Carbon disulfide, alkylation

MUSTARD OH. (Constituents alkyl isothiocyanate carbon disulfide alkyl cyanide). Mustard oil has been handled in aluminum alloy columns and condensers. 

Hydrazine as Nucleophile. Reaction of hydrazine and carbon dioxide or carbon disulfide gives, respectively, hydrazinecarboxyhc acid [471-31-8], NH2NHCOOH, and hydrazinecarbodithioic acid [471-32-9], NH2NHCSSH, in the form of the hydrazinium salts. These compounds are useful starting materials for further synthesis. For example, if carbon disulfide reacts with hydrazine in basic medium with an alkyl haUde, an alkyl dithiocarbazate ester is obtained in a one-step reaction ... 

In another process, 50—150% excess carbon disulfide and a small excess of powdered alkah hydroxide are added, with stirring and cooling to the lower alkyl alcohol. After completion of the reaction, the excess CS2 and resulting water of reaction are removed by applyiag a vacuum to the reactor (80). 

The same diamine, when treated with carbon disulfide in alkaline medium, yielded 2-mercapto- l//-imidazo[4,5-/]quinoline (88PS267,88SC973,86IJC264), which, on treatment with alkyl, aralkyl, and acid halides, gave the corresponding thioethers and thioesters 111, respectively (88PS267, 86IJC264). 

The required xanthates 1 can be prepared from alcohols 5 by reaction with carbon disulfide in the presence of sodium hydroxide and subsequent alkylation of the intermediate sodium xanthate 6. Often methyl iodide is used as the alkylating agent ... 

The reaction of 3-hydrazinophenanthro[9,10-e][l,2,4]triazine 742 with carbon disulfide, thiourea, phenyl isothiocyanate, urea, and phenyl isocyanate led [77ZN(B)569] to the formation of phenanthro[9,10-e][l,2,4]-triazolo[4,3-/j][l,2,4]triazines 743. Alkylation of 743 in aqueous alkaline... 

A similar approach has been used to prepare dithiocarbamates, xanlhates and unsymmetrical trithiocarbonates.478 Thus, unsymmetrical primary and secondary trithiocarbonates arc readily prepared in a one pot reaction by treating a thiol with carbon disulfide in the presence of triethylamine to form a carbotrilhioale salt and then adding the appropriate alkylating agent.457 47 The process is shown in Scheme 9.40 for 231.46j... 

Considerably less is known about the chemistry of palladium and platinum 1,1-dithio complexes. Of late, there has been only one report that dealt with the synthesis of a large number of palladium dithiocar-bamates 392). Twenty-five yellow palladium dithiocarbamate complexes were obtained by reaction of PdCla with NaR2dtc in methanol solution. Several other reports have appeared in which a few dithiocarbamate complexes of palladium were synthesized. Thus, the novel [Pd (OH)2dtc 2], which is soluble in water, was isolated 393). The synthesis of optically active palladium(II) complexes of AT-alkyl-a-phen-ethyldithiocarbamates, similar to (XXIV), via the reaction between the optically active amine, CS2, and PdCl2, has been described. From ORD and CD spectra, it has been established that the vicinal contribution of a remote, asymmetric carbon center could give rise to optical activity of the d—d transitions of palladium 394). Carbon disulfide has been shown to insert into the Pt-F bond of [PtF(PPh3)3]HF2, and X-ray studies indicated the structure (XXIX). 

The addition of alcohols to carbon disulfide in the presence of a base produces xanthates. The base is often OH, but in some cases better results can be obtained by using methylsulfinyl carbanion (MeSOCH ) If an alkyl halide RX is present, the xanthate ester ROCSSR can be produced directly. In a similar manner, alkoxide ions add to CO2 to give carbonate ester salts ROCOO. ... 

Alkyl (0,0 -dialkylphosphono)methanedithioates or phosphonodithioformates 1 (R =Et or iPr) are stable and easily accessible compounds from dialkylphos-phites and carbon disulfide [9]. Most of the synthetic applications of these difunctional compounds result from their reactivity towards nucleophiles and dienes. 

Alcohols can be dehydrated via xanthate esters at temperatures that are much lower than those required for acetate pyrolysis. The preparation of xanthate esters involves reaction of the alkoxide with carbon disulfide. The resulting salt is alkylated with methyl iodide. 

Triazolothiadiazolopyrimidines can be prepared from the reaction of the fused hydrazinothiadiazole 313 with carbon disulfide and pyridine. The thiol product can then be alkylated using standard conditions <1994CHE495> (Scheme 83). 

A novel synthesis of alkylsulfanylisothiazoles 230 starts with sodium a-cyanoketene dithiolates 227, obtained by the reaction of cyanoacetamides 226 with carbon disulfide in the presence of sodium ethoxide <06SC825>. Treatment of 227 with sulphur and piperidine acetate generates sodium isothiazole-3,5-dithiolates 229. The formation of 229 is assumed to arise from the addition of anionic sulphur to the nitrile group in 227 to give the intermediate 228, which cyclizes upon elimination of anionic sulphur to yield 229. Salts 229 are readily alkylated to furnish 3,5-bis(alkylthio)isothiazole derivatives 230. 

As in Section 5.06.9.1, the assignments are sometimes arbitrary. Important routes to oxadiazoles, aminooxadiazoles, oxadiazolinones, and oxadiazolinethiones involving the reaction of hydrazides RCONHNH2 with carboxylic acids, acyl chlorides, alkyl esters, or trialkyl orthoesters are described in Section 5.06.9.2.1, reactions with carbon disulfide... 

The base-catalyzed fragmentation of 4-alkyl-l,2,3-thiadiazoles is a useful method for the preparation of alkyne-1-thiolates <1996T3171>. These alkyne-l-thiolates can then react with carbon disulfide to afford l,3-dithiole-2-thiones. This strategy has been developed to give a synthesis of some novel tetrathiafulvene derivatives <1996T3171>. 

Dithioacids have been generated from carbon disulfide with Grignard reagents or alkyl lithium at 0 °C. Subsequent treatment with sulfonamide in situ gives the corresponding both aliphatic as well as aromatic thioamides in 70-90% yields (Scheme 10).31... 

The present procedure2 describes the conversion of resin-bound, primary aliphatic amines into isothiocyanates and the conversion of the latter into 3-aminothiophenes. The generation of isothiocyanates is related to known procedures,3 in which amines are first treated with carbon disulfide and the resulting dithiocarba-mates are desulfurized by treatment with a condensing agent (alkyl chloroformates, carbodiimides, lead or mercury salts, etc.). The presence of resin-bound isothiocyanates on the polystyrene support could be qualitatively ascertained by infrared spectroscopy (KBr-pellet strong absorption at 2091 cm-1). 

The reaction of hydrazinapyrazoles 218 with acid halides also yields alkyl- and aryl-pyrazolo[5,l-c]-l,2,4-triazoles. Pyrazolo[5,l-c]-triazole-3-thiones are formed from 218 and carbon disulfide [77JCS(P1)2047]. 

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