تفاعل #94984

معادلة التفاعل

sodium hydroxide

bis(4-methoxyphenyl)phosphine-oxide

trichlorosilane

sodium hydroxide

phosphine oxide

→

bis-(4-methoxyphenyl)phosphine

المردود 57.0%

المذيبات

toluene

ظروف التفاعل

المعالجة

1. 1
   أخرىThis resulted
2. 2
   درجة الحرارةin moderate heat
3. 3
   درجة الحرارةThe mixture was heated at 90° for 5 h, whereupon the clear colorless solution
4. 4
   درجة الحرارةwas cooled to 0°
5. 5
   درجة الحرارةwhile cooling the mixture in an ice-bath
6. 6
   أخرىthe vigorous reaction
7. 7
   workup.DISSOLUTIONdissolved (30-90 min)
8. 8
   أخرىleaving two clear
9. 9
   أخرىto separate
10. 10
    استخلاصThe aqueous layer was extracted with 2×20 mL of toluene
11. 11
    تجفيفThe combined toluene extracts were dried
12. 12
    أخرى(deoxygenated brine and sodium sulfate)
13. 13
    ترشيحfiltered
14. 14
    أخرىstripped of solvent on the rotary evaporator at 80°/5 mm Hg
15. 15
    أخرىto give 1.11 g (84.5%) of crude product
16. 16
    workup.DISTILLATIONThe thick oil was distilled by bulb to bulb distillation at 115°-135°/0.02 mm Hg for 1 h

الإجراء التجريبي

A solution-suspension of 1.4 g (5.34 mmol) of bis(4-methoxyphenyl)phosphine-oxide in 18 mL of toluene was treated under argon with 3.35 g (2.5 mL, 25 mmol) of trichlorosilane in one portion. This resulted in moderate heat and gas evolution and led to complete solution of the phosphine oxide. The mixture was heated at 90° for 5 h, whereupon the clear colorless solution was cooled to 0°. With vigorous stirring, 8.0 mL of 2 N aqueous sodium hydroxide solution (16 mmol) was added slowly while cooling the mixture in an ice-bath to moderate the vigorous reaction. When all the sodium hydroxide had been added, the mixture was allowed to warm to room temperature and stirred vigorously until all solid dissolved (30-90 min), leaving two clear, colorless liquid phases. The layers were allowed to separate and the toluene layer was drawn off under argon via a cannula. The aqueous layer was extracted with 2×20 mL of toluene. The combined toluene extracts were dried (deoxygenated brine and sodium sulfate), filtered, and stripped of solvent on the rotary evaporator at 80°/5 mm Hg to give 1.11 g (84.5%) of crude product. The thick oil was distilled by bulb to bulb distillation at 115°-135°/0.02 mm Hg for 1 h to give 0.747 g (57%) of bis-(4-methoxyphenyl)phosphine as a colorless thick oil which shortly crystallized to colorless, slightly greasy crystals.

المصدر