Hydroquinone process

The hydroquinone process was developed by BASF [12]. Hydroquinone-2,5-di-carboxylic acid is prepared by a modified Kolbe-Schmidt synthesis from hydroquinone and carbon dioxide. Subsequent reaction with arylamine in an aqueous-methanolic suspension in the presence of an aqueous sodium chlorate solution and a vanadium salt affords the product in good yield  

Subsequent ring closure of the 2,5-diarylamino-1,4-benzoquinone-3,6-dicarboxylic acid (61) is performed in concentrated sulfuric acid (or with thionyl chloride/ni-trobenzene) to afford the linear trans-quinacridone quinone 62. 

62 is also a component in mixed crystal phases with quinacridones, types of which are commercially available (Sec. 3.2.4). Quinacridone quinone is reduced with zinc or aluminum powder in dilute sodium hydroxide solution, in an aluminum chloride/urea melt, or in sulfuric/phosphoric acid under pressure to form quinacridone. There are certain disadvantages to this method in view of the fact that hydroquinone is relatively expensive, quinacridone is not easily reduced, and ecological problems prevail (wastewater pollution). 

To summarize this discussion, the two latter methods have failed to gain the commercial recognition which is enjoyed by the first two processes (Sec. 3.2.1.1 and 3.2.1.2). 

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Direct production of benzoquinone (BQ) from benzene is one of the targets in industrial chemistry. Considerable efforts have been made to develop the electrochemical oxidation of benzene to p-benzoquinone to the industrial scale thus forming a basis for a new hydroquinone process [40]. Benzene in aqueous emulsions containing sulfuric acid (1 1 mixture of benzene and 10% aqueous H2S04) forms, at the anode, p-benzoquinone which can be reduced cathodically to yield hydroquinone in a paired synthesis. A divided cell with Pb02 anodes is used. 

Although considered an active participant in the process cycle, the tetrahydroaLkylanthraquinone (10) may not be a significant part of the catalytic hydrogenation because, dependent on the concentration in the working solution, these could all be converted to the hydroquinone by the labile shift per equation 17 and not be available to participate. None of the other first- or second-generation anthraquinone derivatives produce hydrogen peroxide, but most are susceptible to further reaction by oxidative or reductive mechanisms. 

During the 1980s few innovations were disclosed in the Hterature. The hydroxylation of phenol by hydrogen peroxide has been extensively studied in order to improve the catalytic system as well as to master the ratio of hydroquinone to catechol. Other routes, targeting a selective access to one of the dihydroxyben2enes, have appeared. World production capacities according to countries and process types are presented in Table 1. 

Aniline Oxidation. Even though this is quite an old process, it still has limited use to produce hydroquinone on a commercial scale. In the first step, aniline is oxidized by manganese dioxide in aqueous sulfuric acid. The resulting benzoquinone, isolated by vapor stripping, is reduced in a second step by either an aqueous acidic suspension of iron metal or by catalytic hydrogenation. 

The yield of hydroquinone is 85 to 90% based on aniline. The process is mainly a batch process where significant amounts of soHds must be handled (manganese dioxide as well as metal iron finely divided). However, the principal drawback of this process resides in the massive coproduction of mineral products such as manganese sulfate, ammonium sulfate, or iron oxides which are environmentally not friendly. Even though purified manganese sulfate is used in the agricultural field, few solutions have been developed to dispose of this unsuitable coproduct. Such methods include MnSO reoxidation to MnO (1), or MnSO electrochemical reduction to metal manganese (2). None of these methods has found appHcations on an industrial scale. In addition, since 1980, few innovative studies have been pubUshed on this process (3). 

Hydroperoxidation of m- or />Diisopropylbenzene. This is an important industrial route to resorcinol and hydroquinone. The process in principle is identical to the cumene process for the manufacturing of phenol (qv). 

