By nitration

Prepared by heating p-nitrochlorobenzene with concentrated aqueous ammonia in an autoclave at 170°C. It is also prepared by alkaline hydrolysis of p-nitroacetanilide or by nitrating and hydrolysing benzylideneaniline. 

A mixture of the two mononitro-chlorobenzenes is prepared by nitration of chlorobenzene. Further nitration of the mixture or of either of the mononitro-compounds gives 2,4-dinitrochlorobenzene, m.p. 5 C, b.p. 315"C. 

Added nitrate ions, and to a smaller extent water, depress the rate of the catalysed reaction, therefore excluding the operation of HNO2 and H2NO2+. The depression of the rate by nitrate obeys the following... 

The facts, in particular the dependence of first-order rate upon the concentration of acetyl nitrate (Appendix),could not be accounted for if protonated acetyl nitrate were the reagent. The same objections apply to the free nitronium ion. It might be possible to devise a means of generating dinitrogen pentoxide which would account for the facts of zeroth- and first-order nitration, but the participation of this reagent could not be reconciled with the anticatalysis by nitrate of first-order nitration. 

Comparison of the behaviour of cinnoline 2-oxide (vi, i = O) with that of 2-methoxycinnolinium (vi, R = OMe) suggests that at high acidities the former is nitrated as its conjugate acid (vi, R = OH), but that as the acidity is lowered the free base becomes active. At high acidities 5- and 8-nitration are dominant, but as the acidity is lowered 6-nitration becomes increasingly important. The 5- and 8-nitro compounds are probably formed mainly or wholly by nitration of the conjugate acid, and the 6-nitro compound wholly or mainly from the free base. ... 

A two-step synthesis of indoles from o-nitrobenzaldehydes proceeds by condensation with nitromcthanc followed by reductive cyclization. Like the Leim-gruber Batcho method, the principal application of the reaction is to indoles with only carbocyclic substituents. The forniation of the o,p-dinitrostyrenes is usually done under classical Henry condensation conditions but KF/18-crown-6 in propanol was found to be an advantageous reaction medium for acetoxy-substituted compounds[1]. The o,p-dinitrostyrenes can also be obtained by nitration of p-nitrostyrenes[2]. 

The overall reactivity of the 4- and 5-positions compared to benzene has been determined by competitive methods, and the results agreed with kinetic constants established by nitration of the same thiazoles in sulfuric acid at very low concentrations (242). In fact, nitration of alkylthiazoles in a mixture of nitric and sulfuric acid at 100°C for 4 hr gives nitro compounds in preparative yield, though some alkylthiazoles are oxidized. Results of competitive nitrations are summarized in Table III-43 (241, 243). For 2-alkylthiazoles, reactivities were too low to be measured accurately. 

Only the 2.4-dinitrothiazole is known, being prepared by nitration of 2-nitrothiazoJe by N204-N02/BF3, The yield is 80% (90). The reduction with Raney Ni/Ac20 of 2,4 dinitrothiazole proceeded smoothly, yielding the corresponding 2.4-diacetamidothiazole,... 

The practical problems He ia the separatioa of the chlorine from the hydrogea chloride and nitrous gases. The dilute nitric acid must be reconcentrated and corrosion problems are severe. Suggested improvements iaclude oxidation of concentrated solutions of chlorides, eg, LiCl, by nitrates, followed by separation of chlorine from nitrosyl chloride by distillation at 135°C, or oxidation by a mixture of nitric and sulfuric acids, separating the... 

Nitroglycol maybe made by nitration of ethylene glycol [107-21-1] with mixed acid with a yield of ca 93%. The demand for both NG and nitroglycol has been gready decreased (115,116). 

Picric Acid and Ammonium Picrate. Picric acid (PA) (2,4,6,-trinitrophenol) was the first modem high explosive to be used extensively as a burster ia gun projectiles. It was first obtained by nitration of iadigo, and used primarily as a fast dye for silk and wool. It offered many advantages when compressed, it was used as a booster for other explosives, and when cast (melting poiat 122.5°C) served as a burster ia shell it was stable, iasensitive, nonhygroscopic, relatively nontoxic, and of high density when cast, and could be made economically by simple nitration. 

There is a drive to develop insensitive or less sensitive munitions, ie, those less likely to accidental or sympathetic detonation. A leading candidate is 3-nitro-l,2,4-triazolin-5-one [930-33-6] (59), made by the reaction of semicarbazide and formic acid to give l,2,4-triazolin-5-one [932-64-9] foUowed by nitration of the triazolone (218). 

Naphthalenesulfonic Acid. The sulfonation of naphthalene with excess 96 wt % sulfuric acid at < 80°C gives > 85 wt % 1-naphthalenesulfonic acid (a-acid) the balance is mainly the 2-isomer (P-acid). An older German commercial process is based on the reaction of naphthalene with 96 wt % sulfuric acid at 20—50°C (13). The product can be used unpurifted to make dyestuff intermediates by nitration or can be sulfonated further. The sodium salt of 1-naphthalenesulfonic acid is required, for example, for the conversion of 1-naphthalenol (1-naphthol) by caustic fusion. In this case, the excess sulfuric acid first is separated by the addition of lime and is filtered to remove the insoluble calcium sulfate the filtrate is treated with sodium carbonate to precipitate calcium carbonate and leave the sodium l-naphthalenesulfonate/7J(9-/4-J7 in solution. The dry salt then is recovered, typically, by spray-drying the solution. 

