Halogenophosphonium salts

In a study of the reactions oi acyclic o-methoxyphenyl-phosphinites (45a), phosphonites (45b) and phosphites (45c) with halogens,the intermediate halogenophosphonium salts (46) are stabilised either by ligand exchange with starting material (not shown) or by elimination of methyl halides to form cyclic phosphoranes ( 47 ) 3 7. ... 

The addition of chlorine to the A -phosphoIen (85) gives the halogenophosphonium salt (86). Spectroscopic studies of (86) have yielded no evidence for the existence of... 

Diazadiphosphetidines form the halogenophosphonium salts (53) on treatment with high-valent chlorides of tin, phosphorus, and antimony, ... 

It was McCormack who, in 1953, in the patent literature, first reported the cycloaddition of phosphorus(III) halides to l,3-dienes . As then represented, the sequence took the form depicted in reaction 13 (X = Cl or Br). The careful addition of water to the crystalline 1 1 adduct, formulated as a halogenophosphonium salt (92), gave the unsaturated phosphinic chloride (93, R = Br or Cl) or acid (93, R = OH). Since the original publication of the procedure, the application of modern spectroscopic techniques has demonstrated that the final products in such reactions are mixtures of the 3-phospholene (93) and 2-phospholene (94) isomers, conveniently represented, when admixed and in unknown proportions, as 95. It has since become apparent that the relative proportions of the isomeric forms 93 and 94 of any derivative depend on the nature of the halogen X and on the manner of work-up thus, in an acidic work-up medium, the products tend to have the structure 94, but neutralization during the hydrolysis step leads to derivatives of the isomeric 93. The reaction consists simply in mixing the reactants at room temperature and... 

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