Nitro-1-naphthylamine

Submitted by Chakles C. Price and Sing-Tuh Voong. Checked by Richard T. Arnold and Jav S. Buckley, Jr. 

Twenty grams (0.1 IS mole) of a-nitronaphthalene (Note 1) and so g. (0.72 mole) of powdered hydroxylamine hydrochloride are dissolved in 1.2 1. of 9S% ethanol contained in a 3-1. flask which is heated in a bath maintained at S0-60°. A filtered solu- 

The a-nitronaphthalene, m.p. 56-57°, was obtained from Eastman Kodak Company. 

The color changes from yellow to orange, and potassium chloride separates. 

In some experiments a few milliliters of dilute hydrochloric acid (1 1) or sulfuric acid (1 1) was added to facilitate the crystallization of the 4-nitro-l-naphthylamine. 

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MNN is obtained in 3—5% yield by the nitration of naphthalene and is present at this level in coml MNN. It is best prepd by indirect methods for example, by the removal of an amino group from an appropriately substituted nitro-naphthylamine. The amine is treated with Na nitrite and acid to form the diazonium salt which is replaced with a H atom by redn with EtOH (Ref 7). It may also be prepd by treatment of 6-nitro-l, 2,3,4-tetrahydronaphthalene with Br to form a dibromo compn (probably the 1,4-isomer), followed by removal of two moles of H bromide by distn in the presence of base (Ref 10). 2-Naphthalenediazonium fluoroborate... 

TABLE 3. Synthesis of tris- and tetrakis(dialkylamino)naphthalenes from (nitro)naphthylamines... 

Chlor-4-nitro-naphthylamin-(l) 12 II 707. z-ChloT-z-nitro-naphthylamin-(l) 18, 1261. 

Fluoronaphthalene [321-38-0] is prepared from 1-naphthylamine by the Balz-Schiemaim reaction in 52% yield or by diazotization in anhydrous hydrogen fluoride in 82% yield. Electrophilic substitution occurs at the 4-position, eg, nitration with fuming nitric acid in acetic acid gave 88% yield of l-fluoro-4-nitro-naphthalene [341 -92-4]. 

Nitro-l-diazo-2-naphthol-4-sulfonic acid prefers the 2-position in spite of the nitro group, and increasing alkalinity favors ortho coupling with diazophenols. 1-Naphthalenesulfamic acid [24344-19-2] (ArNHSO H) and N-nitro-1-naphthylamine [4323-69-7] (ArNHNO ) couple exclusively in the para position. The substitution of resorcinol [108-46-3] and y -phenylenediamine [108-45-2] is compHcated and has been discussed (29,30). The first azo dyes from aniline, eg. Aniline Yellow [60-09-3] (19) (Cl Solvent Yellow 1 Cl 11000) were manufactured in 1861 and Bismark Brown [10114-58-6] (20) (Cl Basic Brown 1 Cl 21000) appeared in 1863. The reaction is as follows ... 

Diazidonaphthalene. Crysts from petr eth (bp 60—90°), mp 108° prepd in four steps starting with l-nitro-2-naphthylamine (Ref 3). It decomps in boiling decalin to evolve N and... 

CA Registry No 2493447-2. It is prepd by bromination of 5,6-dinitro-l,2,3,4-tetrahydro-naphthalene followed by dehydrobromination (Ref 20), from 2-nitro-l-naphthylamine by the same procedure as used for the prepn of the 1,4-isomer (Ref 20)... 

Dinitronaphthalene (1,4-DNN). Long yel needles from MeOH, mp 134° (Refs 6 34) CA Registry No 6921-26-2. It is prepd by the diazotization of 4-nitro-l-naphthylamine followed by treatment of the diazonium salt with powd Cu and Na nitrite (Ref 45)... 

Dinitronaphthalene (Delta-dinitronaphtha-lenet 1,6-DNN). Crysts from acet ac, mp 166-67°, bp at 10mm 235°, 360° with decompn (Refs 2 31) CA Registry No 60746-5. It is prepd by the nitration of 2-nitronaphtha- ene with nitric ac/sulfuric ac in hot acet ac (Ref 21) by diazotization of 5-nitro-2-naphthyl-amine followed by treatment of the diazonium salt with Na cobaltinitrite, yield 40% (Ref 36) or by removal of the amino group from 1,6-dinitro-2-naphthylamine by diazotization followed by redn (Ref 17). The temp of expin is 492°(Refl7)... 

CA Registry No 24824-26-8. It is prepd by the diazotization of 6-nitro-2-naphthylamine followed by treatment of the diazonium salt with... 

Methoxy-anilin 4-MethyI-anilin 4-Brom-anilin 3-Nitro-anilin I-Naphthylamin... 

Acridine and compounds Aniline and compounds Benzanthrone and compounds Benzidine and compounds Chloro compounds Naphthalene and compounds Naphthylamines Nitro compounds... 

Reduction of a nitro compound to the corresponding naphthylamine proceeds exactly as in the benzene series. A batch process using iron and hydrochloric acid is traditional but has been somewhat superseded by catalytic hydrogenation. 

The reduction of aromatic nitro-compounds is of exceptionally great interest, not only scientifically, hut also technically. The conversion of the hydrocarbons of coal tar into useful products began with the discovery of the nitration process the conversion, on the technical scale, of the nitro-group of nitrobenzene into the amino-group gave aniline, the starting material for the preparation of innumerable dyes and pharmaceutical products to aniline were added the homologous toluidines, xylidines, naphthylamines, and so on. 

The high-temperature reaction of aromatic amines with aromatic nitro compounds in the presence of base affords primarily an azo compound [39,40]. Because two independent laboratories have reported reasonable results with this synthesis, the procedure is given here. To be noted is that, while the reaction as described here involves 2-naphthylamine, a known carcinogenic intermediate, it is given only for reference to the procedure. Evidently, other aromatic amines also undergo the reaction. 

Nitro-2-diazo- 1-napbtbol, crysts (from benz), mp 187° (dec) was prepd by diazoti2ation of l-chloro 3-Nitro-2-naphthylamine and pouring the diazonium soln in aq Na acetate (Ref 9) 6-Nitrot2-diazo-l napbtbol [called 6-Nitro-2-... 

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