SOME HETEROCYCLIC PHOSPHOROCHLORIDATES AND THE FORMATION OF OTHER HETEROCYCLIC ORGANOPHOSPHORUS COMPOUNDS

Abstract

Pyrrolidine, morpholine, and β-hydroxyethylmorpholine have been phosphorylated with phosphorus oxychloride, phenylphosphorodichloridate, p-chlorophenylphosphorodichloridate and thiophosphoryl chloride. The resultant phosphorodichloridates have been condensed with a wied range of nucleophilic reagents, e.g. amines, hydrazines, phenols and isobutanol. Piperazine with phosphorus oxychloride (2 mols) gave the N(1) N(4)-diphosphorotetrachloridate, which was characterized as the tetracyclohexylamidate. β-Hydroxyethylpiperazine was similarly phosphorylated to the N,O-diphosphorotetrachloridate which was characterized as the tetraphenylhydrazidate.

Condensation of pyrrolidine (2 mols) with phosphorus oxychloride (1 mol) afforded N,N′-dipyrrolidinophosphorochloridate which was reacted with phenylhydrazide and sodium azide. The phosphoroazide with triphenylphosphine afforded the corresponding triphenylphosphinimine. N-Phenyl N′-pyrrolidinophosphorochloridate with aqueous pyridine gave the corresponding pyrophosphoramide and the stability of the pyrophosphoramide towards hydrolysis was examined. 1,2-Cyclohexanediol was phosphorylated with phenylphosphorodichloridate and thiophosphorylchloride. Trans-4-t-Butylcyclohexyl N,N′-diphenylhydrazinophosphorothioate by reaction with formaldehyde gave a tetra-azaphosphorine P-sulfide. Trans-4-t-Butylcyclohexyl N-phenyl N′-phenylphosphorodiamidic hydrazide reacted with 1,4-dibromobut-2-ene to give a 1,2-diazahex-4-ene.