76480-13-2Relevant academic research and scientific papers
Biologically oriented organic sulfur chemistry. 21. Hydrodisulfide of a penicillamine derivative and related compounds
Heimer, Norman E.,Field, Lamar,Neal, Robert A.
, p. 1374 - 1377 (1981)
For study of the chemistry of an amino acid derived hydrodisulfide (10, Me2C(SR)CH(NHAc)CO2Me, R = SH), a synthetic route to a hydrodisulfide derivative of N-acetyl-DL-penicillamine was developed. Conversion of N-acetyl-DL-penicillamine (3) to the ester (4, R = H) was accomplished with diazomethane. With acetylsulfenyl chloride, 4 gave the acetyl sulfide (5, R = Ac) instead of the disulfide (7, R = SAc). With (methoxycarbonyl)sulfenyl chloride, 4 gave the corresponding unsymmetrical disulfide (8, R = SCO2Me), which could not be converted to the hydrodisulfide. Conversion of 4 to the sulfenyl iodide (9, R = I) and treatment with thioacetic acid regenerated 4. With acetyl methoxycarbonyl disulfide, however, 4 gave the acetyl disulfide 7. Methanolysis of 7 then gave the hydrodisulfide 10. Solutions of 10 in chloroform were unchanged after 6 days at room temperature and 1 day at 55°C and then consumed the expected amount of iodine. Washing with bicarbonate led to immediate decomposition; neat 10 completely decomposed during storage at -10°C for 36 h, and the half-life of 10 in HCl-methanol was about 12 h. Treatment of 10 with cyanide ion gave thiocyanate ion, and treatment with 2,4-dinitrochlorobenzene gave a dinitrophenyl derivative [13, R = 2,4-(NO2)2C6H3S] identical with 13 prepared from 4 by using 2,4-dinitrobenzenesulfenyl chloride.
Thiono Compounds. 1. Interactions of Monoatomic Sulfur, Including Insertion into S-H Bonds
Field, Lamar,Ravan, J. Valerie,Dunkel, John D.,Waites, John A.,White, David W.,et al.
, p. 4651 - 4654 (2007/10/02)
Possible traps for monoatomic sulfur were assessed by determining the reduction in yields of cyclohexanethiol (6) when carbonyl sulfide was photolyzed in cyclohexane containing the potential trap; the identity of 6 was confirmed by GC/MS and other means.Reduction of the yield of 6 by benzene, triethylamine, acetic acid, acetonitrile, and ethanol indicates undesirability of lone pair and ? systems in the assessment procedure.In order of promise as traps, compounds tested were n-Bu3SnH > (n-C5H11S)2 ca.= RSH > (EtO)3SiH > Et3SiH ca.= cyclohexane.Insertion of sulfur was demonstrated with two thiols, chosen as members of one of the most promising classes, by identity with authentic samples of derivatives of the hydrodisulfides generated; this result points to the chemical feasibility of postulated insertions of monoatomic sulfur in biological reactions and also suggests promise of the other potential traps for further study.
