One-Pot Synthesis of Organic Disulfides (Disulfanes) from Alkyl Halides Using Sodium Sulfide Trihydrate and Hexachloroethane or Carbon Tetrachloride in the Poly(ethylene glycol) (PEG-200)

Mohammad Abbasi; Mohammad Reza Mohammadizadeh; Hekmat Moosavi; Narges Saeedi

doi:10.1055/s-0034-1380291

Synlett, Table of Contents

Synlett 2015; 26(09): 1185-1190
DOI: 10.1055/s-0034-1380291

letter

One-Pot Synthesis of Organic Disulfides (Disulfanes) from Alkyl Halides Using Sodium Sulfide Trihydrate and Hexachloroethane or Carbon Tetrachloride in the Poly(ethylene glycol) (PEG-200)

Mohammad Abbasi*

^aChemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran Email: abbassi@pgu.ac.ir Email: pgu.chem@gmail.com

,

Mohammad Reza Mohammadizadeh*

^bChemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran Email: mrmohamadizadeh@pgu.ac.ir

,

Hekmat Moosavi

^aChemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran Email: abbassi@pgu.ac.ir Email: pgu.chem@gmail.com

,

Narges Saeedi

^aChemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran Email: abbassi@pgu.ac.ir Email: pgu.chem@gmail.com

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Abstract

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Abstract

Symmetric disulfides are produced by treating their corresponding organic halides including benzylic, allylic, primary and secondary halides with Na₂S·3H₂O and C₂Cl₆ or CCl₄ in PEG-200 at room temperature in high yields.

