Molecular Structures of Isomeric Ortho, Meta, and Para Bromo-Substituted alpha-Methylsulfonyl-alpha-diethoxyphosphoryl Acetophenones by X-ray and DFT Molecular Orbital Calculations

Author(s)

Rodrigues, Alessandro ^[1] ; Olivato, Paulo R. ^[2] ; Zukerman-Schpector, Julio ^[3] ; Maganhi, Stella H. ^[3] ; Reis, Adriana K. C. A. ^[1] ; Tiekink, Edward R. T. ^[4]

Affiliation

^[1] Univ Fed Sao Paulo, UNIFESP, Inst Environm Chem & Pharmaceut Sci, BR-09972270 Diadema, SP - Brazil

^[2] Univ Sao Paulo, Inst Chem, BR-05513970 Sao Paulo, SP - Brazil

^[3] Univ Fed Sao Carlos, Dept Chem, BR-13565905 Sao Carlos, SP - Brazil

^[4] Univ Malaya, Dept Chem, Kuala Lumpur 50603 - Malaysia

• Document type: Journal article
• Source: Journal of Physical Chemistry A; v. 119, n. 32, p. 8714-8723, AUG 13 2015.
• Web of Science Citations: 0

Abstract

The X-ray single crystal analysis of isomeric ortho, meta, and para bromo-substituted alpha-methylsulfonyl-alpha-diethoxyphosphoryl acetophenones showed that this class of compound adopts synclinal (gauche) conformations for both {[}-P(O)(OEt)(2)] and {[}-S(O)(2)Me] groups, with respect to the carbonyl functional group. The phosphonate, sulfonyl, and carbonyl functional groups are joined through an intramolecular network of attractive interactions, as detected by molecular orbital calculations at the M06-2X/6-31G(d,p) level. These interactions are responsible for the more stable conformations in the gas phase, which also persist in the solid-state structures. The main structural distinction in the title compounds relates to the torsion angle of the aryl group (with respect to the carbonyl group), which gives rise to different interactions in the crystal packing, due to the different positions of the Br atom. (AU)

• FAPESP's process: 13/16644-4 - S-nitrosothiols from Aryl-amide and Aryl-pyrimidin-2-ones (thiones) derivatives - potential double inhibitors of HIV-1-PR and renin: synthesis, structural analysis and biological tests
• Grantee: Adriana Karla Cardoso Amorim Reis
• Support Opportunities: Regular Research Grants
• FAPESP's process: 13/10073-5 - Organocatalysis: design, synthesis and applications in stereoselective organic reactions
• Grantee: Alessandro Rodrigues
• Support Opportunities: Regular Research Grants