Amines carbon disulfide

Cellulose Solvent. Although DMSO by itself does not dissolve cellulose, the following binary and ternary systems are cellulose solvents DMSO—methylamine, DMSO—sulfur trioxide, DMSO—carbon disulfide—amine, DMSO— ammonia—sodamide, DMSO—dinitrogen tetroxide,... 

Dimethyl sulfoxide is a favored solvent for displacement reactions in synthetic chemistry. The rates of reaction in DMSO are many times faster than in an alcohol or aqueous medium [6]. Dimethyl sulfoxide is the solvent of choice in reactions where proton (hydrogen atom) removal is the rate determining step. Reactions of this type include olefin isomerizations and reactions where an elimination process produces an olefin. Another application that uses DMSO is its use as an extraction solvent to separate olefins from saturated paraffins [7]. Several binary and ternary solvent systems containing DMSO and an amine (e.g., methylamine), sulfur trioxide, carbon disulfide/ amine, or sulfur trioxide/ammonia are used to dissolve cellulose, and act as spinning baths for the production of cellulose fibers [8,9]. Organic fungicides, insecticides, and herbicides are readily soluble in DMSO. Dimethyl sulfoxide is used to remove polymer residues from polymerization reactors. 

N-(2-thiazolyl)dithiocarbamates are prepared by the action of carbon disulfide on 2-aminothiazoles (see Section III.3.C and Ref. 505). When refluxed with secondary amines these heterocyclic dithiocarbamates yield l,T-dialkyl-3-(2-thiazoIyI)thioureas (261) (491). 

Recently, it has been reported that l,3-dithiole-2-thione (12) reacts with primary amine to give the corresponding thiourea and A-4-thia2oline-2-thione (Scheme 5) (14). 5-Methylenethiazolidine-2-thione (13) obtained from the reaction of propargyl amine and carbon disulfide... 

Chemical Properties The formation of salts with acids is the most characteristic reaction of amines. Since the amines are soluble in organic solvents and the salts are usually not soluble, acidic products can be conveniendy separated by the reaction with an amine, the unshared electron pair on the amine nitrogen acting as proton acceptor. Amines are good nucleophiles reactions of amines at the nitrogen atom have as a first step the formation of a bond with the unshared electron pair of nitrogen, eg, reactions with acid anhydrides, haUdes, and esters, with carbon dioxide or carbon disulfide, and with isocyanic or isothiocyanic acid derivatives. 

Similarly, carbon disulfide and propylene oxide reactions are cataly2ed by magnesium oxide to yield episulftdes (54), and by derivatives of diethyUiac to yield low molecular weight copolymers (55). Use of tertiary amines as catalysts under pressure produces propylene trithiocarbonate (56). 

Thioureas. Thioureas (11) are typically made from primary amines and carbon disulfide. The amine can be ethylamine, butylamine. 

Carbonyl sulfide occurs as a by-product ia the manufacture of carbon disulfide and is an impurity ia some natural gases, ia many manufactured fuel gases and refinery gases, and ia combustion products of sulfur-containing fuels (25). It tends to be concentrated ia the propane fraction ia gas fractionation an amine sweetening process is needed to remove it. 

Other components in the feed gas may react with and degrade the amine solution. Many of these latter reactions can be reversed by appHcation of heat, as in a reclaimer. Some reaction products cannot be reclaimed, however. Thus to keep the concentration of these materials at an acceptable level, the solution must be purged and fresh amine added periodically. The principal sources of degradation products are the reactions with carbon dioxide, carbonyl sulfide, and carbon disulfide. In refineries, sour gas streams from vacuum distillation or from fluidized catalytic cracking (FCC) units can contain oxygen or sulfur dioxide which form heat-stable salts with the amine solution (see Fluidization Petroleum). 

Diethanolamine (DEA) has replaced MEA as the most widely used amine solvent. High load DEA technologies, such as that developed by Elf Aquitaine, permit the use of high (up to 40 wt % DEA) concentration solutions. The Elf Aquitaine—DEA process allows lower cinculation rates, and has consequent reductions ia capital and utility expenses. DEA tends to be more resistant to degradation by carbonyl sulfide and carbon disulfide than MEA. DEA is, however, susceptible to degradation by carbon dioxide. 

Amine A-oxides 56 were reduced to amines by carbon disulfide (62CPB969). Tire proposed mechanism involved the formation of amines and dithiiranone (57) from the initial adducts 58 the latter is finally hydrolyzed to CO2 and H2S2 (82BCJ3000). 

Disulfiram may be made by the reaction of diethyl amine with carbon disulfide in the presence of sodium hydroxide. The (CjHjljNCSSNa intermediate is oxidatively coupled using hydrogen peroxide to give disulfiram. 

Acetylene works Acrylates works Aldehyde works Aluminum works Amines works Ammonia works Anhydride works Arsenic works Asbestos works Benzene works Beryllium works Bisulfate works Bromine works Cadmium works Carbon disulfide works Carbonyl works Caustic soda works Cement works Ceramic works Chemical fertilizer works Chlorine works Chromium works Copper works Di-isocyanate works Electricity works Fiber works Fluorine works Gas liquor works Gas and coke works Hydrochloric acid works Hydrofluoric acid works Hydrogen cyanide works Incineration works Iron works and steel works... 

When carbon disulfide reacts with either aliphatic or aromatic, primary or secondary amines, dithiocarbamate salts are formed (8, 9). The following is an example. 

