Phenol, thiophosgene

Thiophosgene reacts with alcohols and phenols to form chlorothionoformates or thiocarbonates. The most studied reactions of thiophosgene are with primary amines to give isothiocyanates and with secondary amines to give thiocarbamyl chlorides ... 

Bis(benzotriazol-lyl)methanethione 974 is easily prepared from thiophosgene and l-(trimethylsilyl)benzotriazole <1978JOC337>. In reactions with thiols and triethylamine, thiones 974 are converted to derivatives 973 in modest yields the main side products result from nucleophilic attacks of the thiolate anions on the thione sulfur atom to produce disulfides <2005JOC7866>. In reactions with amines, compounds 974 are smoothly converted to l-(thiocarbamoyl)benzotriazoles 975 <2004JOC2976>. Substitution of one of the benzotriazolyl groups in 974 by phenolate anions yields l-(aryloxythioacyl)benzotriazoles 978 (Scheme 161) <2005JOC7866>. 

Carbonic acid (67) can form three different types of thio derivatives, namely thionocarbonates (68), dithiocarbonates (69) and trithiocarbonates (70) (Figure 4). Only the trithioacid (70) is known to exist as the free acid, although all the acids can be isolated as their salts and esters. The mono-, di-and trithioesters (71-(73) can be prepared by the reaction of thiophosgene with alkoxides, phenolates and thiols, respectively (Scheme 38). 

Phenyl chlorothionocarbonate, C6H5OCCl (1). Mol. wt. 218.11, b.p. 81-8376 mm. The reagent is prepared by reaction of phenol with thiophosgene in aqueous NaOH.1... 

Preparation. The reagent is prepared i n 81 % yield by the reaction of p-chloro-phenol in 1 N NaOH solution with thiophosgene in chloroform.1... 

Chlorothioformic esters are prepared by treating thiophosgene or phosgene with alcohols or phenols or with thiols in the presence of sufficient aqueous... 

Diaryl thiocarbonates 756,759 A monohydric phenol (2 moles) is dissolved in a small excess of 10% sodium hydroxide solution, diluted with the four- to five-fold amount of water, and treated gradually, with vigorous shaking, with thiophosgene (1 mole). If the mixture becomes too warm it must be cooled. The aryl ester produced separates as a white precipitate and is washed free from alkali by water and recrystallized, generally from ethanol. 

Compounds (412) were formed from the thiophenols (411) with phosgene or thiophosgene (X = O, S) <79GEP(0)2811163> or with BrCN (X = NH) <79GEP(0)28lll3i>. (In a similar [5 + 1 fragment] synthesis, the analogous benzoxazines were obtained from the appropriate phenols see Section 8.25.3.6.4.)... 

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