Of anthraquinone

It is prepared by acidifying an alkali solution of anthrone or by reduction of anthraquinone with aluminium powder and concentrated sulphuric acid. 

Reduction of anthraquinone gives dianthryl, anthrone and finally anthracene. 

Prepared by condensing p-chlorophenol with phlhalic anhydride in sulphuric acid solution in the presence of boric acid. The chlorine atom is replaced by hydroxyl during the condensation. It can also be prepared by oxidation of anthraquinone or 1-hydroxyanthraquinone by means of sulphuric acid in the presence of mercury(ll) sulphate and boric acid. 

Reduction of anthraquinone with tin and concentrated hydrochloric acid in the presence of boiling glacial eicetic acid gives anthrone this substance (keto form) under certain conditions passes into the enol form, anthranol ... 

Place 52 g, of anthraquinone, 50 g. of granulated tin and 375 ml. of glacial acetic acid in a 1 htre round-bottomed flask fitted with a reflux condenser. Heat the contents of the flask to boihng and add 125 ml, of... 

Many aromatic compounds are sufficiently basic to be appreciably protonated in concentrated sulphuric acid. If nitration occurs substantially through the free base, then the reactivity of the conjugate acid will be negligible. Therefore, increasii the acidity of the medium will, by depleting the concentration of the free base, reduce the rateof reaction. This probably accounts for the particularly marked fall in rate which occurs in the nitration of anthraquinone, benzoic acid, benzenesulphonic acid, and some nitroanilines (see table 2.4). 

WorkingS olution Regeneration and Purification. Economic operation of an anthraquinone autoxidation process mandates fmgal use of the expensive anthraquinones. During each reduction and oxidation cycle some finite amount of anthraquinone and solvent is affected by the physical and chemical exposure. At some point, control of tetrahydroanthraquinones, tetrahydroanthraquinone epoxides, hydroxyanthrones, and acids is required to maintain the active anthraquinone concentration, catalytic activity, and favorable density and viscosity. This control can be by removal or regeneration. 

When sublimed, anthraquinone forms a pale yeUow, crystalline material, needle-like in shape. Unlike anthracene, it exhibits no fluorescence. It melts at 286°C and boils at 379°—381°C. At much higher temperatures, decomposition occurs. Anthraquinone has only a slight solubiUty in alcohol or benzene and is best recrystallized from glacial acetic acid or high boiling solvents such as nitrobenzene or dichlorobenzene. It is very soluble in concentrated sulfuric acid. In methanol, uv absorptions of anthraquinone are at 250 nm (e = 4.98), 270 nm (4.5), and 325 nm (4.02) (4). In the it spectmm, the double aUyflc ketone absorbs at 5.95 p.m (1681 cm ), and the aromatic double bond absorbs at 6.25 p.m (1600 cm ) and 6.30 pm (1587 cm ). 

Depending on experimental conditions, sodium borohydride reduction of anthraquinone, in a lower ahphatic alcohol, results in 9,10-dihydroxyanthracene... 

Use of mercuric catalysts has created a serious pollution problem thereby limiting the manufacture of such acids. Other catalysts such as palladium or mthenium have been proposed (17). Nitration of anthraquinone has been studied intensively in an effort to obtain 1-nitroanthraquinone [82-34-8] suitable for the manufacture of 1-aminoanthraquinone [82-45-1]. However, the nitration proceeds so rapidly that a mixture of mono- and dinitroanthraquinone is produced. It has not been possible, economically, to separate from this mixture 1-nitroanthraquinone in a yield and purity suitable for the manufacture of 1-aminoanthraquinone. Chlorination of anthraquinone cannot be used to manufacture 1-chloroanthraquinone [82-44-0] since polychlorinated products are formed readily. Consequentiy, 1-chloroanthraquinone is manufactured by reaction of anthraquinone-l-sulfonic acid [82-49-5] with sodium chlorate and hydrochloric acid (18). 

A 95% yield of pure anthraquinone was obtained. This is an almost quantitative yield based on the 100% content of the anthracene used. The cmde anthraquinone was then purified. To a jacketed steel kettie, provided with an agitator, was added cmde anthraquinone and nitrobenzene. Under agitation, the charge was heated at 130—140°C until a complete solution resulted. Under slow agitation, the solution was cooled to 30 °C and the resulting slurry of anthraquinone was filtered on a pressure filter. The cake was washed twice with nitrobenzene, then was reslurried on the filter with nitrobenzene, sucked dry, and transferred to a vacuum dryer where the nitrobenzene was distilled. The dried anthraquinone was discharged to suitable containers. A 99% yield of pure anthraquinone was obtained equal to a recovery of approximately 90% based on the cmde anthraquinone. 

In Europe, where an abundant supply of anthracene has usually been available, the preferred method for the manufacture of anthraquinone has been, and stiU is, the catalytic oxidation of anthracene. The main problem has been that of obtaining anthracene, C H q, practically free of such contaminants as carbazole and phenanthrene. Many processes have been developed for the purification of anthracene. Generally these foUow the scheme of taking the cmde anthracene oil, redistilling, and recrystaUizing it from a variety of solvents, such as pyridine (22). The purest anthracene may be obtained by azeotropic distillation with ethylene glycol (23). 

A continuous process has been described for the manufacture of anthraquinone by the Diels-Alder reaction (49). 

Mechanism of Anthraquinone Acceleration. The mechanism for the dual function of AQ has been the subject of much research (29). Anthraquinone is an effective pulping accelerator in very small quantities and functions as a catalyst in the process. It is generally accepted that AQ functions in a complex redox sequence. 

