2-aminobenzene-, sodium

Heavily fluonnated aminobenzenes, pyridines, and pyrimidines are diazotized in strong-acid media Solid sodium nitrite added directly to the fluonnated amine dissolved in 80% hydrofluonc acid, anhydrous hydrogen fluoride, or (1 1 wt/wt) 98% sulfuric acid in (86 14 wt/wt) acetic and propionic acids affords the electrophilic fluoroarenediazonium ion Addition of an electron rich aromatic to the resultant diazonium solution gives the fluoroareneazo compound [10 II] (equa tions 9 and 10)... 

By heating the diacetyl compound with sodium hydroxide solution partial saponification of the acetyl groups takes place. 25.6 grams of diacetyl compound are heated to boiling for some hours with 100 cc of 2 N sodium hydroxide solution. The precipitate produced by acidification of the solution with acetic acid is filtered off and treated with dilute sodium carbonate solution. The 4-aminobenzene-sulfonacetylamide passes into solution while the simultaneously formed 4-acetylaminobenzene-sulfonamide remains undissolved. It is filtered with suction and the filtrate again acidified with acetic acid. The 4-aminobenzene-sulfon-acetamide separates out and is recrystallized from water. It forms colorless lustrous rhombic crystals Of MP 1B1°C. 

Benzothiadiazole 1,1-dioxide can be conveniently assayed and characterized without isolation by forming its adduct with cyclopentadiene.5 The following procedure illustrates characterization, for assay the same procedure can be applied to an aliquot, with all amounts scaled down in proportion. The dried ether extract of 1,2,3-benzothiadiazole 1,1-dioxide prepared from 1.43 g (0.0080 mole) of sodium 2-aminobenzene-sulfinate is concentrated to about 20 ml at 0°, and 20 ml. of acetonitrile at —20° is added. Twenty milliliters of cold, freshly prepared cyclopentadiene6 is added The mixture is kept overnight at —10° to 0°. Solvent and excess cyclopentadiene are removed by evaporation at 0° under reduced pressure to leave 1.20-1.28 g. (64-68% based on sodium 2-aminobenzenesulfinate) of crude 1-1 adduct, mp. 87° (dec.). For purification it is dissolved in 20 ml. of methylene chloride, 70 ml. of ether is added, and the solution is kept at —70°. Adduct decomposing at 90° crystallizes recovery is about 75%. From pure, crystalline 1, 2, 3-benzothiadiazole 1,1-dioxide the yield of adduct is 92-98%. 

Sulfuric acid as a reaction medium may be replaced by glacial acetic acid or by a mixture of glacial acetic acid/nitrosylsulfuric acid. In the former case, half-concentrated hydrochloric acid is added, and diazotization proceeds in an aqueous sodium nitrite solution. The combination of glacial acetic acid/nitrosylsulfuric acid is a particularly useful medium for the bisdiazotization of 1,2-, 1,3-, or 1,4-di-aminobenzenes (phenylenediamines). 

Once the 3-amino-2,4-diketonate has been prepared, it then shows reactivity typical of an aminobenzene derivative. For example, reaction with nitrous acid and sodium fluoride allows the formation of the 3-fluoro derivative in a Sandmeyer reaction (Fig. 5-10). This may usefully be compared to the reaction sequence from conventional aromatic chemistry... 

Bis[4-methoxyphenyl] Tellurium Uichloride1 A 0.2 molar solution of 4-methoxybenzenediazonium chloride is prepared from 24.6 g (0.23 mol) of aminobenzene, 150 m/ of half concentrated hydrochloric acid, and 14 g (0.21 mol) of sodium nitrite in 20 ml of water. To the cooled and vigorously stirred dia/onium salt solution are added 27 g(0.1 mol) of tellurium tetrachloride or 16 g (0.1 mol) of tellurium dioxide dissolved in 75 ml of concentrated hydrochloric acid. The temperature of the reaction mixture must not exceed — 5° during this addition. The mixture is stirred at — 5° for 20 min and then filtered. The filter cake is washed carefully with three 50 ml portions of acetone, then with diethyl ether, and finally with petroleum ether. The product, bi 4-methoxybenzenediazonium] hexachlorotellurale, is dried in air yield 52.8 g (86%). 

