Novel Thione-Thiol Rearrangement of Dithiocarbonic Acid O-(2,2,6,6-Tetramethylpiperidin-1-yl) Ester in the Context of Controlled Radical Polymerization

Abstract

Addition of the lithium salt of N-hydroxy-2,2,6,6-tetramethylpiperidine 10 to carbon disulfide and subsequent methylation affords the rearranged dithiocarbonic acid S-methyl-S'-(2,2,6,6-tetramethylpiperidin-1-yl)-ester 9 rather than the expected xanthate ester S-methyl-O'-(2,2,6,6-tetramethylpiperidin-1-yl)-ester 8. n-Butylacrylate could be polymerized with the novel compound 9 even though the polymerization was not controlled.

Keywords

• Acyloxyamines
• Alkoxyamines
• Controlled/living radical polymerization
• Newman-kwart rearrangement
• Nitroxides
• Thione-thiol rearrangement