Rapid Transformation of Alkyl Halides into Symmetrical Disulfides Using Sodium Sulfide and Carbon Disulfide

Abstract

An efficient one-pot reaction has been developed for the preparation of symmetrical disulfide derivatives directly from alkyl halides by reaction with a combination of sodium sulfide and carbon disulfide without requirement for any catalyst.

Key words

alkyl halides - carbohydrates - disulfides - sodium sulfide - carbon disulfide

• References

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• 23 Typical experimental procedure for the preparation of symmetrical dialkyl disulfides: To a solution of Na₂S·9H₂O (1.0 mmol) in DMF (2 mL) was added CS₂ (1.0 mmol) at room temperature. The alkyl halide (1.0 mmol) was added to the dark-red reaction mixture at room temperature with vigorous stirring. The color of the reaction mixture changed from red to yellow. The reaction mixture was stirred for the appropriate time (Table 2), then poured into water and extracted with Et₂O (2 × 25 mL). The combined organic layers were dried over Na₂SO₄, filtered and concentrated under reduced pressure. The crude product was purified over SiO₂ using hexane–EtOAc (15:1) as eluant to give the pure dialkyl disulfide derivative (Table 2)
• 24 Spectroscopic data of novel products:Di[2-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)ethyl] Disulfide (11): Yield: 733 mg (90%); Colorless oil; ¹H NMR (500 MHz, CDCl₃): δ = 5.18 (t, J = 7.5 Hz, 2 H), 5.08 (t, J = 9.5 Hz, 2 H), 4.97 (m, 2 H), 4.55 (d, J = 9.0 Hz, 2 H), 4.26 (dd, J = 4.5, 8.0 Hz, 2 H), 4.14–3.95 (m, 4 H), 3.89–3.60 (m, 4 H), 2.96–2.71 (m, 4 H), 2.09, 2.06, 2.02, 2.00 (4 × s, 24 H); ¹³C NMR (125 MHz, CDCl₃): δ = 170.2 (2 C), 169.9 (2 C), 169.0 (2 C), 168.9 (2 C), 100.7 (2 C), 72.7 (2 C), 72.6 (2 C), 71.8 (2 C), 69.6 (4 C), 67.6 (2 C), 61.7 (2 C), 38.3 (2 C), 20.5 (8 C); HRMS (ESI): m/z [M+Na]⁺ calcd. for C₃₂H₄₆O₂₀S₂: 837.1922; found: 837.1916.Di[2-O-(2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl)ethyl] Disulfide (12): Yield: 700 mg (86%); Colorless oil; ¹H NMR (500 MHz, CDCl₃): δ = 5.39-5.31 (m, 2 H), 5.20–5.13 (m, 2 H), 5.05–4.95 (m, 2 H), 4.50 (d, J = 8.0 Hz, 2 H), 4.19–4.09 (m, 4 H), 4.05–3.89 (m, 2 H), 3.81–3.61 (m, 2 H), 2.91–2.71 (m, 4 H), 2.16, 2.07, 2.05, 1.98 (4 × s, 24 H); ¹³C NMR (125 MHz, CDCl₃): δ = 170.1 (2 C), 170.0 (2 C), 169.9 (2 C), 169.2 (2 C), 101.4 (2 C), 70.8 (4 C), 70.7 (2 C), 68.7 (4 C), 66.9 (2 C), 61.1 (2 C), 20.7 (8 C); HRMS (ESI): m/z [M+Na]⁺ calcd. for C₃₂H₄₆O₂₀S₂: 837.1922; found: 837.1917.Di-[2-O-(2,3,4-tri-O-acetyl-α-l-rhamnopyranosyl)ethyl] Disulfide (13): Yield: 594 mg (85%); Colorless oil; ¹H NMR (500 MHz, CDCl₃): δ = 5.31–5.19 (m, 4 H), 5.05 (t, J = 9.5 Hz, 2 H), 4.76 (s, 2 H), 3.98–3.88 (m, 2 H), 3.85–3.69 (m, 4 H), 2.98–2.81 (m, 4 H), 2.15, 2.08, 1.98 (3 × s, 18 H), 1.22 (d, J = 6.0 Hz, 6 H); ¹³C NMR (125 MHz, CDCl₃): δ = 169.9 (2 C), 169.8 (2 C), 169.7 (2 C), 97.5 (2 C), 70.9 (2 C), 70.6 (2 C), 69.7 (2 C), 69.0 (2 C), 66.6 (2 C), 66.3 (2 C), 38.2 (2 C), 20.8 (6 C), 17.4 (2 C); HRMS (ESI): m/z [M+Na]⁺ calcd. for C₂₈H₄₂O₁₆S₂: 721.1812; found: 721.1806