Thiocarbamic salts

Uses. There may be some captive use of carbonyl sulfide for production of certain thiocarbamate herbicides (qv). One patent (38) describes the reaction of diethylamine with carbonyl sulfide to form a thiocarbamate salt which is then alkylated with 4-chloroben2yl haUde to produce 3 -(4-chloroben2yl) A[,A/-diethylthiocarbamate [28249-77-6] ie, benthiocarb [28249-77-6]. Carbonyl sulfide is also reported to be useful for the preparation of abphatic polyureas. In these preparations, potassium thiocyanate and sulfuric acid are used to first generate carbonyl sulfide, COS, which then reacts with a diamine ... 

The diamine first forms the thiocarbamate salt, which is then heated to form the polyurea with liberation of hydrogen sulfide [50] (Eqs. 33, 34). 

Rahman et al. (1989) conducted an experimental study to determine the products of reaction between COS and several different amines. The protonated amine thiocarbamate salt was detected in the reaction products of COS with MEA, DEA, and DGA. The DIPA thiocarbamate salt could not be detected, possibly because the DIPA-COS reaction was too slow to provide enough reaction product for detection by the method employed. The tertiary... 

Reaction wifli Salts and Esters of Thiocarbamic Acid 2-Hydroxythiazoles and Derivatives... 

Salt formation with Brmnsted and Lewis acids and exhaustive alkylation to form quaternary ammonium cations are part of the rich derivati2ation chemistry of these amines. Carbamates and thiocarbamates are formed with CO2 and CS2, respectively the former precipitate from neat amine as carbamate salts but are highly water soluble. 

Analogous to this reaction, thiocarbamates have been prepared using ImCSIm, which is generated in situ from two equivalents of imidazole, CS2, sodium hydride, and one equivalent of a thiazolium salt 2163 ... 

The condensation of JV-cyanoamidines with thiocarbamate esters (107) provides routes to 1,3,5-triazine thioethers (108 Scheme 62), and dimethylamino-l,3,5-triazines (109 Scheme 63). In addition, novel chloromethylenimino salts (e.g. 110 R6 = OPh) may be prepared in situ (Scheme 63). Typical examples are shown in Table 11. 

The electrochemical behavior of thiocarbamates has been studied by several investigators (35,36,38,74-78). At mercury electrodes, thiocarbamates are oxidized in a one-electron process to form insoluble mercury (II) salts. Thioureas undergo a similar process. 

The lithium salts of acyclic secondary amines 92 can be conveniently transformed into the corresponding carbamoyllithiums 89 at —78 °C. Under these reaction conditions they react with trialkyltin chlorides to give carbamoyl stannanes 93 (Scheme 24)98. In the case of benzyl and allyl halides, an alkylation can occur affording products 94. However, when trialkylsilyl chlorides were used as electrophiles no carbamoyl silanes could be detected.. V-Alkyl thiocarbamates 95 can be prepared by reaction of the same intermediates 89 with sulfur followed by. S -alkylation at 0°C (Scheme 24)". 

The most widely applied reagents have been chelating agents which will complex with many metals, e.g. dithizone and the various thiocarbamate derivatives such as diethyldithiocarbamate and pyrrolidine dithiocarbamate. The latter agent as the ammonium salt (APDC) has been shown to complex some thirty elements [19] most of which can be readily extracted into various solvents. 4-Methylpentane-2-one (methyl isobutyl ketone or MIBK) is usually the favoured solvent because of its excellent compatibility with flames. The solubility of MIBK in water is not negligible and this limits the available concentration factor to ten higher molecular weight ketones (e.g. decan-2-one) offer better concentration factors and chloroform up to fifty times, but this latter solvent is only really suitable for electrothermal atomisation. 

SYNS ACETO ZDBD BUTAZATE BUTAZATE 50-D BUTYL ZIMATE BUTYL ZIRAM DIBUTYL-DITHIO-CARBAMIC ACID ZINC COMPLEX DIBLTTYLDITHIOCARBAMIC ACID ZINC SALT USAF GY-5 VULCACURE VULKACIT LDB/C ZINC-BIBUTYLDITHIOCARBAMATE ZINC-DIBUTYLDI-THIOCARBAMATE ZINC-N.N-DIBUTYLDI-THIOCARBAMATE... 

SYNS DIETHYLDITHIOCARBAMIC ACID TELLURIUM SALT NCI-C02857 TELLURIUM DIETHYLDI-THIOCARBAMATE TETRAKIS(DIETHYLCARBAMO-... 

TABtE 11-24 2-HYDROXYTHIAZOLE DERIVATIVES FROM o-HALO-CARBONYL COMPOUNDS AND SALTS AND ESTERS OF THIOCARBAMIC ACID (158a)... 

Carbamoylimidazolium salts 1050 are versatile electrophiles that react with amines, alcohols, phenols, or thiols to give the corresponding ureas (Scheme 252) <1998TL6267>, carbamates or thiocarbamates 1051 <1999TL2669>. Furthermore, salts 1050 react with carboxylic acids in the presence of amines to afford amides 1052, including Weinreb amides <2003TL7485>. 

Many dithiocarbamate complexes of zinc, silver, cadmium or mercury improve emulsion stability, including bis(dibenzyldithiocarbamato)-zinc(II) or -cadmium(II) and silver(I) diethyldi-thiocarbamate. Cadmium salts, mixed with citric acid or tartaric acid and added to the emulsion, are reported to be effective. Mercury(II) complexes of ethylenediaminetetraacetic acid (EDTA) and related ligands and of solubilized thiols such as (4) can be used. Other coordination compounds reported include EDTA and related ligand complexes of Co and Mn, mixtures of Co salts with penicillamine (5) and macrocyclic complexes of Ag such as (6). The latter compounds may be used in diffusion transfer systems in which transferred maximum densities are stabilized. 

The corresponding reactions of 3-alkoxy-5-aryl-5,6-dihydro-1,4,2-dithiazine 1,1-dioxides with aqueous alkali give O-alkyl (styrylsulfonyl)thiocarbamates 2 9 similarly, the sodium salts of 5-aryl-l, 4,2-dithiazine-3-thiol 1,1 -dioxides in the presence of dimethyl sulfate give 5,5-dimethyl JV-(styrylsulfonyl)dithiocarbonimidates, e.g. 3."... 

---