PROCESS FOR THE PREPARATION OF THIETANE DERIVATIVES

Abstract

The present invention relates to processes for the preparation of thietane derivatives of the formula IA

##STR00001##

and thietane derivatives of the formula IB

##STR00002##

wherein R.sup.1, R.sup.2, A.sup.1, A.sup.2, A.sup.3, A.sup.4, B, and n are as defined in the claims. The invention also relates to intermediates useful in the processes, as well as the compounds of formula IA and IB and their use as pesticides.

Claims

1. (canceled)

2. A process for preparing a compound of formula X ##STR00063## comprising i. reacting a compound of formula VII ##STR00064## with triphenylphosphoranyldiene-acetonitrile or (Cyanomethyl)diethoxyphosphine oxide to give a compound of formula VIII ##STR00065## ii. reducing the compound of formula VIII with a suitable reducing agent to give a compound of formula X.

3. A compound of formula IB ##STR00066## wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of one another CH, CR.sup.3, or nitrogen; B is O or CH.sub.2; R.sup.1 is C.sub.1-C.sub.8haloalkyl; R.sup.2 is aryl or aryl substituted by one to five R.sup.4, or heteroaryl or heteroaryl substituted by one to five R.sup.4; each R.sup.3 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.8cycloalkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8haloalkenyl, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, C.sub.1-C.sub.8alkoxycarbonyl-, amino, hydroxy, mercapto, C.sub.1-C.sub.8alkylthio, C.sub.1-C.sub.8haloalkylthio, C.sub.1-C.sub.8alkylsulfinyl, C.sub.1-C.sub.8haloalkylsulfinyl, C.sub.1-C.sub.8alkylsulfonyl, C.sub.1-C.sub.8haloalkylsulfonyl, C.sub.1-C.sub.8alkylcarbonyl, or two R.sup.3 on adjacent carbon atoms together form a CHCHCHCH bridge or a NCHCHCH bridge; each R.sup.4 is independently halogen, cyano, nitro, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, C.sub.2-C.sub.8haloalkenyl, C.sub.2-C.sub.8alkynyl, C.sub.2-C.sub.8haloalkynyl, hydroxy, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8haloalkoxy, mercapto, C.sub.1-C.sub.8alkylthio, C.sub.1-C.sub.8haloalkylthio, C.sub.1-C.sub.8alkylsulfinyl, C.sub.1-C.sub.8haloalkylsulfinyl, C.sub.1-C.sub.8alkylsulfonyl, C.sub.1-C.sub.8haloalkylsulfonyl, C.sub.1-C.sub.8alkylcarbonyl, C.sub.1-C.sub.8alkoxycarbonyl, aryl or aryl substituted by one to five R.sup.5, or heterocyclyl or heterocyclyl substituted by one to five R.sup.5; each R.sup.5 is independently halogen, cyano, nitro, 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-; n is 0, 1 or 2.

4. A compound of formula VIII, X or XV ##STR00067## wherein n is 1 or 2, or a compound of formula XI, XII or XIII ##STR00068## wherein R is C.sub.1-C.sub.6alkyl.

5. (canceled)

6. A method of combating and 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 (IB) as defined in claim 3.

7. An insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (IB) as defined in claim 3, and optionally comprising an additional pesticidally active ingredient.

8. A combination product comprising a pesticidally effective amount of a component A and a pesticidally effective amount of component B, wherein component A is a compound of formula (IB) as defined in claim 3, and component B is imidacloprid, enrofloxacin, praziquantel, pyrantel embonate, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, fipronil, ivermectin, omeprazole, tiamulin, benazepril, milbemycin, cyromazine, thiamethoxam, pyriprole, deltamethrin, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, selamectin, carprofen, metaflumizone, moxidectin, methoprene (including S-methoprene), clorsulon, pyrantel, amitraz, triclabendazole, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, nemadectin, albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, tetramisole, levamisole, pyrantel pamoate, oxantel, morantel, triclabendazole, epsiprantel, fipronil, lufenuron, ecdysone or tebufenozide.

