-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-methyl-pyridine-4-carboxamide was obtained as a white powder with a melting range of 112-161° C.

(60) .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.50 (s, broad, 2H), 8.02 (t, 1H), 7.83 (d, 1H), 7.78 (s, 1H), 7.49 (s, 1H), 7.43 (t, 1H), 7.28 (t, 1H), 7.18 (s, broad, 2H), 6.55 (t, 1H), 4.00 (m, broad, 2H), 1.28 (t, broad, 3H).

Example P5: N-[3-[[2-bromo-6-chloro-4-[1-(difluoromethyl)-1,2,2,2-tetrafluoro-ethyl]phenyl]carbamoyl]-2-methoxy-phenyl]-N-ethyl-pyridine-4-carboxamide (Entry 51 of the table B)

(61) ##STR00049##

(62) A solution of N-[3-[[2-bromo-4-[1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl]-6-chloro-phenyl]carbamoyl]-2-methoxy-phenyl]-N-ethyl-pyridine-4-carboxamide (115 mg, 0.16 mmol, prepared analogously to the methods described above, entry 2, table B) dissolved in toluene (3 mL) was degassed with nitrogen, and then treated with tris(trimethylsilyl)silane (61 mg, 0.2404 mmol) and azo-bis-(isobutyronitrilE, AIBN) (61 mg, 0.016 mmol). The reaction stirred at room temperature for 23 h after which time LCMS showed reaction completion. The reaction mixture was quenched with 5 mL water and extracted with 3×10 mL ethylacetate. The combined organic layers were washed with 10 mL HCl-solution (2 mol.) and afterwards with 20 mL NaCl-solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The crude product was purified by reversed phase chromatography to give the title product as a yellow resin. LCMS: (OA_Standard): 638, 640, 642 (M+H), retention time 1.03 min. .sup.1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.44 (t, J=7.15 Hz, 3H); 3.73 (m, 1H); 3.96 (s, 3H); 4.26 (m, 1H); 5.99-6.41 (m, 1H); 7.25 (br, 1H); 7.32 (d, J=5.50 Hz, 2H); 7.51 (d, J=6.97 Hz, 1H); 7.62-7.70 (m, 1H); 7.78 (s, 1H); 7.96-8.11 (m, 1H) 8.49 (br s, 2H) 8.68 (br. s., 1H).

(63) LC-MS Method: ZCQ13

(64) ZQ Mass Spectrometer from Waters (Single Quadrupole Mass Spectrometer)

(65) 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

(66) 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

(67) TABLE-US-00001 Flow Time A % B % (ml/min) 0.00 90 10 0.85 1.20  0 100.0 0.85 1.50  0 100.0 0.85
LC-MS Method: ZDQ13
ZQ Mass Spectrometer from Waters (Single Quadrupole Mass Spectrometer)

(68) 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

(69) 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

(70) TABLE-US-00002 Flow Time A % B % (ml/min) 0.00 90 10 0.85 1.20  0 100.0 0.85 1.50  0 100.0 0.85
LC-MS Method: OA_STANDARD
ZQ Mass Spectrometer from Waters (Single Quadrupole Mass Spectrometer)

(71) 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

(72) 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

(73) TABLE-US-00003 Flow Time A % B % (ml/min) 0.00 90 10 0.85 1.20  0 100.0 0.85 1.50  0 100.0 0.85

(74) The following compounds illustrate the invention:

