Synthesis of New β,β′-Diketodithioethers via Swern Oxidation and Study of Their Hydrazone Formation Rate

Abstract

The synthesis of β,β′-diketodithioethers 4b–j from corresponding β,β′-dihydroxydithioethers 3b–j was carried out by a Swern oxidation using DMSO-oxalyl chloride as oxidizing agent. β,β′-Dihydroxydithioethers 3b–j were prepared by the reaction of two molar equivalents of epoxides 1b–j with dimercaptoethane 2 in the presence of a saturated aqueous solution of potassium carbonate. The reactivity behavior of imine formation of the β,β′-diketodithioethers 4b–j by 2,4-dinitrophenylhydrazine was also investigated, and a mechanism was proposed by using molecular orbital (MO) calculations. To confirm the proposed mechanism, the role of the thia function to activate hydrazone formation by measuring HOMO-LUMO energy levels was also demonstrated.

Keywords:

• Ab initio
• 2,4-dinitrophenylhydrazine
• HUMO-LUMO
• molecular orbital calculation
• neighboring group participation