Carbon Disulphide amines with

Miscellaneous Reactions.—A full report has appeared of the reactions of carbon dioxide and carbon disulphide with tervalent phosphorus aryl esters and amines the products are ureas and thioureas, respectively.74 The suggested mechanism, previously invoked for similar reactions of carboxylic acids, involves the N-phosphonium salt (97). 

Japanese workers have developed a new synthesis of ureas and thioureas through the reaction of carbon dioxide or carbon disulphide with diphenyl phosphite and primary amines. The reaction is thought to take place via an intermediate (85), followed by elimination to give isocyanate or direct displacement by amine. The principles of this new synthesis have also been applied to the preparation of peptides and amino-acid esters. 

The addition reaction between amines and carbon disulphide has attracted the attention of several research groups because it constitutes a common route to dithiocarbamates. In their latest paper, Fitton and his co-workers, by means of cross-over experiments and the application of optically labelled bases, have further established that the reaction of benzylic, tertiary amines with carbon disulphide proceeds by an inter-molecular addition-elimination-recombination mechanism. On the other hand, Kreutzkamp and his co-workers claim that the insertion reaction of carbon disulphide with tertiary Mannich bases proceeds by an intramolecular mechanism. The synthesis of thiazolidine-2-thiones by the insertion reaction of carbon disulphide with aziridines has been the subject of two recent papers. - One of these deals mainly with the mechanistic and stereochemical aspects of this reaction, which was studied using 2-substituted and cis- and rra/z5 -2,3-disubstituted aziridines as reactants. A mechanism accounting for the stereoselectivity of the reaction has been drawn up by the authors (Scheme 7). 

The most important condensation reactions used for analytical purposes in organic polarography are reactions of carbonyl compounds with the formation of (1) aldimines and ketimines, (2) semicarbazones, (3) hydrazones and (4) oximes. The reactions of carbon disulphide with amines and amino acids are also used (5). 

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],... 

The formation of secondary amines 3 from hindered N,A-disubstituted hydroxylamines by the action of carbon disulphide is thought to proceed by way of the adducts 1, which are in equilibrium with the betaines 2. These break down into the amines 3 and COS2 , which decomposes into the observed by-products carbon oxysulphide and sulphur9. 

Sequential treatment of tertiary amines containing N-methyl or /V-benzyl groups with carbon disulphide and alkyl halides gives alkyl dithiocarbamates in good to excellent yields. Thus IV-methylmorpholine, carbon disulphide and methyl iodide in THF gave 91% of compound 306366. 

We were unable to observe the N H stretching band for diethyl-amine in more than one 4ion-polar solvent. In carbon tetrachloride the frequency value is 3321 cm-1 compared with the unperturbed value 3324 cm"1 for the vapour. For methylaniline the 1ST—H frequency was measured in carbon tetrachloride, carbon disulphide, pentane, hexane and cyclohexane in carbon tetrachloride the frequency is 3440 cm"1. By use of a heated cell we have located the N—H band in methylaniline vapour at 3450 cm"1. These data, for interaction... 

Carbon disulphide reacts additively with primary and secondary aliphatic amines to form alkylammonium salts of alkyldithiocarbamic acids. The products obtained with dimethylamine, diethylamine and piperidine, also certain derivatives of these products, are manufactured on a large scale for use as accelerators in the vulcanisation of rubber. With aromatic amines the disulphide reacts with elimination of hydrogen sulphide and formation of substituted thio-ureas, e.g. thiocarbanilide. 

Carbon disulphide also combines with tertiary amines 1 and phosphines, forming crystalline substances, the most important of which is a scarlet compound with triethylphosphine, CSa.P(C2H5)3, to which the constitution CS—P(CaH5)a is attributed.2 This substance is formed... 

Carbon disulphide reagent test. This test is based upon the formation from a secondary amine and carbon disulphide of a dialkyldithiocarbamate the latter readily forms a nickel derivative with a solution of a nickel salt ... 

The copolymerisation of propylene oxide and carbon disulphide was carried out with a catalyst consisting of diethylzinc and an electron donor, such as tertiary amine, tertiary phosphine or hexamethylphosphoric triamide, in... 

Isothiocyanates are prepared by the reaction of primary amines with carbon disulphide according to Scheme 5.9. Brandenberger and Hellbach [104] made use of this derivative... 

