Dithiocarbamates reactions with

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

Because of the structural requirements of the bielectrophile, fully aromatized heterocycles are usually not readily available by this procedure. The dithiocarbamate (159) reacted with oxalyl chloride to give the substituted thiazolidine-4,5-dione (160) (see Chapter 4.19), and the same reagent reacted with iV-alkylbenzamidine (161) at 100-140 °C to give the 1 -alkyl-2-phenylimidazole-4,5-dione (162) (see Chapter 4.08). Iminochlorides of oxalic acid also react with iV,iV-disubstituted thioureas in this case the 2-dialkylaminothiazolidine-2,4-dione bis-imides are obtained. Thiobenzamide generally forms linear adducts, but 2-thiazolines will form under suitable conditions (70TL3781). Phenyliminooxalic acid dichloride, prepared from oxalic acid, phosphorus pentachloride and aniline in benzene, likewise yielded thiazolidine derivatives on reaction with thioureas (71KGS471). 

Zinc carbamate complexes are well known, and the structural types and stabilities can be compared with thiocarbamates and dithiocarbamates which are discussed in Sections 6.8.11.1.3 and 6.8.7.1.4482 Carbamates of zinc can be formed from the reaction of carbon dioxide with alkylzinc alkyl amides and further reaction with alkylzinc can give a distorted cubane structure.483 The tetrameric diethylcarbamate species initially formed can also be used to produce monomeric or dimeric carbamate structures in reaction with amines tetramethylethylenediamine forms a monomer [(Me2NCH2)2Zn(02CN(C2H5)2)2] with an octahedral zinc center and pyridine forms a dimer[CsH5NZn2Me(02CN(C2H5)2)3] with tetrahedral zinc centers.484... 

Carbon disulphide was used as an extraction solvent when analysing epoxy resins. On one occasion, adding to a hardener produced a vigorous fume-ofif leaving a residue looking like sulfur [1], Amines and complexes thereof are used as hardeners, and the reaction with, especially, polyamines to give dithiocarbamates is surprisingly exothermic [2],... 

A new route to the tetrahydroTTF system is provided by reaction of oxalyl chloride with ethanedithiol followed by dehydration to give 35. When this is treated with aluminium chloride the salt 36 is formed and its X-ray structure is reported <00ZN(B)597>. The preparation of new simple benzoditelluroles 37 has been described <00MI1127>. Treatment of allyl dithiocarbamates 38 with bromine affords the 2-amino-l,3-dithiolanylium salts 39 <97MIP112282, 98MIP113243>. 

Reaction with Carbon Bisulphide.—Ammonia and the primary amines of the aliphatic series combine with carbon bisulphide to form ammonium salts of dithiocarbamic acids, e.g. 

Amines are converted quantitatively to dithiocarbamates (reaction 29), that can be determined by nonaqueous titration with Ce(IV) accuracy 0.8%, RSD 0.7%391. 

In a manner analogous to that used for the formation of 5-alkyl thioacetates using a polymer-supported quaternary ammonium salt (4.1.31), the dithiocarbamate anion can be 5-alkylated under mild conditions [3]. The corresponding arylation reaction with activated aryl systems requires more vigorous conditions ... 

The -arylimino derivative (205 = Ar) on reaction with A-aryl substituted dithiocarbamates... 

Mdssbauer spectra of bonding and structure in, 15 184-187 reactions with diborane, 16 213 stabilization of, 5 17, 18-19 cyanates, 17 297, 298 cyanide complexes of, 8 143-144 cyclometallated bipyridine complex, 30 76 diazene complexes, 27 231-232 dinitrogen complexes, 27 215, 217 diphosphine complexes of, 14 208-219 dithiocarbamates, 23 253-254 -1,2-dithiolene complexes, 22 323-327 hydrogen bonding, 22 327 halide complexes with phosphine, etc., 6 25 hexaflouride, structure, 27 104 hydride complexes, 20 235, 248-281, see also Transition metal-hydride complexes... 

A series of complexometric extractions were performed to optimize the mobUiza-tion/purging of metallic ions from samples of processing condensate of chromated copper arsenate (CCA). Whereas Cr(VI) and Cu(II) were rapidly mobilized into isobu-tylmethyl ketone-amended SCCO2 after reaction with dithiocarbamate or alkylxan-... 

The biocidal activity of the thiadiazine (12) is probably related to the production of methyl isocyanate inside the cell by hydrolysis (equation 7). Isocyanates are known to have fungicidal properties (B-69MH1502), thought to be due to their reaction with sulfhydryl groups to form dithiocarbamates. The formation of these last mentioned compounds, by ring cleavage, might also explain the activity of 2-mercaptobenzothiazole (16). 

Diones are normally synthesized from /3-hydroxy acids in two steps first, conversion into carbamates by reaction with sodium cyanate, and then cyclization with thionyl chloride (Scheme 103) (54JCS839). Alternative preparations utilize oxetanes, which may be combined either with isocyanates in the presence of boron trifluoride (68JAP6808278) or with S-alkylthioureas (Scheme 104) (69ZOR1844). In the last example the initial products are imines (224) which may readily be hydrolyzed to the required diones. Similar methods can be applied to the synthesis of tetrahydro-l,3-thiazine-2,4-diones, and, for instance, the 4-oxo-2-thioxo derivative (225) is obtained from /3-propiolactone and dithiocarbamic acid (Scheme 105) (48JA1001). 

---