Sulphoxides alkylthiomethyl

The anions of alkyl alkylthiomethyl sulphoxides have found a much broader application. Methyl methylthiomethyl sulphoxide 324 was first introduced by Ogura and Tsuchihashi in 1971412 and ethyl ethylthiomethyl sulphoxide 325 was synthesized by Schlessinger and coworkers in 1973413. Ogura and Tsuchihashi performed alkylation of 324 and obtained a series of substituted dithioacetal monoxides 326 which were then hydrolysed to the corresponding aldehydes (equation 181 Table 17)412. 

The mechanism of the nucleophilic substitution of a-halogenosulphoxides depends on structural factors and the nature of a nucleophile and may occur according to two competitive mechanisms a direct 8 2 substitution and an elimination-addition process . Thus, chloromethyl and bromomethyl sulphoxides react with alkoxide and mercaptide anions via an 8, 2 mechanism to give the corresponding a-alkoxy and a-alkylthiomethyl sulphoxides 502, respectively (equation 305). Optically active a-alkoxymethyl and a-alkylthiomethyl sulphoxides can also be obtained in this way - . 

Simple alkylation at sulphur in merc tomethyl moieties occurs with alkyl halides-alkali and also with trialkyl phosphites , and the resultant dialkyl (alkylthiomethyl)-phosphonates are oxidized to the corresponding sulphoxides by KMn04 ", m-chloroper-... 

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