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Hudson, Harry Robinson (1960) Interaction of boron trichloride with secondary amines. Doctoral thesis, Northern Polytechnic.
Current interest in semi-organic polymers based on boron-nitrogen systems led to this present work which is chiefly concerned with aminoborazoles and polymers derived therefrom. It also forms a logical part of the investigations at the Northern Polytechnic into the reactions of inorganic halides with organic compounds. Synthesis of aminoborazoles from secondary amines and boron trichloride has been carried out in a number of steps, the first of which involves formation of a complex, for which in certain cases an ionic structure [(R NH)₂BC1₂] + [BC1₄] - has been proposed. The formation of such complexes and of tetrachloroborates by direct interaction of amines with boron trichloride, is discussed. Subsequent dehydrochlorination affords aminoboron dichlorides which with ammonia or primary amines give B-aminoborazoles, although group exchange reactions complicate the system and give rise to polymers. A series of B-tris(secondary amino)borazoles has been prepared from B-trichloroborazole, and their characterisation constants, infrared spectra, and chemical properties have been recorded. Pyrolysis causes amine elimination with linking of borazole rings to give polymers which, like the aminoborazoles, are readily hydrolysed.
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