2- Nitronaphthalene, nitration

The successive nitration of naphthalene allows the introduction of four nitro groups. Nitration of naphthalene with concentrated nitric acid mainly yields 1-nitronaphthalene and a small amount of 2-nitronaphthalene. Nitration of pure 1-nitronaphthalene with mixed acid yields... 

Ward and Hawkins [27] nitrated 1-nitronaphthalene with a mixture of nitric (sp. gr. 1.42) and sulphuric (sp. gr. 1.84) acids, at a volume ratio 4 1 at 0°C and obtained a mixture of 1,8- and 1,5-dinitronaphthalenes, their ratio being about 70 30. 2-Nitronaphthalene, nitrated under similar conditions, gave a mixture of 1,6- and 1,7-dinitronaphthalenes along with 1,3,8-trinitronaphthalene, at a ratio of about 42 52 9. 

In the nitration of benzene, wj-dinilro- and sym-trinitrobenzenes are obtained under more vigorous conditions. With naphthalene, 1-nitronaphthalene is the first product and further nitration gives a mixture of 1,5- and 1,8-dinitronaphthalenes 2-nitronaphthalene is never obtained. 

Nitration. Naphthalene is easily nitrated with mixed acids, eg, nitric and sulfuric, at moderate temperatures to give mostly 1-nitronaphthalene and small quantities, 3—5%, of 2-nitronaphthalene. 2-Nitronaphthalene [581-89-5] is not made in substantial amounts by direct nitration and must be produced by indirect methods, eg, the Bucherer reaction starting with 2-naphthalenol (2-naphthol [135-19-3]). However, the 2-naphthylamine [91-59-8] made using this route is a carcinogen thus the Bucherer method is seldom used in the United States. 

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). 

Nitronaphthalenesulfonic Acids. Nitronaphthalenesulfonic acids can be obtained either by the sulfonation of 1-nitronaphthalene or by the nitration of 1- or 2-naphthalenesulfonic acid. Thus the sulfonation of 1-nitronaphthalene with oleum at ca 25°C gives mainly 5-nitro-l-naphthalenesulfonic acid/77521-00-5]. The mononitration of 1-naphthalenesulfonic acid gives mainly 5- and 8-nitro-l-naphthalenesulfonic acid/717-41-9] and mononitration of 2-naphthalenesulfonic acid gives mainly 5-nitro-2-naphthalenesulfonic acid [86-69-1] and 8-nitro-2-naphthalenesulfonic acid [18425-74-6]. These... 

H-acid, l-hydroxy-3,6,8-ttisulfonic acid, which is one of the most important letter acids, is prepared as naphthalene is sulfonated with sulfuric acid to ttisulfonic acid. The product is then nitrated and neutralized with lime to produce the calcium salt of l-nitronaphthalene-3,6,8-ttisulfonic acid, which is then reduced to T-acid (Koch acid) with Fe and HCl modem processes use continuous catalytical hydrogenation with Ni catalyst. Hydrogenation has been performed in aqueous medium in the presence of Raney nickel or Raney Ni—Fe catalyst with a low catalyst consumption and better yield (51). Fusion of the T-acid with sodium hydroxide and neutralization with sulfuric acid yields H-acid. Azo dyes such as Direct Blue 15 [2429-74-5] (17) and Acid... 

The oxidation of 1-nitronaphthalene by ceric ammonium nitrate has been reported (16). The resulting 1-iiitronaphthoquinone condenses with 1,3-butadiene followed by air oxidation under alkaline conditions to form 1-nitroanthraquinone, or l-aminoanthraquinone is formed direcdy by an intramolecular redox reaction. 

Dinitronaph thalene (1,7-DNN). Yell ow crysts from EtOH, mp 156° (Refs 7 21) CA Registry No 24824-25-7. It is prepd by the nitration of 2-nitronaphthalene with nitric ac/ sulfuric ac in hot acet ac (Ref 21) or by the diazotization of 8-nitro-2-naphthylamine, followed by treatment of the diazonium salt with Na cobaltinitrite (Ref 35)... 

Dinitronaphthalene-2-sulfonic Acid. Solid which explds on heating prepd by nitration of 8-nitronaphthalene-2-sulfonic ac with mixed ac at 0-15° (Ref 2)... 

P-Nitronaphthalene is not formed by direct nitration. For the preparation of p-naphthylamine, the Bucherer reaction may be applied to p-naphthol, i.e., by heating with ammoniacal ammonium sulphite solution at 150° (under pressure). The reaction involves the addition of the bisulphite to the keto form of p-naphthol ... 

Nitration [63], unlike sulphonation, is not reversible and results very largely in a substitution, yielding 1-nitronaphthalene (4.27). 

