A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine
2015 (English)In: Journal of Physical Organic Chemistry, ISSN 0894-3230, E-ISSN 1099-1395, Vol. 28, no 6, 403-413 p.Article in journal (Refereed) Published
Nucleophilic substitution and dehydrochlorination reactions of a number of the ring-substituted 1-(arylsulfonyl)-2-R-4-chloro-2-butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general rapidity, cheapness, and simplicity providing moderate to high yields of 1-arylsulfonyl 1,3-butadienes (48-95%), 1-(arylsulfonyl)-2-R-4-(N,N-dialkylamino)-2-butenes (31-53%), 1-(arylsulfonyl)-2-R-2-buten-4-ols (37-61%), and bis[4-(arylsulfonyl)-3-R-but-2-enyl]sulfides (40-70%). The density functional theory B3LYP/6-311++G(2d,2p) calculations of the intermediate allylic cations in acetone revealed their high stability occurring from a resonance stabilization and hyperconjugation by the SO2Ar group. The reactivity parameters estimated at the bond critical points of the diene/allylic moiety display a high correlation (R-2>0.97) with the Hammett (sigma(p)) constants. 1-Arylsulfonyl 1,3-butadienes are characterized by a partly broken conjugated system, which follows from analysis of the two-centered delocalization () and localization () index values. The highest occupied molecular orbital energies of 1-arylsulfonyl 1,3-butadienes are lower than those of 1,3-butadiene explaining their low reactivity towards the Diels-Alder condensation.
Place, publisher, year, edition, pages
2015. Vol. 28, no 6, 403-413 p.
1-(arylsulfonyl)-2-R-4-chloro-2-butenes, 1-arylsulfonyl 1, 3-dienes, conceptual density functional theory, electrophile-nucleophile interactions, quantum theory of atoms in molecules
IdentifiersURN: urn:nbn:se:kth:diva-169252DOI: 10.1002/poc.3425ISI: 000354807200004ScopusID: 2-s2.0-84930212337OAI: oai:DiVA.org:kth-169252DiVA: diva2:821973
FunderSwedish National Infrastructure for Computing (SNIC), SNIC 020/11-23
QC 201506162015-06-162015-06-122015-06-16Bibliographically approved