Aniline Naphthylamine

Fig. 12.14 Delocalisation of electrons in aniline, naphthylamine and diphenylamine molecules...

Because of the higher CH acidity (by 7-8 pKa units) of alkylidene malonates (441), as compared with that of dialkyl malonates (87JA809), one-pot syntheses of alkylidene aminomethylenemalonates (442) could be carried out readily with a wide variety of primary and secondary aliphatic and cycloaliphatic amines, anilines, naphthylamines and heterocyclic amines, trialkyl orthoformate, and alkylidene malonates (83MI1 86MI9). It was proposed that the higher CH acidity of alkylidene malonates was a consequence of the electrostatic (dipole-dipole) repulsion effects... 

Stiihmer and Hess war b1M have reported addition of aniline, ) -naphthylamine, and others to ci - and bmu-atilbene oxide to afford tkreo and erythro adducts respectively, as shown in Eq. <627), Their observations are consistent with the premise that ring-opening is accompanied by Walden inversion at the site of nucJecphiJic attack. 

Preparation of aniline black from aniline naphthylamine violet from naphthylamine salts alizarine from anthraquinone—Toluidene—Alethyl-aniline— Diphenylamine— Methyl-diphenylamine—Naphthylamine.60-62... 

A) PRIMARY AROMATIC AMINES. RNH. Aniline, o-, m-, and p-toluidine (and other nuclear-substitiited anilines) 1- and 2-naphthylamines. (For note on Aliphatic Amines, cf. p. 375 )... 

Thus good yields (> 60 per cent) are obtained with aniline and methyl, ethyl, n-propyl and n-butyl phosphates with a- and P-naphthylamine and methyl or ethyl phosphate nuclear substituted anilines and methyl or ethyl phosphate. 

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 ... 

Heating arylamines with carbon dioxide at 200 C (8500 atm) gives good yields of 3-aryl derivatives of 2,4-dihydroxyquinazoline ° (see 5e). The method is unsatisfactory when riitro, halo, and phenolic anilines and a- or p-naphthylamines are used. 

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. ... 

Table 3-1. Equilibrium constants Kxno (Scheme 3-28) and rate constants for diazotization of aniline (Ar2, Scheme 3-29) and of 1-naphthylamine (k2 and k-2/k Scheme 3-34) in water by nitrosyl chloride, nitrosyl bromide, nitrosyl thiocyanate, S-nitrosothiuronium ion [(NH2)2CSNO], and dinitrogen trioxide at 25 °C.

For substituted anilines (Thompson and Williams, 1977) and for 1-naphthylamine and a series of derivatives thereof (Castro et al., 1986a), k2 and the ratio Ar 2/Ar3 have been determined for nucleophilic catalysis with Cl-, Br-, SCN-, and SC(NH2)2. The values of k2 correspond fairly well to those found for the diazotization of aniline, but those of Ar 2/Ar3 increase markedly in the above sequence (Table 3-1). As k3 is expected to be independent of the presence of Cl- or Br- and to show little dependence on that of SCN- or thiourea, the increase in k 2/k3 for this series must be due mainly to 2. Indeed, the value of log(Ar 2/Ar3) shows a linear correlation with Pearson s nucleophilicity parameter n (Pearson et al., 1968). This parameter is based on nucleophilic substitution of iodine (as I-) in methyl iodide by various nucleophiles. The three investigations on nucleophilic catalysis of diazotization demonstrate that Pearson s criteria for bimolecular nucleophilic substitution at sp3 carbon atoms are also applicable to substitution at nitrogen atoms. 

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... 

Primary aromatic amines (e.g., aniline) and secondary aliphatic-aromatic amines (e. g., 7V-methylaniline) usually form triazenes in coupling reactions with benzenedi-azonium salts. If the nucleophilicity of the aryl residue is increased by addition of substituents or fused rings, as in 3-methylaniline and 1- and 2-naphthylamine, aminoazo formation takes place (C-coupling). However, the possibility has also been noted that in aminoazo formation the initial attack of the diazonium ion may still be at the amine N-atom, but the aN-complex might rearrange too rapidly to allow its identification (Beranek and Vecera, 1970). 