(75) TABLE-US-00004 TABLE A Radicals of formula (I) (I) 0 Wherein: Line X1 X2 Q 1 F H 4-Pyridyl 2 OCH3 H 4-Pyridyl 3 H H 4-Pyridyl 4 F CN 4-Pyridyl 5 OCH3 CN 4-Pyridyl 6 H CN 4-Pyridyl 7 F H 3-Pyridyl 8 OCH3 H 3-Pyridyl 9 H H 3-Pyridyl 10 F CN 3-Pyridyl 11 OCH3 CN 3-Pyridyl 12 H CN 3-Pyridyl 13 F H 4-Cyanophenyl 14 OCH3 H 4-Cyanophenyl 15 H H 4-Cyanophenyl 16 F CN 4-Cyanophenyl 17 OCH3 CN 4-Cyanophenyl 18 H CN 4-Cyanophenyl 19 F H 4-Pyridyl-N-Oxide 20 OCH3 H 4-Pyridyl-N-Oxide 21 H H 4-Pyridyl-N-Oxide 22 F CN 4-Pyridyl-N-Oxide 23 OCH3 CN 4-Pyridyl-N-Oxide 24 H CN 4-Pyridyl-N-Oxide 25 F H 3-Pyridyl-N-Oxide 26 OCH3 H 3-Pyridyl-N-Oxide 27 H H 3-Pyridyl-N-Oxide 28 F CN 3-Pyridyl-N-Oxide 29 OCH3 CN 3-Pyridyl-N-Oxide 30 H CN 3-Pyridyl-N-Oxide 31 F H 4-Cyano-2-methylphenyl 32 OCH3 H 4-Cyano-2-methylphenyl 33 H H 4-Cyano-2-methylphenyl 34 F CN 4-Cyano-2-methylphenyl 35 OCH3 CN 4-Cyano-2-methylphenyl 36 H CN 4-Cyano-2-methylphenyl

(76) Table 1 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Cl, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(77) Table 2 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Cl, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(78) Table 3 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Cl, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(79) Table 4 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A lines 1-36.

(80) Table 5 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(81) Table 6 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A lines 1-36.

(82) Table 7 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Me, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(83) Table 8 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Me, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(84) Table 9 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Me, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(85) Table 10 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(86) Table 11 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(87) Table 12 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(88) Table 13 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(89) Table 14 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(90) Table 15 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Cl, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(91) Table 16 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(92) Table 17 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A lines 1-36.

(93) Table 18 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(94) Table 19 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(95) Table 20 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(96) Table 21 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(97) Table 22 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A lines 1-36.

(98) Table 23 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A lines 1-36.

(99) Table 24 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Br, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-30 lines 1-36.

(100) Table 25 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(101) Table 26 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A lines 1-36.

(102) Table 27 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(103) Table 28 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Me, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(104) Table 29 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Me, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(105) Table 30 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Me, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(106) Table 31 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(107) Table 32 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(108) Table 33 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(109) Table 34 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(110) Table 35 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(111) Table 36 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Me, R2 is H, and X1, X2 and Q are as defined in Table A lines 1-36.

(112) Table 37 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Et, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(113) Table 38 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Et, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(114) Table 39 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Et, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(115) Table 40 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Et, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(116) Table 41 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Et, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(117) Table 42 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Et, R2 is H, and X1, X2 and Q are as defined in Table A, lines 1-36.

(118) Table 43 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Cl, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(119) Table 44 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Cl, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(120) Table 45 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Cl, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(121) Table 46 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(122) Table 47 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(123) Table 48 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(124) Table 49 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Me, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(125) Table 50 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Me, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(126) Table 51 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Me, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(127) Table 52 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(128) Table 53 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(129) Table 54 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(130) Table 55 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(131) Table 56 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(132) Table 57 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Cl, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(133) Table 58 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(134) Table 59 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(135) Table 60 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(136) Table 61 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(137) Table 62 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(138) Table 63 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(139) Table 64 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(140) Table 65 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(141) Table 66 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Br, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(142) Table 67 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(143) Table 68 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(144) Table 69 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(145) Table 70 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Me, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(146) Table 71 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Me, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(147) Table 72 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Me, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(148) Table 73 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(149) Table 74 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(150) Table 75 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(151) Table 76 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(152) Table 77 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(153) Table 78 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Me, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(154) Table 79 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Et, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(155) Table 80 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Et, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(156) Table 81 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Et, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(157) Table 82 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Et, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(158) Table 83 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Et, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(159) Table 84 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Et, R2 is Me, and X1, X2 and Q are as defined in Table A, lines 1-36.

