Phosphinoselenothioic acids and their salts: Synthesis, characterization, and reaction with electrophiles

Tsutomu Kimura, Toshiaki Murai, Akihiro Miwa, Daisuke Kurachi, Haruhisa Yoshikawa, Shinzi Kato

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26 Citations (Scopus)

Abstract

Phosphinoselenothioic acid ammonium salts were synthesized in good yields by reacting phosphinoselenothioic acid S-[2-(trimethylsilyl)ethyl] esters with ammonium fluorides. Phosphinoselenothioic acid alkali metal salts were obtained as 18-crown-6 ether complexes with high efficiency by treating the esters with alkali metal fluorides and 18-crown-6 ether. The salts were stable under air and soluble in water. The structures of the phosphinoselenothioic acid tetramethylammonium salt and P-methylseleno-P-methylthiophosphonium triflate were determined by X-ray molecular structure analyses. These salts exhibited monomeric structures, and the central phosphorus atoms adopted tetrahedral structures. Alkylation of the ammonium salts selectively gave phosphinoselenothioic acid Se-alkyl esters, whereas acylation of the salts preferentially gave S-acyl products. Protonation of the salts selectively gave the phosphinoselenothioic S-acid. The S-acid generated in situ was reacted with α,β-unsaturated carbonyl compounds and cyclohexene oxide to give the adducts. Molecular orbital calculations were carried out for the model compound H2P(Se)S- to elucidate the electronic structure.

Original languageEnglish
Pages (from-to)5611-5617
Number of pages7
JournalJournal of Organic Chemistry
Volume70
Issue number14
DOIs
Publication statusPublished - 8 Jul 2005

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