Coupling primary aromatic amines

Some reference to the use of nitrous acid merits mention here. Primary aromatic amines yield diazonium compounds, which may be coupled with phenols to yield highly-coloured azo dyes (see Section IV,100,(iii)). Secondary aromatic amines afford nitroso compounds, which give Liebermann a nitroso reaction Section IV,100,(v). Tertiary aromatic amines, of the type of dimethylaniline, yield p-nitroso derivatives see Section IV,100,(vii). ... 

Dyes. Sodium nitrite is a convenient source of nitrous acid in the nitrosation and diatozation of aromatic amines. When primary aromatic amines react with nitrous acid, the intermediate diamine salts are produced which, on coupling to amines, phenols, naphthols, and other compounds, form the important azo dyes (qv). The color center of the dye or pigment is the -N=N- group and attached groups modify the color. Many dyes and pigments (qv) have been manufactured with shades of the entire color spectmm. 

Synthesis. Almost without exception, azo dyes ate made by diazotization of a primary aromatic amine followed by coupling of the resultant diazonium salt with an electron-rich nucleophile. The diazotization reaction is carried out by treating the primary aromatic amine with nitrous acid, normally generated in situ with hydrochloric acid and sodium nitrite. The nitrous acid nitrosates the amine to generate the N-nitroso compound, which tautomerizes to the diazo hydroxide. 

Primary aromatic amines are first diazotized and then coupled to yield azo dyestuffs [4],... 

Discussion. The formation of coloured compounds by coupling phenols with diazotised primary aromatic amines has long been recognised as a method of determining phenols, and procedures have been evolved whereby the phenol solution is titrated with a diazonium solution which has been calibrated against known concentrations of the phenol. The resultant reaction products are coloured, but many are only sparingly soluble in water and organic solvents and do not therefore lend themselves to colorimetric determination. 

Diarylamines couple with considerably more difficulty than alkylarylamines. In contrast to primary aromatic amines and alkylarylamines, dialkylarylamines are substituted by diazonium ions only in the 4-, not in the 2-position. This is due to the considerable sensitivity of azo coupling reactions to steric hindrance. 

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). 

Diazoamino compounds, (LXIII) produced by coupling a diazonium ion with a primary aromatic amine, viz. 

Coupling reactions with diazonium salts to yield intensely colored azo derivatives have often been used for the detection of phenols, primary aromatic amines and electron-rich heterocyclics. 

Primary aromatic amines are first diazotized by the action of sodium nitrite in acid solution and then coupled, for instance, with 1-naphthol to form azo dyes (cC Bratton-Marshall reagent, Vol. 1 a). ... 

In the presence of acids, sulfanilic acid — like other primary aromatic amines — reactt with nitrite to yield a diazonium compound that can couple with a suitable aromatic amine to yield an azo dye. 

N-Alkylation of primary aromatic amines increases their nucleophilic character, making them couple much more readily, the introduction of the azo group occurring in the 4-position. Thus, in contrast to aniline, N-methylaniline couples readily and N,N-dimethyl-aniline very readily with simple diazonium salts. Diphenylamine also couples in the 4-position, but less readily than N-methylaniline. 

Of some importance as textile dyes are aza analogues of polymethine (cyanine) dyes. Azacarbocyanines result when Fischer s aldehyde is heated with primary aromatic amines. Thus Cl Basic Yellow 11 (6.220) is obtained when Fischer s aldehyde is condensed with 2,4-dimethoxyaniline. The equivalent reaction with 2-methylindoline gives Cl Basic Yellow 21 (6.221), which has superior light fastness but has been classified by ETAD as toxic [73]. The tinctorially strong golden yellow diazacarbocyanine dye Cl Basic Yellow 28 (6.222) is prepared by coupling diazotised p-anisidine with Fischer s base (6.223), followed by quaternisation with dimethyl sulphate. Some triazacarbocyanine dyes are also used commercially. 

Azo pigments are typically formed by a reaction sequence of diazotization and coupling, involving a primary aromatic amine, which is referred to as a diazo component, and a nucleophilic aromatic or aliphatic compound with active methylene groups as a coupling component [1-3]. 

A sample of the reaction mixture should not become turbid when sodium acetate solution is added. But if now a few drops of a solution of an aniline salt are poured in, there is precipitated yellow diazoaminobenzene, which can be re-dissolved with concentrated hydrochloric acid after a few small pieces of ice have been added. Further, when a few particles of j8-naphthol or of R-acid are dissolved in a small excess of 2 A-sodium hydroxide solution and a sample of the diazo-solution is added, an intense red colour is produced. The development of this colour, which results from coupling , is an infallible test for a diazonium salt, and hence also for the corresponding primary aromatic amine. 