(160) Table 85 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Cl, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(161) Table 86 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Cl, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(162) Table 87 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Cl, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(163) Table 88 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(164) Table 89 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(165) Table 90 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(166) Table 91 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Me, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(167) Table 92 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Me, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(168) Table 93 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Me, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(169) Table 94 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(170) Table 95 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(171) Table 96 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(172) Table 97 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(173) Table 98 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(174) Table 99 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Cl, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(175) Table 100 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(176) Table 101 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(177) Table 102 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(178) Table 103 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(179) Table 104 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(180) Table 105 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(181) Table 106 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(182) Table 107 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(183) Table 108 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Br, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(184) Table 109 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Br, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(185) Table 110 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Br, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(186) Table 111 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Br, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(187) Table 112 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Me, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(188) Table 113 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Me, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(189) Table 114 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Me, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(190) Table 115 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(191) Table 116 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(192) Table 117 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(193) Table 118 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in A, lines 1-36.

(194) Table 119 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(195) Table 120 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Me, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(196) Table 121 provides 36 compounds of formula (I) wherein X0 is H, Y1 is Et, Y2 is Et, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(197) Table 122 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is Et, Y2 is Et, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(198) Table 123 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is Et, Y2 is Et, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(199) Table 124 provides 36 compounds of formula (I) wherein X0 is H, Y1 is OCHF2, Y2 is Et, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(200) Table 125 provides 36 compounds of formula (I) wherein X0 is Cl, Y1 is OCHF2, Y2 is Et, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(201) Table 126 provides 36 compounds of formula (I) wherein X0 is Br, Y1 is OCHF2, Y2 is Et, R2 is Et, and X1, X2 and Q are as defined in Table A, lines 1-36.

(202) TABLE-US-00005 TABLE B Properties of Prepared Compounds RT [M + H] MP Entry STRUCTURE (min) (measured) Method ° C. 1 1.20 740, 742, 744 ZDQ13 2 1.11 716, 718, 720 ZDQ13 3 1.10 688, 690, 692 ZDQ13 4 1.07 708, 710, 712 ZCQ13 5 1.15 732, 734, 736 ZCQ13 6 1.00 724, 726, 728 ZCQ13 7 1.10 736, 738, 740 162- 164 8 1.17 760, 762, 764 ZCQ13 9 1.11 748, 750, 752 ZCQ13 10 0 1.18 772, 774, 776 ZCQ13 11 1.06 664, 666, 668 ZCQ13 118- 157 12 1.08 664, 666, 668 ZCQ13 140- 151 13 1.15 688, 690, 692 ZCQ13 116- 151 14 172- 174 15 1.10 676, 678, 680 ZCQ13 90- 170 16 .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm): 8.90 (s, 1H), 8.67 (d, J = 8.1 Hz, 1H), 8.46 (s, 1H), 8.03 (d, J = 9 Hz, 2H), 7.90-7.80 (m, 4H), 7.52 (s, 1H), 7.39 (t, J = 8.1 Hz, 1H), 6.63 (t, J = 73 Hz, 1H), 4.04 (s, 3H). 97- 172 17 1.10 626, 628, 630 ZCQ13 108- 190 18 171- 173 19 1.17 650, 652, 654 ZCQ13 123- 202 20 0 1.12 638, 640, 642 ZCQ13 99- 162 21 1.12 638, 640, 642 ZCQ13 87- 168 22 1.19 662, 664, 666 ZCQ13 110- 170 23 230- 232 24 197- 201 25 1.02 692, 694, 696 ZCQ13 177- 186 26 1.02 692, 694, 696 ZCQ13 172- 179 27 1.02 642, 644, 646 ZCQ13 222- 230 28 237- 239 29 1.04 654, 656, 658 ZCQ13 158- 167 30 0 229- 231 31 1.17 716, 718, 720 ZCQ13 80- 150 32 1.19 728, 730, 732 ZCQ13 80- 159 33 1.19 678, 680, 682 ZCQ13 99- 173 34 1.22 690, 692, 694 ZCQ13 106- 152 35 1.10 692, 694, 696 ZCQ13 106- 154 36 1.12 704, 706, 708 ZCQ13 112- 161 37 1.12 654, 656, 658 ZCQ13 120- 171 38 1.14 666, 668, 670 ZCQ13 90- 155 39 1.11 692, 694, 696 ZCQ13 100- 162 40 0 1.13 704, 706, 708 ZCQ13 110- 164 41 1.14 652, 654, 656 ZDQ13 96- 144 42 1.16 666, 668, 670 ZDQ13 80- 137 43 1.03 708, 710, 712 ZCQ13 115- 203 44 1.04 720, 722, 724 ZCQ13 109- 228 45 1.05 670, 672, 674 ZCQ13 118- 209 46 1.04 + 1.06 682, 684, 686 ZCQ13 112- 220 47 1.03 708, 710, 712 ZCQ13 98- 211 48 1.04 720, 744, 724 ZCQ13 104- 202 49 1.05 670, 672, 674 ZCQ13 118- 230 50 00 1.06 682, 684, 686 ZCQ13 99- 208 51 01 1.03 638, 640, 642 OA_STANDARD

