Improved Synthesis of 1-Bromo-3-buten-2-one

Abstract

A convenient procedure for the synthesis of 1-bromo-3-buten-2-one, 4, from commercially available 2-ethyl-2-methyl-1,3-dioxolane, 1, is described. The procedure involves three reaction steps: (1) The acetal 1 is converted to 2-(1-bromoethyl)-2-bromomethyl-1,3-dioxolane, 2, by reacting 1 with elemental bromine in dichloromethane to yield 98% of 2. (2) Dehydrobromination of 2 with potassium tert-butoxide in tetrahydrofuran gives 2-bromomethyl-2-vinyl-1,3-dioxolane, 3, in 84–93% yield. (3) Removal of the acetal protection from 3 by formolysis for 6–10 h afforded 1-bromo-3-buten-2-one, 4, in 85–94% yield. A more rapid method is acid hydrolysis of 3 under microwave activation (100 °C, 8–10 min), by which 4 was obtained in 75% yield. Full experimental details are given.

Keywords:

• Acetal deprotection
• bromination
• 2-bromomethyl-2-vinyl-1,3-dioxolane
• dehydrobromination
• formolysis
• microwave activation

ACKNOWLEDGMENTS

We thank the American Chemical Society for the kind permission to reproduce the experimental proceddure for the synthesis of the dibromoactal, 2 published in Ref. [2]. We also thank the Research Council of Norway for financial support via the KOSK-II program.