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Rothenbury, Raymand Albert (1961) Reactions of borazole derivatives with organo phosphorus compounds. Doctoral thesis, Northern Polytechnic.
B-trichloroborazole and trialkyl phosphates in 1:3 molar proportions form strongly hydrogen bonded complexes, which undergo elimination of alkyl chloride to form the B-tris(dialkoxyphosphoryl)borazoles. These condense by the intermolecular elimination of trialkyl phosphate to form the B-monoalkoxyphosphoryl polyborazoles, which undergo further thermal degradation at 400—600°, eliminating ammonia and olefin (except for the methyl phosphate system, when methane is obtained) to give thermally stable inorganic polymers.
The 1:1 hydrogen bonded complex eliminates alkyl chloride and forms a polyborazole, which undergoes thermal decomposition at 500-600°, ammonia and some alkyl chloride being eliminated to afford an inorganic polymer. This polymer is less resistant to hydrolysis than that obtained from the 1:3 complex.
The interaction of B-trichloroborazole with triphenyl phosphate follows a very different course, some mutual replacement of phenoxy group and chlorine occurs.
Heating B-trichloro-N-trimethyl or B-trichloro-N- triphenylborazoles with trialkyl phosphates in 1:3 molar proportions results in the elimination of alkyl chloride; further pyrolysis affords the trialkyl phosphate, but with the N-triphenylborazole ring fission also occurs with the formation of the N-alkylanilines. Continued pyrolysis of the polymers obtained results in the formation of olefins (except with the methyl phosphate system when methane is obtained) and an inorganic polymer.
After a mixture of B-trichloro-N-trimethylborazole and triphenyl phosphate has been heated, the components are recovered on distillation.
Dialkyl hydrogen phosphites with B-trichloroborazole in 1:1 molar proportions react almost instantaneously, and eliminate the alkyl chloride. At 360° the evolution of alkyl chloride is complete, but in the later stages is accompanied by hydrogen chloride evolution, which causes ring rupture with the formation of ammonium chloride. The inorganic polymers obtained, although thermally stable, are not hydrolytically stable.
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