1- Naphthylamine, 5-amino

Di-Me ether 5,6-Dimethoxy-1-naphthylamine. 5-Amino-l,2-dimethoxynaphthalene C12HJ3NO2 M 203.240 Cryst. (EtOH). Mp 97-98°. 

Stilben-4-yl)naphthotriazoles (2) are prepared by diazotization of 4-amino-stilbene-2-sulfonic acid or 4-amino-2-cyano-4 -chlorostilbene, coupling with an ortho-coupling naphthylamine derivative, and finally, oxidation to the triazole. 

Technologically, the most important examples of such couplers are 1-naphthylamine, 1-naphthol, and sulfonic acid derivatives of 1-naphthol (Fig. 2). Of great importance in the dyestuff industry are derivatives of l-naphthol-3-sulfonic acid, such as H-acid (8-amino-l-naphthol-3,6-disulfonic acid [90-20-0])... 

All the evidence suggests that such groups always exist in the amino form, and the reactions and behavior of these compounds resemble those of aniline and the naphthylamines. For example, the amino form of 7-aminophenazin-2-ones (246) would be expected to be more stable than the imino form (247), and their weak basicity supports this expectation. ... 

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... 

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)... 

If the coupling component is not ionic, however, more dramatic effects occur, as found by Hashida et al. (1979) and by Tentorio et al. (1985). Hashida used N,N-bis(2-hydroxyethyl)aniline, while Tentorio and coworkers took 1-naphthylamine and l-amino-2-methylnaphthalene as coupling components. With cationic arenediazo-nium salts and addition of sodium dodecyl sulfate (SDS), rate increases up to 1100-fold were measured in cases where the surfactant concentration was higher than the critical micelle concentration (cmc). Under the same conditions the reaction... 

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. 

P-Bromonaphthalene. The preparation from p-naphthylamine, which has carcinogenic properties, is avoided by the use of 2-naphthylamine-1-sulphonic acid ( 2-amino-1-naphthalenesulphonic acid ) the latter is obtained commercially by cautious treatment of p-naphthol with sulphuric acid—the SOjH group first enters the 1-position—followed by the Bucherer reaction. Diazotisation and reaction with cuprous bromide yields 2-bromonaphthalene-l-sulphonic acid heating with sulphuric acid eliminates the sulphonic acid group to give 2-bromonaphthalene. 

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... 

Abstract Hazardous effects of various amines, produced in the environment from the partial degradation of azo dyes and amino acids, adversely affect the quality of human life through water, soil and air pollution and therefore needed to be degraded. A number of such studies are already available in the literature, with or without the use of ultrasound, which have been summarized briefly. The sono-chemical degradation of amines and in the combination with a photocatalyst, TiC>2 has also been discussed. Similar such degradation studies for ethylamine (EA), aniline (A), diphenylamine (DPA) and naphthylamine (NA) in the presence of ultrasound, Ti02 and rare earths (REs) La, Pr, Nd, Sm and Gd, in aqueous solutions at 20 kHz and 250 W power have been carried out and reported, to examine the combinatorial efficacy of ultrasound in the presence of a photocatalyst and rare earth ions with reactive f-electrons. 

The role of N-sulfonyloxy arylamines as ultimate carcinogens appears to be limited. For N-hydroxy-2-naphthylamine, conversion by rat hepatic sulfotransferase to a N-sulfonyloxy metabolite results primarily in decomposition to 2-amino-l-naphthol and 1-sulfonyloxy-2-naphthylamine which are also major urinary metabolites and reaction with added nucleophiles is very low, which suggests an overall detoxification process (9,17). However, for 4-aminoazobenzene and N-hydroxy-AAF, which are potent hepatocarcinogens in the newborn mouse, evidence has been presented that strongly implicates their N-sulfonyloxy arylamine esters as ultimate hepatocarcinogens in this species (10,104). This includes the inhibition of arylamine-DNA adduct formation and tumorigenesis by the sulfotransferase inhibitor pentachlorophenol, the reduced tumor incidence in brachymorphic mice that are deficient in PAPS biosynthesis (10,115), and the relatively low O-acetyltransferase activity of mouse liver for N-hydroxy-4-aminoazobenzene and N-OH-AF (7,114,115). 

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. 

