Dimethylthiocarbamoyl chloride

Since the exocyclic sulfur is more reactive in the ambident anion than in A-4-thiazoIine-2-thione. greater nucleophilic reactivity is to be expected. Thus a large variety of thioethers were prepared in good yields starting from alkylhalides (e.g.. Scheme 38 (54, 91, 111, 166-179). lactones (54, 160), aryl halides (54, 152. 180, 181), acyl chlorides (54. 149, 182-184). halothiazoles (54, 185-190), a-haloesters (149. 152. 177. 191-194), cyanuric chloride (151). fV.N-dimethylthiocarbamoyl chloride (151, 152. 195. 196), /3-chloroethyl ester of acrylic acid (197), (3-dimethylaminoethyl chloride (152). l,4-dichloro-2-butyne (152), 1,4-dichloro-2-butene (152), and 2-chloro-propionitrile (152). A general... 

Hydroxythiadiazoles can be converted into chloro compounds by the usual methods, for example with POCI3. The 0-acylation of the sodium salt of hydroxythiadiazoles with dimethylthiocarbamoyl chloride followed by thermal rearrangement of the thiolcarbamate and hydrolysis is a convenient route to l,2,5-thiadiazole-3-thiones <73CJC2349>. 

Hydroxy-2-methyl-4.//-pyrido[l,2-a]pyrimidin-4-ones510 (R1 = Hor CN R2 = H, Me) reacted with dimethylthiocarbamoyl chloride in acetone to afford 9-dimethylthiocarbamoyloxy derivatives 511 (R1 = H, CN R2 = H, Me) (Scheme 30) (87EUP218423 89EUP329126). When compounds 511 were heated in Dowtherm A, the 9-dimethylthiocarbamoyloxy group rearranged to give 9-(dimethylcarbamoylthio)-2-methyl-4//-pyrido[l,2-a]pyrimidin-4-ones 512 in excellent yield. The treatment of pyridopyrimidin-4-one 512 (R1 = H, R2 = Me) with sodium hydride... 

A convenient reaction of organolithium with easily available thiuram disulfides was reported by Gronowitz et al. [45], and the reaction of Grignard reagents with N,AT-dimethylthiocarbamoyl chloride was found [46] to be nicely catalysed by NiCl2(dppe) to afford thioamides. An analogous route with palladium[II] catalysis allowed Hartke et al. [47] to prepare a number of interesting a-acetylenic thioamides. 

DMAP Dimethylaminopyridine DMTCl Dimethylthiocarbamoyl chloride DETCl Diethylthiocarbamoyl chloride PTC Phase transfer catalyst BINOL Binaphthol... 

The rearrangement has been apphed to the synthesis of 2-, and 6-azu-lenethiols [55]. In this case, however, it was not possible to start from the corresponding hydroxyazulenes. In fact, the reaction of the alcoholic fimc-tional group with dimethylthiocarbamoyl chloride in the presence of sodium hydroxide afforded a complex reaction mixture, involving electrophihc substitution at various positions. In order to avoid this problem, the correspond-... 

The method has proved to be valuable for the synthesis of basic thio-phenols in industrial synthesis, as shown by the manufacture of the starting material dimethylthiocarbamoyl chloride [104]. 

Preparation. The reagent has more recently been prepared1 by chlorination of bis(dimethylaminothiocarbamoyl)disulfide (Thiram2). Compare the previously reported preparation of dimethylthiocarbamoyl chloride.3... 

Olefin synthesis from alcohols. Primary and secondary alcohols containing a /3-hydrogen can be converted into olefins by conversion into the alkoxide (sodium hydride, DMF) and then reaction of the alkoxide with N,N-dimethylthiocarbamoyl chloride to form an O-alkyl dimethylthiocarbamate. These derivatives on heating to 180-200° for 2 hours decompose to form olefins. The other product is dimethylammonium dimethylthiocarbamate (2). The complete sequence is formulated as follows ... 

The structure of 3,5-dimethyl-5,6-dihydro-2//-l,3,5-oxadiazine-4(3//)-thione, an unexpected byproduct in the oxidation of A, A -dimethylthiourea with singlet oxygen, has been confirmed by x-ray analysis <92Ml 618-01 >. In a similar manner, the product formed by the action of potassium thiocyanate on A, A(-dimethylthiocarbamoyl chloride (Me2NCSCl) has been shown to be the 1,3,5-thiadiazine-2-thione dithiocarbamate (26) <891ZV909>. 

Treatment of A,A-dimethylthiocarbamoyl chloride (214) with potassium thiocyanate affords the... 

A method has been described for the conversion of phenols to thiophenols employing dimethylthiocarbamoyl chloride. 2- And 4-pyridone and 3-pyridinols were typical among twenty-nine compounds studied. The carbamyl chloride and... 

Allylic thiocarbamates (145) are available from ketones by sequential condensation with vinyl-lithium species and dimethylthiocarbamoyl chloride followed by a [3,3] sigmatropic rearrangement. It has now been shown that these can be used as precursors to a,jS-unsaturated esters by bis-sulphenylation and mercury(ii)-promoted hydrolysis (Scheme 39). Only the B-isomers are produced when the final product (146) is unsubstituted i.e. = H) or carries an a-methyl... 

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