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Please login or sign up for a free trial to access the full content. Variation 2: Via In Situ Formation of Alkanesulfinyl Chlorides from Dialkyl Disulfides

DOI: 10.1055/sos-SD-039-00272

Braverman, S.; Cherkinsky, M.; Levinger, S.Science of Synthesis, (200839218.

The alkanesulfinate esters 72 may be prepared directly by low-temperature chlorination of dialkyl disulfides in alcohols.[‌145‌,‌146‌] The synthesis involves converting the disulfide into the sulfinyl chloride, which, without isolation, reacts with the appropriate alcohol (Scheme 44). When the disulfide and chlorine are used in stoichiometric amounts with a small excess of alcohol, the crude esters are produced in 6085% yields. The crude esters thus prepared can be purified from sulfonyl chloride contaminants by treatment with an aromatic amine, such as p-toluidine. The low molecular weight alkyl alkanesulfinates are then best separated from the excess amine by distillation. Those of higher molecular weight and low water solubility can be extracted with dilute acid to remove the excess amine. Glacial acetic acid can also be used as a solvent in the chlorination step of this one-pot protocol, with subsequent distillation of acetyl chloride.[‌145‌] Equally good results are obtained when sulfuryl chloride is used as the chlorinating agent.[‌145‌]

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