9. The compound of claim 4, wherein the compound is the compound of formula VIII.

10. The compound of claim 4, wherein the compound is the compound of formula X.

11. The compound of claim 4, wherein the compound is the compound of formula XV.

12. The compound of claim 4, wherein the compound is the compound of formula XI.

13. The compound of claim 4, wherein the compound is the compound of formula XII.

14. The compound of claim 4, wherein the compound is the compound of formula XIII.

Description

EXPERIMENTAL PROCEDURES

Example A.1: thietane-3-carbonitrile

[0294] ##STR00049##

[0295] To a solution of epithiochlorohydrine (2.7 g) in benzene (10 ml) was added at room temperature a solution of potassium cyanide (4 g) in water (10 ml). The resulting mixture was heated to 50 C. for 12 hours. The mixture was extracted with benzene then the organic phase was washed with aqueous saturated sodium hydrogenocarbonate solution then water and brine. The organic phase was dried with sodium sulphate then the solvent was evaporated to dryness to give the crude residue as a yellow oil (1.76 g). 1 g of the crude was purified by a flash chromatography to obtain the title product as a brown solid (0.5 g). .sup.1H-NMR (CDCl.sub.3, 400 MHz): 3.25-3.35 (m, 2H), 3.65-3.75 (m, 2H), 4.10-4.25 (m, 1H). .sup.1H-NMR (CDCl.sub.3, 100 MHz) 27.3 (1C), 28.7 (2C), 119.7 (1C). GCMS (Method C): rt=5.07 min (87%) m/z: [M-CN].sup.+=73; [M+1].sup.+=100.

Example A.2: thietane-3-carbonitrile

[0296] ##STR00050##

[0297] To a solution of epithiochlorohydrine (5.4 g) in tetrahydrofuran (20 ml) was added at room temperature a solution of potassium cyanide (4.9 g) in water (20 ml). The resulting mixture was heated to 50 C. for 12 hr. The mixture was extracted with tetrahydrofuran then the organic phase was washed with aqueous saturated sodium hydrogenocarbonate solution then water and brine. The organic phase was dried with sodium sulphate then the solvent was evaporated to dryness to give the crude title product as a violet oil (3.75 g), which was analysed by NMR and GCMS (see example A.1) and contained ca 10% of 2-aminothiophene.

Example B: thietan-3-ylmethanamine

[0298] ##STR00051##

[0299] To a solution of lithium aluminium hydride (540 mg) in diethyl ether (30 ml) was added in a suspension of thietane-3-carbonitrile (1.4 g) in diethyl ether (30 ml) at 0 C. then the mixture was stirred at room temperature for 30 min. The mixture was then diluted with ether (50 ml), cooled to 0 C. then water (0.55 ml), 15% aqueous sodium hydroxide (0.55 ml) and water (1.60 ml) were added. The mixture was allowed to warm to room temperature and stirred for 15 min. Anhydrous magnesium sulphate was added and stirring was continued for 15 min, then the suspension was filtered on a celite pad. The solvent was evaporated to dryness to give the crude title product as an oil (980 mg). .sup.1H-NMR (CDCl.sub.3, 400 MHz): 3.21 (m, 3H); 3.00 (m, 2H); 2.86 (m, 2H).

Example C: 2-(thietan-3-ylidene)acetonitrile

[0300] ##STR00052##

[0301] To a solution of thietan-3-one (900 mg) in 10 ml of dry methylene chloride was added a solution of (triphenylphosphoranylidene)acetonitrile (3.31 g) in 20 ml of dry methylene chloride at 0 C. The solution was allowed to warm to room temperature and after stirring for 15 min the solvent was removed under reduced pressure. The residue was purified by a flash chromatography (silica gel: Dichloromethane as an eluant) to give the title compound (785 mg) as a yellow-brown oil. GC/MS (Method C): rt=2.89 min (54.7%) m/z: [M+1].sup.+=112. .sup.1H-NMR (CDCl.sub.3, 400 MHz): 5.11 (m, 1H), 4.15 (m, 2H), 4.03 (m, 2H).