In the above reaction mechanisms it is noteworthy that the sulphonic acid group introduced has been shown to enter at the 3-position and not the 4-position as previously postulated. A consequence of this situation is that an attempted Bucherer reaction on a naphthol (or a naphthylamine) carrying a sulphonic acid group located meta to the hydroxy (or amino) group would require a second sulphonic acid group to be introduced at this position. Since it is impossible to locate two sulphonic acid groups on the same carbon atom, these compounds cannot undergo the transformation. 

Unmetallised disazo dyes of the type A—>M—>E in Winther symbols (section 4.7) dominate this sector. The A component is usually a disulphonated aniline or naphthylamine. Orthanilic acid or p-xylidine (2,5-dimethylaniline) for yellow browns, or a variety of monosulphonated 1-naphthylamines for redder browns, are selected as the M and E components. The terminal amino group provides the site for attachment of the reactive... 

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. 

Anilines, bis(2-amino-4-chlorophenyl)disulfide, naphthylamine, 2- and 3-aminopyridines, 2-aminopyrimidines, 2-, 3-, 5-, 6-, 7-, and 8-aminoquino-lines, 6-aminocoumarin, and 2-aminopyrazine were reacted in the absence or presence of a solvent (ethanol, toluene) with ethyl orthoformate and isopropylidene or 4-heptylidene malonates to give alkylidene (het)aryl-aminomethylenemalonates (442, R = R2 = Me, Pr) in 32-100% yields [69BRP1147759 75USP3907798 88JAP(K)239269]. p-Toluenesulfonic acid monohydrate was sometimes applied as catayst. 

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). 

In naphthylamines reduction with sodium in refluxing pentanol affected exclusively the substituted ring, giving 51-57% of 2-amino-l,2,3-4-tetrahy-dronaphthalene [715]. 

Naphthylamine, 4-aminodiphenyl, 4-chloro-2-toluidine, benzidine, 2,4,5-trimethylaniline, 2,4-diaminoanisol, 2,4-toluylenediamine, 2-amino-4-nitrobenzene, 3,3 -dichlorobenzidine, 3,3 -dimethoxybenzidine, 3,3 -dimethylbenzidine, 3,3 -4,4 -diaminodiphenylmethane, 4,4 -diaminodiphenybnethane, 4,4 -methylene-bis-(2-chloroaniline), 4,4 -Oxydianiline, 4,4 -thiodianiline, 2-aminoazotoluene,... 

The amino structure for 9-aminoacridine (77) has been confirmed by IR studies (65JCS5230), and NMR spectral data in DMSO are consistent with the diamino structures (78) and (79) (64JCS1423). Amino groups on fused benzene rings and (3 to nitrogen in hetero rings exist in the amino form, and the reactions of these compounds are similar to those of aniline and the naphthylamines. Aminopyridine JV-oxides exist very predominantly in the amino form (57JCS4375). 

Co-exposures 4,4 -Methylene bis (2-methylaniline) (2B) Magenta (2B) Safranine T or/ oNitrotoluene (3) 2,5-Diaminotoluene (3) Aniline (3) ori/io-Amino-azotoluene (2B) Multiple ejqjosures including 4-chloro-o/t/io-toluidine and 4-chloroacetyl-or/Zio-toluidine A/ Acetyl-or//io-toluidine 6-Chloro-or//io-toluidine 4-Chloro-or//io-toluidine (2A) Aniline (3) Hydroquinone (3) Toluene (3) Carbon disulfide Sulfur Benzothiazole 4-Aminobiphenyl (contaminant) (1) 2-Mercaptobenzothiazole (Ward et al, 1996) (Proprietary chemical) Aniline (3) 2-Mercaptobenzothiazole Phenyl-p-naphthylamine (3)... 

Typical primary amines which undergo such nitrosation are m-toluidine, p-xylidine, m-anisidine, 2-amino-4-methoxytoluene, 3-amino-4-methoxy-toluene, m-aminophenol, a-naphthylamine, l-naphthylamine-2-, -6-, -7-, and -8-monosulfonic acids, and l-naphthylamine-4-monosulfonic acid (which reacts with displacement of the sulfonic acid group). The secondary amines derived from these primary amines also can be nitrosated directly (i.e., without the intermediate formation of an JV-nitroso compound which needs to be subjected to the Fischer-Hepp rearrangement). The entering nitroso group appears to substitute exclusively in the para position. 

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