It has been found possible to construct the 1,4-benzothiazine ring by direct interaction of bis-(2-aminobenzene) disulfide (96) with carbonyl compounds.139,140 The reaction is most efficient when conducted under a nitrogen atmosphere with a 1 1 ratio of reactants otherwise, the principle products are benzothiazoles. While reduction of the benzothiazine 97 with sodium borohydride gives a stable dihydro derivative, the unsaturated benzothiazines themselves were prone to autoxidation, giving rise to benzothiazoles and benzothiazine sulfoxides.141... 

At high temperature, ethyl nitrate would react with hydrazinobenzene to produce aminobenzene, ammonium nitrate, and ammonium. If sodium ethoxide is used in the reaction, even at high temperature, the products would not include nitrous acid ions, nitrogen, benzene, phenyl azide, azobenzene, nitrobenzene, aminobenzene, acetic acid, and aldehyde. 

See Sodium C14-17 alkyl sec sulfonate Sulfonic acids, C14-C18-alkane hydroxy and C14-C18-alkene, sodium salts. See Sodium C14-18 olefin sulfonate Sulfonic acids, C9-C22-sec-alkane, sodium salts. See Sodium C9-22 alkyl sec sulfonate Sulfonic acids, petroleum, barium salts. See Barium petroleum sulfonate Sulfonic acids, petroleum, calcium salts. See Calcium petroleum sulfonate Sulfonic acids, shale oil, sodium salts. See Sodium shale oil sulfonate Sulfonphthal. See Phenol red 1,1 -Sulfonylbis (4-aminobenzene). See 4,4 -Diaminodiphenyl sulfone 3,3 -Sulfonylbis (aniline). See 3,3 -Diaminodiphenyl sulfone 4,4 -Sulfonylbisaniline 4,4 -Sulfonylbisbenzamine p,p-Sulfonylbisbenzamine p,p-Sulfonylbisbenzenamine. See 4,4 -Diaminodiphenyl sulfone 1,1 -Sulfonylbisbenzene. See Diphenyl sulfone... 

Acetal Acetamide Acetone sodium bisulfite Acetophenone Aconitic acid Acrylonitrile Adipamide Alcohol Alloxan monohydrate Allyl amine Allyl anthranilate 2-Aminobenzene sulfonic acid 4-Amino-4 -hydroxy-3-methyldiphenylamine Aminomethyl propanediol Aminomethyl propanol Ammonium hydroxide Arachidic acid Arsine Azelaic acid Benzil... 

Then, using radiolabeled ( C) bromobenzene (CeHsBr), it was shown that the aniline (aminobenzene, C6H5NH2) resulting from the reaction with sodium amide in liquid ammonia was a 1 1 mixture of ipso- and ortho-[ Ci]-anihnes (aminoben-zenes) (Equation 7.65). 

Similarly, naphthols and other phenolic aromatics also undergo substitution with the same set of electrophilic reagents as phenol and simple substituted phenols. Thus, as shown in Equation 8.32,1-naphthol (a-naphthol) reacts with the potent electrophilic benzenediazonium ion (generated from aminobenzene [aniline] and sodium nitrite [NaN02] in acid solution and is written here as the tetralluoroborate [BF4 ] salt) to produce the corresponding brightly colored phenyldiazonaphthale-nol, in which substitution has occurred para to the hydroxyl. 

Aminobenzene, generally known by its common name aniline (p.243), can be treated wath nitrous add (HONO) or its sodium salt (Na ONO) and HCl, to produce benzenediazonium chloride, which is explosive when dry, but a relatively safe material when wet (Rg. 14.50). A molecule of the structure R—N2 is called a diazomum ion. We win soon use them in a number of important reactions. 

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