Amines nitrocompounds

Almost insoluble in cold water. Higher alcohols (including benzyl alcohol), higher phenols (e.g., naphthols), metaformaldehyde, paraldehyde, aromatic aldehydes, higher ketones (including acetophenone), aromatic acids, most esters, ethers, oxamide and domatic amides, sulphonamides, aromatic imides, aromatic nitriles, aromatic acid anhydrides, aromatic acid chlorides, sulphonyl chlorides, starch, aromatic amines, anilides, tyrosine, cystine, nitrocompounds, uric acid, halogeno-hydrocarbons, hydrocarbons. 

It is also possible to reduce the nitrocompounds to amines which can be used as flash reducing agents in propints... 

Nitroaminocompounds or Nitroamines. Compds containing both —N02 and —NH2 radicals attached to different C atoms, eg, nitroaniline, 02N.C6H4.NH2, etc. Nitroamines can be prepd either by the nitration of amines, or by partial reduction of nitrocompounds contg several —N02 groups. Another method is to treat a chloronitrocompound with ammonia, as in the prepn of dinitroaniiine... 

Aromatic Amine and Nitrocompounds, Their Toxicity and Potential Dangers , US Public Health Bull No 271, Washington, DC (1941), 105 6) Davis (1943), 140... 

It is worth noting, however, that up until fairly recently the reduction of aromatic nitrocompounds to the corresponding amines was commonly performed on an industrial scale, e.g. in the synthesis of azo dyes, with a mixture of iron and hydrochloric acid. This so-called Bechamp reduction has an E factor of ca. 15 compared to 1 for catalytic hydrogenation. 

The effect of temperature on the reduction of nitro-alkanes has been extensively exploited in the synthesis of cp-ephedrine analogues [i5,21,22] starting from 1-aryl-2-nitropropenes which are easily converted to the substrates 2. Reduction of these nitrocompounds below 20° C affords the hydroxylamine. The amine is formed above 55° C. Neutralisation of either reaction mixture causes rapid intramolecular migration of the acetyl group from oxygen to nitrogen, a reaction which implies a... 

Electrolytic reduction of an emulsion of the nitro compound in 1 M zinc chloride solution at high current density is another proposed method for conversion to the amine. Finely divided zinc is produced and this reduces the nitrocompound. Zinc ions also function as Lewis acid in the reduction of arylhydroxylamines [44]. 

The alkylation of ammonia, Gabriel synthesis, reduction of nitriles, reduction of amides, reduction of nitrocompounds, and reductive amination of aldehydes and ketones are methods commonly used for preparing amines. 

Aromatic amines are normally prepared by reduction of the corresponding aromatic nitrocompound. 

Gas chromatography has been applied to the determination of a wide range of organic compounds in trade effluents including the following types of compounds which are reviewed in Table 15.15 aromatic hydrocarbons, carboxylic acids aldehydes, non ionic surfactants (alkyl ethoxylated type) phenols monosaccharides chlorinated aliphatics and haloforms polychlorobiphenyls chlorlignosulphonates aliphatic and aromatic amines benzidine chloroanilines chloronitroanilines nitrocompounds nitrosamines dimethylformamide diethanolamine nitriloacetic acid pyridine pyridazinones substituted pyrrolidones alkyl hydantoins alkyl sulphides dialkyl suphides dithiocaibamate insecticides triazine herbicides and miscellaneous organic compounds. 

Figure 3.55. Plot of cf)es versus AG for the ECL systems involving Ru(phen)3+ (a), Ru(bipy)3+ (b), and Ru(baph)3+ (c) ions in 0.1 M (C2H5)4NPF6 acetonitrile solutions. Data for the ECL systems with nitrocompounds ( ), quinones (o), iV-methylpyridinium cations ( ), and aromatic amines or 2,3,7,8-tetramethoxythianthrene ( ). (From Ref. 193.)...

Every year, over 50 million tons of waste containing nitro-related compounds is created aU over the world. Nitrocompounds are formed by nitration of not only amines, but also amides, urea, guanidines, carbamates, cyanides, and sulfonamides. Because of their chemical properties they are divided easily into hydrolyzable N-nitrosamides and relatively stable N-nitrosamines. Nitrosamines are stable compounds that slowly decompose when exposed to light or in acidic aqueous solutions. 

