Process for the preparation of certain substituted sulfilimines
A technology of sulfimine and haloalkyl, which is applied in the field of preparing certain substituted sulfimines
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Embodiment 1
[0069] Example 1 (1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)(methyl)-λ 4 -Preparation of sulfoiminonitrile
[0070]
[0071] The solution of 22.1g (0.1mol) 3-[1-(methylthio)ethyl]-6-(trifluoromethyl)pyridine and 5.04g (0.12mol) cyanamide in 150mL acetonitrile was cooled to -5 ℃. To this solution was added dropwise 150 g of NaOCl aqueous solution (0.115 mol, Clorox TM 5.7%wt). The reaction mixture was stirred at -5°C for 45 minutes, then warmed to 5°C. To the mixture was added 5 mL of 25% aqueous sodium metabisulfite and the biphasic mixture was allowed to settle. 5.7 mL (0.1 mol) of glacial acetic acid was added to the organic phase, and the solution was concentrated in vacuo to an oil. Dissolve the oil in 70 mL CH 2 Cl 2 , washed with 50 mL of water. The aqueous layer was washed with 30mL CH 2 Cl 2 Re-extract. The combined organics were then subjected to MgSO 4 dry. After filtration, the dichloromethane solution was analyzed by LC to contain the above-mentione...
Embodiment 2
[0072] Example 2: (1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)(methyl)-λ 4 -Preparation of sulfoiminonitrile
[0073]
[0074] A solution of 110.6g (0.475mol, 95% determination) 3-[1-(methylthio)ethyl]-6-(trifluoromethyl)pyridine and 25.2g (0.6mol) cyanamide in 600mL acetonitrile Cool to -5°C. To this solution was added dropwise 750 g of NaOCl aqueous solution (0.575 mol, Clorox TM 5.7%wt), while keeping the temperature below 0°C. The reaction mixture was stirred at -1°C for 30 minutes. A solution of 9.5 g (0.05 mol) of sodium metabisulfite in 25 mL of water was added to the mixture and the biphasic mixture was allowed to settle. The aqueous phase was extracted twice more with 50 mL of acetonitrile. The organics were combined and the acetonitrile / sulfilimine solution was used directly in the subsequent oxidation. LC analysis indicated two isomers in a 40:54 (area) ratio.
Embodiment 3
[0075] Example 3: (1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)(methyl)-oxidation-λ 4 -Preparation of sulfoiminonitrile
[0076]
[0077] 100mL of acetonitrile, 200mL of water and 160g (0.45mol) of 40% NaMnO 4 The mixture in aqueous solution (Aldrich) was cooled to 15°C. To a solution of sulfilimine (about 0.475 mol, from Example 2) in about 700 mL of acetonitrile was added 26 mL (0.45 mol) of glacial acetic acid. The sulfilimine solution was added to the permanganate mixture over 50 minutes with rapid stirring. During this time the temperature of the ice bath was lowered or raised to maintain the reaction temperature around 19°C. The reaction mixture was allowed to continue for 45 minutes. The mixture was cooled to 12°C and a solution of 171 g (0.9 mol) sodium metabisulfite in 300 mL water was added with rapid stirring over 15 minutes. The mixture was stirred at room temperature for 30 minutes, then filtered. The off-white solid was rinsed with 50 mL of acetonitrile. T...
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