Thiocarbonyl perchloride

A. Preparation of Thiocarbonyl Per chloride.—In a 5-I. bottle arranged for cooling by running water is placed 500 g. (6.58 moles) of dry carbon disulfide (Note i) to which 0.5 g. of iodine has been added. Dry chlorine is passed into the cooled carbon disulfide at such a rate that the temperature does not rise above 25°, until the liquid weighs 1770 g. (17.9 moles chlorine) (Note 2). The time required is about forty hours. The product is a deep red liquid, a mixture of impure thiocarbonyl perchloride and sulfur chloride. 

The crude, dry thiocarbonyl perchloride is distilled through an efficient 60-cm. column (Note 9). The distillate below 140 is discarded. The fraction boiling at 140-155 at atmospheric pressure amounts to about 600 g. The boiling point of pure thiocarbonyl perchloride is 149°. 

In the flask A are placed 750 g. (6.3 moles) of granulated tin (Note 10) and 1500 cc. of commercial hydrochloric acid (about 28 per cent). The mixture is heated until the action is vigorous. The thiocarbonyl perchloride is run in from the funnel T (Note ii). The resulting reaction is very violent. The vapors are... 

Thiophosgene has been prepared in small yield by the chlorination of carbon disulfide in the presence of iodine and by the reduction of thiocarbonyl perchloride. ... 

Thiobenzoic acid, 32,101 Thiocarbonyl perchloride, 32, 69 Thiolacetic acid, 31,105... 

The above procedure is essentially that of Tieckelmann and Post.3 Ethyl orthocarbonate has been prepared by the reaction of chloropicrin and sodium ethoxide by Bassett4 and Rose.5 Thiocarbonyl perchloride has been reported 3 6 to react with sodium ethoxide to give good yields of ethyl orthocarbonate. 

Tetraphenylarsonium chloride HYDROCHLORIDE, 30, 95 Tetraphenylethylene, 31, 104 2,2,3,3-Tetraphenylpropionitrile from diphenylacetonitrile and benzhydryl chloride, 39, 74 Tetra-K-propyltin, 36, 88 3-Thenaldehyde, 33, 93 3-Thenoic acid, 33, 94 3-Thenyl bromide, 33, 93, 96 7-Thiabicyclo(4.1.0)heptane, 32, 39 Thiobenzoic acid, 31,101 Thiobenzophenone, 35, 97 Thiocarbonyl perchloride, 32, 69 Thioether, preparation of dithiane,... 

No reference was made to Helfrich and Reid, J. Am. Chem. Soc. 43, 591 (1921), who describe what appears to be a simpler method for preparing the intermediate thiocarbonyl perchloride. Axjtenrieth and Hefner, Ber. 58, 2151 (1925), have also studied and made improvements in the preparation of thiophosgene. 

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