Considerably less is known about the chemistry of palladium and platinum 1,1-dithio complexes. Of late, there has been only one report that dealt with the synthesis of a large number of palladium dithiocar-bamates 392). Twenty-five yellow palladium dithiocarbamate complexes were obtained by reaction of PdCla with NaR2dtc in methanol solution. Several other reports have appeared in which a few dithiocarbamate complexes of palladium were synthesized. Thus, the novel [Pd (OH)2dtc 2], which is soluble in water, was isolated 393). The synthesis of optically active palladium(II) complexes of AT-alkyl-a-phen-ethyldithiocarbamates, similar to (XXIV), via the reaction between the optically active amine, CS2, and PdCl2, has been described. From ORD and CD spectra, it has been established that the vicinal contribution of a remote, asymmetric carbon center could give rise to optical activity of the d—d transitions of palladium 394). Carbon disulfide has been shown to insert into the Pt-F bond of [PtF(PPh3)3]HF2, and X-ray studies indicated the structure (XXIX). 

The Addition of Amines to Carbon Disulfide and Carbon Dioxide... 

Salts of dithiocarbamic acid can be prepared by the addition of primary or secondary amines to carbon disulfide. This reaction is similar to 16-9. Hydrogen sulfide can be eliminated from the product, directly or indirectly, to give isothiocyanates (RNCS). Isothiocyanates can be obtained directly by the reaction of primary amines and CS2 in pyridine in the presence of DCC. ° In the presence of diphenyl phosphite and pyridine, primary amines add to CO2 and to CS2 to give, respectively, symmetrically substituted ureas and thioureas ... 

AnUine, however, is too toxic for use in mbber products. Its less toxic reaction product with carbondisulfide, thiocarbanihde, was introduced as an accelerator in 1907. Further developments led to guanidine accelerator [4]. Reaction products formed between carbon disulfide and aliphatic amines (dithiocarbamates) were first used as accelerators in 1919 [5]. These were and still are the most active accelerators in respect to both cross-finking rates and extent of cross-link formation. However, most dithiocarbamates accelerators give little or no scorch resistance and therefore cannot be used in aU applications. 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

Dithiocarbamates have been prepared by the reaction of carbon disulfide with primary or secondary amines. The addition of DMF, cesium carbonate and a sulfonamide to the crude dithiocarbamate, give di-, tri- and tetra-substituted thioureas in 65-76% yields (Scheme 41).121... 

Reaction of carbon disulfide with primary amines, using MCM-41-TBD (mesoporous MCM-41 silica, TBD l,5,7-triazabicyclo[4.4.0]dec-5-ene) as catalyst, has given symmetrical thioureas under heterogeneous conditions. The MCM-41-TBD could be reused as a catalyst (Scheme 43).123... 

Reaction of carbon disulfide with primary amine hydrochloride in the presence of dimethyl aminopyridine (DMAP) and A,A -dicyclohexylcarbodii-mide (DCC) affords symmetrical thioureas (Scheme 44).124,125... 

The amine-terminated poly(EA) was prepared by the chain transfer polymerization of EA in the presence of the salt of aminomercaptan, followed by the reaction with carbon disulfide to give the polymeric iniferter 31. The polymerizations of St and MMA with 31 provided the triblock copolymers, poly(EA)-block-poly(St)-fcfoc/c-poly(EA) and poly(E A)-Woc/c-poly(MMA)-fcfoc/c-poly(EA), respectively, as shown in Eq. (29) [ 147] ... 

The present procedure2 describes the conversion of resin-bound, primary aliphatic amines into isothiocyanates and the conversion of the latter into 3-aminothiophenes. The generation of isothiocyanates is related to known procedures,3 in which amines are first treated with carbon disulfide and the resulting dithiocarba-mates are desulfurized by treatment with a condensing agent (alkyl chloroformates, carbodiimides, lead or mercury salts, etc.). The presence of resin-bound isothiocyanates on the polystyrene support could be qualitatively ascertained by infrared spectroscopy (KBr-pellet strong absorption at 2091 cm-1). 

In carbohydrate chemistry, the most described method for the preparation of saccharidic thionocarbamates involves preliminary introduction of the amine function on a partially or non-protected saccharidic template. The condensation of amino sugars with carbon disulfide or thiophosgene leads to cyclization in 1,3-oxazolidine- or l,3-oxazine-2-thiones. This reaction involves the formation of an intermediate isothiocyanate, which reacts further with a 3- or y-located hydroxyl group. The viability and facility of this process depends on the saccharidic ring size and the inherent strain. Some major rules can be put into light from the cases studied 30... 

Saccharidic templates bearing an amino group in C-2, C-6, C-3, C-5. Generally, an amine located on non-anomeric position reacts similarly through the condensation reaction with carbon disulfide or thiophosgene, the preliminary formed isothiocyanate leads to spontaneous or base-induced cyclization into 1,3-oxazolidine- or l,3-oxazine-2-thiones, as previously mentioned. Several extensive studies are reported about the selective introduction of thionocarbamate moieties on carbohydrate scaffolds.3 22 23 320 34 38... 

Hofmann mustard-oil reaction org chem Preparation of alkylisothiocyanates by heating together a primary amine, mercuric chloride, and carbon disulfide. haf-man mos-tord, 6il re,ak-sh3n ... 

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