Amines from nitration

Ammonia also may be present as the result of the partial breakdown of amines used for condensate system protection, from hydrazine, or potentially even from nitrate. 

It is conceivable that nltrosamlnes can be synthesized In the Intestine, since the precursors are present. While the conditions for aqueous nltrosatlon reactions are not optimum at pH values encountered In the lower gastrointestinal tract, several studies have shown that these reactions can be catalyzed (39, 40, 41). It has been suggested that the Intestine might be a site for the formation of nltrosamlnes by bacterial action (42). Sander (43) has demonstrated the formation of nltrosamlnes by bacterial action from precursor amines and nitrate at neutral pH and Klubes and coworkers have reported the formation of NDMA. upon Incubation of l C-dlmethylamlne and sodium nitrite with rat fecal contents (44, 45). 

A strain of Escherichia coli produces a naphthotriazole from 2,3-diaminonaphthalene and nitrite that is formed from nitrate by the action of nitrate reductase. The initial product is NO, which is converted by reactions with oxygen into the active nitrosylating agent that reacts chemically with the amine (Ji and Hollocher 1988). A comparable reaction may plausibly account for the formation of dimethylnitrosamine by Pseudomonas stutzeri during growth with dimethylamine in the presence of nitrite (Mills and Alexander 1976) (Figure 2.2f). 

Many activations involve compounds which are used as pesticides. In the case of N-nitrosation, the precursors are secondary amines and nitrate. The former are common synthetic compounds and the latter is an anion found in nearly all solid and aqueous phases. The N-nitrosation of a secondary amine [R-NH-R ] occurs in the presence of nitrite formed microbiologically from nitrate. The product is an N-nitroso compound (i.e., a nitrosamine [RR -N-N=0]). The reason for concern with nitrosamines is their potency, at low concentrations, as carcinogens, teratogens, and mutagens. 

Fig. 1.1.17 Composition domains of well-defined particles formed by aging at 90"C for 1 h solutions containing zinc nitrate and different bases. TEA triethanolamine En ethylenedi-amine. (From Ref. 110.)...

At an earlier stage Orton [31] found that some aniline derivatives which are difficult to nitrate in the ring, are liable to form N-nitramines when treated with nitric acid and acetic anhydride. For example, he prepared the corresponding nitr-amine from 2,4,6-tribromaniline ... 

Vapor-phase nitration of paraffin hydrocarbons, particularly propane, can be brought about by uncatalyzed contact between a large excess of hydrocarbon and nitric acid vapor at around 400°C, followed by quenching. A multiplicity of nitrated and oxidized products results from nitrating propane nitromethane, nitroethane, nitropropanes, and carbon dioxide all appear, but yields of useful products are fair. Materials of construction must be very oxidation-resistant and are usually of ceramic-lined steel. The nitroparaffins have found limited use as fuels for race cars, submarines, and model airplanes. Their reduction products, the amines, and other hydroxyl compounds resulting from aldol condensations have made a great many new aliphatic syntheses possible because of their ready reactivity. 

This involves the use of tertiary amine extraction of the An ions from acidic 11 M LiCl solutions. Spectroscopic studies have indicated that, in the cases of Am and Nd at least, the octahedral trianionic hexachloro complexes are extracted from 11 M LiCl. Stability constant data for the chloride complexing of Am , and Cfin media of ionic strength 1,0 have been reported. Tertiary amines also extract Pu and a study of extraction from nitrate media by trilaurylamine (TLA) in xylene has been reported. " This showed that the mass transfer rate was controlled by the reactions between Pu from the bulk phase and interfacially adsorbed TLA-HNOs. The separation of individual transplutonium elements from the Tramex actinide product may be achieved using ion exchange or precipitation techniques." ... 

In certain applications, the quaternary ammonium salts have advantages over tertiary amines for actinide extractions. Quantitative extraction of the transplutonium elements from nitrate media by quaternary ammonium salts can be achieved with a lower aqueous-phase nitrate concentration than is required for tertiary amines thus, aluminum nitrate may be used instead of lithium nitrate. The separation factor between Am and Cm can be as high as three in a quaternary ammonium nitrate system (50). The effect of the length of the alkyl chain on Cm, Am, Bk, Cf, and Es extraction by alkyldioctylammonium nitrates suggests that steric factors substantially influence the extraction selectivity (51). A comparison of the extraction of tetravalent and hexavalent actinides by tetraheptyl ammonium nitrate shows that tetravalent ions are more easily extracted than hexavalent ions e.g.,... 

