Preparation and reactivity of acetoacetonitrile dianion

✍ Scribed by Fredric J. Vinick; Yolanda Pan; Heinz W. Gschwend

• Book ID: 104246210
• Publisher: Elsevier Science
• Year: 1978
• Tongue: French
• Weight: 231 KB
• Volume: 19
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)95186-x

✦ Synopsis

Dianions of 1,3-dicarbonyl and 1,3-dicarbonyl-like compounds l,2 have become a valuable part of present day methodology in organic synthesis. We wish to report the preparation of a new reagent of this general type, acetoacetonitrile dianion (s), and its reaction with a number of electrophiles.

After a preliminary investigation of various experimental conditions3, it was found that 2a is most conveniently prepared by treatment of 5-methylisoxazole 4a (la) with two -equivalents of lithium diisopropylamide (LDA) in THF at -1O'C. When ally1 bromide (1.1 equivalents) was added to this solution, compound 3a 1IR (film) 2253, 1725 cm -l; NMR (CDCl,)5 -6 2.20-2.93 (m, 4H), 3.62 (8, 2H), 4.87-6.18 (m, 3H)] was obtained in 60% yield following standard aqueous work-up.