5-alkyl dithiocarbamate

Pyrolysis of 5-ethyl iV-disubstituted dithiocarbamates gives ethylene, CS2, and secondary amines and/or a trisubstituted thiourea and ethanethiol. NNSS -Tetrasubstituted dithiocarbamidium iodides, obtained by 5-alkylating dithiocarbamates, are in equilibrium with their precursors, and this equilibrium has been used in the conversion of allylic dithiocarbamates, particularly allylic 1-pyrrolidine-carbodithioates (147), into allylic iodides by treatment with methyl iodide bis(methylthio)methylenepyrrolidinium iodide (148) is insoluble, and it precipitates from the reaction mixture (Scheme 15). AW55 -Tetramethyldithiocarbamidium iodide (149) reacts with hydroxylamine or semicarbazide with displacement of the dimethylamino-group, but with other nucleophiles, e.g. thiosemicarbazide or... 

O-Alkyl xanthates and A -ary l-A -alkyl dithiocarbamates are effective with vinyl acetate. 97 Dithioesters and trithiocarbonates give severe retardation or even inhibition which is attributed to slow fragmentation of the adduct radical. 

Sequential treatment of tertiary amines containing N-methyl or /V-benzyl groups with carbon disulphide and alkyl halides gives alkyl dithiocarbamates in good to excellent yields. Thus IV-methylmorpholine, carbon disulphide and methyl iodide in THF gave 91% of compound 306366. 

TABLE 4.25 Polymer-supported synthesis of alkyl dithiocarbamates R.NCS.SR1 ... 

Kinetic studies of the acid hydrolysis of iV-alkyl dithiocarbamates (372) have been reported. " The tertiary amine-catalysed addition of CS2 (373) to 1,2-diaminobenzene (375) involves initial formation of the zwitterionic adduct (374), which then reacts with the diamine (375) to yield 2-mercaptobenzimidazole (376). ... 

Kwak Y, Matyjaszewski K (2008) Effect of initiator and ligand structures on ATRP of styrene and methyl methacrylate initiated by alkyl dithiocarbamate. Macromolecules 41 6627-6635... 

The simultaneous photolyses of two different species of dithiocarbamates (R - DC and R2 - DC) in the absence of monomers and at high concentrations result in enforced recombination between alkyl radicals produced by photolysis to produce three types of alkyl-alkyl recombination product namely Ri - Ri, R2 - Ri and Ri- R2, as shown in Scheme 5. If the concentration of one species (Ri - DC) is much higher than the other R2 - DC), a relative fraction of heterotopically recombined product, Ri - R2, must increase. If such a heterotopic cross-recombination reaction predominantly occurs at a solution/solid interface, an it2-alkylated dithiocarbamated surface is converted into an it 1-alkylated surface, as schematically shown in Scheme 6. 

Freund,168-160 formulating the oxides as substituted 1,2,4-thia-diazolidines (152) and the sulphides as 1,2,4-dithiazolidines (155), justified the assignment of unlike hetero-nuclei on the grounds that sulfides were also obtainable by the action of bromine on alkyl dithiocarbamates (see below), while oxides were unobtainable by the corresponding reaction of alkyl thiocarbamates. Hantzsch and... 

Thirty-nine different dithiocarbamates have been efficiently prepared through a one-pot reaction of an aliphatic primary or secondary amine, carbon disulfide and an alkyl halide (Figure 2.16). " Typically, all reagents were liquids and the mixture slowly solidified upon reaction. Therefore, although the reaction does not use solvents, the reagents are probably acting as the solvent in this procedure. Additionally, the reactions were quenched with water and extracted with ethyl acetate, so solvent was used. Nevertheless, this is an excellent synthetic method for the preparation of S-alkyl dithiocarbamates, which are useful compounds for the pharmaceutical and agrochemical industries. 

Alkylated dithiocarbamates with chain lengths C2-C6 are often added... 

Reaction of S-alkyl dithiocarbamates. With amino carboxylic... 

The reaction of aminoacetic acid with carbon disulfide has been much studied especially in the presence of various alkylating agents. S-alkyl dithiocarbamates (CLXXXII) are formed as intermediates. These are then converted to the 2-(alkylthio)-z]2-thiazolin-5-one (CLXXXIII) by means of the classical dehydrating agents (224. ... 

S-alkyl dithiocarbamates and a-amino carboxylic acid derivatives... 

Reaction of [Pd(C8Hi2)Cl2] with MN -dialkyl- or 0-alkyl-dithiocarbamates yields dinuclear complexes (12). which were found to be good percursors for a variety of reaction (Scheme 1). In addition a route to the monomeric complexes [(S-S)X-... 

West B and Sundeeman FW (1958) Nickel poisoning. VII. The therapeutic effectiveness of alkyl dithiocarbamates in experimental animals exposed to nickel carbonyl. Am J Med Sd 236 15—25. 

The nucleophilic reactivity of dithiocarbamate anions has been the subject of a variety of papers, describing the reactions of alkali-metal dithiocarbamate salts with the common organic solvents methylene chloride, chloroform, and acetonitrile, with alkyl halides, a-halogeno-ketones and -aldehydes, chloroacetates, chloro-substituted j-triazines, phthaloyl chloride, oxalyl chloride, and with AW-dimethyl-5 S -dimethyldithiocarbamidium perchlorate. The nucleophilic addition reaction of dialkylammonium NN-dialkyldithiocarbamates with olefins, yielding alkyl dithiocarbamates, has also been described. ... 

The nucleophilic reactivity of the thiocarbonyl sulphur atom in alkyl dithiocarbamates has been confirmed by Russian workers, who obtained the malonic acid derivative (324) from the reaction of carbon suboxide with twice the theoretical amount of alkyl dithiocarbamate. The same... 

In addition, diphenyl thiourea can be produced via the reaction of aliphatic amine and 82- Firstly, alkyl dithiocarbamate is prepared by the following reaction ... 

Then diphenyl thiourea forms when alkyl dithiocarbamate is neutralized by aliphatic amine ... 

Thionocarbamates can be considered as that the —SH of alkyl dithiocarbamic acids (RNHCSSH) is substituted by —OR. And thionocarbamates can also be considered as that the —SH of xanthic acids (ROCSSH) is substituted by —HNR. Therefore, thionocarbamates can be considered as the derivatives of dithiocarbamic acids or xanthic acids. 

This [25] is an alternative method for determining the sum of primary and secondary amines, without distinguishing between them. The primary and secondary amines are converted to alkyl dithiocarbamic acids by reaction with carbon disulphide ... 

Synthesis.—A standard method for the preparation of G-alkyl thiocarba-mates and S-alkyl dithiocarbamates depends on the reaction of isothiocyanates with alcohols and thiols, respectively, and several new examples of its applicability have appeared during the past two years (refs. 132, 252, 634, and 635). In special cases the products, either spontaneously or promoted by a catalyst present, underwent a subsequent ring-closure reaction to form heterocycles containing the thionocarbamate or the dithiocarbamate moiety. Phenols and thiophenols reacted with isothiocyanates in a similar way. Some Oethyl selenonocarbamates have been obtained in good yields by ethanolysis of isoselenocyanates, and Mayer and his co-workers have reported on the successful synthesis of the heterocyclic... 

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