Substituent effects in the ring-chain tautomerism of 4-alkyl-2-aryl substituted oxazolidines and tetrahydro-1,3-oxazines

✍ Scribed by Márta Juhász; László Lázár; Ferenc Fülöp

• Publisher: Journal of Heterocyclic Chemistry
• Year: 2007
• Tongue: English
• Weight: 555 KB
• Volume: 44
• Category: Article
• ISSN: 0022-152X
• DOI: 10.1002/jhet.5570440635

✦ Synopsis

Abstract

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The condensation products of 2‐aminoethanol or 3‐aminopropanol (bearing an alkyl substituent on the carbon adjacent to the nitrogen) with substituted benzaldehydes proved to exist in CDCl~3~ at 300 K as threecomponent tautomeric mixtures of the diastereomeric five‐ or six‐membered 1,3‐O,N‐heterocyclic ring forms and the corresponding imines. For each equilibrium, the electronic effects of the 2‐aryl substituents were characterized by the Hammett equation. The steric effects of the alkyl groups could be described by Hansch‐type equations for the equilibria involving oxazolidine ring forms. While the alkyl substituents did not cause any significant effect on the ring cis‐chain and the ring trans‐chain equilibria for tetrahydro‐1,3‐oxazines, increasing bulk of the 4‐alkyl group increased the stability of the cyclic tautomers for the analogous oxazolidines.