Diethyldithiocarbamate formation

A comparative study of the electronic structures of A,A-diethyldithiocarbamate and pyrrole-A-carbodithioate has been undertaken.961 The enthalpy of formation of [Ni(S2CNMe2)2] (—146.1 10.9 kJmol-1) has been measured.962 The square planar dithiocarbamate complexes can be oxidized to the corresponding five-coordinate Ni111 dithiocarbamate complexes [Ni(S2CNR2)2X] (X = I, Br, C104) using Br2, I2, or (N0)C104.963,964... 

The 0,5-dialkyl dithiocarbonates (Table 4.8) are readily prepared under phase-transfer catalytic conditions by the reaction of an alkylating agent with potassium O-alkyl dithiocarbonate [35, 39], which can be obtained from carbon disulphide and the appropriate potassium alkoxide [cf. 40]. Monosaccharides are converted into 5-glycosyl dithiocarbonates via the in situ formation of the tosylate, followed by reaction with potassium O-alkyl dithiocarbonate (Scheme 4.6) [41], In a similar manner, 5-glycosyl 7V,7V-diethyldithiocarbamates are obtained from the monosaccharide and A.A-diethyldithiocarbamate (see 4.3.2) [42]. 

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... 

Fig. 8.5. Examples of complex formation by chelating ligands, showing (a) a four-membered ring with diethyldithiocarbamate (dtc), (b) formation of five-membered rings with ethylenediaminetetraacetate EDTA and (c) a six-membered ring with acetylacetonate (acac).

Merry and Zarcinas [33] have described a silver diethyldithiocarbamate method for the determination of arsenic and antimony in soil. The method involves the addition of sodium tetrahydroborate to an acid-digested sample which has been treated with hydroxylammonium chloride to prevent the formation of insoluble antimony compounds. The generated arsine and stib-ine react with a solution of silver diethyldithiocarbamate in pyridine in a gas washtube. Absorbance is measured twice at wavelengths of 600 and 504 nm. 

Thiram is absorbed via the skin, mucous membranes, respiratory, and gastrointestinal tracts. Thiram is rapidly absorbed from the gastrointestinal tract. Thiram and other dimethyldithiocarbamates are metabolized to diethyldithiocarbamic (DDC) acid, diethylamine, and carbon disulfide. DDC is rapidly absorbed by the gastrointestinal tract and further metabolized by hepatic enzymes. A portion of the acid is excreted unchanged or as glucuronide conjugate. Further metabolism can result in the formation of dimethylamine and carbon disulfide residues. 

OrganometaUic compounds such as metalocenes and organoleads were quantitatively adsorbed on Cgg via the formation of neutral complexes or chelates, and the adsorption constant was dramatically increased by the use of classical reagents such as pyrrolidinedithiocarbamate or diethyldithiocarbamate. It was therefore concluded [122] that the fuUerenes possess a high analytical potential for preconcentrating organometaUic compounds, which is superior to that of conventional sorhents such as RP-C18, silica gel and activated carbon. 

Ether that is stored over a clean sodium wire can be considered as peroxide-free. Formation of further peroxide or aldehyde is claimed15 as prevented by addition of 0,05% of sodium 7V,iV-diethyldithiocarbamate. 

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