반응 #5736

반응 방정식

di-t-butylperoxide

1,5cyclooctadiene

phenylphosphine

Di-t-butylperoxide

undecane

→

9-Phenyl-9-Phosphabicyclononane

반응 조건

후처리

1. 1
   기타All glassware is dried at 120° C.
2. 2
   기타a purge of argon
3. 3
   기타A 250 mL, 3-neck flask is fitted with magnetic spin bar
4. 4
   온도thermometer, reflux condenser, a rubber syringe septum, argon inlet, and flowmeter
5. 5
   기타The reactor system is purged overnight with argon flowing at 3 mL/min.
6. 6
   workup.ADDITIONadded with a syringe pump over 1 hour
7. 7
   온도while maintaining
8. 8
   기타the temperature of the exothermic reaction at 135°-145° C
9. 9
   온도the temperature is increased to 150° C.
10. 10
    workup.WAITheld for an additional hour
11. 11
    기타Periodic aliquots, taken with a syringe through the septa
12. 12
    workup.DISTILLATIONThe reaction mixture is distilled through a 6-inch Vigreux column
13. 13
    기타a mixture, 58.3 g (67%) of 9-phenyl-9phosphabicyclo[4.2.1]nonane and 9-phenyl-9phosphabicyclo[3.3.1]nonane, is collected [b.p
14. 14
    기타septum-sealed flask under a nitrogen gas atmosphere
15. 15
    세척earlier eluting isomer) and 33% 9-pheny-9-phosphabicyclo[3.3.1]nonane

실험 절차

This procedure is a modification of Mason and Van Winkle's. See U.S. Pat. No. 3,400,163. All glassware is dried at 120° C. and assembled hot under a purge of argon. A 250 mL, 3-neck flask is fitted with magnetic spin bar, thermometer, reflux condenser, a rubber syringe septum, argon inlet, and flowmeter. The reactor system is purged overnight with argon flowing at 3 mL/min., and then charged with redistilled 1,5cyclooctadiene [43.3 g (49.1 mL), 0.4 mole, density =0.882 g/mL, from Aldrich Chemical Co.] and phenylphosphine [44.0 g (44.0 mL), 0.4 mole, density =1.00 g/mL, from Strem Chemicals]while under a stream of argon. The reaction solution is heated to 135° C. Di-t-butylperoxide [1.46 g (1.8 mL), 0.01 mole, density=0.796 g/mL, from Aldrich Chemical] is mixed with 5 mL of undecane and added with a syringe pump over 1 hour while maintaining the temperature of the exothermic reaction at 135°-145° C. A second portion of di-t-butylperoxide (1.8 mL in 5 mL of undecane) is added rapidly, and the temperature is increased to 150° C. and held for an additional hour. Periodic aliquots, taken with a syringe through the septa, are examined by infrared spectroscopy, and the disappearance of the olefin band at 1645 cm- 1 and the P-H band at 2300 cm- 1 is monitored. After two hours total reaction time, both of these bands had disappeared. The reaction mixture is distilled through a 6-inch Vigreux column and a mixture, 58.3 g (67%) of 9-phenyl-9phosphabicyclo[4.2.1]nonane and 9-phenyl-9phosphabicyclo[3.3.1]nonane, is collected [b.p. 123-125 at 0.1 mmHg], and stored in a refrigerated and septum-sealed flask under a nitrogen gas atmosphere. Reported b.p.: 134°-135° C. at 0.3 mm (Hg). Gas chromatography shows the mixture is 67% 9- phenyl-9-phosphabicyclo[4.2.1]nonane (the earlier eluting isomer) and 33% 9-pheny-9-phosphabicyclo[3.3.1]nonane.

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