Thiophosgene properties

Physical Properties. Thiophosgene [463-71-8] (thiocarbonyl chloride), CSCI2, is a malodorous, red-yeUow Hquid (bp 73.5°C, ( 20 1.5442). It is only slightly soluble with decomposition in water, but it is soluble in ether and various organic solvents. 

Because of the objectionable properties of thiophosgene, care should be exercised in its use. 

Chemical Properties. Thiophosgene is more resistant to hydrolysis than its oxygen analogue, phosgene, but it is slowly hydrolyzed to carbon dioxide, hydrogen sulfide, and hydrochloric acid. It can be oxidized to a lacrimatory thiophosgene 5-oxide (41). Its utility in organic synthesis has been... 

Health and Safety Factors. Thiophosgene has an LD50 (rat, oral) of 929 mg/kg and an LC50 (inhalation, rat) of 370 mg/m3 (45). It has both irritant and systemic toxic properties. 

SiS2 (125)72, Cl(H)Si=S (126)51 and Cl2Si=S (127)50 were prepared and isolated in low temperature matrices. The properties of these species are of interest as the silicon analogues of carbon disulfide (CS2), thioformyl chloride [S=C(H)C1] and thiophosgene (S=CCl2), which are well-known thiocarbonyl compounds. 

The anomalous photophysical properties of sulphur compounds continue to attract interest. Quenching studies of the luminescent S2 state of a number of aromatic thioketones show a range of lifetimes between 10 and 10 s. A variety of solvents shows the role of transient interactive effects and environmental viscosity. In the case of the S2 state of thiophosgene in perfluoro-solvents, molecular dissociation is found to be the most... 

Reaction of methyl j8-aminocrotonate (LXXVI) with thiophosgene under the catalysis of triethylamine led to the formation of LXXVII. A possible mechanism is shown above. Deuteration studies showed that C-5 has a considerable amount of anionic character, a property utilized later in the synthesis. Treatment of LXXVII with A-bromosuccinimide provided LXXVIII. Subsequent formation of the Wittig reagent with triphenylphosphine and reaction with 3,4,5-trimethoxybenzaldehyde gave LXXIX. The styrene double bond was selectively reduced with diimide and the carbomethoxy group transformed into an aldehyde... 

The heterocyclic products show, in general, the expected properties the carbamoyl chlorides (95) are convertible into ureas (97 X = NHj etc,) or urethanes (97 X = OR), whereas the 2-alkylamino-l, 3,4-thiadiazolin-5-ones (94) are acylated to (98). They also yield, with thiophosgene, a series of thio-analogues of (95), (96), and (97). ... 

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