تفاعل #531613

معادلة التفاعل

p-bromo-t-amylbenzene

magnesium

hydrochloric acid

phosphorus trichloride

sodium carbonate

phosphorus

hydrogen

→

expected product

المردود 72.0%

Tris(p-t-amylphenyl) phosphine

المردود 72.0%

المذيبات

tetrahydrofuran

methanol

water

water

chloroform

ظروف التفاعل

المعالجة

1. 1
   درجة الحرارةcooled
2. 2
   درجة الحرارةreflux
3. 3
   workup.ADDITIONcondenser, addition funnel
4. 4
   workup.ADDITIONwas added from the addition funnel with rapid stirring
5. 5
   درجة الحرارةan increase in the temperature of the reaction mixture
6. 6
   workup.ADDITIONthe remainder of the solution was added at a rate which
7. 7
   درجة الحرارةmaintained the reaction mixture at the boiling point without external heating
8. 8
   workup.ADDITIONcompletion of the addition the reaction mixture
9. 9
   درجة الحرارةwas heated at the boiling point for two hours
10. 10
    workup.ADDITIONwas then added at a rate which
11. 11
    درجة الحرارةmaintained the temperature of the reaction mixture at from 15° to 25° C
12. 12
    workup.ADDITIONcompletion of the addition the reaction mixture
13. 13
    درجة الحرارةwas heated to the boiling point for two hours
14. 14
    درجة الحرارةto cool
15. 15
    workup.ADDITIONpoured
16. 16
    workup.STIRRINGStirring
17. 17
    workup.ADDITIONwas gradually added until the pH of the solution
18. 18
    أخرىthe organic layer was separated
19. 19
    أخرىthe water in this phase was removed
20. 20
    أخرىThe chloroform was then removed by evaporation under the reduced pressure
21. 21
    أخرىproduced by a water aspirator
22. 22
    أخرىto yield a yellow solid
23. 23
    workup.ADDITIONmixed thoroughly for one hour
24. 24
    أخرىmelted from 129.5° to 130° C.

الإجراء التجريبي

A glass reactor equipped with a water-cooled reflux condenser, addition funnel, mechanically driven stirrer, thermometer and a nitrogen inlet was charged with 37 g (1.55 mole) of magnesium chips. A 30 cc portion of a solution containing 340.5 g (1.5 mole) of p-bromo-t-amylbenzene and one liter of tetrahydrofuran was added from the addition funnel with rapid stirring. When the reaction initiated, as indicated by an increase in the temperature of the reaction mixture, the remainder of the solution was added at a rate which maintained the reaction mixture at the boiling point without external heating. Following completion of the addition the reaction mixture was heated at the boiling point for two hours and allowed to cool to 15° C. A solution containing 68.8 g (0.5 mole) of phosphorus trichloride was then added at a rate which maintained the temperature of the reaction mixture at from 15° to 25° C. Following completion of the addition the reaction mixture was heated to the boiling point for two hours, allowed to cool and then poured with stirring into a mixture containing one liter of ice and 100 cc of concentrated aqueous hydrochloric acid. Stirring was continued until all of the ice melted, at which time sodium carbonate was gradually added until the pH of the solution was 7. One liter each of chloroform and water was added, the organic layer was separated and the water in this phase was removed using anhydrous magnesium sulfate. The chloroform was then removed by evaporation under the reduced pressure produced by a water aspirator to yield a yellow solid. This material was combined with a portion of methanol, pulverized and mixed thoroughly for one hour. The dried solid material weighed 170 g (72% yield), melted from 129.5° to 130° C. and was found to contain 83.3% carbon, 9.34% hydrogen and 6.50% phosphorus. The calculated values for the expected product are 83.9% carbon, 9.53% hydrogen and 6.57% phosphorus.

المصدر