Example D: 2-(thietan-3-yl)acetonitrile

[0302] ##STR00053##

[0303] To a stirred solution of 2-(thietan-3-ylidene)acetonitrile (2.775 g) in dry methanol (250 mL), cooled to 0 C., was added sodium borohydride (9.250 g) in small portions over 30 min. The reaction mixture was allowed to warm to room temperature and stirred for a further hour. The solvent was removed under reduced pressure. The purple residue was dissolved in ethyl acetate (50 ml) and extracted with saturated sodium hydrogenocarbonate (250 ml). The organic layer, dried over sodium sulphate, filtered and the solvent was removed under reduced pressure to yield a oil yellow. The residue was purified by a flash chromatography (silica gel: cyclohexane/ethyl acetate as an eluant) to give the title compound (2.2 g) as a yellow oil. GC/MS (Method C): rt=5.99 min (100%) m/z: [M+1].sup.+=114. .sup.1H-NMR (CDCl.sub.3, 400 MHz): 3.56 (m, 1H), 3.35 (dd, 2H), 3.09 (dd, 2H), 2.55 (d, 2H).

Example E: 2-(thietan-3-yl)ethanamine

[0304] ##STR00054##

[0305] To a solution of lithium aluminium hydride (76 mg) in diethyl ether (4 ml) was added in a suspension of 2-(thietan-3-yl)acetonitrile (226 mg) in diethyl ether (30 ml) at 00 C. then the mixture was stirred at room temperature until the end of the gas evolution. The mixture was then diluted with ether (6 ml), cooled to 00 C. then water (0.08 ml), 15% aqueous sodium hydroxide (0.08 ml) and water (0.25 ml) were added. The mixture was allowed to warm to room temperature and stirred for 15 min. Anhydrous magnesium sulphate was added and stirring was continued for 15 min, then the suspension was filtered on a celite pad. The solvent was evaporated to dryness to give the crude title product as a brown oil (196 mg). .sup.1H-NMR (CDCl.sub.3, 400 MHz): 3.4-3.35 (m, 1H); 3.20-3.10 (2H); 3.1-3.0 (m, 2H); 2.6 (m, 2H). GC/MS (Method C): rt=5.80 min (90%) m/z: [M+1].sup.+=118.

Example F: Method for preparing compounds of the invention from a carboxylic acid

4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3-ylmethyl)benzamide

[0306] ##STR00055##

[0307] To a suspension of 4-[5-(3,5-dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-benzoic acid (836 mg, prepared as described for example in WO200/9080250) in dichloromethane (30 ml) was added oxalyl chloride (280 mg) and then one drop of N,N-dimethylformamide. The reaction mixture stirred at room temperature until the solids were dissolved, and the solvent was evaporated in vacuo to give a solid, which was dissolved in dichloromethane (10 ml) and the resulting solution added dropwise to a solution of triethylamine (0.5 ml) and thietan-3ylmethanamine (example B, 250 mg) in dichloromethane (20 ml) at room temperature, under argon. The reaction was stirred overnight at room temperature, diluted with water, and the organic layer washed with 1 N hydrochloric acid solution, then with 1 N sodium hydroxide solution, then with brine. The organic phase dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. Purification by column chromatography (eluent heptane/ethyl acetate) afforded the title compound as a solid (570 mg). .sup.1H-NMR (CDCl.sub.3, 400 MHz): 7.60-7.40 (m, 6H), 6.02 (m, 1H), 4.10 (d, 1H), 3.70 (d, 1H), 3.65 (t, 2H), 3.55 (m, 1H), 3.33 (t, 2H), 3.05 (dd, 2H), 2.50 (s, 3H).

Example G: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1.1-dioxo-thietan-3-ylmethyl)benzamide

[0308] ##STR00056##

[0309] To a solution of 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3-ylmethyl)benzamide (505 mg) in dichloromethane (50 ml) at 0 C. was added a solution of sodium hydrogenocarbonate (504 mg) in water (10 ml) then 3-chloroperbenzoic acid (70% w/w, 615 mg). The resulting mixture was allowed to stir at room temperature for 1 hour. The reaction mixture was then extracted with dichloromethane then the organic phase was washed twice with water, dried over anhydrous sodium sulfate, filtered and evaporated to give the crude product as a solid. Purification by chromatography using the ISCO Rf machine (dichloromethane then 5% methanol) afforded the title product (300 mg) as a white solid. .sup.1H-NMR (CDCl.sub.3, 400 MHz): 7.60-7.40 (m, 6H), 6.25 (m, 1H), 4.30 (dd, 2H), 4.10 (d, 1H), 4.00 (dd, 2H), 3.75 (t, 2H), 3.72 (d, 1H), 3.00 (m, 1H), 2.50 (s, 3H).

