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  

Study of Caged Bicyclic Phosphate Derivatives——Ⅵ. Study on the Eeaction of 4-Substituted-2, 6, 7-trioxa-1 phosphabicyclo [2.2.2] octane

作　　者：李玉桂[1] 包建春[1] 

机构地区：[1]南开大学元素有机化学研究所,天津300071

出　　处：《化学学报》1993年第6期602-606,共5页Acta Chimica Sinica

基　　金：国家自然科学基金

摘　　要：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着明显的不同.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.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. We study the reactions of compound 1 with sulphuryl chloride, chlorine, bromine and phosphorus pentachloride, respectively. It is found that 1 undergoes the reactions which are similar to Arbuzov reaction to yield the same stereo-conformation ring opening compounds. We have also studied the phosphonothiolation reaction of bicyclic phosphite 2, the result shows that DMAP(4-N, N-dimethylamino-pyridine) is an effective catalyst in the reaction.

关 键 词：双环笼状 亚磷酸酯 

分 类 号：O627.51[理学—有机化学]