Nitration of naphthalene-1-sulphonic acid produces two isomeric nitronaphthalenes that have very similar solubilities. It is convenient to reduce the mixture without separation, giving a mixture of l-naphthylamine-8-sulphonic acid (4-44 Peri acid) and 1-naphthylamine-5-sulphonic acid (4.45 Laurent s acid), as in Scheme 4-29. These two... 

Figure 4.12 Nitration of 1 -nitronaphthalene with mixed acid - Ref. 59...

We observe that nitration of naphthalene using nitric acid-sulfuric acid gives predominantly 1-nitronaphthalene (sometimes a-nitronaphthalene), and... 

Other important expls obtd on nitration of products of distillation of coal tar were Di- and Tri nitrobenzene (Vol 2 of Encycl, pp B46ff and Nitronaphthalenes, which will be described under Naphthalene and Derivatives... 

Beilstein Kuhlberg investigated nitration of toluene with mixed nitric-sulfuric acid of various concns and isolated for the first time several isomers of mono- and dinitro-toluene. They also prepd in 1870 TNT, but did not prepare Trinitrobenzene. At about the same time, mono-, di-, tri- and tetra-nitronaphthalenes were prepd (Ref 12, p 18). Trinitrobenzenes were prepd in 1882 by P. Hepp... 

Piombite. Accdg to Caprio (Ref 11, Vol 2, p 96) and Belgrano (Ref 31, p 351), it is an expl mixture consisting of Lead nitrate 76, Tri-nitronaphthalene 16, Calcium silicide 5 vaseline 3%. Trauzl Test value 155cc vs 285cc for TNT. It was used in mining expls... 

Ammonium nitrate Sodium nitrate Nitronaphthalene Dinitronaphthalene... 

Ammonium nitrate explosives usually contain a certain amount of nitro compounds from mononitro (e.g. nitronaphthalene) to trinitro compounds (e.g. trinitrotoluene). 

Nitrophthalic acid has been prepared by the oxidation of nitronaphthalene,1 and by the nitration of phthalic acid in a variety of ways by many different workers.2 The present method is based on those of Bogert and Boroschek3 and of Lawrance.4... 

Nitration. Naphthalene is easily nitrated with mixed acids, e.g., nitnc and sulfuric., at moderate temperatures to give mostly 1-nitroiiaphthakne and small quantities, 3-5%, of 2-nitronaphthalene,... 

The nitro group does not undergo migration of the naphthalene ring during the usual nitration procedures. Therefore, mono- and polynitration of naphthalene is similar to low temperature sulfonation, The nitronaphthalenes and some of their physical properties arc listed in fable 2. Many of these compounds are not accessible by direct nitration of naphthalene but are made by indirect methods, e.g nitrite displacement of diazonium halide groups in the presence of a copper catalysts, decarboxylation of nitronaphtbalcnccar-boxylic acids, or deamination of nitronaphthalene amines. They are nsed in the manufacture of chemicals, dye intermediates, and colorants for plastics. 

Naphthalene nitrates more readily than benzene, the first nitro group taking the a-position which is ortho on one nucleus to the side chain which the other nucleus constitutes. The second nitro group takes one or another of the expected positions, either the position meta to the nitro group already present or one of the a-positions of the unsubstituted nucleus. The dinitration of naphthalene in actual practice thus produces a mixture which consists almost entirely of three isomers. Ten different isomeric dinitronaphthalenes are possible, seven of which are derived from a-nitronaphthalene, seven from /3-nitronaphthalene, and four... 

None of the nitrated naphthalenes is very sensitive to shock. a-Nitronaphthalene is not an explosive at all and cannot be detonated. Dinitronaphthalene begins to show a feeble capacity for explosion, and trinitronaphthalene stands between dinitrobenzene and dinitrotoluene in its explosive power. Tetranitro-naphthalene is about as powerful as TNT, and distinctly less sensitive to impact than that explosive. Vennin and Chesneau report that the nitrated naphthalenes, charged in a manometric bomb at a density of loading of 0.3, gave on firing the pressures indicated below.46... 

Randal ite. A mining expl patented in Fr in 1895 by Randale of the USA Na nitrate 58—76, nitrophenol 34—16, and nitronaphthalene (resin, sulfur or charcoal) 8%... 

Nitration of naphthalene by use of cerium(IV) ammonium nitrate suspended on silica gel, or in homogeneous solution, in the presence of alcohols, sodium or tetrabutylammonium nitrite and acid gives mainly l-alkoxy-4-nitronaphthalenes together with some of the 2-nitro isomers.34 The results are consistent with initial attack by N02- alone or complexed with cerium(IV) ion at the 1- and 2-positions in a ratio of 5 1. 

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