Conformational and electronic interaction studies of some p-substituted alpha-methylsulfonyl-alpha-diethoxyphosphorylacetophenones

Conformational and electronic interaction studies of some p-substituted alpha-methylsulfonyl-alpha-diethoxyphosphorylacetophenones

Author Reis, Adriana Karla C. A. Autor UNIFESP Google Scholar
Olivato, Paulo R. Google Scholar
Tormena, Claudio F. Google Scholar
Rittner, Roberto Google Scholar
Dal Colle, Maurizio Google Scholar
Institution Universidade de São Paulo (USP)
Universidade Federal de São Paulo (UNIFESP)
Universidade Estadual de Campinas (UNICAMP)
Univ Ferrara
Abstract The analysis of the IR carbonyl band of the alpha-methylsulfonyl-alpha-diethoxyphosphoryl p-substituted acetophenones p-Y-Ph-C(O)CH(SO(2)Me)[P(O)(OEt)(2)] (Y = OMe 1, H 2, F 3, Cl 4, Br 5 and NO(2) 6) supported by HF/6-31G(d,p) ab initio calculations of the alpha-methylsulfonyl-alpha-diethoxyphosphoryl acetophenone 2, indicated the existence of a single stable cl conformer in gas phase and in solvents of increasing polarity, along with the presence of second less stable conformation in gas phase. the cl conformer present the (SO(2)Me) group and the [P(O)(OEt(2))] groups in a syn-clinal (gauche) geometry and is stabilised through of the 0('60)... P(%), 01NO(owl Crco), ONO)... C(,C*.), 060)... S(`S`02.,) and 0('S-02) q o) electronic interactions 08along with H(8S*o2M,). 0(660). HU(5C_H2)lP0Erl- 0(8so2m), H(6 +Ph)- - - (co) and H(8o+'-Ph). 0( 'Po) intramolecular hydrogen bonds. the almost co nstant negative carbonyl frequency shifts (Av) for the title compounds 1-6 with respect to the parent acetophenones 7-14 corroborates the prevalence of the electronic interactions over the -l(y inductive effect of the ot-substituents for the title compounds and gives strong support for the existence of the crossed 0'('C-O)... S'(1S+02m,) and 0(S-02) C('C+O) (charge transfer and electrostatic); 08-) (co P('i o) and 01'M-OFt)l C(' o), (electrostatic) interactions. 0 2008 Elsevier B.V. All rights reserved.
Keywords Conformational analysis
Infrared spectroscopy
Theoretical calculations
p-Substituted alpha-methylsulfonyl-alpha-diethoxyphosphorylacetophenones
Language English
Sponsor Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
University of Ferrara
Date 2008-12-15
Published in Journal of Molecular Structure. Amsterdam: Elsevier B.V., v. 892, n. 1-3, p. 300-304, 2008.
ISSN 0022-2860 (Sherpa/Romeo, impact factor)
Publisher Elsevier B.V.
Extent 300-304
Access rights Closed access
Type Article
Web of Science ID WOS:000261711400049

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