A solution containing 1 mg of a free base in 1 ml of ethyl acetate was shaken with 0.5 ml of carbon disulphide for 30 min. Under reduced pressure the solution was evaporated to dryness and the residue dissolved in 1 ml of ethyl acetate. Aliquots of 1 pi were taken for analysis. For phenolic and indolic amines 100-pg aliquots of isothiocyanate derivatives are subjected to reaction with a mixture of BSTFA and TMCS (99 1) at 90°C for 15 min. 

With carbon disulphide. Another reaction which distinguishes the aromatic amines from the aliphatic amines is the one with carbon disulphide. When methyl amine is treated with carbon disulphide a product is obtained according to the following reaction ... 

Acetone should be colourless and completely miscible with water. Its specific gravity should not exceed 0 800 at 15 It should give no turbidity on mixing with twenty times its volume of carbon disulphide, and no residue on evaporation. It should be free from acidity, except for traces of dissolved carbon dioxide (approximately o oi per cent,). To test acidity the acetone is boiled to remove carbon dioxide, diluted with an equal volume of water (free from carbon dioxide) and titrated with alkali, using phenol phthalein as indicator. Alkalinity should be absent, as it indicates the presence of amines it is tested for by diluting... 

Acetonitrile is frequently used for the desorption of 2,4-dinitrophenylhydra-zones of carbonyl compounds collected on silica gel [39,40,59], while CS2 is used for samples collected onto charcoal and dichloromethane for samples collected onto Anasorb 747 [59]. Carbon disulphide is particularly suitable for the desorption of nonpolar compounds but gives less satisfactory outcomes for the polar compounds. To overcome this shortcoming, polar cosolvents such as dimethylformamide, dimethylsulfoxide and ethanol are added to CS, to increase the recovery of polar analytes [36]. In addition, the use of CS2 suffers from a number of other drawbacks, including the facts that (1) it reacts with amines and volatile chlorocarbons (2) it is unsuitable when electron detectors (e.g. electron capture detectors, ECDs) are used, (3) it is toxic and (4) has an unpleasant odour [36]. 

The preparation typically involves a condensation reaction of acidic molybdenum sources such as molybdenum trioxide, molybdic acid and ammonium molybdate with dialkylammonium dialkyldithiocarbamate salts formed in situ by reaction of carbon disulphide and dialkylamine [45]. The extent of sulphurisation of the molybdenum core can be increased by the introduction of sulphurising agents such as sodiumhydrosulphide [46]. Patent literature reports that the greatest antioxidant effect of molybdenum dialkyldithiocarbamates is seen when combined with aminic and phenolic antioxidants [47]. 

A fused pyrimidin-2-one may be prepared in good yield by heating a 1,3-diamine with urea. Phosgene reacts at ambient temperature with a 2-imino-amine to form a fused pyrimidin-2-one. Quinoline-1,8-diamine and carbon disulphide react to give a yield of 89% of the pyrimidinethione. 

Primary amines in biological samples (plasma, urine, cerebrospinal fluid and tissues) were converted to isothiocyanates by treatment with carbon disulphide, and were determined by GC using a nitrogen detector ... 

Isocyanates can be determined by indirect titration of dibutylamine or by GC determination of this reagent, after reaction 39 (X = O R = R" = Bu) goes to completion. A variation of this procedure for isothiocyanate insecticides and other formulations consists of treating a solution in acetonitrile with excess primary amine, scavenging the excess amine with carbon disulphide, yielding a dithiocarbamate and determining the concentration by a 3-step titration with Cu(II) in acetonitrile... 

Arsenic(iii) tris(dithiocarbamates) As[SC(S)NR2l3 result when arsenic trichloride reacts with amines and carbon disulphide, and analogous antimony compounds can also be obtained. The reaction is considered to proceed by CS2 insertion into the As—bonds of the trisamino-derivatives and the products are considered to have an octahedral arrangement around arsenic which is distorted owing to the effect of the lone pair. The compounds... 

Treatment of hydroxylamines 4 (R = cyclohexyl, Ph or 3,4-(MeO)2C6H3) with acetone gives nitrones 5, which are transformed by Grignard reagents R MgBr (R = Me, Et, Bu, Ph or allyl) into the hydroxylamines 6 the latter are converted into the hindered secondary amines 7 by means of carbon disulphide . 

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