Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/74988
Type: Artigo de periódico
Title: The conformational energies of 2-methyl- and 4-methyl-1,3-dithiane. The breakdown of 1,3-syn diaxial repulsion hypothesis
Author: Ribeiro, DS
Rittner, R
Abstract: The conformational enthalpies (DeltaH) of 2-methyl-(-1.76 kcal mol(-1)) and 4-methyl-1,3-dithiane (-1.75 kcal mol(-1)) were obtained by the analysis of C-13 chemical shifts as a function of temperature. These energies are in excellent agreement both with calculated values (B3LYP/6-31G(d,p)) and with literature values based on 2,4-dialkyl-1,3-dithiane. The results confirm the similarity between the conformational energies of the methyl group at the 2 and 4 positions of the dithiane ring and that of methylcyclohexane, despite the larger distances between ring 1,3-syn-axial hydrogens and the closest methyl axial hydrogen in the dithiane ring. The possibility of a buttressing effect on the 2,4-dialkyl-1,3-dithianes previously studied and the rationale of 1,3-syn-axial steric interaction are discussed. (C) 2003 Elsevier B.V. All rights reserved.
Subject: dithianes
VT NMR
conformational equilibrium
syndiaxial repulsions
Country: Holanda
Editor: Elsevier Science Bv
Rights: fechado
Identifier DOI: 10.1016/S0022-2860(03)00357-0
Date Issue: 2003
Appears in Collections:Artigos e Materiais de Revistas Científicas - Unicamp

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