The constitution of N-substituted 2-(Iminomethyl)benzenethiols (o-Mercaptobenzaldimines)

Abstract

The constitution of a number of 2-(iminomethyl)benzenethiols and 2- (iminomethyl)-4-nitrobenzene-thiols has been studied by 1H N.M.R. spectroscopy. A zwitterionic imminium structure is suggested for all the compounds studied except for the 4'-methoxyphenylimine derivative which exists in the thiol form.

NMR, MP2, and DFT study of thiophenoxyketenimines (o‐thio‐Schiff bases): Determination of the preferred form

“…[1] The study by Corrigan et al revealed that most compounds preferred the NH form. [2] This was also confirmed in the solid state by an X-ray investigation by Krinsky et al for derivatives of o-thioacetophenones. [3] A characteristic is the NH proton chemical shift being above 17 ppm for derivatives based on 2-mercaptoacetophenones and panisidine or p-toluidine.…”

“…They do show tautomerism as their oxygen analogues; this was suggested by Minkin et al for Schiff bases of o ‐mercaptobenzladehydes . The study by Corrigan et al revealed that most compounds preferred the NH form . This was also confirmed in the solid state by an X‐ray investigation by Krinsky et al for derivatives of o ‐thioacetophenones .…”

“…The present compounds like the o ‐hydroxythioketones seems very suitable for studies of deuterium isotope effects on chemical shifts and their transmission pathways as the S…N distance is very long and very different from that of the corresponding oxygen analogues. So far, only a single molecule has been found at the SH form in nonpolar solvents . Derivatives based on o ‐thioaldehydes have a tendency to rearrange into dithiocins and are usually not isolated as pure compounds.…”

“…So far, only a single molecule has been found at the SH form in nonpolar solvents. [2] Derivatives based on o-thioaldehydes have a tendency to rearrange into dithiocins and are usually not isolated as pure compounds. A couple of derivatives based on 2-mercaptoacetophenones and panisidine or p-toluidine have been synthesized and characterized partly by nuclear magnetic resonance (NMR) and by X-ray crystallography.…”

Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes

“…[92,121,122] Therefore, we performed DFT calculations using a functional and basis sets that have been shown to well reproduce experimental data for these compounds. [92,121,122] Therefore, we performed DFT calculations using a functional and basis sets that have been shown to well reproduce experimental data for these compounds.…”