4-Chlorophenyl Chlorothionoformate

[937-64-4]  · C7H4Cl2OS  · 4-Chlorophenyl Chlorothionoformate  · (MW 207.08)  · C7H5BrN2  · 3-Bromo-3-phenyldiazirine  · C7H5ClN2  · 3-Chloro-3-phenyldiazirine

(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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