Synthesis of .alpha.-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of Meldrum's acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates

Autor:	Primoz Lorencak, Abdelhamid Ben Cheikh, Klaus Peter Netsch, Curt Wentrup, Josselin Chuche, Jean Claude Pommelet, Noel Manisse
Rok vydání:	1991
Předmět:	chemistry.chemical_compound Acrylate chemistry Organic Chemistry Thermal decomposition Aminal Cyanoacetaldehyde Methylene Meldrum's acid Tautomer Medicinal chemistry Enamine
Zdroj:	The Journal of Organic Chemistry. 56:970-975
ISSN:	1520-6904 0022-3263
Popis:	The syntheses and flash vacuum thermolyses of 5-[(alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 13a-i are described. Thermolysis of 13a as well as of ethyl 3-(tert-butylamino)acrylate (22) gives a tautomeric mixture of cyanoacetaldehyde (14) and 3-hydroxypropenenitrile (15). Thermolysis of 13b gives iminoacrolein 26 and not cyanoacetone (29). Thermolysis of 13c,d gives S-methyl cyanothioacetate (30), and 13f-h give cyanoacetamides 31 in high yields. 2-Cyanopent-4-enoic acid derivatives 32 are obtained from Meldrum's acids 13e,i. The results are discussed in terms of facile 1,3-shifts of methylthio and alkylamino groups in imidoylketenes, interconverting imidoylketenes and acylketene imines.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::d62e9ec5cfd2730af0f39ba60f6c18b6 https://doi.org/10.1021/jo00003a014 Zobrazit plný text záznamu