E N - O) may be deduced from the heat of formation of hydroxyh amine, NH2OH. This is not very reliably established and the heat of vaporization must be estimated, sc the resulting value of E N 0), 39 kcal, may not be very accurate. It is also possible to estimate E(N -O) by noting that the heat of atomization of a nitric ester is greater than that of the corresponding nitrocompound by E C - O) + E 0 - N) E C - N). Using the figures... 

The most important applications of peroxyacetic acid are the epoxi-dation [250, 251, 252, 254, 257, 258] and anti hydroxylation of double bonds [241, 252, the Dakin reaction of aldehydes [259, the Baeyer-Villiger reaction of ketones [148, 254, 258, 260, 261, 262] the oxidation of primary amines to nitroso [iJi] or nitrocompounds [253], of tertiary amines to amine oxides [i58, 263], of sulfides to sulfoxides and sulfones [264, 265], and of iodo compounds to iodoso or iodoxy compounds [266, 267] the degradation of alkynes [268] and diketones [269, 270, 271] to carboxylic acids and the oxidative opening of aromatic rings to aromatic dicarboxylic acids [256, 272, 271, 272,273, 274]. Occasionally, peroxyacetic acid is used for the dehydrogenation [275] and oxidation of aromatic compounds to quinones [249], of alcohols to ketones [276], of aldehyde acetals to carboxylic acids [277], and of lactams to imides [225,255]. The last two reactions are carried out in the presence of manganese salts. The oxidation of alcohols to ketones is catalyzed by chromium trioxide, and the role of peroxyacetic acid is to reoxidize the trivalent chromium [276]. 

In the laboratory, other metals, like iron, zinc, etc., in connection with an add, are only rarely used in the place of tin or stannous chloride, for the. reduction of nitro-compounds. On the large scale, iron, owing to its cheapness, is used in the preparation of bases like aniline, toluidine, a-naphthyl amine, etc., from the corresponding nitrocompounds. By the use of iron and hydrochloric acid, the reduction should theoretically take place in accordance with the following equation ... 

Besides the reducing agents mentioned, there is still a large number of others which find only an occasional application in reducing nitrocompounds to amines. They will be referred to under the different preparations. 

The nonphosgene production of isocyanates takes place through the thermolysis of the corresponding carbamate. The carbamate synthesis may involve a number of possible alternative ways, such as the reaction of a nitrocompound with CO, or the reaction of an amine with CO and O2, with urea and alcohol, or with a carbonic ester. Among these routes, the reaction of DMC or DPC with aliphatic amines is a very efficient way to produce carbamates. 

The carbonylation of amines and of nitrocompounds is of interest because it provides a non phosgene route to the synthesis of carbamates, isocyanates and ureas which are products of remarkable commercial value. 

As the rhodium has been found to be active to catalyze the carbonylation of amines and nitrocompounds [8, la], the materials in title have been tested for these reactions. In this paper we describe some of the results obtained. 

It is well known that the oxidative carbonylation of aniline and the reductive carbonylation of nitrocompounds to give DPU or MPC occur according to the stoichiometry of reactions (1-2) and (4-5). Alkoxycarbonyl complexes (M-COOR 1) and carbamoyl complexes (M-CONHR 2) which then evolve into the final products, are believed to be key intermediates for these reactions. The two accepted different mechanisms for the formation of 1 and 2 along with their catalytic cycles are illustrated in the schemes 1 and 2 for the oxidative carbonylation of amines catalyzed by noble metals. Both the cycles involve a two electron redox process. 

ISOPROPANOL AMINE (78-96-6) Combustible liquid (flash point 159°F/71°C). Violent reaction with strong oxidizers. A strong organic base. Violent reaction with acids, strong oxidizers, cellulose nitrate, 2,4-hexadienal, nitromethane. Incompatible with organic anhydrides, isocyanates, vinyl acetate, acrylates, substituted allyls, alkylene oxides, epichlorohydrin, ketones, aldehydes, alcohols, glycols, phenols, cresols, caprolactam solution, nitrocompounds, perchlorates. May attack aluminum, copper, lead, tin, zinc, and their alloys, and some plastics, rubber, and coatings,... 

TRIPHENYL AMINE (603-34-9) Incompatible with aldehydes, ketones, nitrates, acids, organic anhydrides, isocyanates, aldehydes, nitrocompounds, oxidizers, oxygen, and peroxides. 

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