S-Alkylation of thiols and thiolates

6 real reactions from the literature, on halohydrins, primary alkyl bromides, primary alkyl chlorides and thiols. Each scheme shows starting materials, conditions and products, with the yield and reference where the source reports them.

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1. S-alkylation: 2-chloroethanol (a halohydrin) with NaSCH3; CH3CH2OH, Δ gives 2-(methylthio)ethanol (the thioether).

   S-alkylationOrg. Synth. Coll. Vol. 2, p. 345

2. S-alkylation: 1,4-dichlorobutane (a primary alkyl chloride) with Na2S; DMF, H2O, Δ gives tetrahydrothiophene (the thioether).

   S-alkylationOrg. Synth. Coll. Vol. 4, p. 892

3. S-alkylation: 2-chloroethanol (a halohydrin) with Na2S, H2O; Δ; (2 equiv.) gives thiodiglycol (the thioether).

   S-alkylationOrg. Synth. Coll. Vol. 2, p. 576

4. S-alkylation: 1-bromo-2,2-dimethylpropane (a primary alkyl bromide) and sodium benzenethiolate (a thioanisole) with C16H33P(CH3)3+ Br–; H2O, 70 °C gives 2,2-dimethylpropylsulfanylbenzene (the thioether).

   S-alkylationOrg. Synth. Coll. Vol. 6, p. 833

5. S-alkylation: 1,4-dibromo-2,2-dimethylbutane (a primary alkyl bromide) with Na2S, DMSO gives 3,3-dimethyl-thiacyclopentane (the thioether).

   S-alkylationChem. Pharm. Bull. 1985, 33, 5048

6. S-alkylation: 1,3-propanedithiol and 1,4-dibromobutane (a primary alkyl bromide) with Cs2CO3; DMF gives 1,5-dithionane (the thioether).

   S-alkylationJ. Org. Chem. 1981, 46, 4481