Stereochemical dependence of 3JCH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives

Denize C Favaro; Lucas C Ducati; Francisco P dos Santos; Rubén H Contreras; Cláudio F Tormena

doi:10.1021/jp2083456

Stereochemical dependence of 3JCH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives

J Phys Chem A. 2011 Dec 22;115(50):14539-45. doi: 10.1021/jp2083456. Epub 2011 Nov 23.

Authors

Denize C Favaro¹, Lucas C Ducati, Francisco P dos Santos, Rubén H Contreras, Cláudio F Tormena

Affiliation

¹ Chemistry Institute, State University of Campinas, Campinas SP, Brazil.

PMID: 22060817
DOI: 10.1021/jp2083456

Abstract

Theoretical and experimental studies on (3)J(C2H6eq) NMR spin-spin coupling constants in both the 2-X-4-t-butyl-cyclohexanone (X = H, CH(3), F, Cl, and Br) and in their alcohol derivatives series are reported. Results thus found are rationalized in terms of the transmission of the Fermi contact contribution to such couplings. To this end, dependencies of (3)J(C2H6eq) couplings versus the C(2)-C(1)-C(6) angle are compared in both series for equatorial and axial X orientations. The main trend is described in terms of the rear lobes interaction. Besides, for X = halogen atom in equatorial orientation a rather strong interaction between oxygen and halogen lone pairs is observed, and its influence on (3)J(C2H6eq) couplings is discussed and rationalized in terms of different Fermi contact transmission pathways.