A Facile and Efficient Method for the Reduction of Sulfoxides into Sulfides with an Al-NiCl₂·6H₂O System

Abstract

It has been observed that alkyl aryl and dialkyl sulfoxides can be conveniently and rapidly converted to the corresponding sulfides with an Al-NiCl₂·6H₂O system in high yields. Ketones are not affected under these reaction conditions.

sulfoxides - reduction - sulfides - aluminium - nickel chloride hexahydrate

References

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18

General Procedure:
In a typical procedure, NiCl₂·6H₂O (10 mmol) and aluminum powder (10 mmol) were added to an ice-cooled solution of the substrate (1.0 mmol) in freshly distilled THF. An exothermic reaction took place immediately and stirring was continued for a specified period of time. The reaction mixture was monitored by TLC. After completion of the reaction, the reaction mixture was diluted with EtOAc and filtered. The residue was washed with EtOAc several times, and the combined filtrate and washings were dried (Na₂SO₄) and evaporated to dryness. Finally, the crude product thus obtained was purified by column chromatography using EtOAc and hexane as eluent and characterized by IR, NMR and elemental analysis.¹⁹

19

Ethyl Octadecyl Sulfide: ¹H NMR (300 MHz): δ = 0.88 (t, J = 6.0 Hz, 3 H, -CH₃), 1.35 (m, 33 H, CH₂-, -CH₃), 1.55 (m, 2 H, -CH₂-), 2.53 (m, 4 H, -CH₂SCH₂-). IR: 2925, 2863, 1465, 723 cm^-1. Anal. Calcd for C₂₀H₄₂S: C, 76.35; H, 13.46; S, 10.19. Found: C, 76.52; H, 13.17; S, 10.38.
n -Pentyl-2-hydroxyethyl Sulfide: ¹H NMR (300 MHz): δ = 0.88 (t, J = 6.0 Hz, 3 H, -CH₃), 1.34 (m, 4 H, 2-CH₂-), 1.57 (m, 2 H, -CH₂-), 2.50 (t, J = 7.2 Hz, 2 H, -SCH₂-), 2.70 (t, J = 6.0 Hz, 2 H, -SCH₂-), 3.69 (t, J = 6.0 Hz, 2 H, -CH₂-O-). IR: 3391, 2960, 2935, 2858, 1465, 1050, 1015, 774 cm^-1. Anal. Calcd for C₉H₁₈O₂S: C, 56.80; H, 9.53; S, 16.85. Found: C, 57.12; H, 9.36; S, 17.14.
n -Pentyl Phenyl Sulfide: ¹H NMR (300 MHz): δ = 0.87 (t, J = 7.0 Hz, 3 H, -CH₃), 1.37 (m, 4 H, 2-CH₂-), 1.65 (m, 2 H, -CH₂-), 2.8 (t, J = 7.11 Hz, 2 H, -S-CH₂-), 7.54 (m, 5 H, aromatic). IR: 2930, 2858, 1588, 1486, 1107, 1025, 748
cm^-1. Anal. Calcd for C₁₁H₁₆S: C, 73.27; H, 8.94; S, 17.78. Found: C, 73.43; H, 9.18; S, 17.52.
2-Ethylsulfinyl Ethyl Acetate: ¹H NMR (300 MHz): δ = 1.38 (t, J = 7.38 Hz, 3 H, -CH₃), 2.07 (s, 3 H, CH₃CO-), 2.55 (t, J = 7.50 Hz, 2 H, -CH₂S-), 2.74 (t, J = 7.50 Hz, 2 H,
-CH₂S-), 4.22 (t, J = 6.90 Hz, 2 H, -CH₂-OAc). IR: 2965, 2924, 1741, 1460, 1229, 1034, 748 cm^-1.
Phenysulfinylacetone: ¹H NMR (400 MHz): δ = 2.27 (s, 3 H, -CH₃), 3.66 (s, 2 H, -SOCH₂CO-), 7.21 (m, 2 H, ArH), 7.32 (m, 3 H, ArH). ¹³C NMR (100 MHz): δ = 28.42, 45.06, 127.10, 129.35, 129.70, 134.84, 203.56. IR: 3073, 2935, 1711, 1358, 1235, 1163, 1025, 743 cm^-1.

20a Shiota and co-workers prepared precipitated nickel by adding wet NiCl₂·6H₂O and hot zinc powder. See: Ishige M. Shiota M. Can. J. Chem.  1975,  53:  1700 

20b

When added to NiCl₂·6H₂O, aluminum powder reacts vigorously without heating. The reaction must be cooled for the heat to subside.