The structural study of the electrophilic intermediates obtained from carboxamides and chlorinated Lewis acids is extended to the phosphoric amides. The action of COCl2 and POCl3 on hexamethylphosphotriamide (HMPT) can lead to a chlorophosphonium salt (3a) the structure of which is proved by nmr spectroscopy (1H, 13C, 31P, 15N). The mechanism of formation is comparable to that of the chloroiminium chloride (Vilsmeier reagent) from the corresponding amides. The action of chlorine on HMPT does not lead to a stable salt of the same kind but essentially to the substitution product (2). A new biphosphorylated compound (6) has been identified when an excess of chlorine is reacted with HMPT.
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