N-alkylation of amidothiophosphoryl compounds under phase-transfer catalysis conditions. Synthesis and properties of 1,3,2-thiazaphosphacyclanes

Abstract

N (ω Haloalkyl)amidothiophosphates, N (ω haloalkyl)amidothiophosphonates, and N (ω haloalkyl)amidothiophosphinates (Hal = Cl or Br) were obtained in high yields by alkylation of phosphorus(V) acid thioamides with α,ω dihaloalkanes under phase transfer catalysis (PTC) conditions or through the use of NaH as a base. Thermal rearrangement of N (3 iodopropyl) or N (4 iodobutyl)amidothiophosphate and N (3 iodopropyl) or N (4 iodo butyl)amidothiophosphonate obtained in situ by the Finkelstein reaction provides a convenient route to 2 oxo 1,3,2 thiazaphosphinanes and 2 oxo 1,3,2 thiazaphosphepanes. Reactions of N (ω haloalkyl)amidothiophosphinates with NaClO 4 in MeCN afforded the first example of stable 1,3,2 thiazaphosphacyclanium salts containing P-C bonds.