Reactions of sodium hydride with ω-hydroxyalkyl-phosphonium, -arsonium and -ammonium salts

Abstract

The reaction of sodium hydride with ω-hydroxyalkyltriphenylphosphonium salts Ph₃P(CH₂)_nOH X^–(I) has been investigated. The salt (I; n= 1, X = I) gave triphenylphosphine and formaldehyde. The salt (I; n= 2, X = I) gave triphenylphosphine oxide and ethylene. The salts (I; n= 4 or 5, X = I or Cl) could not be prepared. The salt (I; n= 6, X = I) gave mainly triphenylphosphine and hex-5-en-1-ol with some 6-hydroxyhexyldiphenylphosphine, 6-phenoxyhexyldiphenylphosphine, and 6-phenoxyhexylidenetriphenylphosphorane. The salt (I; n= 11, X = Br) gave 11-phenoxyundecyldiphenylphosphine, 11-hydroxyundecyldiphenylphosphine, and 11-phenoxyundecylidenetriphenylphosphorane. Sodium hydride with 2,3-dihydroxypropyltriphenylphosphonium iodide gave triphenylphosphine oxide and allyl alcohol.

Similar reactions were carried out with ω-hydroxyalkyltriphenylarsonium salts, Ph₃As(CH₂)_nOH X^–(XIV). The salt (XIV; n= 6, X = I) gave triphenylarsine and hex-5-en-1-ol. The salt (XIV; n= 11, X = Br) gave mainly triphenylarsine and undec-10-en-1-ol.

Similar reactions were carried out with ω-hydroxyalkyldimethylphenylammonium salts, Ph(Me)₂N(CH₂)_nOH X^–(XV). The salt (XV; n= 3, X = I) gave dimethylaniline and allyl alcohol. The salt (XV; n= 11, X = Br) gave 11-methoxyundecylmethylphenylamine.