Anomalous Reaction of Ethyl Bromofluoro- and Difluoro-Acetates with Dialkylphosphonites

Abstract

The Michaelis–Arbuzov reaction of ethyl α -bromo-α -fluoro- and α, α -difluoro-acetates with dialkyl phenylphosphonites leads to the formation of unusual products including a fluorophosphinate. The reaction of ethyl bromofluoracetate with diisopropyl- and dimethyl-phenylphosphonites furnishes a complex mixture of eight and five compounds respectively. Five different compounds are obtained when ethyl bromodifluoroacetate is reacted with diisopropyl phenylphosphonite. Dimethyl phenylphosphonite yields three compounds when heated with bromochloromethane. The probable mechanism of formation of the compounds and their mass spectral characterization using GC-MS, tandem MS-MS and DART™ techniques are presented in this paper.

Keywords:

• α-fluoro- and difluoro-esters
• DART mass spectrometry
• dialkylphosphonites
• free radical Arbuzov reaction
• GC-MS
• MS-MS
• Michaelis–Arbuzov reaction

Notes

*All Br and Cl containing compounds showed their corresponding isotope peaks.