57733-41-2Relevant academic research and scientific papers
Barriers to Rotation about the Amide (N-CO) and Sulphenamide (N-S) Bonds in Methyl N-Arylsulphenyl-N-benzylurethanes. A Simple Molecular Orbital Model to Explain Substituent Effects on Sulphenamide Rotational Barriers
Kost, Daniel,Zeichner, Arie,Sprecher, Milon S.
, p. 317 - 325 (2007/10/02)
Barriers to rotation about both the N-S and N-CO bonds have been measured in a series of substituted methyl N-arylsulphenyl-N-benzylurethanes, XC6H4SN(CH2C6H5)CO2CH3, by analysis of the temperature dependent n. m. r. spectra of the benzyl methylene protons.N-S Torsional barriers increase linearly with increasing electron demand of the substituents (?- substituent constant), while N-CO barriers are substituent independent.This result is inconsistent with a mechanism for S-N torsion involving (p-d)? conjugation between the nitrogen lone pair and sulphur.An alterantive rationale is proposed, based on a simple perturbational molecular orbital model.Application of the model to various experiment is discussed, with the conslusion that it adequately rationalizes all the currently available (and sometimes inexplicable) results on sulphenamides.
