反应详情

温度

26 °C

Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (16 g, 0.25 mol) in hexane was added to a solution of tetramethylethylenediamine (28.6 g, 0.246 mol) in 120 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-trimethylsilylbenzylamine (21.6 g, 0.12 mol) in 60 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 cooled to -76° C. using a solid carbon dioxide-acetone bath. A solution of phenylphosphonic dichloride (25 g, 0.128 mol) in 120 ml. of anhydrous cyclohexane was rapidly added to the suspension causing the temperature of the reaction to increase to -15° C. The reaction mixture was allowed to cool to -76° C., after which time the solid carbon dioxide-acetone bath was removed and the reaction mixture was stirred for 3 hours. The reaction mixture was cooled to 0° C., then quenched with the rapid addition of 24 ml. of acetic acid. After stirring the reaction mixture for 5 minutes, the cyclohexane was removed on a rotary evaporator, and the resulting residue was partitioned between methylene chloride and water. The layers were separated and the methylene chloride layer was dried over magnesium sulfate and concentrated in vacuo to yield an oil. Distillation of this oil at 180° C. and 0.3 mm yielded 1-phenyl-2-trimethylsilyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide.

1. temperatureWhile maintaining
2. customthe temperature of the reaction at 0° C.
3. customto produce a suspension
4. temperaturecooled to -76° C.
5. customthe temperature of the reaction
6. temperatureto increase to -15° C
7. temperatureto cool to -76° C.
8. customafter which time the solid carbon dioxide-acetone bath was removed
9. stirringthe reaction mixture was stirred for 3 hours
10. temperatureThe reaction mixture was cooled to 0° C.
11. customquenched with the rapid addition of 24 ml
12. stirringAfter stirring the reaction mixture for 5 minutes
13. customthe cyclohexane was removed on a rotary evaporator
14. customthe resulting residue was partitioned between methylene chloride and water
15. customThe layers were separated
16. dry with materialthe methylene chloride layer was dried over magnesium sulfate
17. concentrationconcentrated in vacuo
18. customto yield an oil
19. distillationDistillation of this oil at 180° C.