Nitronaphthalene method

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. 

Likewise with 2-nitronaphthalcne (6), 1 //-2-benzazepin-l -yl phosphonates 7 are formed in good yields, and the method can also be used to synthesize pyridoazepines from nitroquinolines (see Section 3.2.1.4.1.5.). The reaction fails, however, with 2-substituted 1-nitronaphthalenes. 

I, 4-benzoquinone.4 Other methods that have been employed include the oxidation of naphthalene with hydrogen peroxide,5 the oxidation of 1,4-naphthalenediamine 6 and naphthylamine sulfonic acid 7 and the oxidation of 4-amino-1-naphthol prepared by electrolytic reduction of 1-nitronaphthalene.8... 

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... 

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. 

To this end some nitration methods recommend introducing into the nitrator a certain quantity of nitronaphthalene from the previous batch before the process... 

This method has been applied at I. G. Leverkusen. It consists in charging naphthalene into a nitrator, containing a part of the spent acid and nitronaphthalene from the previous batch. To this the nitrating acid is added. 

The nitration of naphthalene to dinitronaphthalene (after Pascal [20a]) is effected in a nitrator essentially of die sane type as that used for the nitration of naphthalene to nitronaphthalene by the French method (Fig. 108, p. 441), the only difference being in the outlet which is wider at the bottom - 8 cm in diameter - since the nitration product is solid. 

Problem 30.13 Diazonium salts can be converted into nitro compounds by treatment with sodium nitrite, usually in the presence of a catalyst. Suggest a method for preparing 2-nitronaphthalene. 

This method is essentially that described by Goldhahn. 4-Nitro-l-naphthylamine has also been prepared by the nitration of a-naphthylamine, acetyl-a-naphthylamine, and ethyl-1-naphthyloxamate, by the oxidation of 4-nitroso-l-naphthyl-amine, and by reaction of 4-chloro-l-nitronaphthalene with ammonia. ... 

The following yields were obtained by this method 1-nitronaphthalene 68 %, 2-nitronaphtha-lene 60%, p-nitrotoluene 69 %, p-nitroanisole 68 %, and o-nitrotoluene 61 %.172... 

Nitration of nitronaphlhalcnc to trinifronaphthalcne French method 2-Meihyl-l-nitronaphthalene Literature... 

An alternative method for the preparation of benz[c]azepines and their pyrido analogues is the treatment of nitronaphthalenes and nitroquinolines with dimethyl phosphate under basic conditions <85CC1792, 91J0C1283>. Thus, treatment of 2-nitronapthalene or 6-nitroquinoline with secondary amines and sodium methoxide affords the phosphonates (250 X = CH or N) whereas 1-nitro-naphthalene and 5-nitro- or 8-nitroquinoline form a mixture of the tautomers (251 X and Y = CH or N) and (252 X and Y = CH or N). 

A comparison of mutagenic activity using normal and nitroreductase-deficient bacteria provides a method for detection and identification of nitroaromatic mutagens. But this idea is complicated by the existence of several bacterial nitroreductases with differing specificities (11). Three different nitroreductase-deficient derivatives of the normal tester strain TA98 were obtained from Dr H. S. Rosenkranz at Case Western University who has isolated and characterized these strains. Strain TA98NR was selected for its resistance to the nitrocompound niridazole and subsequently found to be resistant to the mutagenicity of niridazole, and also to that of the nitrofurans, nitronaphthalenes, and nitrofluorene (3). It is also resistant to 1-nitropyrene and a number of other nitro-PAH... 

The reaction of 1-nitronaphthalene with the Danishefsky s diene to give 3-hydroxyphenantrene has been theoretically studied using DFT methods. This reaction is a domino process that is initialized by a polar DA reaction between the p>ar dienophile/diene to give the formally [2 + 4] cydoadduct. The subsequent concerted elimination of nitrous... 

The reaction of OH with 1,4-naphthoquinone (a by-product of 1-nitronaphthalene pho tolysis) has been determined by Atkinson et al. (1989b), using the relative rate method. Using an updated value for the reference reaction, they find k = 2.9 x 10 molecule" s". The study is summarized in table V-F-5. 

The rate coefficients for the reaction of OH with 1- and 2-nitronaphthalene have been measured by Atkinson et al. (1989b) at 298 K and atmospheric pressure of air by a relative rate method. Arey et al. (1990b) have investigated the reaction of OH with 2-methyl-1-nitronaphthalene, where they have also used a relative rate method at atmospheric pressure and ambient temperature see table VIII-L-5. 

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