Synthetic scope, computational chemistry and mechanism of a base induced 5-endo cyclization of benzyl alkynyl sulfides.

We present an experimental and computational study of the reaction of aryl substituted benzyl 1-alkynyl sulfides with potassium alkoxide in acetonitrile, which produces 2-aryl 2,3-dihydrothiophenes in poor to good yields. The cyclization is most efficient with electron withdrawing groups on the aromatic ring. Evidence indicates there is rapid exchange of protons and tautomerism of the alkynyl unit prior to cyclization.

A new method to evaluate the surface dipole potential of thiol and disulfide self-assembled monolayers and its application to a disulfidated tetraoxyethylene glycol.

A procedure to evaluate the surface dipole potential chi of thiol and disulfide self-assembled monolayers (SAMs) is described. The procedure consists of self-assembling the monolayers on a hanging mercury drop electrode and of measuring the charge involved in a progressive expansion of the mercury drop. This measurement is then combined with an estimate of the charge density q experienced by diffuse layer ions, obtained by measuring the diffuse layer capacitance of the SAM at different electrolyte concentrations by electrochemical impedance spectroscopy.