Thiocarbamoyl

Prepared from Clj and [Mc2NC(S)S ]2 or the corresponding thiocarbamoyl chloride. 

N-acetylsarcosinethioamide reacts in a similar way (482). l-(2-Thiazolyl)-2-imidazolones (47) were synthesized in alcoholic solution frcMii l-thiocarbamoyl-2-imidazolones (46) and a-bromoketones in... 

Phenyl-l,2,3,4-thiatriazole was prepared in this laboratory in 1952 and shown by its infrared spectrum not to be an azide. However, this observation was made in conjunction with rather extensive studies of thioacids and their derivatives and was not published until 1961, when sixteen 5-aryl- and 5-heterocyclyl-l,2,3,4-thiatriazoles were described. Independently, 5-phenyl-1,2,3,4-thiatriazole was also obtained by Bacchetti and Alemagna, Kirmse, and Smith and Kenny and shown by its infrared spectrum not to be an azide. The last two groups of investigators also prepared some other 5-sub-stituted-l,2,3,4-thiatriazoles. Finally, Scottcommented on the anomalous infrared spectra of thiocarbamoyl azides and concluded that they were actually thiatriazoles. 

These compounds exhibit no infrared absorption in the 2100-2200 cm range/ and this definitely rules out the thiocarbamoyl... 

Condensation of 165 with ethoxymethylenemalononitrile gave 171, and with ethyl ethoxymethylenecyanoacetate or methyl bis(methylmercapto)-methylene cyanoacetate it yielded 172 (80AP108). The reaction of 172 with urea, thiourea, and benzyl nitrile afforded 173 (91PHA98). Treatment of hydrazino derivatives 165 with alkyl, aryl, or aralkyl isothiocyanates yielded (86JHC1731) 3-(/V-substituted-thiocarbamoyl)-hydrazino[l,2,4]triazino[5,6-b]indoles which have been evaluated for in vitro antimicrobial activity (Scheme 36). 

A number of differently substituted A-(thiocarbamoyl)benzamidines (521) (R = Et, Bu NR2 = morpholino) have been complexed with Ni11. The ligands function in a bidentate manner, coordinating via the primary amine N and thione S atoms.1371... 

The reaction of CdCl2 with tV,7V -bis(thiocarbamoyl)hydrazine gave [Cd SC( = NH)NH2 2Cl2] which has been used as a single-source precursor. Upon thermolysis in TOPO at 230 °C it produced CdS particles which showed an absorption edge blue shift of 37 nm in relation to that of the bulk material no chlorine contamination was reported.385... 

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>. 

Tetramethylthiuram disulphide (TMTD) has proved to be a useful reagent for the thiocarbamoylation of amine containing compounds. Thus, reaction of a series of hydrazones of aromatic aldehydes with TMTD in a 1 1 ratio gave amongst other products, 4,4-dimethylthiosemicarbazide 86 and 5-dimethylamino-l,3,4-thiadiazole-2-thiol 85. It was confirmed that 86 was an intermediate in the synthesis of 85 as treatment of 86 with TMTD gave 85 in 85% yield <00RCB344>. 

Sekine, M., Yamaguchi, H., and Hata, T., A general and convenient method for the synthesis of unesterified carbamoyl- and thiocarbamoyl-phosphonic acids, Tetrahedron Lett., 3031, 1979. 

The synthesis of other biologically active thiazoles was described by Ohsumi et al. [50] and is shown in Scheme 16. Condensation of phosphonium bromide and 4-methoxy-3-nitrobenzaldehyde gave a 1 1 mixture of (Z)- and (-E)-stilbenes. ( )-stilbene 64 was purified by crystallization and then converted to bromohydrin 65 by NBS-H2O. Oxidation of the bromohydrin by DMSO-TFAA gave the bromoketone intermediate 66, which was condensed with thiocarbamoyl compounds in the presence of Na2C03 in DMF to give the corresponding 2-substituted thiazole derivatives (67a and b). Compound 67a... 

Xanthates, on the other hand, are photolyzed to yield the corresponding alcohols, and the yield reported, for instance for l,2 3,4-di-0-iso-propylidene-6-0-[(methylthio)thiocarbamoyl]-a-D-galactopyranose (50%, see Scheme 13) is apparently lowered by partial removal of isopropyli-dene groups under the reaction conditions. 

The condensation of isocyanate esters with diguanides proceeds in an entirely comparable manner, providing a corresponding series of s-triazin-2-ones (i.e. substituted ammelines) 378). However, since loss of water from carbamoyl-intermediates [e.g. RNHCONH C( NH)NH C( NH) -NH2] occurs much less readily than loss of hydrogen sulphide from their thiocarbamoyl-analogues, melamines are not formed in this reaction 378). The production of adducts from phenyl isocyanate and tetra-. 

The latter case has been demonstrated with the reaction of [ReCl3(PPh3)2(CH3CN)] with a large excess of sodium diethyldithiocarbamate which results in sulfur abstraction and in the formation of a mixed phosphine/diethyldithiocarbamato/r/ -thiocarbamoyl complex. For the molecular structure of this compound see formula (225) which represents that of the corresponding rhe-nium(IV) cation which is formed by oxidation of the primarily formed Re complex and contains one rhenium-carbon bond. The formation of thiocarbamoyl compounds seems to be an essential... 

The naphthalene-catalyzed (3%) lithiation of carbamoyl or thiocarbamoyl chlorides 91 in the presence of carbonyl componnds or imines as electrophiles in THF at temperatnres ranging between —78 to 20 °C led to the expected fnnctionalized amides or thioamides 92 after hydrolysis (Scheme 39) . ... 

The conversion of 2,4-bis(4-cyanophenyl)-6-dimethylamino-13,5-triazine into the corresponding diaryl cyclic diamidine via reaction with an excess of 1,2-diaminopropane saturated with hydrogen sulfide has been reported. 2,4-Bis(4-cyanophenyl)-133-triazine is resistant to cyclization in reacting with 1,4-diaminobutane under similar conditions and affords 2,4-bis[4-[V-(4-aminobutyl)thiocarbamoyl]phenyl]-133-triazine <99TL2841>. 

An acylation on the thiophene ring occurs when 58 is allowed to react with either acetyl isothiocyanate or phenyl isothiocyanate to form the corresponding thiocarbamoyl derivatives 59a and 59b, respectively (Equation 23) <1997IJB612>. 

Replacement of the urethane carbonyl function by an aromatic ring leads to a benzo-thiazole that is described as an immune function modulator. In an analogous approach to that used above, anilinothiol (63-1) is condensed with the thiocarbamoyl chloride (63-2) again in the presence of a base. This leads directly to frentizole (63-3) [66]. 

This group of syntheses comprises the oxidation of compounds containing the thiocarbamoyl group, including thioamides and thioureas ... 

Two modifications of the well-known benzothiazole preparation have been employed to prepare unusual heteropoly cycles. Konig et al.ils treated l-thiocarbamoyl-l,2,3,4-tetrahydroquinoline (236) with bromine in chloroform to give the thiazolo[3,4,5-J,i]quinoline derivative 237. In a process which requires disruption of the resonance stabilization of the pyridine ring, Harris416 reported that treatment of l-(2-pyridyl)-2-thiourcas with sulfuryl chloride or with bromine gives the hydrohalide salts of 2-imino-2//-[l,2,4]thiadiazolo[2,3-a]pyridines (238). 

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