Example H: 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1,1-dioxothietan-3-ylmethyl)benzamide (compound H1)

[0310] ##STR00057##

Step A: 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3-ylmethyl)benzamide

[0311] ##STR00058##

[0312] To a suspension of 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3-ylmethyl)benzoic acid (prepared as described in WO 2011067272, 8.36 g, ee 90%) in dichloromethane (225 ml) and a drop of DMF under argon atmosphere at room temperature, was added dropwise oxalylchloride (3.05 g) then the resulting mixture was stirred until the solid was dissolved (2 hours). The solution was concentrated in vacuo and the residue was dissolved in dichloromethane (100 ml), and added dropwise over 1 hour to a solution of thietan-3-ylmethanamine (prepared as described in Step B, 3.98 g) and triethylamine (8.62 ml) in dry dichloromethane (275 ml) at room temperature. The reaction mixture was quenched with an addition of 200 ml of water then the organic phase was washed 3 times with 50 ml saturated aqueous sodium hydrogenocarbonate solution, water and brine solution then dried over sodium sulphate. The solvent was removed under reduced pressure to dryness to give 10 g of a crude residue, which was purified by column chromatography (ethyl acetate, heptane) to afford the title product (8 g) as a white solid. .sup.1H-NMR (CDCl.sub.3, 400 MHz): 2.48 (s, 3H), 3.07 (m, 2H), 3.32 (m, 2H), 3.55 (m, 1H), 3.64 (t, 2H), 3.71 (d, 1H), 4.11 (d, 1H), 6.10 (br t, 1H), 7.40-7.60 (m, 6H).

Step B: 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1,1-dioxothietan-3-ylmethyl)benzamide

[0313] ##STR00059##

[0314] To a solution of 4-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(thietan-3-ylmethyl)benzamide (13 g) in dichloromethane (500 ml) at 00 C. was added a solution of meta-chloroperbenzoic acid in dichloromethane (200 ml). The resulting mixture was allowed to room temperature and stirred for one night. The reaction mixture was washed twice with water, dried over anhydrous sodium sulfate, filtered and evaporated to give a crude residue, which was purified by column chromatography (ethyl acetate, heptane) to afford the title product (13.5 g) as a white solid. .sup.1H-NMR (CDCl.sub.3, 400 MHz): 2.38 (s, 3H), 2.90 (m, 1H), 3.60-3.70 (m, 3H), 3.85-3.92 (m, 2H), 4.00 (d, 1H), 4.19 (m, 2H), 6.20 (brt, 1H), 7.30-7.50 (m, 6H). Chiral HPLC analysis using a Waters UPLCHclass, DAD Detector Waters UPLC. Column: Daicel CHIRALPAK IA, 3Dm, 0.46 cm10 cm. Mobile phase: TBME/EtOH 98/02. Flow rate: 1.0 ml/min. Detection: 266. Sample concentration: 1 mg/mL in Hept/iPrOH 50/50. Injection: 2DL. Peak 1: 9.15 min; 92.4%; Peak 2: 10.39 min; 7.6%.

Example I: (1,1-dioxothietan-3-yl)methanamine

Step A: Synthesis of 1,1-dioxothietan-3-carbonitrile

[0315] ##STR00060##

[0316] 3-cyano-thietane (198 mg) in dichloromethane (50 ml) at 00 C. was treated portionwise with meta-chloroperbenzoic acid (0.9 g) and the resulting solution was stirred overnight at room temperature. The mixture was poured into diluted aqueous sodium hydrogencarnonate solution, extracted with dichloromethane. Combined organic layers were dried over sodium sulphate, then the solvent was evaporated to afford the crude title product as a white solid.

[0317] 1H NMR (CDCl.sub.3): 4.45 (m, 4H); 3.40 (m, 1H).

