· 4-Chlorophenyl Chlorothionoformate
· (MW 207.08)
(dehydrating agent;1 has been used in radical deoxygenation;2 serves as a building block in the synthesis of penems3 and heterocycles;4 used for introduction of the thiocarbonyl group5)
Alternate Name: O-(4-chlorophenyl) carbonochloridothioate.
Physical Data: bp 82 °C/0.8 mmHg;6 114-116 °C/0.8 mmHg.7
Form Supplied in: distillable liquid; commercially available.
Preparative Method: from thiophosgene and p-chlorophenol in the presence of sodium hydroxide.2,6
Handling, Storage, and Precautions: protect from moisture.
Use as Dehydrating Agent.
The reagent converts oximes to nitriles under mild conditions (rt, 1.5 h) (eq 1).1
Use in the Chugaev Reaction.
The closely related reagent, p-tolyl chlorothionoformate, has been used for Chugaev eliminations (eq 2);8 presumably, p-chlorophenyl chlorothionoformate could serve the same function.
Use in Radical Deoxygenation.
The reagent has been used in radical deoxygenation (eq 3).2
Use as a Building Block.
The reagent has been incorporated into the structure of a thiopenem antibiotic (eq 4).3
The reagent is also useful for introducing the thiocarbonyl function, since the chlorine atom and chlorophenol residues can be replaced successively by nucleophiles (eq 5).4,5
- 1. Clive, D. L. J. CC 1970, 1014.
- 2. Barton, D. H. R.; Dorchak, J.; Jaszberenyi, J. Cs. T 1992, 48, 7435.
- 3. Cooke, M. D.; Moore, K. W.; Ross, B. C.; Turner, S. E. CC 1983, 1005.
- 4. Müller, E.; Gröbner, P. M 1975, 106, 27.
- 5. Richter, P.; Oertel, D.; Oertel, F. Pharmazie 1988, 43, 753 (CA 1989, 110, 173 200h).
- 6. Garmaise, D. L.; Uchiyama, A.; McKay, A. F. JOC 1962, 27, 4509.
- 7. Lancaster catalog, 1991/1992.
- 8. Gerlach, H.; Huong, T. T.; Müller, W. CC 1972, 1215. Gerlach, H.; Müller, W. HCA 1972, 55, 2277.
Maarten H. D. Postema & Derrick L. J. Clive
University of Alberta, Edmonton, AB, Canada
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