Sodium cyanodithioformate

Chlorination of sodium cyanodithioformate gives 3,4-dichloro-5-cyanoisothiazole (227), probably via the isothiazolodithiine (226) (72AHC(l4)l). The thienoisothiazole (228) undergoes cycloaddition with alkynic esters to give adducts such as compound (229), which... 

Dimerization of the dimethylformamide-solvated sodium cyanodithioformate takes place in carbon tetrachloride and dichloromethane with elimination of sulfur1,18 but at a much lower rate than in water. 

The nature of the arylthio substituent at C-4 of a 5(277)-oxazolone dictates which of two different synthetic strategies can be used. The first involves the use of sodium cyanodithioformate and the corresponding ketone as starting materials. The reaction occurs through a thiazolone 45 that must be alkylated on the sulfur atom followed by treatment with Hg(OAc)2 to afford the corresponding 4-(alkylthio)-5(2//)-oxazolone 47. The second strategy involves the addition of thiophenol to... 

TABLE 7.5. SYNTHESIS OF 4-(ALKYLTHIO)-5(2H)-OXAZOLONES FROM SODIUM CYANODITHIOFORMATE, KETONES AND ALKYLATING AGENTS-... 

Benzoylimino-6-mercapto[l,2]dithiolo[4,3-c]isothiazole is formed by double ring closure from sodium cyanodithioformate and benzoyl chloride (equation 79) (81EGP148341). 

Sodium cyanodithioformate readily, and quickly, dimerizes in water with elimination of sulfur in the presence of transition-metal ions, forming directly, in this process, a dithiolato-metal complex. The general procedures described below have been used in the preparation of most of the bis(dicyanoethenedi-thiolato) complexes described previously6 and also of some tris(cfs-l,2-dicyanoethene-l,2-dithiolato) complexes of the first-row transition metals. Although the yields of these complexes obtained by this method are somewhat lower than those described previously, the method possesses the advantage of speed and relative convenience. 

Thienothiophens, Thienoselenophens, and Related Systems.—The thiophen derivative (738) cyclises to the thieno[2,3- >]tiiiophen (739)/ Electrochemical reduction of carbon disulphide in acetonitrile gives the di-anion (740), which forms the dithiolodithiole (741) on treatment with thiophosgene. The di(acylimino)tetrathiapentalenes (742) are obtained by the action of acid chlorides RCOCl on the complex of sodium cyanodithioformate with Perchloric acid transforms the bis-dithiocarbamate (743 R2N = piperidine) into the salt (744) the tetraselenium analogue has been prepared similarly/ ... 

Methyl cyanodithioformate. Oxygen, singlet 4-Phenyl-l,2,4-tiiazoline-3,5-dione. EPOXIDATION Biacetyl. r-Butyl hydroperoxide. /-Butyl hydiopcroxlde-Vanadyl acetyl-acctatc. m-Chloroperbenzoic acid. Iodine. Sodium hypochlorite. 

Synthesis of Dithiocarboxylic Acids and their Derivatives.—The preparation of thioterephthalic acid from l,4-di(chloromethyl)benzene, sulphur, and sodium methoxide (see Vol. 5, p. 179) has beeil reported by another group. In a similar reaction, the addition of chloroacetonitrile to sulphur and triethylamine in DMF, followed by alkylation, gave methyl and ethyl cyanodithioformates. These were not isolated, but they condensed when water was added, giving EfZ mixtures of l,2-di(alkylmercapto)-l,2-dicyanoethylenes. Ethylene dithioacetals from aromatic aldehydes are decomposed by sodium hydride in DMF containing HMPA, with elimination of ethylene and the liberation of an aryIdithiocarboxylate anion this may be alkylated to give the dithioester (Scheme 8). ... 

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