Step B: Synthesis of (1,1-dioxothietan-3-yl)methanamine

[0318] ##STR00061##

[0319] 1,1-dioxothietane-3-carbonitrile (0.1 g) dissolved in methanol (45 ml) was passed through H-Cube equipped with a Ra-Ni cartridge at 50 bars, 1 ml/min and room temperature. The reaction mixture was poured into HCl (4M in dioxane) and after evaporation of the solvent, 60 mg of (1,1-dioxothietan-3-yl)methanamine hydrochloride as a yellow solid was obtained. 1H NMR (D.sub.2O): 4.49-4.49 (m, 2H); 4.2-4.07 (m, 2H); 3.46 (d, 1H, J=7.3 Hz); 3.34 (d, 1H, J=7.3 Hz); 3.12-2.93 (m, 1H).

[0320] GC/MS methods:

TABLE-US-00001 Method C Volatile Cl/El GCMS was conducted on a Thermo, MS: DSQ and GC: TRACE GC ULTRA with a column from Zebron phenomenex: Phase ZB-5ms 15 m, diam: 0.25 mm, 0.25 m, H.sub.2 flow 1.7 ml/min, temp injector: 250 C., temp detector: 220 C., method: hold 2 min at 40 C., 25 C./min until 320 C., hold 1 min 12 s at 320 C., total time 15 min. Cl reagent gas: Methane, flow 1 ml/min

[0321] LC/MS Methods:

[0322] Method e:

[0323] ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

[0324] Instrument Parameter:

[0325] Ionisation method: Electrospray

[0326] Polarity: positive ions

[0327] Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature ( C.) 100,

[0328] Desolvation Temperature ( C.) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400

[0329] Mass range: 150 to 1000 Da

[0330] HP 1100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ)/binary pump (ZDQ), heated column compartment and diode-array detector.

[0331] Column: Phenomenex Gemini C18, 3 om, 303 mm,

[0332] Temp: 60 C.

[0333] DAD Wavelength range (nm): 200 to 500

[0334] Solvent Gradient:

[0335] A=water+0.05% HCOOH

[0336] B=Acetonitril/Methanol (4:1, v:v)+0.04% HCOOH

TABLE-US-00002 Time A % B % Flow (ml/min) 0.00 95.0 5.0 1.700 2.00 0.0 100.0 1.700 2.80 0.0 100.0 1.700 2.90 95.0 5.0 1.700 3.00 95.0 5.0 1.700

[0337] Method i:

[0338] ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

[0339] Instrument Parameter:

[0340] Ionisation method: Electrospray

[0341] Polarity: positive or negative ions

[0342] Capillary (kV) 3.00, Cone (V) 30.00 V, Extractor (V) 2.00, Source Temperature ( C.) 100, Desolvation Temperature ( C.) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas

[0343] Flow (L/Hr) 400

[0344] Mass range: 100 to 900 Da

[0345] HP 1100 HPLC from Agilent: solvent degasser, quaternary pump (ZCQ)/binary pump (ZDQ), heated column compartment and diode-array detector.

[0346] Column: Phenomenex Gemini C18, 3 om, 303 mm,

[0347] Temp: 60 C.

[0348] DAD Wavelength range (nm): 200 to 500

[0349] Solvent Gradient:

[0350] A=water+0.05% HCOOH

[0351] B=Acetonitril/Methanol (4:1, v:v)+0.04% HCOOH

TABLE-US-00003 Time A % B % Flow (ml/min) 0.00 95.0 5.0 1.700 2.00 0.0 100.0 1.700 2.80 0.0 100.0 1.700 2.90 95.0 5.0 1.700 3.00 95.0 5.0 1.700

[0352] Method k:

[0353] SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)

[0354] Instrument Parameter:

[0355] Ionization method: Electrospray

[0356] Polarity: positive and negative ions

[0357] Capillary: 3.00 kV

[0358] Cone: 45.00 V

[0359] Extractor: 2.00 V

[0360] Source Temperature: 150 C.,

[0361] Desolvation Temperature: 250 C.

[0362] Cone Gas Flow: 0 L/Hr

[0363] Desolvation Gas Flow: 650 L/Hr

[0364] Mass range: 100 to 900 Da

[0365] Acquity UPLC from Waters:

[0366] Binary pump, heated column compartment and diode-array detector.

[0367] Solvent degasser, binary pump, heated column compartment and diode-array detector.

