Nitro-* hydrochloric Acid

When mixed with hydrochloric acid it forms a solution resembling that of nitro-hydrochloric acid in its properties and capable of dissolving noble metals, e.g. platinum ... 

Foreign Metals. — Dissolve 1 gm. of the metal in nitro-hydrochloric acid, evaporate the solution to dryness on the... 

Fischer-Hepp rearrangement The nitros-amines of aromatic secondary amines when treated with hydrochloric acid give nuclear substituted nitrosoamines. Among the benzene derivatives, if the para position is free the -NO group displaces the hydrogen atom there in naphthalene derivatives it enters the 1-position ... 

N-phenylhydroxylamine, PhNHOH and further reduction can give azoxybenzene, azobenzene, hydrazobenzene and aniline. The most important outlet commercially for the nitro-compounds is the complete reduction to the amines for conversion to dyestufTs. This is usually done in one stage with iron and a small amount of hydrochloric acid. 

Both aliphatic and aromatic nitro-compounds can be readily reduced in acid solution to the corresponding primary amine. Thus when a mixture of nitrobenzene and tin is treated with hydrochloric acid, the tin dissolves to give stannous chloride, SnCh, which in these circumstances then reacts with more acid to give stannic chloride, SnCl, and the nascent hydrogen produced from... 

Drop 1 g. of sodium into 10 ml. of ethyl alcohol in a small flask provided with a small water condenser heat the mixture until all the sodium has dissolved. Cool, and add 1 g. of the ester and 0-5 ml. of water. Frequently the sodium salt of the acid will be deposited either at once or after boiling for a few minutes. If this occurs, filter oflF the solid at once, wash it with a little absolute ethyl alcohol (or absolute methylated spirit), and convert it into the p-bromophenacyl ester, p-nitro-benzyl ester or S-benzyl-tso-thiuronium salt (for experimental details, see Section 111,85). If no solid separates, continue the boiling for 30-60 minutes, boil oflF the alcohol, allow to cool, render the product just neutral to phenolphthalein with dilute sulphuric or hydrochloric acid, convert the sodium salt present in solution into a crystalline derivative (Section 111,85), and determine its melting point. 

Arylamines are generally prepared by the reduction of nitro compounds. When only small quantities are to be reduced and the time element is important and cost is a secondary consideration, tin and hydrochloric acid may be employed, for example ... 

Nitro compounds are reduced in acid solution (for example, by tin and hydrochloric acid) to the corresponding primary amines, which may be detected as described under II ... 

Reduction of a nitro compound to a primary amine. In a 50 ml. round-bottomed or conical flask fitted with a reflux condenser, place 1 g. of the nitro compound and 2 g. of granulated tin. Measure out 10 ml. of concentrated hydrochloric acid and add it in three equal portions to the mixtiue shake thoroughly after each addition. When the vigorous reaction subsides, heat under reflux on a water bath until the nitro compound has completely reacted (20-30 minutes). Shake the reaction mixture from time to time if the nitro compound appears to be very insoluble, add 5 ml. of alcohol. Cool the reaction mixture, and add 20-40 per cent, sodium hydroxide solution imtil the precipitate of tin hydroxide dissolves. Extract the resulting amine from the cooled solution with ether, and remove the ether by distillation. Examine the residue with regard to its solubility in 5 per cent, hydrochloric acid and its reaction with acetyl chloride or benzene-sulphonyl chloride. 

Reduction of 2.4-dimethyl-5-nitrothiazole with activated iron gives a product that after acetylation yields 25% 2.4-dimethyl-5-acetamido-thiazole (58). The reduction of 2-methyl 5-nitrothiazole is also reported (351 to give a mixture of products. The nitro group of 2-acetylhydrazino-5-nitrothiazole is reduced by TiCl in hydrochloric acid or by Zn in acetic acid (591. 

Attack on the electrophilic C-2 may occur as in the 2-aminothiazoles series, which probably explains the rearrangements observed in acidic medium (121, 711, 712, 723, 724), in aqueous medium with NaOAc (725), or with aqueous NaHCOj (725) (Scheme 232). That the initial attack probably involves the C-2 atom is substantiated by the fact that this rearrangement occurs under extremely mild conditions for 2-iinino-3-substituted-5-nitro-4-thiazolines (725). As the whole mechanism proposed (see p. 92) is reversible, when imino derivatives are submitted to such rearrangement conditions the rearrangement is expected to occur faster if steric interaction between 3- and 4-substituents exists in the 2-imino isomer. Another reaction may occur in acidic medium phenylimino-2-bipheny]-3,4-4-thiazoline hydrolyzed with hydrochloric acid gives the corresponding 4-thiazoline-2-one and aniline (717). 

Nitro groups are readily reduced to primary amines by a variety of methods Cat alytic hydrogenation over platinum palladium or nickel is often used as is reduction by iron or tin m hydrochloric acid The ease with which nitro groups are reduced is especially useful m the preparation of arylamines where the sequence ArH ArN02 ArNH2 IS the standard route to these compounds... 

