Conformational and electronic interaction studies of alpha-substituted carbonyl compounds. XV. alpha-(arylsulfinyl)-p-substituted acetophenones

dc.creatorOlivato, PR
dc.creatorGuerrero, SA
dc.creatorRittner, R
dc.date2000
dc.date2014-12-02T16:29:50Z
dc.date2015-11-26T17:35:50Z
dc.date2014-12-02T16:29:50Z
dc.date2015-11-26T17:35:50Z
dc.date.accessioned2018-03-29T00:18:04Z
dc.date.available2018-03-29T00:18:04Z
dc.identifierPhosphorus Sulfur And Silicon And The Related Elements. Gordon Breach Sci Publ Ltd, v. 156, n. 255, n. 277, 2000.
dc.identifier1042-6507
dc.identifierWOS:000088788600020
dc.identifier10.1080/10426500008045008
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/56516
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/56516
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/56516
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1285694
dc.descriptionThe V-CO IR analysis of alpha-(p-phenylsulfinyl)-p-substituted acetophenones X-phi C(O)CH2S(O) phi-Y 1-8, being X and Y = NO2, H and OMe substituents, supported by ab initio calculations of the alpha-methylsulfinyl/acetophenone (model compound) along with the X-ray geometrical data for 1, 7 and 8, indicates the existence of the cis(2) and gauche rotamers for compounds 1-4 and 6. Compounds 5, 7 and 8 present another less stable and more polar cis(1) rotamer. The cis(2) rotamer concentration for 4 (ca. 97% in CCl4) is reduced to ca. 50% for 2, 3, 5-7 and to ca. 20% for 1 and 8. This behavior is discussed in terms of O-(CO)(delta-)-S-(SO)(delta+) charge transfer and Coulombic interactions, which stabilize the cis(1) rotamer, and the pi(CO)/sigma*(C-S), pi*(CO)/n(s) and pi*(CO)/sigma(C-S) orbital interactions, which stabilize the gauche rotamers. The progressive more negative carbonyl cis(2) shifts (Delta v(c)), when X varies from NO2 to H and to OMe for the same Y, along with the unexpected NAE values of the alpha-methylene carbon chemical shifts for compounds 1-8 give further support for the existence of a strong intramolecular complex between C=O and S=O dipoles which stabilizes the cis(2) rotamer. The progressive more negative carbonyl gauche shifts (Delta v(g)), when X varies from NO2 to H and to OMe for the same Y, is in line with the higher contribution of the interaction pi(CO)/sigma*(C-S), which stabilizes the gauche rotamer of the title compounds.
dc.description156
dc.description255
dc.description277
dc.languageen
dc.publisherGordon Breach Sci Publ Ltd
dc.publisherReading
dc.publisherInglaterra
dc.relationPhosphorus Sulfur And Silicon And The Related Elements
dc.relationPhosphorus Sulfur Silicon Relat. Elem.
dc.rightsfechado
dc.sourceWeb of Science
dc.subjectconformational studies
dc.subjectelectronic interactions
dc.subjectIR and C-13 NMR spectroscopies
dc.subjectalpha-(p-phenylsulfinyl)-p-substituted acetophenones
dc.subjectUltraviolet Photoelectron-spectroscopy
dc.subjectKetones
dc.titleConformational and electronic interaction studies of alpha-substituted carbonyl compounds. XV. alpha-(arylsulfinyl)-p-substituted acetophenones
dc.typeArtículos de revistas


Este ítem pertenece a la siguiente institución