反应详情

Two hundred ml. of dry tetrahydrofuran was combined with 8.1 g. of diisopropylamine, and the mixture was chilled to -70° under a nitrogen stream. A 36 ml. portion of 2.2-molar n-butyllithium in hexane was added, and the mixture was stirred for 5 minutes. Then a suspension of 18.8 g. of 1-dimethylamino-2-(3-trifluoromethylphenyl)-1-butene-3-one in 100 ml. of tetrahydrofuran was added at a rate such that the temperature of the mixture remained below -60°. The mixture was then stirred for 30 minutes more, and to it was added 10 g. of trifluoromethylsulfenyl chloride in 40 ml. of tetrahydrofuran, maintaining the temperature of the mixture below -60°. After the addition was complete, the reaction mixture was stirred for 15 minutes more, and was then allowed to warm to 10° over a period of 1 hour. The reaction was then quenched by the addition of saturated potassium dihydrogen phosphate solution and was diluted with water and diethyl ether. The organic layer was separated, dried over magnesium sulfate and evaporated to dryness under vacuum to obtain a dark oil which solidified on standing. The oil was chromatographed on a 500 g. silica gel column, with 1:9 ethyl acetate:dichloromethane as the eluting solvent. The product-containing fractions were combined and evaporated to dryness under vacuum to obtain 4.3 g. of the expected product, which was identified by nmr (CDCl3): δ7.3-7.7 (m, 5H); 3.7 (s, 2H); 2.65 (s, 6H).

1. additionThen a suspension of 18.8 g
2. customremained below -60°
3. stirringThe mixture was then stirred for 30 minutes more
4. additionto it was added 10 g
5. additionAfter the addition
6. stirringthe reaction mixture was stirred for 15 minutes more
7. temperatureto warm to 10° over a period of 1 hour
8. customThe reaction was then quenched by the addition of saturated potassium dihydrogen phosphate solution
9. additionwas diluted with water and diethyl ether
10. customThe organic layer was separated
11. dry with materialdried over magnesium sulfate
12. customevaporated to dryness under vacuum
13. customto obtain a dark oil which
14. customThe oil was chromatographed on a 500 g
15. customevaporated to dryness under vacuum
16. customto obtain 4.3 g