114532-45-5Relevant academic research and scientific papers
ORGANIC DISULFIDES AND RELATED SUBSTANCES. 48. CYCLIC DI- AND TRISULFIDES BASED ON 1,4-DITHIOLS
Singh, Pramod K.,Field, Lamar,Sweetman, Brian J.
, p. 61 - 72 (2007/10/02)
Based on 1,4-dithiols, the seven-membered cyclic trisulfide 1,5-dihydro-2,3,4-benzotrithiepin (3), the nonbenzenoid counterpart (17), related oxides, and open-chain analogs were investigated.The monoxide 4a, n = 1, of 3 upon oxidation lost sulfur and gave 1,4-dihydro-2,3-benzodithiin-2-monoxide (12a, n = 1).The 2,2-dioxide (4b, n = 2) could not be isolated; only 4a, 12a, or 1,4-dihydro-2,3-benzodithiin-2,2-dioxide (12b, n = 2) could be obtained.With related open-chain disulfides in the benzo series of the structure 1,2-(RSSCH2)2C6H4, when R was -(CH2)4SO2Na, ca. 50percent disproportionation occured in H2O in ca. 0.5 h, but the unsymmetrical disulfides with R = p-CH3C6H4- or HOCH2CH(OH)CH2- were relatively stable.The nonbenzenoid counterpart of 3, i.e. 4,7-dihydro-1,2,3-trithiepin (17) could not be obtained pure from the appropriate dichloride (19a), Bunte salt 16a or thiosulfonate (22a), nor could be the disulfide counterpart of 17, i.e. 3,6-dihydro-1,2-dithiin (23), be oxidized to the 1,1-dioxide 24.Bisdisulfides (14ab; 15ab), however, could be obtained satisfactorily, as in the benzo series.Both Z-(14a) and E-disulfides (15a) could be obtained from the Bunte salt and thiosulfonate by reaction with p-toluenethiol; the Z-disulfide readily isomerized to the E-isomer. 2,3-Dihydroxypropanethiol also could be converted to the Z and E disulfides (14b, 15b).Key words: Disulfides; dithiins; 1,4-dithiols; sulfur (extrusion of); trisulfides; trithiepins.
Organic Disulfides and Related Substances. 49. Preparation of Cyclic Thiosulfinates and Reactions with Thiols
Singh, Pramod K.,Field, Lamar,Sweetman, Brian J.
, p. 2608 - 2612 (2007/10/02)
The four stereoisomers of 1,2-dithiane-4,5-diol 1-oxide were prepared by oxidizing the corresponding dithianes with H2O2 in MeOH/H2O by using tungstic acid as a catalyst, MnO2 to destroy excess H2O2 and chromatography to separate products.These cyclic thiosulfinates (8,9,12, and 13), tohether with 1,4-dihydro-2,3-benzodithin 2-oxide (2), were converted to bisunsymmetrical disulfides, Ra(SSRb)2 with p-toluenethiol and 3-mercaptopropanediol as models respectively for arene- and alkanethiols. 1,5-Dihydro-2,3,4-benzotrithiepin 2-oxide (5) gave the disulfide trisulfide s 6a and 6b, Ra(SSRb)(SSSRb), with these thiols but 6a and 6b were quite unstable.Mass spectra are discussed; tetramethylene sulfone may provide a useful matrix for both positive- and negative-ion FAB spectra of organosulfur compounds.