The reduction of the nitro group to yield aniline is the most commercially important reaction of nitrobenzene. Usually the reaction is carried out by the catalytic hydrogenation of nitrobenzene, either in the gas phase or in solution, or by using iron borings and dilute hydrochloric acid (the Bechamp process). Depending on the conditions, the reduction of nitrobenzene can lead to a variety of products. The series of reduction products is shown in Figure 1 (see Amines byreduction). Nitrosobenzene, /V-pbenylbydroxylamine, and aniline are primary reduction products. Azoxybenzene is formed by the condensation of nitrosobenzene and /V-pbenylbydroxylamine in alkaline solutions, and azoxybenzene can be reduced to form azobenzene and hydrazobenzene. The reduction products of nitrobenzene under various conditions ate given in Table 2. 

Nitration of > -hydroxyben2oic acid with filming nitric acid in the presence of sulfuric acid and acetic anhydride gives a mixture of the 2-nitro [602-00-6] and 4-nitro [619-14-7] substitution products. Bromination and iodination yield the 4-halogenated derivatives (4-bromo [14348-38-0] and 4-iodo [58123-77-6]). When > -hydroxyben2oic acid is treated with formalin in the presence of hydrochloric acid, 4-hydroxyphthahde [13161 -32-5] is obtained as shown in equation (10). 

Nitropyridazines are reduced catalytically either over platinum, Raney nickel or palladium-charcoal catalyst. When an N-oxide function is present, palladium-charcoal in neutral solution is used in order to obtain the corresponding amino N-oxide. On the other hand, when hydrogenation is carried out in aqueous or alcoholic hydrochloric acid and palladium-charcoal or Raney nickel are used for the reduction of the nitro group, deoxygenation of the N- oxide takes place simultaneously. Halonitropyridazines and their N- oxides are reduced, dehalogenated and deoxygenated to aminopyridazines or to aminopyridazine N- oxides under analogous conditions. 

Nitrophenylarsonic acid has been prepared by heating p-nitrobenzenediazonium chloride with arsenious acid in hydrochloric acid, by the action of -nitrobenzenediazonium chloride on sodium arsenite, by the action of sodium arsenite on sodium -nitrobenzeneisodiazo oxide, by the diazotization of -nitro-aniline in acetic acid in the presence of arsenic chloride and cuprous chloride, and by the reaction of -nitrobenzenediazonium borofluoride with sodium arsenite in the presence of cuprous chloride. ... 

Other possibilities are the reduction of nitro groups by applying the sample solutions to adsorbent layers containing zinc dust and then exposing to hydrochloric acid vapors [110] 3,5-Dinitrobenzoates and 2,4-dinitrophenylhydrazones can also be reduced in the same way on tin-containing silica gel phases [111] Cellulose layers are also suitable for such reactions [112] Seiler and Rothweiler have described a method of trans-salting the alkali metal sulfates to alkali metal acetates [113]... 

Note Sulfuric acid (4%) can also be employed in place of hydrochloric acid [3]. If ammoniacal mobile phases are employed the ammonia should be removed completely (e.g. heat to 105 °C for 10 min) before dipping or spraying otherwise background discoloration can occur. The addition of titanium(III) chloride to the reagent allows also the staining of aromatic nitro compounds [6]. 

By a modified Bischler-Napieralsky reaction, 6 -nitrophenylaceto-jS-3 4-methylenedioxyphenylethylamide, resulting from the condensation of -3 4-methylenedioxyphenylethylamine with 2-nitrophenylacetyl chloride, was converted into 6 nitro-l-benzyl-6 7-methylenedioxy-3 4-dihydroisoquinoline. The methiodide of the latter was reduced with zinc and hydrochloric acid to 6 -amino-l-benzyl-2-methyl-6 7-methylenedioxy-1 2 3 4-tetrahydro/soquinoline dihydrochloride, which by the Pschorr ring-closure reaction, produced dZ-roemerine (IV, p. 317), m.p. 85-7°. By treatment in succession with d- and Z-tartaric acids, the dZ-base was resolved into Z- and tZ-forms. Synthetic Z-roemerine is dimorphic, m.p. 85-7° and 102°, and has [aju — 79-9° (EtOH), these constants being in good agreement with those of the natural base. 

Ewins has synthesised both substances from m-methoxybenzoic acid, which on nitration gave 2-nitro-3-methoxybenzoic acid, and this, on reduction and treatment with methyl iodide, yielded damasceninic acid, which, by esterification with methyl alcohol, furnished damascenine. Kaufmann and Rothlen found that the additive product of 8-methoxy-quinoline and methyl sulphate, on oxidation with permanganate, yields formyldamasceninic acid, MeO. CgH3(NMe. CHO). COOH, which can be transformed into damasceninic acid by warming with dilute hydrochloric acid. ... 

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