One-Step Conversion of Alcohols into Thioesters

Abstract

A one-step conversion of alcohols into thioesters under solvent-free conditions is reported. The alcohols were reacted with primary thioamides in the presence of p-toluenesulfonic acid under solvent-free conditions to produce the corresponding thioesters in good to excellent yields.

Key words

alcohols - carbocations - esters - sulfur - green chemistry

References and Notes

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Complete experimental procedures and relevant ^¹H and ^¹³C NMR spectra and elemental microanalyses for new compounds are available in the Supporting Information

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General Procedure: In a round-bottom flask, thioamide (1 mmol), alcohol (1.2 mmol), and p-TsOH (1 mmol) were heated to melt and heating was continued at 100 ˚C for 60 min. The reaction mixture was then poured into H₂O (10 mL) with vigorous stirring. Thereafter an oily residue was left, which soon solidified to a semi-crystalline mass. The solid was filtered and washed with H₂O (2 × 10 mL). Finally the solid compound was recrystallized from EtOH (95%) to afford pure thioesters as white or pale-yellow needles with a characteristic odor. Compound 3s: Mp 127-129 ˚C (EtOH); ^¹H NMR (400 MHz, CDCl₃): δ = 7.86 (d, J = 7.6 Hz, 2 H), 7.40 (d, J = 7.6 Hz, 2 H), 2.27 (m, 6 H), 2.11 (s, 3 H), 1.75-1.85 (m, 6 H); ^¹³C NMR (100 MHz, CDCl₃): δ = 191.3, 139.2, 136.7, 128.7, 128.3, 51.5, 41.9, 36.3, 29.9; Anal. Calcd for C₁₇H₁₉ClOS: C, 66.54; H, 6.24; S, 10.45. Found: C, 66.75; H, 6.09; S, 10.59