反应详情

温度

26 °C

Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (8.45 g, 0.132 mol) in hexane was added to a solution of tetramethylethylenediamine (15.3 g, 0.132 mol) in 60 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-trimethylsilylbenzylamine (10.8 g, 0.06 mol) in 30 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound. This suspension was stirred for 16 hours at 26° C. and then was dropwise added to a solution of phenylphosphonic dichloride (12.5 g, 0.064 mol) in 120 ml. of anhydrous cyclohexane over a period of 1 hour at 26° C. After stirring for 2 hours, the reaction mixture was partitioned in methylene chloride and water. The layers were separated and the methylene chloride layer was washed with water, dried over sodium sulfate and then concentrated in vacuo to yield an oil. The oil was chromatographically separated on a silica gel column using ethyl acetate as the eluant. Fractions containing the benzazaphosphole were combined and concentrated in vacuo to produce a crude product. The crude product was crystallized from petroleum ether to yield 1-phenyl-2-(trimethylsilyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide as a crystalline solid. A second crop was obtained to give a total yield of 2.45 g, 14% yield to yield 1-phenyl-2-(trimethylsilyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide having a melting point of 90°-94° C. and the following analysis:

1. temperatureWhile maintaining
2. customthe temperature of the reaction at 0° C.
3. customto produce a suspension
4. stirringAfter stirring for 2 hours
5. customthe reaction mixture was partitioned in methylene chloride
6. customThe layers were separated
7. washthe methylene chloride layer was washed with water
8. dry with materialdried over sodium sulfate
9. concentrationconcentrated in vacuo
10. customto yield an oil
11. customThe oil was chromatographically separated on a silica gel column
12. additionFractions containing the benzazaphosphole
13. concentrationconcentrated in vacuo
14. customto produce a crude product
15. customThe crude product was crystallized from petroleum ether