Nitrobenzene, catalytic hydrogenation

The reduction of the nitro group to yield aniline is the most commercially important reaction of nitrobenzene. Usually the reaction is carried out by the catalytic hydrogenation of nitrobenzene, either in the gas phase or in solution, or by using iron borings and dilute hydrochloric acid (the Bechamp process). Depending on the conditions, the reduction of nitrobenzene can lead to a variety of products. The series of reduction products is shown in Figure 1 (see Amines byreduction). Nitrosobenzene, /V-pbenylbydroxylamine, and aniline are primary reduction products. Azoxybenzene is formed by the condensation of nitrosobenzene and /V-pbenylbydroxylamine in alkaline solutions, and azoxybenzene can be reduced to form azobenzene and hydrazobenzene. The reduction products of nitrobenzene under various conditions ate given in Table 2. 

Catalytic hydtogenation is the most efficient method for the large scale manufacture of many aromatic and ahphatic amines. Some of the commercially important amines produced by catalytic hydrogenation include aniline (from nitrobenzene), 1,6-hexanediamine (from adiponitrile), isophoronediamine (from 3-nitro-l,5,5-trimethylcyclohexanecarbonitrile), phenylenediamine (from dinitrobenzene), toluenediamine (from dinitrotoluene), toluidine (from nitrotoluene), and xyhdine (from nitroxylene). As these examples suggest, aromatic amines ate usually made by hydrogenating the... 

Additional catalytic processes. Nitrobenzene is hydrogenated to aniline (U.S. Patent 2,891,094). Melamine and isophthalouitrile are produced in catalytic fluidized-bed readers. Badger has announced a... 

Rylander in Catalytic Hydrogenation Over Platinum Metals (p. 39, Academic Press, New York, 1967). Nitrobenzene in ethanol was hydrogenated at room temperature and 1 atm over various amounts of 5% Pd on carbon. Four loading levels of catalyst were used. At each level, the reduction was carried out in two different types of batch reactor. 

Amination of aromatic nitro compounds is a very important process in both industry and laboratory. A simple synthesis of 4-aminodiphenyl amine (4-ADPA) has been achieved by utilizing a nucleophilic aromatic substitution. 4-ADPA is a key intermediate in the rubber chemical family of antioxidants. By means of a nucleophibc attack of the anilide anion on a nitrobenzene, a o-complex is formed first, which is then converted into 4-nitrosodiphenylamine and 4-nitrodiphenylamine by intra- and intermolecular oxidation. Catalytic hydrogenation finally affords 4-ADPA. Azobenzene, which is formed as a by-product, can be hydrogenated to aniline and thus recycled into the process. Switching this new atom-economy route allows for a dramatic reduction of chemical waste (Scheme 9.9).73 The United States Environmental Protection Agency gave the Green Chemistry Award for this process in 1998.74... 

Catalytic hydrogenation processes in which copper is the catalytic agent have also been recently introduced into industrial practice for the preparation of aniline from nitrobenzene. 

Reductions at noble metal electrodes in acidic protic media often form adsorbed hydrogen, which is the actual reductant. For example, reduction of nitrobenzene at a Pd/C electrode in acetic acid-methanol mixtures affords aniline via adsorbed hydrogen28. This reaction is more closely related to catalytic hydrogenation of nitro groups than to the... 

Aniline is an important derivative of benzene that can be made in two steps by nitration to nitrobenzene and either catalytic hydrogenation or acidic metal reduction to aniline. Both steps occur in excellent yield. Almost all nitrobenzene manufactured (97%) is directly converted into aniline. The nitration of benzene with mixed acids is an example of an electrophilic aromatic substitution involving the nitronium ion as the attacking species. The hydrogenation of nitrobenzene has replaced the iron-... 

Aniline is discussed further in Chapter 11, Section 6. It is made by the reduction of nitrobenzene (83%) by either catalytic hydrogenation or acidic... 

Pyrrolidone is a lactone used for the production of nylon-4. This reactant may be produced by the reduction ammoniation of maleic anhydride. s-Caprolactam, used in the production of nylon-6, may be produced by the Beckman rearrangement of cyclohexanone oxime (structure 17.11). The oxime may be produced by the catalytic hydrogenation of nitrobenzene, the photolytic nitrosylation of cyclohexane (structure 17.9), or the reaction of cyclohexanone and hydroxylamine (structure 17.10). Nearly one-half of the production of caprolactam is derived from phenol. 

