Organo–Phosphorus–Sulfur Heterocycles by Reactions of Phenylphosphine with Ketones

Abstract

The reaction of phenylphosphine (PhPH₂) with ketones showed conversion into a 5-membered heterocyclic ring of the type P₂SOC if 2–2.5 equivalents of sulfur (S₈) were used. X-Ray data and ³¹P, ¹³C, ¹H NMR spectra proved the formation of the (Z) diastereomer of 1,3,2,4-oxathiadiphospholane 1 ((PhPS)₂SOCMe₂) if acetone is used. Mechanistic studies displayed that small changes in the reaction pathway lead toward the formation and characterization of intermediates including 1,3,2,4,5-dithiatriphospholane, 2,4,5-triphenyl-2-sulfide (PhP)₃S₃ and 1,3,2,4-oxathiadiphospholane, and 5,5-dimethyl-2,4-diphenyl-2-sulfide ((PhPS)(PhP)SOCMe₂), which undergo reactions with acetone, subsequently yielding the abovementioned heterocyclic ring.

GRAPHICAL ABSTRACT

Keywords:

• α-Hydroxymethylphosphansulfides 1, 3, 2, 4, 5-dithiatriphospholane 2, 4, 5-triphenyl-2-sulfide 1, 3, 2, 4-oxathiadiphospholane 5, 5-dimethyl-2, 4-diphenyl-2, 4-disulfide 1, 3, 2, 4-oxathiadiphospholane 5, 5-dimethyl-2, 4-diphenyl-2-sulfide ³¹P-NMR

Additional information

Funding

The authors are grateful to the Graz University of Technology as well as the NAWI Graz project for financial support.