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Type: Artigo de periódico
Title: Conformational And Electronic Interaction Studies Of Some Para-substituted S-phenyl α-ethylsulfonylthioacetates
Author: Olivato P.R.
Hui M.L.T.
Rodrigues A.
Ruiz Filho R.
Rittner R.
Zukerman-Schpector J.
Distefano G.
Dal Colle M.
Abstract: The preferred conformations of some p-substituted S-phenyl α-ethylsulfonylthioacetates, p-X-Ph-SC(O)CH2SO2Et (X = NO2 1, Cl 2, Br 3, H 4, Me 5 and OMe 6) are determined through νCO infrared analysis and ab initio HF/6-31G** calculations, which show the occurrence of two stable conformations, i.e. the gauche2(syn) and the gauche1(anti), with the former being the most stable. The lower frequency and more intense component of the doublet for the carbonyl absorption is then attributed to gauche2(syn) while the higher frequency and less intense component is attributed to the gauche1(anti) conformer. Experimental and theoretical data of the corresponding p-substituted-S-phenyl thioacetates (X = NO2 10, Cl 11, Br 12, H 13, Me 14 and OMe 15), not bearing an α-ethylsulfonyl group, lead to similar results, confirming the frequency assignments. The progressive increase of the gauche2(syn)/gauche1(s-anti) infrared population ratio for compounds 1-6, on going from electron attracting to electron donating substituents at the para position, along with larger negative carbonyl frequency shifts (δν) for the gauche2(syn) conformer relative to the gauche1(anti) conformer, and the ab initio data for the corresponding thioacetate methylsulfones 7-9 are interpreted in terms of the predominance of the summing up of the O(CO)δ-⋯S (SO2)δ+ and H(SO2Me)δ+⋯ O(CO)δ- interactions over the O(SO2δ-⋯ C(CO)δ+ interaction which stabilises the gauche2(syn) conformer into a larger extent than the gauche1(anti) conformer. X-ray single crystal diffraction analyses for the S-phenyl- (4) and p-methyl-S-phenyl α-ethylsulfonylthioacetates (5) indicate that these compounds exist in the solid state as a slightly distorted gauche2(syn) conformation, which is stabilised by dipole moment coupling along with intermolecular hydrogen bond interactions. © 2002 Elsevier Science B.V. All rights reserved.
Rights: fechado
Identifier DOI: 10.1016/S0022-2860(02)00570-7
Date Issue: 2003
Appears in Collections:Unicamp - Artigos e Outros Documentos

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