Bacteria, algae, and diatoms that accumulate on the coarse sand layer of the filter bed metabolize nutrients, etc., from the supply, thereby removing them. Among the benefits of slow filtration is removal of up to 50% of any chlorinated pesticide content of the influent water [6]. Slow filtration may require a prior aeration step to ensure that the biochemical processes remain aerobic, since anaerobic operation can form sulfides and amines from sulfate and nitrate, which would contribute bad odors or tastes to the supply. 

Crystallise the amine from EtOH/ CgH6 under N2, and store away from CO2. It provides two crystalline forms an a-form with m 44.4° and a 3-form with m 51.8°. The hydrochloride has m 207-208°(dec, from isoProOH), the hydroiodide has m 23.8-234°(dec, sealed capillary) and the nitrate has m 125.4-125.2°(dec. sealed capillary) when crystallised from MeOH/Me2CO. [Hoerret al. J Am Chem Soc 65 328 1943, Hoerr Harwood 7 Org Chem 16 779 1951, Beilstein 4 III 412, 4 IV 801.]... 

Blangey314 obtained direct C-nitration of some primary amines when he added the amine to an ice-cold solution of sodium nitrite in concentrated sulfuric acid with exclusion of moisture. After complete consumption of the nitrous acid the products were precipitated by ice-water and proved in each case to be the / -nitroso amine. Thus were obtained the 4-nitroso derivatives of 1-naphthylamine and its 2-, 6-, 7-, and 8-monosulfonic acids, and in the benzene series those of m-anisidine, m-toluidine (NH2 = 1), etc. The sulfo group was split off from naphthionic acid, which gave a good yield of the product obtained from 1-naphthylamine. For the preparation of C-nitroso derivatives of primary amines from nitrosophenols see page 529. 

Many of the reactions producing imidazoles in tobacco and tobacco smoke involve the interaction of carbohydrates with ammonia, which has several precursors in tobacco. Amino acids and proteins can contribute to the formation of smoke amines and the formation of ammonia. Johnson et al. (1964) conclusively demonstrated through experiments with W-glycine that it is an ammonia source. In addition to amino acids, nitrates have been shown to be efficiently converted during the smoking of a cigarette to ammonia (1964). This ammonia from nitrates was shown to participate in the formation of many nitrogenous compounds in smoke. Thus, leaf nitrates as well as amino acids and proteins are considered the major sources of ammonia in tobacco smoke. 

Dehydration Catalysts. In the production of amines from alcohols and ammonia or from alcohols and various amines, catalysts prepared by dehydrating alumina or silica gel are generally used. For specific reactions, these catalysts are promoted with various metals, their oxides or salts. For example, a dehydration catalyst has been made by incorporating aluminum phosphate in alumina gel prior to dehydrating the gel. An amination catalyst made by treating absorptive alumina with calcium and copper nitrates, followed by calcination and then reduction with hydrogen in a vapor-phase reactor, was used to produce an excellent yield of mono-methylaniline from aniline and methanol. ... 

Halogenation and nitration of arenes, substitution reactions ofaliphatics Ether and ester formation, thiols from alcohols and H2S, amines from alcohols and NHj (mordenite, erionite)... 

Barger (80) starting from phenethyl alcohol, obtained phenethyl chloride, which, when heated with dimethylamine, yielded dimethyl-phen ethyl amine. By nitration, reduction, diazotization, etc. a base identical with natural hordenine was obtained. Rosenmund (81) condensed p-methoxybenzaldehyde with nitromethane and reduced the alkoxy nitrostyrene to p-methoxyphenethylamine. With methyliodide a mixture of bases was formed from which, after demethylation with boiling hydroiodic acid, hordenine was obtained in low yield. Voswinckel (82) treated p-methoxyphenacyl chloride with dimethylamine, then demethylated and reduced to hordenine. Ehrlich and Pistschimuka (83) started from tyrosol, p-0H-C6H4-CH2CH2OH, converted it to the chloride, which, with dimethylamine gave hordenine. Further synthesis have been elaborated by Spath and Sobel (84) and by Kindler (38). Raoul (67, 69) obtained hordenine in 50 % yield, by methylating tyramine with formaldehyde and formic acid. 

An asymmetric systhesis of amines from chiral nitrates and racemic alcohols has been achieved under Ritter reaction conditions (Scheme 4). ... 

---