S oda—Anthraquinone. A few mills worldwide use soda pulping of hardwoods. In such cases, the addition of anthraquinone is immediately justifiable in terms of increased yield and upgraded pulp quaHty. The conversion of existing kraft mills is not as simple because AQ contributes no alkalinity to the process as sulfide does, and most kraft causticizing systems would have to be expanded by about 33%. This conversion is probably not justifiable in terms of the yield gain. The greatest benefit from AQ is for new mills in which expenditures for air pollution abatement devices can be reduced. 

Dyes, Dye Intermediates, and Naphthalene. Several thousand different synthetic dyes are known, having a total worldwide consumption of 298 million kg/yr (see Dyes AND dye intermediates). Many dyes contain some form of sulfonate as —SO H, —SO Na, or —SO2NH2. Acid dyes, solvent dyes, basic dyes, disperse dyes, fiber-reactive dyes, and vat dyes can have one or more sulfonic acid groups incorporated into their molecular stmcture. The raw materials used for the manufacture of dyes are mainly aromatic hydrocarbons (67—74) and include ben2ene, toluene, naphthalene, anthracene, pyrene, phenol (qv), pyridine, and carba2ole. Anthraquinone sulfonic acid is an important dye intermediate and is prepared by sulfonation of anthraquinone using sulfur trioxide and sulfuric acid. 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Heterocyclic Azo Dyes. One long-term aim of dyestuffs research has been to combine the brightness and high fastness properties of anthraquinone dyes with the strength and economy of azo dyes. This aim is now being realized with heterocychc azo dyes, which fall into two main groups those derived from heterocychc coupling components, and those derived from heterocychc diazo components. 

In 1894 the first two anthraquinone acid dyes. Cl Acid Violet 43 [4430-18-6] (2) (Cl 60730) and Cl Acid Green 25 [4403-90-1] (3) (Cl 61570) were invented. This encouraged the subsequent development of various kinds of anthraquinone acid dyes, which were used to dye wool in fast, brilliant shades without need for pretreatment. 

In 1901, mercury cataly2ed a-sulfonation of anthraquinone was discovered, and this led to the development of the chemistry of a-substituted anthraquinone derivatives (a-amino, a-chloro, a-hydroxy, and a,a -dihydroxyanthraquinones). In the same year R. Bohn discovered indanthrone. Afterward flavanthrone, pyranthrone, and ben2anthrone, etc, were synthesi2ed, and anthraquinone vat dyes such as ben2oylaniinoanthraquinone, anthrimides, and anthrimidocarba2oles were also invented. These anthraquinone derivatives were widely used to dye cotton with excellent fastness, and formed the basis of the anthraquinone vat dye industry. 

The appearance of synthetic fibers in the 1920s accelerated the further development of anthraquinone dyes. Soon after British Celanese succeeded in commerciali2ing cellulose acetate fiber in 1921, anthraquinone disperse dyes for this fiber were invented by Stepherdson (British Dyestuffs Corp.) and Celatenes (Scottish Dyes) independendy. Anthraquinone disperse dyes for polyester fiber were developed after the introduction of this fiber by ICI and Du Pont in 1952. These dyes were improved products of the disperse dyes that had been developed for cellulose acetate fiber 30 years before. 

In the 1950s acid dyes were successively developed to dye nylon carpet with excellent fastness and uniform leveling. Development of polyacrylonitrile fiber stimulated the invention of anthraquinone basic dyes, modified disperse dyes in which quaternary ammonium groups are introduced. 

Production of anthraquinone reactive dyes based on derivatives of bromamine acid (8) was first commercialized in 1956. Some improvements have been made and now they ate predominandy used among the reactive blue dyes. Cl Reactive Blue 19 [2580-78-1] (9) (Cl 61200) (developed by Hoechst in 1957) has the greatest share among them including dye chromophores other than anthraquinones. 

The manufacturing process of anthraquinone vat dyes is more compHcated, and, in the extreme case of Cl Vat Blue 64 [15935-52-1] (12) (Cl 66730), requites 11 steps starting from phthaUc anhydride. 

World dye manufacturers have already begun to develop new types of dyes that can replace the anthraquinones technically and economically (1). Some successful examples can be found in a2o disperse red and blue dyes. Examples are brilliant red [68353-96-6] and Cl Disperse Blue 165 [41642-51 -7] (Cl 11077). They have come close to the level of anthraquinone reds and blues, respectively, in terms of brightness. In the reactive dye area intensive studies have continued to develop triphenodioxa2ine compounds, eg, (13), which are called new blues, to replace anthraquinone blues. In this representation R designates the substituents having reactive groups (see Dyes, reactive). 

In addition to the color and the tinctorial strength, which ate very important factors for the molecular design of anthraquinone dyes, affinity for fibers, various kinds of fastness (light, wet, sublimation, nitrogen oxides (NO ) gas, washing, etc), and apphcation properties (sensitivity for dyeing temperature, pH, etc) must be considered thoroughly as well. 

Nitroanthraquinone is prepared from anthraquinone by nitration in sulfuric acid (11), or in organic solvent (12). Nitration in nitric acid is dangerous. The mixture of anthraquinone and nitric acid forms a Sprengel mixture (13,14) which may detonate. However, detonation can be prevented by a dding an inert third component such as sulfuric acid. Experimental results of the steel-tube detonation tests for the anthraquinone—HNO2—H2SO4 system have been pubUshed (13). 

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