双环笼状磷酸酯衍生物的研究Ⅵ:4-取代-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷的反应研究

双环笼状亚磷酸酯类衍生物由于其笼状结构所引起的张力及高位阻性 ,使得它同一般直链亚磷酸酯类化合物相比,在亲核取代反应性等方面有关明显的不同.本文用化合物1分别同SO~2Cl~2,Cl~2, Br~2, PCl~5等反应,结果表明,1均发生了类Arbuzov反应,生成具有相同立体构型的开环产物.本文还对化合物2的磷酰化反应进行了研究,发现在这类高位阻性的双环笼状亚磷酸酯衍生物的磷酰化反应中,DMAP是一个较有效的催化剂.

Study of caged bicyclic phosphate derivatives.Ⅵ.study on the reaction of 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane

Compared with straight chain phosphites, caged bicyclic phosphites have great differences in nucleophilic reactions due to the tension and high steric hindrance caused by the caged bicyclic structure. The reactions of compound I with sulfuryl chloride, chlorine, bromine, and phosphorus pentachloride was studied. I undergoes the reactions which are similar to Arbuzov reaction to yield the same stereo-conformation ring opening compounds The thiophosphorylation reaction of bicyclic phosphite II was studied and the result shows that 4-N,N-dimethylamino-pyridine is an effective catalyst in the reaction.