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Chainani, G. R. (1959) Mutual replacement of halogen and alkoxyl (or aryloxyl) in inorganic non-metal halide systems. Doctoral thesis, Northern Polytechnic.
The work is a contribution to a comprehensive investigation into the factors determining the sequence of reactions between an inorganic non-metal halide and the esters of phosphoric, phosphorous, phosphonic, sulphurous, boric and silicic acids and certain related compounds. Two general types of sequence have been discerned by other workers engaged in this investigation. These are a mutual replacement of alkoxyl by halogen, there being a general drift in one direction, and elimination of alkyl halide resulting in the development of a polymer.
Interaction of n-butyl borate and phosphorus trichloride to afford the phosphite and boron trichloride would have been technically important for both products. Because of the drift referred to, no reaction occurred. Nor was there any observed reaction between the borate and silicon tetrachloride or thionyl chloride. Phosphorus oxychloride did react slowly, and phosphorus pentachloride much more readily to afford alkyl halide and degeneration products.
Trimethyl borate was more reactive, but the course of reaction was of no technical significance. In these systems ferric chloride was catalytic, but merely effected the formation of alkyl halide and insignificant degeneration products.
The interaction of boron trichloride with certain phosphonic esters shows an elimination of alkyl chloride and a condensation polymerisation due to P-O-B- linkages. Certain other systems were examined.
The results are correlated to those obtained by co-workers in the general investigation.
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