Naphthalene 3-Naphthylamine

The nitro substitution products of naphthalene are easily prepared by the action of nitric acid on the hydrocarbon. By such direct nitration the product obtained is alpha-nitro naphthalene. This is proven by the following series of reactions. Nitro-naphfhalene by reduction yields amino naphthalene, naphthylamine, which by the diazo reaction yields hydroxy naphthalene, naphthol. Now the naphthol so obtained is identical with the one resulting from the phenyl vinyl acetic acid synthesis (p. 768) and this must be the alpha compound. 

Sulfonation is also easier in the presence of hydrogen fluoride, boron trifluoride112 (e.g., for benzene, toluene, naphthalene, naphthylamine, naphthol, phenol, carbazole, and biphenyl), or boric acid166 (e.g., for 6-quinizarinsul-fonic acid), but iodine is reported111 not to influence the course of a sulfonation. 

In the naphthalene series, a-naphthylamine is easily obtained by the reduction of the readily accessible a-nitronaphthalene ... 

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]. 

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. 

Miscellaneous uses include several organic compounds and intermediates, eg, 1-naphthalenol, 1-naphthylamine [134-32-7] 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene, and chlorinated naphthalenes. 

An important reaction in the chemistry of naphthalenes is the Bucherer reaction,i.e. the conversion of naphthols 1 to naphthylamines 2 as well as the reverse reaction. The reaction is carried out in aqueous medium in the presence of catalytic amounts of a sulfite or bisulfite. Apart from very few exceptions it does not apply to benzene derivatives, which limits the scope of that reaction. 

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... 

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 ( Gamma-dinitronaph-thalene, 1,3-DNN), Bright yel needles from aq pyridine, mp 144°, bp subl (Refs 1 32) CA Registry No 606-37-1. It is prepd by the action of nitric ac/sulfuric ac on naphthalene at low temps (Refs 14 33) by the nitration of 1-MNN with a mixt of 17.3% nitric ac, 61.2% sulfuric ac, and 21.5% w, temp 59-75°, time 90min (Ref 52) by the action of powd Cu (Ref 18) or hydrazine (Ref 22) on l-chioro-2,4-dinitro-naphthalene by the diazotization of 2,4-dinitro-1-naphthylamine followed by redn of the dia-zonium salt with EtOH (Ref 25) or by the action of Br on 5,7-dinitro-l,2,3,4-tetrahydro-naphthalene followed by dehydrobromination (Ref 13). It is used to prep more highly nitrated naphthalenes... 

Dinitro-1 -Naphthol (4,6-Dinitro-1 -oxy-naphthalene). Crysts from methanol (as Na salt), mp 240°. Sol in chlf. Prepn from 1,4,6-trinitro-2-naphthylamine by diazotization in AcOH-sulfuric acid to yield 4j6-dinitro-2-diazo-... 

A slightly related reaction involves the amino group of naphthylamines can be replaced by a hydroxyl group by treatment with aqueous bisulfite. The scope is greatly limited the amino group (which may be NH2 or NHR) must be on a naphthalene ring, with very few exceptions. The reaction is reversible (see 13-6), and both the forward and reverse reactions are called the Bucherer reaction. 

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

Naphtha (petroleum), see Petroleum ether Naphtha, varnish makers and painters, 50° flash Naphtha, varnish makers and painters, high flash Naphtha, varnish makers and painters, regular Naphthalene 2-Naphthol 1 -Naphthylamine Natural gas Nickel carbonyl Nicotine... 

Morpholine Naphtha (coal tar) Naphthalene (5-Naphthylamine Nickel carbonyl Nickel metal ST CT CT 1... 

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... 

This reaction [65-67] is only rarely encountered in the benzene series but is extremely useful for appropriate derivatives of naphthalene, where the mechanism of the reaction has been investigated extensively. The reaction allows a hydroxy group to be exchanged for an amino group or vice versa. When a hydroxy group is to be converted into an amino group, the naphthol is heated under pressure with ammonium bisulphite (often produced in situ by introduction of ammonia liquor and sulphur dioxide into a sealed autoclave) at a temperature of 100-150 °C the naphthol is thereby converted into the corresponding naphthylamine. The mechanism of the reaction is outlined in Scheme 4.22. 

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... 

In all the above sequences, single isomers are produced by careful control of the reaction conditions combined with purification by selective isolation at various points in the synthesis. Occasionally two isomers are produced which give dyestuffs that have very similar properties in these cases it is often quite acceptable and economically beneficial not to separate the individual components but to use the total mixture in dye preparation. An example is the mixture of l-naphthylamine-6- and 7-sulphonic acids (4.46 mixed Cleve s acids), which arises by nitration and reduction of naphthalene-2 Sulphonic acid (Scheme 4.30). 

Naphthylamine and also its sulphonic acids are likewise employed technically for the manufacture of azo-dyes. In the same way a-naph-thol is made from naphthalene-a-sulphonic acid by fusion with sodium hydroxide although on a smaller scale than /3-naphthol. a-Naphthyla-mine, on the other hand, is obtained by the reduction of a-nitronaph-thalene (analogy to aniline). The fusion of alkali salts of arylsulphonic acids with alkali also serves technically for the production of pure phenol and of many phenol derivatives. 

The PE spectra of a- and /i-naphthylamine (13,14) were studied by Maier86 and by Klasinc and coworkers87. Maier86 has also analysed the spectra of peri-amino and dimethylamino naphthalenes (15-19). 

The expectations regarding 714 are excellently confirmed in a-naphthylamine (13) (Figure 8). The IP(tT4) value of this compound is practically the same as that of naphthalene while, for 713 and 715, AIP values of ca 0.3 eV are found. However, also AIP(tt2) is very small. For /i-naphthylamine (14) 712-715 are destabilized in a much more uniform manner relative to naphthalene by 0.4-0.7 eV. 

Synonyms AI3-00085 AIDS-18991 1-Aminonaphthalene a-Aminonaphthalene BRN 0386133 CCRIS 423 C.I. 37265 C.I. azoic diazo component 114 EINECS 205-138-7 Fast garnet B base Fast garnet base B Naphthalen-1-amine 1-Naphthalenamine Naphthalidam Naphthalidine a-Naphthylamine alpha-Naphthylamine NSC 4154 RCRA waste number U167 UN 2077. 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

Naphthalamine, see 2-Naphthylamine Naphthalane, see Decahydronaphthalene Naphthalen-l-amine, see l-Naphthylamine... 

Naphthalenediyl)benzene, see Fluoranthene 1-Naphthalenol methylcarbamate, see Carbaryl a-Naphthalenyl methylcarbamate, see Carbaryl 1-Naphthalenylthiourea, see ANTU Naphthalidam, see l-Naphthylamine Naphthalidine, see l-Naphthylamine Naphthalin, see Naphthalene... 

---