The dehydration of secondary alcohols in refluxing hexamethylphosphoric triamide (HMPT) without added catalysts proceeds in good yield (70-98%) to afford unrearranged olefins.1 We now report stereochemical studies which partly elucidate the mechanism of the reaction.

Suinvzary Benzyl alcohols react readily with hexamethyl-The chemistry of HMPT,4*5 as well as thc report by White phosphoric triamide (HMPT) a t reflux affording the and Elligerg on the reactions of the analogous NN-dimethylcorresponding benzyldimethylamines in modest yield.sulphamates, suggest the reaction pathway ( 1) and (2).

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Aliphatic and aromatic carboxamides are found to undergo ready dehydration in hexamethylphosphoric triamide at 220-240" affording the corresponding nitriles in good yield.Les carboxamides aliphatiques et aromatiques subissent une dkshydratation facile dans le HMPT a 220-240" et conduisent aux nitriles correspondants avec un bon rendement.

Sekundäre Alkohole werden durch Hexamethylphosphorsäuretriamid (I) zu Olefinen dehydratisiert, wobei intermediär unter Eliminierung von Dimethylamin die Bildung von Esteramid‐Strukturen der Art (II) angenommen wird.