Ar NHi = Sulphanilic acid ArH = l-Naphthylamlne-4-sulphonic acid Aniline l-Naphthylamine-8-sulphonic acid 4-Nitroaniline Indole ... 

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

The diazonium salts precursors can be aniline, o- and p-toluidine, o-and p-anisidine, o- and p-phenetidine. or /3-naphthylamine. The resulting formazans are crystalline and intensely colored. They are soluble in organic solvents, giving a red-violet coloration that darkens to blue. Dehydrogeneration gives the corresponding tetrazolium salts, which are isolated as perbromides (Scheme 51. Table X-13). 

The scope and mechanism of the isomerization of arylamines to methyl-substituted aromatic heterocycles have been studied. Aniline, toluidines, naphthylamines and m-phenylenediamine all gave the corresponding ortho-methyl-substituted aza-aromatics when exposed to high NHj pressure and elevated temperature in the presence of acid catalysts, e.g., zeolites. The yiel of pyridines formed by this process range from low to moderate <95JC(155)268>. 

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

Amines. Aniline Benzidine a-Naphthylamine p-Nitroaniline Dimethylaniline. 

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. 

Cytotoxicity of methylamine [45], kidney liver and myocardial damage due to ethylamine [46], hepatosplenomegaly and eosinophilia due to aniline [47], euphoria, dyspnea, teratogenicity, renal failure, hematuria, proteinurea, anorexia and methanoglobinemia due to a-naphthylamine and diphenylamine have been reported in the literature [48-54]. Therefore the remediation and mineralization of amines is... 

A marginal hydrogenation of the benzenic ring of 1-naphthylamine leading to 5,6,7,8-tetrahydro-l-naphthylamine [72] was explained as due to a weaker adsorption of the benzene part than of the aniline part of the naphthylamine. However, this reaction was disregarded for the HDN of 1-naphthylamine, as the minor role it could play under the studied conditions. 

Aniline, methyl aniline, 1-naphthylamine, and diphenylamine at trace levels were determined using this technique and electrochemical detection. Two electrochemical detectors (a thin-layer, dual glassy-carbon electrode cell and a dual porous electrode system) were compared. The electrochemical behavior of the compounds was investigated using hydrodynamic and cyclic voltammetry. Detection limits of 15 and 1.5nmol/l were achieved using colourimetric and amperometric cells, respectively, when using an in-line preconcentration step. 

Historically, bladder tumors have been associated with exposures in the aniline dye industry. However, conclusive evidence for any one particular exposure could not be obtained in these studies since the workers were exposed to many chemicals within the same work area. For example, Case et al. (1954) investigated the incidence of bladder tumors among British workers in the chemical dye industry. In addition to aniline, the workers were exposed to other aromatic amines, including a- and P-naphthylamine, benzidine, and auramine. Although exposures could not be quantified, there was insufficient evidence to suggest that aniline was a cause of bladder cancers. More recent studies indicate that P-naphthylamine, 4-aminodiphenyl, 4-nitrodiphenyl, 4,4-diaminodiphenyl, or o-toluidine may be involved in increased cancers in the dye industry (Ward et al. 1991 Benya and Cornish 1994). 

In this method the order of addition of the reactants is changed. The most general application is to the diazotisation of aniline- and naphthylamine-sulphonic acids, many of which are sparingly soluble in acidic media and form sparingly soluble diazonium salts. Typically, the arylaminesulphonic acid is dissolved as its sodium salt in dilute alkali and sodium nitrite is then added to the solution. The resulting solution is run slowly into a mixture of hydrochloric acid and ice, the diazonium salt being formed almost instantaneously. 

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