Biological Examples

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

(204) Bemisia tabaci (Cotton White Fly):

(205) Cotton leaf discs are 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 are infested with adult white flies. After an incubation period of 6 DAI, samples are checked for mortality.

(206) The following compound gave at least 80% control of Bemisia tabaci: 2, 3, 4, 5, 6, 7.

(207) Diabrotica balteata (Corn Root Worm):

(208) 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 The following compound gave at least 80% control of Diabrotica balteata: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51.

(209) Frankliniella occidentalis (Western Flower Thrips):

(210) Sunflower leaf discs are 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 are infested with a Frankliniella population of mixed ages. After an incubation period of 7 DAT, samples are checked for mortality.

(211) The following compound gave at least 80% control of Frankliniella occidentalis: 2, 3, 4, 5, 6, 7.

(212) Heliothis virescens (Tobacco Budworm):

(213) 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 larval mortality.

(214) The following compound gave at least 80% control of Heliothis virescens: 1, 2, 3, 4.

(215) Myzus persicae (Green Peach Aphid):

(216) 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.

(217) The following compounds gave at least 80% control of Myzus persicae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51.

(218) Myzus persicae (Green Peach Aphid):

(219) Roots of pea seedlings, infested with an aphid population of mixed ages, are placed directly in the test solutions at an application rate of 24 ppm. 6 days after introduction, samples are checked for mortality.

(220) The following compounds gave at least 80% control of Myzus persicae: 14, 43, 44, 45, 46.

(221) Myzus persicae (Green Peach Aphid):

(222) Test compounds were applied by pipette into 24 well plates and mixed with Sucrose solution. Application rate: 12.5 ppm. The plates were closed with a stretched Parafilm. A plastic stencil with 24 holes is placed onto the plate and infested pea seedlings were placed directly on the Parafilm. The infested plate is closed with a gel blotting paper and another plastic stencil and then turned upside down. 5 days after infestation the samples were checked on mortality.

(223) The following compounds gave at least 80% control of Myzus persicae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51.

(224) Plutella xylostella (Diamond Back Moth):

(225) 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. The following compound gave at least 80% mortality of Plutella xylostella: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50.

(226) Spodoptera littoralis (Egyptian Cotton Leafworm):

(227) 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 3 days after treatment (DAT).

(228) The following compound gave at least 80% mortality of Spodoptera littoralis: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51.

(229) Spodoptera littoralis (Egyptian Cotton Leaf Worm):

(230) Test compounds were applied by pipette into 24 well plates and mixed with agar. Application rate: 12.5 ppm. Lettuce seeds were placed on the agar and the multi well plate is closed by another plate which contains also agar. After 7 days the roots have absorbed the compound and the lettuce has grown into the lid plate. The lettuce leafs were now cut off into the lid plate. Spodoptera eggs were pipetted through a plastic stencil on a humid gel blotting paper and the plate closed with it. The samples are checked for mortality 6 days after infestation.

(231) The following compound gave at least 80% control of Spodoptera littoralis: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 21, 23, 24, 25, 26, 31, 32, 35, 36, 39, 40, 41, 43, 44, 47, 48, 50.

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

(233) 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 were checked for mortality.

(234) The following compounds gave at least 80% mortality of Tetranychus urticae: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51.

(235) Thrips tabaci (Onion Thrips):

(236) 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.

(237) The following compounds gave at least 80% control of Thrips tabaci: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51.