Resorcinol or hydroquinone production from m- or -diisopropylben2ene [100-18-5] is realized in two steps, air oxidation and cleavage, as shown above. Air oxidation to obtain the dihydroperoxide (DHP) coproduces the corresponding hydroxyhydroperoxide (HHP) and dicarbinol (DC). This formation of alcohols is inherent to the autooxidation process itself and the amounts increase as DIPB conversion increases. Generally, this oxidation is carried out at 90—100°C in aqueous sodium hydroxide with eventually, in addition, organic bases (pyridine, imidazole, citrate, or oxalate) (8) as well as cobalt or copper salts (9). 

This process has been widely studied and led to the constmction of new and original industrial units. Interest in the reaction stems from the simplicity of the process as well as the absence of undesirable by-products. However, in order to be economically rehable, such a process has to give high yield of dihydroxybenzenes (based on hydrogen peroxide as well as phenol) and a great flexibiUty for the isomeric ratio of hydroquinone to catechol. This last point generated more research and led to original and commercial processes. 

The yield of hydroquinone based on bisphenol A is close to 90%. The phenol and the acetone formed can easily be recycled. However, this process has not been industrialized. 

Hydroquinone and catechol are important industrial intermediates, and there has been significant research and development of processes for manufacturing their derivatives. 

The synthesis of chlorarul [118-75-2] (20) has been improved. The old processes starting from phenol or 2,4,6-trichlorophenol have been replaced by new ones involving hydroquinone chlorination. These processes allow the preparation of chlorarul of higher purity, avoiding traces of pentachlorophenol. Different types of chlorination conditions have been disclosed. The reaction can be performed according to the following stoichiometry, operating with chlorine in aqueous acetic acid (86,87), biphasic medium (88), or in the presence of surfactants (89). 

Phthahc resins are usually processed to an acid number of 25—35, yielding a polymer with an average of 1800—2000. The solution viscosity of the polymer is usually followed to ascertain the polymer end point. The resin is cooled to 150°C and hydroquinone stabilizer (150 ppm) is added to prevent premature gelation during the subsequent blending process with styrene at 80°C. The final polymer solution is cooled to 25°C before a final quaUty check and dmmming out for shipment. 

Stabilizers. Hydroquinone [123-31 -9] (4) is widely used in commercial resins to provide stabiHty during the dissolution of the hot polyester resin in styrene during the manufacturing process. Aeration of the styrene with oxygen (air) is required to activate the stabilizer, which is converted to an equiHbrium mixture of quinone and the quinhydrone (5) (11). At levels of 150 ppm, a shelf life of over 6 months can be expected at ambient temperatures. 

Neither the mechanism by which benzene damages bone marrow nor its role in the leukemia process are well understood. It is generally beheved that the toxic factor(s) is a metaboHte of benzene (107). Benzene is oxidized in the fiver to phenol [108-95-2] as the primary metabolite with hydroquinone [123-31-9] catechol [120-80-9] muconic acid [505-70-4] and 1,2,4-trihydroxybenzene [533-73-3] as significant secondary metabolites (108). Although the identity of the actual toxic metabolite or combination of metabolites responsible for the hematological abnormalities is not known, evidence suggests that benzene oxide, hydroquinone, benzoquinone, or muconic acid derivatives are possibly the ultimate carcinogenic species (96,103,107—112). 

Recendy, the myelotoxicity has been proposed to occur through initial conversion of benzene to phenol and hydroquinone in the fiver, selective accumulation of hydroquinone in the bone marrow, followed by conversion of hydroquinone to benzoquinone via bone marrow myeloperoxidase. Benzoquinone is then proposed to react with macromolecules dismpting cellular processes (108). 

It is also used to manufacture chlorarule, [118-75-2] a coloring agent, but a new process to synthesize this product has gready reduced this market. This new process, with hydroquinone as raw material (64—67), has the advantage of giving a product of much higher quaUty than can be obtained with 2,4,6-ttichlorophenol. 

The oxidation-reduction process that connects hydroquinone and benzoquinone involves two 1-electron transfers ... 

Photosynthesis is the process that plants use to convert sunlight into chemically useful energy. One part of this process involves using sunlight to convert water and a plastoquinone, Q, into oxygen and a hydroquinone, QH2 (R = (CH2CH=C(Me)CH2) H where n = 6-10). 

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