Dichloro- -phosphine

The reaction given here has been described before as a general reaction,2 and there can be a wide variety of alkyl, aryl, and halo substituents on the diene and phosphorus. Dibromophosphines are appreciably more reactive than dichlorophosphincs. If a free-radical catalyst is used instead of an inhibitor, the copolymers can be made in good yield.3 The 1,4-addition of dichloro-phosphines to 1,3-dienes is of theoretical interest because of its analogy to the well-known 1,4-addition of sulfur dioxide to 1,3-dienes. 

The chemistry of the phosphirene system is attracting increasing attention, with the eventual goal of preparing the potentially aromatic Huckel system (214). A simple preparation of tervalent phosphirenes (215) is afforded by the reactions of dichloro-phosphines with alkynes in the presence of aluminium chloride,... 

A range of reactions of 2-chlorocyclohexyl(dichloro)phosphine (60) with alcohols and epoxides has been described, largely with a view to the synthesis of polymer intermediates and flame-retardants.50 The copolymerization of dichloro(phenyl)-phosphine with styrene and vinyl butyl ether in the presence of maleic anhydride has been studied.61... 

Simple silanes, such as trichlorosilane (5), have been used to reduce the complexes formed by phosphorus pentachloride and alkenes. The products are alkenyl-(dichloro)phosphines (6), although the yields are quite variable. The related chlorophosphines (7) have been prepared from alkyl acetates. ... 

Miscellaneous Aspects.—Ad initio M.O. calculations have been published for the phospha-alkenes (56). Blue ferrocenium complexes have been reported to be formed when benzene solutions of ferrocene are treated with simple dichloro-phosphines. ... 

This area of phosphorus chemistry continues to grow rapidly. A new route to the diphosphene (150) (and confirmation of the structure of the product by X-TAy studies) has been reported which involves the reaction of 2,4,6-tri-t-butylphenyldichlorophosphine with tris(trimethylsilyl)silyl-lithium. Apart from a chemical shift for this compound of +493 p.p.m., the physical properties are similar to those published in 1981 by Yoshifuji and his co-workers for the product [formulated as (150)] of the reaction of the above dichloro-phosphine with magnesium, for which a phosphorus chemical shift of —59 p.p.m. was reported. This work has now been reinvestigated by Cowley s group, and the desired phosphene isolated and shown to have 8( P) = +494 p.p.m. The compound responsible for the signal at 8 = —59 p.p.m. has been... 

The relevance of iV-trimethylsilyl-aminophosphines in several fields of chemistry led Wrackmeyer to develop the synthesis of the novel, fairly stable A/-trimethylsilyl-amino(dichloro)phosphine 8, in which the nitrogen atom bears a 9-borabicyclo[3.3.1]nonyl group (Scheme 2). 

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