[0368] Column: Phenomenex Gemini C18, 3 om, 302 mm,

[0369] Temp: 60 C.

[0370] DAD Wavelength range (nm): 210 to 500

[0371] Solvent Gradient:

[0372] A=H2O+5% MeOH+0.05% HCOOH

[0373] B=Acetonitril+0.05% HCOOH

TABLE-US-00004 Time A % B % Flow (ml/min) 0.00 100 0 0.850 1.2 0 100.0 0.850 1.50 0 100.0 0.850

TABLE-US-00005 TABLE A (I-a) [00062] retention Compound LC/MS time observed number X1 X2 X3 X4 R2 Method (min) mass A096 CCl CH CCl CF3 thietan-2- ylmethyl- * A097 CCl CH CCl CF3 (1- oxothietan-2- yl)methyl- e 1.96 519 A098 CCl CH CCl CF3 (1,1- dioxothietan- 2-yl)methyl e 1.97 535 A130 CCl CH CCl CF3 thietan-3- ylmethyl- * A131 CCl CH CCl CF3 2-(thietan-3- yl)ethanyl * A132 CCl CH CCl CF3 1,1-Dioxo- thietan-3- ylmethyl * A133 CCl CH CCl CF3 2-(1,1- dioxothietan- 3-yl)ethanyl * A178 CCl CH CCl CF3 2-(1- oxothietan-3- yl)ethanyl i 2.04 ES+: 533/534 A184 CCl CH CCl CF3 2-(3- methoxythietan- 3-yl)ethyl i 2.22 ES+: 547/549 A192 CCl CH CCl CF3 1-oxo- thietan-3- ylmethyl- k 1.02 ES: 519/521 Table A discloses compounds of formula (I-a) where R.sup.5 is methyl, Y.sup.1, Y.sup.2, Y.sup.3 are CH, G.sup.1 is oxygen and R.sup.1 is hydrogen. *: NMR data as follows: .sup.1H-NMR (400 MHz, CDCl.sub.3, in ppm)

[0374] A096: 2.50 (s, 3H), 2.74 (m, 1H), 3.05 (m, 2H), 3.22 (m, 1H), 3.73 (m, 3H), 4.00 (m, 1H), 4.09 (d, 1H), 6.27 (m, 1H), 7.44 (m, 2H), 7.53 (m, 4H).

[0375] A130: 7.55 (m, 4H), 7.50-7.40 (m, 2H), 6.0 (t br, 1H), 4.15-4.10 (d, 1H), 3.75-3.70 (d, 1H), 3.65-3.6 (m, 2H CH2), 3.55-3.5 (m, 1H), 3.40-3.30 (t, 2H), 3.10-3.05 (q, 2H), 2.50 (s, 3H)

[0376] A131: 7.55 (m, 4H), 7.50-7.40 (m, 2H), 5.80 (t br, 1H), 4.10 (d, 2H), 3.40 (m, 3H), 3.25 (t, 2H), 3.10 (t, 2H), 2.50 (s, 3H), 1.90 (q, 2H),

[0377] A132: 7.55-7.50 (m, 4H), 7.45-7.40 (m, 2H), 6.20 (t br, 1H), 4.30-4.25 (m, 2H), 4.10-4.05 (d, 1H), 4.0-3.9 (m, 2H), 3.75-3.65 (m, 3H), 3.0 (m, 1H), 2.50 (s, 3H)

[0378] A133: 7.55-7.50 (m, 4H), 7.45-7.40 (m, 1H), 7.35 (m, 1H), 5.9 (t br, 1H), 4.30-4.25 (m, 2H), 4.10-4.05 (d, 1H), 3.9-3.8 (m, 2H), 3.75-3.65 (d, 1H), 3.5-3.4 (q, 2H), 2.6 (m, 1H), 2.45 (s, 3H), 2.0 (q, 2H).

[0379] Table E discloses other compounds.