In the manufacture of 2-naphthalenol, 2-naphthalenesulfonic acid must be converted to its sodium salt this can be done by adding sodium chloride to the acid, and by neutralizing with aqueous sodium hydroxide or neutralizing with the sodium sulfite by-product obtained in the caustic fusion of the sulfonate. The cmde sulfonation product, without isolation or purification of 2-naphthalenesulfonic acid, is used to make 1,6-, 2,6-, and 2,7-naphthalenedisulfonic acids and 1,3,6-naphthalenetrisulfonic acid by further sulfonation. By nitration, 5- and 8-nitro-2-naphthalenesulfonic acids, [89-69-1] and [117-41-9] respectively, are obtained, which are intermediates for Cleve s acid. All are dye intermediates. The cmde sulfonation product can be condensed with formaldehyde or alcohols or olefins to make valuable wetting, dispersing, and tanning agents. 

Nitronaphthalene. 1-Nitronaphthalene is manufactured by nitrating naphthalene with nitric and sulfuric acids at ca 40—50°C (37). The product is obtained in very high yield and contains ca 3—10 wt % 2-nitronaphthalene and traces of dinitronaphthalene the product can be purified by distillation or by recrystaUization from alcohol. 1-Nitronaphthalene is important for the manufacture of 1-naphthalenearnine. Photochemical nitration of naphthalene by tetranitromethane in dichioromethane and acetonitrile to give 1-nitronaphthalene has been described (38). 

By sulfonation of the appropriate naphthaleneamine or aminonaphthalenesulfonic acid. By nitration/reduction of the appropriate naphthalene (poly) sulfonic acid. 

The y -phenylenediamiaes are easily obtained by dinitrating, followed by catalyticaHy hydrogenating, an aromatic hydrocarbon. Thus, the toluenediamiaes are manufactured by nitrating toluene with a mixture of sulfuric acid, nitric acid, and 23% water at 330°C which first produces a mixture (60 40) of the ortho and para mononitrotoluenes. Further nitration produces the 80 20 mixture of 2,4- and 2,6-dinitrotoluene. Catalytic hydrogenation produces the commercial mixture of diamiaes which, when converted to diisocyanates, are widely used ia the production of polyurethanes (see Amines, aromatic, DIAMINOTOLUENES) (22). 

Nitroanthraquinone is prepared from anthraquinone by nitration in sulfuric acid (11), or in organic solvent (12). Nitration in nitric acid is dangerous. The mixture of anthraquinone and nitric acid forms a Sprengel mixture (13,14) which may detonate. However, detonation can be prevented by a dding an inert third component such as sulfuric acid. Experimental results of the steel-tube detonation tests for the anthraquinone—HNO2—H2SO4 system have been pubUshed (13). 

OCjOC -Dinitroanthraquinones and Related Compounds. 1,5- and 1,8-Dinitroanthraquiaone are the key iatermediates for manufacturiag disperse blue dyes via dinitrodihydroxyanthraquiaoae and vat dyes via diaminoanthraquiaones. 1,5-Diaitroanthraquinone [82-35-9] (49) and 1,8-dinitroanthraquinone [129-39-5] (50) are prepared by nitration of anthraquiaone with nitric acid ia sulfuric acid. a,P -Dioitroanthraquiaoaes are also formed ia the reactioa. 

Dioitroanthraquiaoae and 1,8-dinitroanthraquinone can also be prepared by nitration of anthraquiaone ia coaceatrated nitric acid (70). The 1,5-isomer can then be easily separated from the reaction mixture by filtration, since 1,8- or other isomers than 1,5-dinitroanthraquinone are completely dissolved in concentrated nitric acid. However, this process is unsuitable for industrial production for safety reasons the mixture of dinitroanthraquiaone and concentrated nitric acid forms a detonation mixture (71). Addition of sulfuric acid makes it possible to work outside the detonation area. 

Dinitroanthraquinones are industrially prepared by nitration of anthraquiaone in mixed nitric—sulfuric acid at 0—50°C. The reaction mixture is then heated to a temperature slightly higher than the nitration reaction temperature to enrich the content of 1,5-dinitroanthraquinone in soHd phase, and then cooled and filtered to obtain the 1,5-dinitroanthraquinone wet cake. Mother Hquor is concentrated by distillation of nitric acid and crystallised 1,8-isomer is separated. The filtrate is again distilled, and precipitated ( -isomers are filtered off and filtrate is recycled to the nitration step (72—74). 

Methyl-1-nitroanthraquiaone [129-15-7] (57) is an important precursor for l-nitroanthraquiaone-2-carboxyhc acid (58) and is prepared by nitration of 2-methylanthraquiaone (56) (87). This compound is probably carciaogenic (88). 

The starting material is an acid dye, ie, Cl Acid Blue 45 which is prepared from 1,5-dihydroxyanthraquiaone by sulfonation followed by nitration and then reduction. 

There are many synthetic routes to alloxan. Probably the best is direct oxidation of barbituric acid (1004 R = H) with chromium trioxide (5208(32)6) but it may be made from barbituric acid via its benzylidene derivative by direct or indirect oxidation of uric acid from 5-chlorobarbituric acid (1004 R = C1) by nitration or from 5-nitrobarbituric acid (1004 R = N02) by chlorination, both via the intermediate (1005) (64M1057) or by permanganate oxidation of uracil (1006) under carefully controlled conditions (73BSF1167). 

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