Insecticidal N-substituted (heteroaryl)alkyl sulfilmines
A technology of halogenated alkyl and alkyl, applied in the field of N-substituted (heteroaryl) alkylsulfimides with insecticidal effect
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Embodiment I
[0071] Example I: {1-[6-(trifluoromethyl)pyridin-3-yl]methyl}(methyl)-λ 4 -Preparation of sulfoiminonitrile (1)
[0072]
[0073] To a solution of 3-chloromethyl-6-(trifluoromethyl)pyridine (5.1 g, 26 mmol) in dimethylsulfoxide (DMSO; 20 mL) was added sodium methylthiolate (1.8 g, 26 mmol) in one portion . A violent exothermic reaction was observed, causing the reaction mixture to turn black. The reaction mixture was stirred for 1 hour. Additional sodium methylthiolate (0.91 g, 13 mmol) was then added slowly. The reaction mixture was stirred overnight, after which it was poured into H 2 O, add a few drops of concentrated HCl. The mixture was washed with Et 2 O (ether, 3×50mL) was extracted, the organic layers were combined, washed with brine, washed over MgSO 4 Dry, filter and concentrate. The crude product was purified by chromatography (Preparative 500, 10% acetone / hexanes, v / v) to afford sulfide (A) as a pale yellow oil (3.6 g, 67%). 1 HNMR (300MHz, CDCl 3 )δ8....
Embodiment II
[0076] Example II: (1-{6-[chloro(difluoro)methyl]pyridin-3-yl}ethyl)(methyl)-λ 4 -Preparation of sulfoiminonitrile (2)
[0077]
[0078] Dissolve (3E)-1-chloro-4-ethoxy-1,1-difluorobut-3-en-2-one (7.36g, 40mmol) in anhydrous toluene (40mL) at room temperature with 3 - Treatment with dimethylaminoacrylonitrile (4.61 g, 48 mmol). The solution was heated at 100°C for 3.5 hours. The solvent was then removed under reduced pressure and the residual mixture was redissolved in dimethylformamide (DMF; 20 mL), treated with ammonium acetate (4.62 g, 60 mmol) and stirred at room temperature overnight. Water was added to the reaction mixture, and the resulting mixture was washed with ether-CH 2 Cl 2 (1:2, v / v) extracted twice. The combined organic layers were washed with brine, dried, filtered and concentrated. The residue was purified on silica gel to afford 3.1 g of 6-[chloro(difluoro)methyl]pyridine-3-carbonitrile (A) as a light oil in a yield of 41%. GC-MS: C 7 h 3 CIF 2 N...
Embodiment III
[0089] Example III: {1-[6-(trichloromethyl)pyridin-3-yl]ethyl}(methyl)-λ 4 -Preparation of sulfoiminonitrile (3)
[0090]
[0091] A mixture of 5-ethylpyridine-2-carboxylic acid (1.98 g, 13 mmol), phenylphosphonicdichloride (2.8 g, 14.3 mmol), phosphorus pentachloride (7.7 g, 32 mmol) was stirred and heated slowly. Once a clear yellow liquid had formed, the mixture was heated to reflux overnight. After cooling, the volatiles were removed under reduced pressure. The residue was carefully poured into saturated aqueous sodium carbonate solution (cooled in an ice-water bath). Then the aqueous phase was washed with CH 2 Cl 2 Extract twice. The combined organic layers were washed with brine, washed with anhydrous Na 2 SO 4 Drying, filtration, concentration and partial purification on silica gel (eluting with 10% EtOAc / hexanes (v / v)) afforded 2.7 g of crude product containing both 5-ethyl-2-(trichloromethyl ) pyridine contains 5-(1-chloroethyl)-2-(trichloromethyl)pyridine ...
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