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Davies, Henry John Woodcock (1962) Interaction of organic sulphites with boron trihalides. Doctoral thesis, Northern Polytechnic.
This work is a contribution to a comprehensive investigation into the factors which determine whether in the interaction of non-metal halides, and alkoxyl (or aryloxyl) derivatives of the same or a different non-metal, the non-metals become linked through oxygen, with elimination of alkyl halide, or there is a mutual exchange of alkoxyl and halogen. An example of the first type of reaction is the interaction of the alkyl sulphates and boron trichloride to give an alkyl halide and a compound approximating to the mixed anhydride (B₂S₃O₁₂)n. An example of the second type of reaction is the interaction of n-butyl phosphite and boron trichloride, to give the chloroborinate and phosphorochloridite. Di-n-butyl sulphite reacts readily with boron trichloride, exchange of alkoxyl and chlorine occurring. There is no interaction between the intermediate chloro-esters, and indeed, n-butyl chlorosulphinate does not react with boron trichloride. The n-butyl dichloroborinate and even the chloroboronate can react with the sulphite. Diphenyl sulphite undergoes similar mutual exchange reactions. Phenyl chlorosulphinate reacts readily with boron trichloride. The course of the reactions is rendered complicated by the tendency of the phenyl chloro-boron esters to disproportionate, giving finally triphenyl borate and boron trichloride. Ethylene sulphite and boron trichloride in the molar ratio of 2:1 give bis(2-chlorosulphinoxyathyl) chloroboronate. Reaction of ethylene sulphite and the boron trichloride in other proportions gives tri(2-chloroethyl) borate, and ethylene chloro boronate and thionyl chloride as well as the bis(2-chlorosulphinoxy ethyl) chloroboronate. o-Phenylene sulphite and boron trichloride give o-phenylene chloroboronate and thionyl chloride. A noteworthy feature of this system is the production of highly coloured materials, and the sequence of colour changes accompanying the reactions.
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