Alkyl- and substituted alkyldithiobutanesulfinate salts of the structure RSS(CH2)4SO2Na were prepared in 62–81% yield by cleavage of 1,2-dithiane 1,1-dioxide (1) by thiolate salts. Compounds are reported with R = (CH3)3C (2), CH3(CH2)3(3), CH3CH2(4), HO(CH2)2(5), HO2CCH2CH(CO2H) (6), NaO2S(CH2)4SS(CH2)3(7), and NaO2S(CH2)4SS(CH2)5(8). These compounds disproportionated in water to permit extraction of the symmetrical disulfide RSSR (3,5), or a mixture of RSSR and the dioxide1(2,4), or1only (6), or1plus insoluble polymer (7,8). The order of increasing resistance to disproportionation, where polymer was not involved, was estimated to be3<6<4≤5≪2.