Calculate the conversion in a fluidized bed reactor for the catalytic hydrogenation of nitrobenzene to analine. 

Vavon and Husson G.R. clxxv. 277,1922) have likewise clearly demonstrated the existence of patches of varying activity in platinum black by showing that the progressive addition of a poison such as carbon disulphide will first inhibit. the catalytic hydrogenation of substances more difficult to hydrogenate such as acetophenone without appreciably affecting the activity in respect to hy ogena-tion of nitrobenzene which is readily reduced. 

Reduction of nitrobenzene Aniline can be prepared from nitrobenzene by either chemical reduction using acid and metal or catalytic hydrogenation using molecular hydrogen. 

Initial complexes formed from the interaction of CoH and hydrogen peroxide, nitrobenzene, or anthiaquinone either react further with the excess CoH present to form pentacyanocobaltate(II) or are spontaneously hydrolyzed to yield hydroxypentacyanocobaltate(III). The latter species may then undergo the reverse aging process with CoH, forming pentacyanocobaltate(II), thereby effecting catalytic hydrogenation. 

With nitrobenzene, reduction to an intermediate stage results in the formation of a complex which, as is also the case with the initial complexes formed with ferricyanide, benzoquinone, and benzaldehyde, cannot react in the manner shown in the first conclusion. These species require the presence of added alkali, which apparently effects the displacement of reduced substrate by hydroxyl anion to yield hydroxypentacyanocobaltate(III). All of the substrates mentioned have been found to undergo catalytic hydrogenation when added to the catalyst system in less than stoichiometric quantities in the presence of alkali. 

Mesitylene is converted to a dye intermediate, 2,4,6-trimethylaniline [88-05-1] (mesidine), via nitration to l,3,5-trimethyl-2-nitrobenzene [603-71-4] followed by reduction, eg, catalytic hydrogenation (38). Trinitromesitylene has been prepared for use in high temperature tolerant explosives (39). The use of mesitylene to scavenge contaminant NO from an effluent gas stream has been patented (40). 

The possibility of using of aliphatic alcohols as hydrogen donors for the catalytic transfer reduction of nitro group over MgO was examined. Catalytic hydrogen transfer was found to be effective and selective method for reduction of nitrobenzene, A-nitrotoluene, A-chloronitrobenzene, 4-nitro-m-xylene, 3-nitro-styrene, 3-nitrobenzaldehyde, 1-nitropropane, and 1-nitrobutane. Conversion of starting nitro compound into desired product depended on the alcohol used as a donor. Adsorption of reactant and catalyst deactivation were studied by esr. New aspects of a role of one-electron donor sites in hydrogen transfer over MgD were demonstrated. 

Compensation trends are found in the kinetic data reported for the catalytic hydrogenation of several hydrocarbons on bimetallic systems, including the reactions of ethylene on Ni-Cu and on Ni-Au alloys (252), buta-1,3-diene on Ni- Cu alloys (183), benzene on Ni-Cu (but the behavior of benzene on Cu-Pd was less obviously compensatory) (253), and the liquid phase hydrogenation of nitrobenzene on Pd Ag alloys (56). The kinetic characteristics of but-2-yne on Pd-Au alloys (28) was different in that E underwent little variation, while the value of log A systematically diminished as the proportion of palladium in the alloys was reduced. It was concluded that palladium was the active constituent and gold was an inactive diluent. 

Aniline is an important derivative of benzene that can be made in two steps by nitration to nitrobenzene and either catalytic hydrogenation or acidic metal reduction to aniline. 

The condensation of 1,2-diamino-4-nitrobenzene with bornane-2,3-dione has been investigated.290 Catalytic hydrogenation of fenchone oxime (203 X = NOH) gives the imine (203 X = NH) exclusively, whereas camphor oxime gives only the exo-amine (204) reduction with di-isobutylaluminium hydride yields predominantly heterocyclic secondary amines thus (203 X = NOH) gives (205) as the major product together with (206) and (204) and its endo-isomer.291... 

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