Synthesis of Novel α,β-Unsaturated Sulfonic Acid Derivatives Containing Dithiocarbamate/Xanthate Groups by Ring Opening of an α,β-Unsaturated γ-Sultone

Abstract

An efficient method is disclosed for the synthesis of novel α,β-unsaturated sulfonic acid derivatives containing dithiocarbamate/xanthate groups through ring opening of an α,β-unsaturated γ-sultone with dithiocarbamic acid salts or xanthates prepared in situ. Treatment of the primary products with hydrochloric acid afforded the corresponding β-chloro-γ-(dithiocarbamato)propanesulfonic acids in excellent yields.

Key words

dithiocarbamates - sultones - xanthates - sulfonic acids - nucleophilic substitution - propene sultone

• References and Notes

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• 51 3-{[(Amino)carbonothioyl]sulfanyl}prop-1-ene-1-sulfonates 2a–l; General Procedure The appropriate secondary amine (0.5 mmol, 1 equiv) and CS₂ (2 mmol, 4 equiv) were added to a solution of K₃PO₄ (0.525 mmol, 1.05 equiv) in H₂O (3 mL) at 0 °C, and the mixture was stirred at rt for 30 min. Sultone 1 (0.5 mmol, 1 equiv) was then added, and stirring was continued at rt for 4 h. The solvent was removed under vacuum and the remaining solid was stirred with MeOH and filtered. The filtrate was evaporated under reduced pressure to give the product. If needed, further purification was carried out by crystallization from the minimum amount of MeOH or by washing the precipitate with Et₂O. Potassium (1Z)-3-{[(Dimethylamino)carbonothioyl]sulfanyl}prop-1-ene-1-sulfonate (2a) White solid; yield: 129 mg (93%); mp 222 °C (dec.). ¹H NMR (400 MHz, D₂O): δ = 6.33 (dt, J = 11.1, 1.4 Hz, 1 H), 6.14 (dt, J = 11.1, 7.7 Hz, 1 H), 4.31 (dd, J = 7.8, 1.3 Hz, 2 H), 3.45 (s, 3 H), 3.32 (s, 3 H). ¹³C NMR (400 MHz, D₂O): δ = 195.8, 134.5, 132.1, 45.5, 41.9, 33.3. HRMS (ESI^–): m/z [M – K]^– calcd for C₆H₁₀O₃NS₃: 239.9828; found: 239.9826.