As we have already seen in the case of aniline, primary aromatic amines do not couple normally a triazene derivative, diazoamino-benzene, is produced by linkage through the NH2-group just as in the case of aliphatic amines, e.g. dimethylamine ... 

Brede, C., Skjevrak, I. and Herikstad, H. (2003). Determination of primary aromatic amines in water food simulant using solid-phase analytical derivatization followed by gas chromatography coupled with mass spectrometry, J. Chrom. A, 983, 35-42. 

The primary aromatic amines which will be preferentially nitrosated rather than diazotized are those which do not bear strongly electron-withdrawing substituents and are capable of coupling with diazonium salts to give azo dyes. 

Almost without exception, azo dyes are made by diazotization of a primary aromatic amine followed by coupling of the resultant diazonium salt with an electron-rich nucleophile. 

Azo dyes, characterized by the presence of one or more azo groups (-N=N-), are the most commercially important class of dyes. These compounds are synthesized using a diazoti-zation reaction in which a primary aromatic amine reacts with nitrous acid to form a diaz-onium salt. The diazonium compound then typically is coupled with phenols, napthols, aromatic amines, heterocycles, or a variety of other compounds containing active methylene groups. Azo dyes are used in acid, direct, disperse, fiber reactive, and mordant applications. 

Primary aromatic amines react with nitrous acid to give aryldiazonium ions, ArN2+, which are useful intermediates in synthesis of aromatic compounds. The process by which they are formed is called diazotization. The nitrogen in these ions can readily be replaced by various nucleophiles (OH, Cl, Br, I, CN). Diazonium ions couple with reactive aromatics, such as amines or phenols, to form azo compounds, which are useful as dyes. 

Tetraphenylethylene cyclizes anodically to 9,10-diphenylphenanthrene analogously to its photooxidative cyclization. The attempted anodic cyclization of cis- or frans-stilbene to phenanthrene however failed due to electrophilic reaction of the intermediate radical cation with the solvent 37S Primary aromatic amines are oxidized to radical cations which, depending on the pH of the electrolyte couple to aminodiphenylamines (C-N coupling (84) in Eq. (172) ), yield benzidines (85) at low pH (C-C coupling) or dimerize to hydrazobenzene (86) (N-N coupling) which is subsequently oxidized to azobenzene (Eq. (172) ) 2 5,376,377)... 

Aryldiazonium salts are weak electrophiles. Consequently, they undergo Ar-SE reactions via sigma complexes (azo couplings) only with the most strongly activated aromatic compounds. Only phenolates and secondary and tertiary aromatic amines react with them. Primary aromatic amines react with diazonium salts, too, but via their N atom. Thus, triazenes, that is, compounds with the structure Ar—N=N—NH—Ar are produced. Phenol ethers or nonde-protonated phenols can react with aryldiazonium salts only when the latter are especially good... 

All classical azo reds contain at least one azo group, by definition, and are all produced by a similar reaction sequence involving the chemical reaction termed dia-zotization followed by coupling. Diazotization involves reacting a primary aromatic amine with nitrous acid to yield a diazonium salt, which is then immediately coupled to the other half of the molecule to yield the colored pigment as a bright red precipitate. 

Salts of primary aromatic amines react with nitrous acid to produce diazonium salts. The reaction is usually performed by adding a cold solution of sodium nitrite to a cold solution of the arylamine in aqueous mineral acid. The end point of the reaction is conveniently determined by the detection of excess nitrous acid with potassium iodide-starch paper. Sulfamic acid has long been used both in industry and in the laboratory to remove excess nitrous acid. It has been found to react with the more active diazo compounds. In most cases, high temperatures are avoided to prevent the formation of phenols and the decomposition of the unstable nitrous acid. An excess of mineral acid is necessary to prevent coupling between the diazonium salt and unreacted amine (cf. method 494). If the amine salt is somewhat insoluble, a fine crystalline form, which is produced by rapid crystallization from a warm aqueous solution, may be employed. ... 

Azoic dyes. Azo dyes contain at least one azo group (—N=N—) attached to one or often two aromatic rings. They are produced in textile fibers (usually cotton, rayon, and polyester), by diazotization of a primary aromatic amine followed by coupling of the resulting diazonium salt with an electron-rich nucleophile (azo coupling). A variety of hues can be obtained... 

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