Key words

disulfides - alkyl halides - sodium sulfide - C₂Cl₆ - CCl₄ - thiols

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References

References and Notes
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25 General Procedure: Na₂S·3H₂O (0.291 g, 2.2 mmol) was added to a magnetically stirred solution of an alkyl halide (2 mmol) and C₂Cl₆ or CCl₄ (1.5 mmol) in PEG-200 (2 mL) at r.t. The stirring was continued until the starting halide was completely consumed (30–150 min). Next, the reaction mixture was diluted with H₂O (1 mL) and extracted with EtOAc–hexane (1:1; 4 × 2 mL). The organic extracts were combined, concentrated and purified by chromatography on silica gel. The desired disulfides were produced in excellent yields (Table 1). Benzyl Disulfide (1): white crystals; mp 68–70 °C [Lit.^13c mp 69–70 °C]. ¹H NMR (400 MHz, CDCl₃): δ = 7.26–7.34 (m, 10 H), 3.61 (s, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 138.6, 130.7, 129.7, 128.7, 44.4. Anal. Calcd for C₁₄H₁₄S₂: C, 68.25; H, 5.73; S, 26.02. Found: C, 68.12; H, 5.69; S, 26.19. Bis(2-methylbenzyl) Disulfide (4): white crystals; mp 71–73 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.13–7.21 (m, 8 H), 3.67 (s, 4 H), 2.38 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 135.8, 134.0, 129.5, 129.4, 126.7, 124.9, 40.5, 18.2. Anal. Calcd for C₁₆H₁₈S₂: C, 70.02; H, 6.61; S, 23.37. Found: C, 69.94; H, 6.50; S, 23.56. Bis(3-methylbenzyl) Disulfide (5): yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.20–7.26 (m, 2 H), 7.04–7.14 (m, 6 H), 3.60 (s, 4 H), 2.36 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 137.1, 136.2, 129.1, 127.4, 127.2, 125.4, 42.3, 20.4. Anal. Calcd for C₁₆H₁₈S₂: C, 70.02; H, 6.61; S, 23.37. Found: C, 70.16; H, 6.52; S, 23.32. Bis(4-methylbenzyl) Disulfide (6): colorless oil. ¹H NMR (250 MHz, CDCl₃): δ = 7.05–7.33 (m, 8 H), 3.71 (s, 4 H), 2.21 (s, 6 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 137.6, 134.8, 129.8, 129.1, 43.1, 21.4. Anal. Calcd for C₁₆H₁₈S₂: C, 70.02; H, 6.61; S, 23.37. Found: C, 70.05; H, 6.49; S, 23.46. Bis(2-chlorobenzyl) disulfide (8): yellow crystals; mp70–72 °C [Lit.²⁷ mp 74 °C]. ¹H NMR (400 MHz, CDCl₃): δ = 7.19–730 (m, 2 H), 7.11–7.19 (m, 6 H), 3.70 (s, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 133.9, 133.1, 130.5, 128.8, 127.9, 125.7, 40.0. Anal. Calcd for C₁₄H₁₂Cl₂S₂: C, 53.34; H, 3.84; S, 20.34. Found: C, 53.21; H, 3.77; S, 20.42. n-Decyl Disulfide (13): colorless oil. ¹H NMR (250 MHz, CDCl₃): δ = 2.64 (t, J = 7.3 Hz, 4 H), 1.59–1.71 (m, 4 H), 1.21–1.35 (m, 28 H), 0.82 (t, J = 6.2 Hz, 6 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 39.2, 31.8, 29.6, 29.5, 29.3, 29.2, 29.0, 28.5, 22.8, 14.2. Anal. Calcd for C₂₀H₄₂S₂: C, 69.29; H, 12.21; S, 18.50. Found: C, 69.16; H, 12.26; S, 18.58. Cyclopentyl Disulfide (18): colorless oil. ¹H NMR (250 MHz, CDCl₃): δ = 3.39–3.45 (m, 2 H), 1.94–1.97 (m, 4 H), 1.51–1.69 (m, 12 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 50.7, 32.9, 24.7. Anal. Calcd for C₁₀H₁₈S₂: C, 59.35; H, 8.97; S, 31.68. Found: C, 59.51; H, 8.99; S, 31.50. Cyclohexyl Disulfide (19): colorless oil. ¹H NMR (250 MHz, CDCl₃): δ = 2.64–2.73 (m, 2 H), 1.99–2.06 (m, 4 H), 1.70–1.82 (m, 4 H), 1.52–1.64 (m, 2 H), 1.17–1.31 (m, 10 H). ¹³C NMR (62.5 MHz, CDCl₃): δ = 50.1, 32.7, 26.1, 25.7. Anal. Calcd for C₁₂H₂₂S₂: C, 62.55; H, 9.62; S, 27.83. Found: C, 62.40; H, 9.75; S, 27.85. Bis(3-hydroxypropyl)disulfide (21): colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 3.78 (t, J = 6.0 Hz, 4 H), 3.02–3.14 (m, 4 H), 2.82 (br s, 2 H), 2.00–2.08 (m, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 60.9, 35.2, 31.5. Anal. Calcd for C₆H₁₄O₂S₂: C, 39.53; H, 7.74; S, 35.17. Found: C, 39.72; H, 7.89; S, 34.98.
26 Typical Scale-Up Procedure for the Preparation of n-Octyl Disulfide: Na₂S·3H₂O (4.365g, 33 mmol) was added to a magnetically stirred solution of n-octyl bromide (5.182 mL, 30 mmol) and CCl₄ (2.25 mL, 22.5 mmol) in PEG-200 (30 mL) at r.t. The starting halide was completely consumed within 90 min. Then, the mixture was diluted with H₂O (15 mL) and extracted with EtOAc–hexane (1:1; 4 × 15 mL). The upper layers were decanted, combined, and concentrated. The crude product was purified by silica gel chromatography using n-hexane as eluent to provide octyl disulfide in 88% yield (3.836 g) yield. n-Octyl Disulfide (12): colorless oil. ¹H NMR (250 MHz, CDCl₃): δ = 2.64 (t, J = 7.3 Hz, 4 H), 1.53–1.68 (m, 4 H), 1.27–1.36 (m, 20 H), 0.81 (t, J = 6.2 Hz, 6 H); ¹³C NMR (62.5 MHz, CDCl₃): δ = 39.2, 31.7, 29.4, 29.2, 29.1, 28.6, 22.7, 14.1. Anal. Calcd for C₁₆H₃₄S₂: C, 66.14; H, 11.79; S, 22.07. Found: C, 65.99; H, 11.81; S, 22.20.
27 Srivastava SK, Rastogi R, Rajaram P, Butcher RJ, Jasinski JP. Phosphorus, Sulfur, Silicon Relat. Elem. 2010; 185: 455