Amines dithiocarboxylates

Dithiobenzoic acid metal complexes, 2, 646 colours, 2, 646 Dithiobiuret metal complexes, 2, 640 Dithiocarbamates chelating resins mineral processing, 6,826 Dithiocarbamic acid metal complexes, 2,585 amine exchange, 1,428 photographic emulsions, 6,98 nickel poisoning, 6,768 tellurium(Il) complexes photothermography, 6,121 Dithiocarbazic acid metal complexes, 2,803 Dithiocarbimic acid metal complexes, 2,588 Dithiocarbimic acid, cyano-metal complexes, 2,808 Dithiocarboxylic acids metal complexes, 2,646 Dithiodiacetic acid metal complexes, 2, 806 Dithiodiketones... 

Compound 96 reacts with SR-, with ring cleavage and loss of sulfur, to form the methyl ester of the 1-alkylmercaptocyclopent-l-ene 2-dithiocarboxylic acid (97). Compound 96 reacts in a similar manner with primary amines (see below). 

The addition of amine to the bicyclic salt (96) initially takes place not in position 3, but in position 5, as in the reaction with mercaptans the reaction then proceeds by the same steps to yield the ester of the 1-aminocyclopent-l-ene 2-dithiocarboxylic acid (118). This ester (118) is obtained in yields of 30-65% its structure has been confirmed by independent synthesis from 119. This reaction course is again confined to the special system 118, the homologous tetramethylene-trithionium salts yielding Schiff s bases on reaction with primary amines under the same conditions.50... 

Contrary to carboxylic acids which, under normal conditions, only give salts with amines, dithiocarboxylic acids, RCS2H, are quite reactive in nucleophilic displacement reactions. However, the compounds are unpleasant to handle and, due to their limited stability, often give only low yields of thioamides in the reaction with amines.The approach was successfully employed in the synthesis of thiobenzoyl azolides, e. g. in the formation of (7) according to equation (4). °... 

Thioacylation reactions with dithiocarboxylic acids are not limited to amines, but, employing the Mg salt, can also be carried out with hydroxylamine to give thiohydroxamic acids or with hydrazine and some substituted hydrazines to provide thiohydrazides. ... 

The reaction of CH acidic compounds with CS2 in the presence of excess base yields dianions of dithiocarboxylic acids. Starting from camphor, neutralization with HCl and addition of primary amines yields 3-oxonorbomanethiocarboxamides (11) with undefined stereochemistry (Scheme 3). ... 

Dithiocarboxylates, R CSSR give a faster reaction with amines than G-alkyl thiocarboxylates (2 cf. Section 2.4.2. ). As shown in equation (8), this pronounced reactivity may lead to an undesired in situ reaction with the liberated ammonia to give a primary thioamide, when the ester is generated by thiolysis of a thioimidate. ... 

On the other hand, dithiocarboxylates allow the chemoselective thioacylation of the amine moiety in tryptamine or tryptophane (16 equation 9). ... 

Thioamide synthesis from dithiocarboxylates and amines under basic conditions gives thiols as rather unpleasant parallel products. This problem is avoided by using S-thioacylated thioglycolic acids (17), as... 

In a heterocyclic environment, the dithiocarboxylate functionality may give a more complex reaction pattern, as shown by dithiolactones (19). Here, secondary aliphatic amines lead to ring cleavage providing 2-(thioacylamino)thiobenzamides (20), whereas primary aliphatic or aromatic amines give thiolac-tams (21 Scheme 5). ... 

In accord with the special reactivity of a dithiocarboxylate moiety, 0,5-dialkyl dithiocarbonates, ROCSSR, yield 0-alkyl thiourethanes, ROCSNR 2, on addition of amines. Similarly, trithiocarbo-nates, (RS)2CS, yield thioureas. - ... 

In general, thiocarbonyl halides (59) function as thioacylation reagents with a variety of nucleophiles to yield the appropriate thio derivatives (60) (Scheme 31). For example, (59) on condensation with thiols, amines, potassium cyanide or potassium thiocyanide yields the corresponding thio compounds (60). Thiolocarboxylic acids (50) characteristically acylate alcohols and amines with desulfuration (Scheme 32). Dithiocarboxylic acid esters (54b) react with organolithium or Grignard reagents to give the dithioketals (61) after treatment with an alkyl halide (Scheme 33). 

Convenient syntheses for ammonium311 320 and alkali metal salts (from trimethylsilyl dithiocarboxylates and alkali metal fluorides),321,322 useful for preparative purposes of their metal complex and organometallic derivatives, are now available. The reactions of bis(thioacyl)disul-fanes, [RC(S)S]2 (R = Pr , Ph, p-MeOC6H4, p-Tol, p-ClC6H4, CK-C10H7) with secondary amines yield substituted ammonium dithiocarboxylates, [R NHJP CSJ.323... 

Figure 13.21. Major glucuronidation reactions involving phenols, alcohols, carboxylic acids, car-bamic acids, hydroxylamines and hydroxylamides, carboxamides, sulfonamides, various amines, thiols, dithiocarboxylic acids, and 1,3-dicarbonyl compounds.

The desulfurization of organosulfur compounds with trivalent organophospho-rus compounds has been studied for more than four decades [118]. A variety of such reagents has been used to convert disulfides to monosulfides, trisulfides to disulfides or monosulfides, /3-keto sulfides to ketones, and sulfenimides to amines. They have also been used to remove sulfur from thioethers, thiols, and organometallic dithiocarboxylates, and oxygen from sulfones. 

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