PHOSPHONIUM SALTS .I. ALKALINE HYDROLYSIS OF SOME BIS-PHOSPHONIUM SALTS

被引:30
作者
BROPHY, JJ
GALLAGHE.MJ
机构
[1] Department of Organic Chemistry, University of New South Wales, Kensington, NSW, 2033
基金
澳大利亚研究理事会;
关键词
D O I
10.1071/CH9691385
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ethane- and ethene-1,2-bisphosphonium salts are cleaved by alkali into a phosphine and a phosphine oxide with loss of the two-carbon bridge. When the phosphorus atom carries benzyl substituents, loss of the benzyl groups is competitive with loss of the bridge. Based on a kinetic study, a synchronous mechanism, analogous to the alkaline hydrolysis of acyclic monophosphonium salts, is proposed to account for the fragmentation. With 6-membered 1,4-diphosphonio heterocyclic salts the nature of the products is dependent on whether alkali or phosphonium salt is present in excess. With an excess of alkali a synchronous mechanism again appears to operate, while with an excess of salt the reaction proceeds stepwise and without loss of the bridge. A partial explanation of these facts is advanced in terms of non-bonded interactions in the intermediate phosphoranes. The synchronous reaction appears to be favoured by coplanarity of the P-C-C-P system. © 1969, CSIRO. All rights reserved.
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页码:1385 / &
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