Naphthylamines sulfonation

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... 

Congo red org chem C32H22N5Na205S2 An azo dye, sodium diphenyldiazo-bis-a-naphthylamine sulfonate, used as a biological stain and as an acid-base indicator it is red in alkaline solution and blue in acid solution. kag-go red ... 

Naphthoquinone has been prepared by the oxidation of naphthalene,1 1,4-aminonaphthol,2 1,4-naphthylene diamine,2 and 1,4-naphthylamine sulfonic acid.3 Recent work4 has shown that the oxidation of the 1,4-aminonaphthol is the most convenient method of preparation. 

When a single product is sought, the baking reaction is often employed (Fig. 13.60). In this process, the sulfate salt of aniline is prepared, dried, and then baked in an oven under vacuum. The product in this case is the important dye intermediate, sulfanilic acid. Similarly, naphthylamine sulfonic acid can be produced, and if the para-position is occupied, sulfonation of an ort/m-position occurs (Fig. 13.61). 

Arylamines that contain an acid group (sulfo or carboxyl) are diazotized by the so-called indirect method . They are dissolved in aqueous alkali, treated with a solution of the calculated amount of sodium nitrite, and dropped into an excess of acid the diazonium salt then usually separates as a solid. This method has been used with success for diazotizing aminobenzoic acid and aniline- and naphthylamine-sulfonic acids weakly basic amines such... 

OTHER COMMENTS used in the manufacture of phthalic and anthranilic acids, naphthols, naphthylamines, sulfonic acid and similar compounds used in the dye industry used... 

Anisotropy of a Libeled Protein Naphthylamine sulfonic acids are widely used as extrinsic labels of proteins. A number of doivtUives are available. One little known but particularly useful dmvatlve Is 2-diethylamino-S-... 

Naphtholsulfonic acid - 402, 409 Naphthoquinone - 201 Naphthylamine sulfonic acid - 201 Naphthylbenzene - 832... 

Bronner sacid orgchem CioH6(NH2)S03H A colorless, water-soluble naphthylamine sulfonic acid that forms needle crystals used in dyes. Also spelled Broenner s acid. bren-orz as-ad ... 

By direct sulfonation of 1-naphthylamine, four of the seven possible 1-naphthylamine-sulfonic acids may be formed. The main product under proper conditions is the 1,4-isomer. Direct sulfonation of 2-naphthyl-amine yields primarily a mixture of 2,5- and 2,8-isomers. 

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. 

Llthol Reds. Lithol Red or Pigment Red 49 1/7103-38-4] is one of the most important of the precipitated salt pigments. They comprise a family of sodium (PR 49), barium (PR 49 1), calcium (PR 49 2), and strontium (PR 49 3) salts of dia2oti2ed Tobias acid or 2-naphthylamine-l-sulfonic acid coupled with 2-naphthol. The most popular are the barium and calcium salts, the former being yellower in shade. These reds are used where brightness, bleed resistance, and low cost ate of primary importance. They are neither resistant to heat nor chemicals, and are used primarily in printing inks and some inexpensive air-dried industrial paints where good durabiUty is not requited. 

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])... 

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 ... 

Bake sulfonation is an important variant of the normal sulfonation procedure. The reaction is restricted to aromatic amines, the sulfate salts of which ate prepared and heated (dry) at a temperature of approximately 200°C in vacuo. The sulfonic acid group migrates to the ortho or para positions of the amine to give a mixture of orthanilic acid [88-21-1] and sulfanilic acid [121 -57-3] respectively. This tendency is also apparent in polynuclear systems so that 1-naphthylamine gives 1-naphthy1amine-4-su1fonic acid. 

Naphthylamine-6-sulfonic acid [93-00-5] M 223.3, m >200 (dec). Crystd from a large volume of hot water. 

Badflfissigkeit, /. bath liquid, bath solution. Badian, m. Chinese anise, star anise, badian Illicium verum). -ol, n. star anise oil. badisch, a. of Baden. — badische Saure, badische acid, 2-naphthylamine-8-sulfonic acid. 

The best source of information on preparative aspects of coupling reactions is still the book of Fierz and Blangey (1952). Four examples of coupling reactions can be found in Organic Syntheses (Conant et al., 1941, and Fieser, 1943 Azo coupling with 1- and 2-naphthol Hartwell and Fieser, 1943 8-Hydroxy-l-naphthylamine-2,4-di-sulfonic acid Clarke and Kirner, 1941 A/,7V-Dimethylaniline). 

Boldyrev and Grivnak (1984) reported that 4-nitrobenzenediazothiosulfonic acid adducts (4-N02 — C6H4 — N2 — S — S02 — Ar ), which were obtained by reaction of 4-nitrobenzenediazonium salts with benzene- and 4-toluenethiosulfonic acid salts (Ar — S02 — S K+), form azo compounds with 2-naphthol and 1-naphthylamine-4-sulfonic acid. 

Bagal et al. (1975) investigated in more detail the role of donor-acceptor complexes in the azo coupling reaction of the 4-nitrobenzenediazonium ion with 2-naphthylamine-3,6-disulfonic acid and that of the 4-chlorobenzenediazonium ion with 2-naphthol-6-sulfonic acid. Their kinetic results are, as would be expected, compatible with the mechanisms shown in Schemes 12-74 or 12-75. 

The development of azo pigment lakes was initiated by the discovery of Lithol Red by Julius (BASF) in 1899. Lithol Red, which is synthesized by an indirect diazotization procedure using 2-naphthylamine-l-sulfonic acid as a diazonium compound, was initially employed in the form of its calcium and barium salts, which were precipitated onto inorganic carrier materials. The pigment was used in its pure form after it became apparent that the carriers contribute very little to the application properties of the product. Lithol Red is one of the earliest colorant developed specifically for application as pigment. 

M acid ORG chem NH2CioH5(OH)S03H A sulfonic acid formed by alkaline fusion of a disulfonic acid of a-naphthylamine used as a dye intermediate. em, as-3d Macquer s salt See potassium arsenate. mo kerz, s6lt ... 

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. 

An early example of a monosubstituted stilbene was introduced by Geigy as Tinopal RBS (89) and used for cotton and polyamide (nylon). Conversion of the sulfonic acid group into A-ethylsulfonamide, via the sulfonyl chloride, yields an FBA for polyester and plastics (55USP2713057). The triazole ring is formed by diazotization of the 4-aminostilbene followed by coupling with 2-naphthylamine and oxidation with ammoniacal copper(II) sulfate, occasionally in pyridine (21CB2191). 

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