Chemistry:Chlorocarbonylsulfenyl chloride
sulfenyl_chloride.svg)
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| Properties | |
| Cl–C(=O)–S–Cl | |
| Molar mass | 130.97 g·mol−1 |
| Appearance | colorless liquid |
| Density | 1.552 g/cm3 |
| Boiling point | 98 °C (208 °F; 371 K) |
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| GHS Signal word | Danger |
| H314 | |
| P260, P264, P280, P301+330+331, P302+361+354Script error: No such module "Preview warning".Category:GHS errors, P304+340, P305+354+338Script error: No such module "Preview warning".Category:GHS errors, P316Script error: No such module "Preview warning".Category:GHS errors, P321, P363, P405, P501 | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
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Chlorocarbonylsulfenyl chloride is the chemical compound with the formula Cl–C(=O)–S–Cl. It is a colorless, distillable liquid that is related to phosgene. It features two reactive functional groups, an acyl chloride and a sulfenyl chloride. According to X-ray crystallography, the molecule is planar.[1]
Preparation and reactions
Chlorocarbonylsulfenyl chloride is prepared by hydrolysis of trichloromethane sulfenyl chloride in sulfuric acid as solvent:[2]
- Cl
3C–S–Cl + H
2O → Cl–S–C(=O)–Cl + 2 HCl
The compound, being bifunctional, has been used for the preparation of several heterocycles including oxathiazol-2-ones, oxathialones, and oxathiazoles.[3]
Treatment with formamides gives dithiazolidinediones (also known as dithiasuccinoyl, or DTS).[4]
Relevant to amino acid chemistry, ethylthionocarbamates react with chlorocarbonylsulfenyl chloride to give DTS derivatives:[5][6]
- Cl–S–C(=O)–Cl + CH
3CH
2–O–C(=S)–NH–R → [[Chemistry:
1,
2,−
4Dithiazolidine−
3,−
5dione|S
2(CO)
2NR]] + HCl + CH
3CH
2Cl
Alcohols and amines react at the acyl chloride position to form alkoxycarbonylsulfenyl chlorides and carbamoylsulfenyl chlorides. Thiols selectively react at the sulfenyl chloride position to form S-alkylchlorocarbonyl disulfides:[2]
ROH + Cl–S–C(=O)–Cl → Cl–S–C(=O)–OR + HCl
RNH2 + Cl–S–C(=O)–Cl → Cl–S–C(=O)–NHR + HCl
RSH + Cl–S–C(=O)–Cl → RS–S–C(=O)–Cl + HCl
These reagents are useful for the derivatization of biological thiols. Methoxycarbonylsulfenyl chloride, a related reagent derived from the above chemistry, is used in solid-phase peptide synthesis for selective disulfide bond formation via conversion of the acetamidomethyl (Acm) cysteine protecting group to thiol-labile S-alkylsulfenyl thiocarbonate (carbomethylsulfenyl, Scm) protecting group.[7]
References
- ↑ Romano, Rosana M.; Della Védova, Carlos O.; Downs, Anthony J.; Parsons, Simon; Smith, Caroline (2003). "Structural and vibrational properties of CLC(O)SY compounds with y = Cl and CH3". New Journal of Chemistry 27 (3): 514–519. doi:10.1039/B209005H.
- ↑ 2.0 2.1 Zumach, G.; Kühle, E. (1970). "Chlorosulfenylated Carbonic Acid Derivatives". Angewandte Chemie International Edition in English 9: 54–63. doi:10.1002/anie.197000541.
- ↑ Lin, Gang; Li, Dongyang; De Carvalho, Luiz Pedro Sorio; Deng, Haiteng; Tao, Hui; Vogt, Guillaume; Wu, Kangyun; Schneider, Jean et al. (2009). "Inhibitors selective for mycobacterial versus human proteasomes". Nature 461 (7264): 621–626. doi:10.1038/nature08357. PMID 19759536. Bibcode: 2009Natur.461..621L.
- ↑ Martinez, Ana; Alonso, Mercedes; Castro, Ana; Dorronsoro, Isabel; Gelpí, J. Luis; Luque, F. Javier; Pérez, Concepción; Moreno, Francisco J. (2005). "SAR and 3D-QSAR Studies on Thiadiazolidinone Derivatives: Exploration of Structural Requirements for Glycogen Synthase Kinase 3 Inhibitors". Journal of Medicinal Chemistry 48 (23): 7103–7112. doi:10.1021/jm040895g. PMID 16279768.
- ↑ Barany, George; Merrifield, R. B. (1977). "A new amino protecting group removable by reduction. Chemistry of the function". Journal of the American Chemical Society 99 (22): 7363–7365. doi:10.1021/ja00464a050. PMID 915158. Bibcode: 1977JAChS..99.7363B.
- ↑ Wood, Mark E. (2007). "1,2,4-Dithiazolidine-3,5-dione". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/9780470842898.rn00717. ISBN 978-0-471-93623-7.
- ↑ Spears, Richard J.; McMahon, Clíona; Chudasama, Vijay (2021). "Cysteine protecting groups: applications in peptide and protein science" (in en). Chemical Society Reviews 50 (19): 11098–11155. doi:10.1039/D1CS00271F. ISSN 0306-0012. https://pubs.rsc.org/cs/article/50/19/11098-11155/723480.
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