Amines aromatic aniline methylation

The portions of the methyl orange molecule set off by the dotted lines come from aromatic amines like aniline. Aniline is indeed the starting material from which methyl orange and related dyes ( azo dyes ) are made. 

AMINES - MAINES, AROMATIC - ANILINE AND ITS DERIVATIVES] (Vol 2) Methyl anisate [121-98-2]... 

Furthermore, it has to be noted that the nitro groups in the NMCs are metabolized by microorganisms and animals such as fish and rats. It is known that aromatic amines (substituted anilines) are acetylated to acetanilides. Some of these compounds possess anti-androgenic properties [351 b, c, d]. It is supposed that some N-acetylated metabolites of NMCs, e.g. 2-methyl-3-nitro-4-methoxy-5-ferf-butyl-acetanilide (metabolite of musk ambrette) and 4-ferf-butyl-2,6-di-methyl-3,5-dinitro-acetanilide (metabolite of musk xylene) are bound to the androgen receptor (AR) and may act as weak anti-andxogens [351 e]. 

Common nomenclature of simple amines involves presenting the name of the alkyl group followed by the word amine (such as propylamine) this type of nomenclature is acceptable in IUPAC for simple amines. In IUPAC nomenclature, the name is based on the longest continuous chain of carbon atoms followed by the suffix -amine (such as 1-propanamine). Substituents on the carbon chain are located by a number substituents on the nitrogen are located with N (such as N-methyl-1-propanamine). The simplest aromatic amine is aniline. 

Silylation of Amines. While there are several effective methods for preparation of Af-(trimethylsilyl)amines, only a few successful procedures for Af,Af-bis(trimethylsilyl)alkylamines synthesis have been reported. If silylation of ethylamine is attempted with trimethylsilyl chloride, only 13% of NJ -bis(trimethylsilyl)ethylamine is obtained in addition to the major product iV-(trimethylsilyl)ethylamine. However, N,N-bis(trimethylsilyl)amines can be prepared by silylation of monosi-lylamines with trimethylsilyldiethylamine in the presence of catal3Tic ammonium sulfate or ammonium chloride. Another convenient method for the preparation of Af,A-bis(tri-methylsilyl)alkylamines has recently been reported. There trimethylsilyldiethylamine has been found to be effective in the conversion of primary amines, especially aromatic systems, and their monotrimethylsilyl derivatives into the corresponding bistrimethylsilyl products in high yields. For example, when isopropyl amine (or aniline) is refluxed with 1.1 equiv of trimethylsilyldiethylamine and 1.15 equiv of methyl iodide in toluene for 4 h, bis(trimethylsilyl)isopropylamine [or bis(trimethylsilyl)aniline] can be obtained in 99% yield (or 88% yield based on GC) (eqs 16 and 17). 

Varney and Preston [42] discussed the measiuement of trace aromatic amines in estuary and sea water using high performance liquid chromatography. 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 behaviour of the compounds was investigated using hydrodynamic and cyclic voltammetry. Detection limits of 15 and 1.5nM... 

Doebner-von Miller reaction Condensation of an aromatic amine with an aldehyde or ketone in the presence of hydrochloric acid to form a quinoline derivative. A general method, thus aniline and ethanal give 2-methyl-quinoline (quinaldine) and p-phenetidine. 

C-alkylation of secondary and tertiary aromatic amines by hexafluoroacetone or methyl trifluoropyruvate is performed under mild conditions [172] (equation 147) The reaction of phenylhydrazme with hexafluoroacetone leads selectively to the product of the C-hydroxyalkylation at the ortho position of the aromatic ring The change from the para orientation characteristic for anilines is apparently a consequence of a cyclic transition state arising from the initial N hydroxy alky lation at the primary amino group [173] (equation 148)... 

Aniline and other aromatic amines are valuable industrial raw materials. They form an important starting point from which many of our dyestuffs, medicinals, and other valuable products are prepared. For example, you have used the indicator, methyl orange, in your laboratory experiments. Methyl orange is an example of an anQine-derived dye, although it is used more as an acid-base indicator than for dyeing fabrics. The structure of methyl orange is as follows ... 

FIGURE 6.16 Rp values of aromatic amines obtained on silica gel plate 1, 3 — isocratic development with 5 and 50% solutions of methyl ethyl ketone in cyclohexane, respectively, 2 — two-stepwise gradient development with both solvents open squares, N, N-dimethyla-niline, open triangles, iV-ethylaniline, open circles, aniline, diamonds, 2-phenylenediamine, filled squares, 3-phenylenediamine, filled triangles, 4-phenylenediamine, filled circles, 3-aminopyridine. (From Soczewinski, E. and Czapinska, K., J. Chromatogr. 168, 230-233, 1979. With permission.)... 

Then, contrary to our previous hypothesis, the reaction proceeds via a Bai2 displacement of aniline on DMC. The product, mono-A -methyl aniline (PhNHMe), plausibly adsorbs into the zeohte in a different way with respect to anihne, because different H-bonds (N H — O-zeolite) take place with the solid. As recently reported by Su et al., A-methyl amines also may interact with NaY by H-bonding between the protons of the methyl group and the oxygen atoms of the zeolite this probably forces the molecule a bit far from the catalytic surface in a fashion less apt to meet DMC and react with it. This behavior can account for the mono-A-methyl selectivity observed, which is specific to the use of DMC in the presence of alkali metal exchanged faujasites in fact, the bis-A-methylation of primary aromatic amines occurs easily with conventional methylating agents (i.e., dimethyl sulfate). ... 

More recendy, the use of MEC was also reported by us in the methylation of primary aromatic amines (P-XC6H4NH2, X = H, Cl, NO2) and of ambident anilines such as those listed in Scheme In the presence of a NaY faujasite... 

A different mode of reaction, however, is observed in photoreductions of nitroaromatics by aromatic tertiary amines. Irradiation of benzene solutions of N-methylated anilines and either m-chloronitrobenzene or 1-nitronaphthalene results in oxidative demethylation of the amines accompanied with reduction of the nitro compound to the corresponding arylamine 49). The authors suggest that hydrogen abstraction from the methyl group takes place as the primary chemical event. 

The enamine adducts formed in the reaction of aromatic amines with DMAD have been found to undergo cyclization leading to heterocyclic compounds, and the mode of these reactions is to a considerable extent influenced by the reaction conditions, the catalyst employed, and also the nature of the functional groups present in the starting amine. The reaction of aniline with methyl propiolate in presence of cuprous acetate, for example, is reported to give a mixture of 2(lH)-quinolone (1) and 4(l//)-quinolone (2) [Eq. (1)]." On the other hand, dimethyl anilinofumarate (3), formed from aniline with DMAD, undergoes... 

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