TABLE-US-00006 retention Compound LC/MS time observed number Compound name Method (min) mass E3 4-[4-(3,5-Dichloro-phenyl)-4- i 1.94 533 trifluoromethyl-4,5-dihydro-3H-pyrrol- 2-yl]-N-(1,1-dioxo-1-thietan-3- ylmethyl)-2-methyl-benzamide E4 4-[4-(3,5-Dichloro-phenyl)-4- i 1.85 515 trifluoromethyl-4,5-dihydro-3H-pyrrol- 2-yl]-2-methyl-N-(1-oxo-1-thietan-3- ylmethyl)-benzamide E5 4-[4-(3,5-Dichloro-phenyl)-4- i 2.19 501 trifluoromethyl-4,5-dihydro-3H-pyrrol- 2- yl]-2-methyl-N-thietan-3-ylmethyl- benzamide E9 2-Methyl-N-thietan-2-ylmethyl-4-[4- i 2.14 537 (3,4,5-trichloro-phenyl)- 4-trifluoromethyl-4,5-dihydro-3H- pyrrol-2-yl]-benzamide E10 N-(1,1-Dioxo-1-thietan-2-ylmethyl)-2- i 2.01 569 methyl-4-[4-(3,4,5-trichloro-phenyl)- 4-trifluoromethyl-4,5-dihydro-3H- pyrrol-2-yl]-benzamide E11 2-Methyl-N-thietan-3-ylmethyl-4-[4- i 2.26 537 (3,4,5-trichloro-phenyl)- 4-trifluoromethyl-4,5-dihydro-3H- pyrrol-2-yl]-benzamide E12 2-Methyl-N-(1-oxo-1-thietan-2- i 2.01 553 ylmethyl)-4-[4-(3,4,5-trichloro- phenyl)-4-trifluoromethyl-4,5-dihydro- 3H-pyrrol-2-yl]-benzamide E13 2-Methyl-N-(1-oxo-1-thietan-3- i 1.96 553 ylmethyl)-4-[4-(3,4,5-trichloro- phenyl)-4-trifluoromethyl-4,5-dihydro- 3H-pyrrol-2-yl]-benzamide E14 N-(1,1-Dioxo-1-thietan-3-ylmethyl)-2- i 2.03 569 methyl-4-[4-(3,4,5-trichloro- phenyl)-4-trifluoromethyl-4,5-dihydro- 3H-pyrrol-2-yl]-benzamide

BIOLOGICAL EXAMPLES

[0380] This Example illustrates the insecticidal and acaricidal properties of compounds of formula (I). Tests were performed as follows:

[0381] Spodoptera littoralis (Egyptian Cotton Leafworm):

[0382] 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).

[0383] The following compounds gave at least 80% control of Spodoptera littoralis: A096, A097, A098, A130, A131, A132, A133, A178, A184, A192, E3, E4, E5, E9, E10, E11, E12, E13, E14.

[0384] Heliothis virescens (Tobacco Budworm):

[0385] 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.

[0386] The following compounds gave at least 80% control of Heliothis virescens:

[0387] A096, A097, A098, A130, A131, A132, A133, A178, A184, A192, E3, E4, E5, E9, E10, E11, E12, E13, E14, H1

[0388] Plutella xylostella (Diamond Back Moth):

[0389] 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.

[0390] The following compounds gave at least 80% control of Plutella xylostella:

[0391] A096, A097, A098, A130, A131, A132, A133, A178, A184, A192, E3, E4, E5, E9, E10, E11, E12, E13, E14, H1

[0392] Diabrotica balteata (Corn root worm):

[0393] 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

[0394] 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.

[0395] The following compounds gave at least 80% control of Diabrotica balteata:

[0396] A096, A097, A098, A130, A131, A132, A133, A178, A184, A192, A193, A194, A195, A198, E3, E4, E5, E9, E10, E11, E12, E13, E14, H1 Thrips tabaci (Onion Thrips):

[0397] 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 a thrip population of mixed ages. After an incubation period of 7 days, samples were checked for mortality.

[0398] The following compounds gave at least 80% control of Thrips tabaci:

[0399] A096, A097, A098, A130, A131, A132, A133, A178, A184, A192, E3, E4, E5, E9, E10, E11, E12, E13, E14, H1.

[0400] Tetranychus urticae (Two-Spotted Spider Mite):

[0401] 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.

[0402] The following compounds gave at least 80% control of Tetranychus urticae:

[0403] A096, A097, A098, A130, A131, A132, A133, A178, A184, A192, E3, E4, E5, E9, E10, E11, E12, E13, E14, H1.