Catalytic hydrogenations aniline

Aromatic amines are hydrogenated in the rings by catalytic hydrogenation. Aniline yields 17% of cyclohexylamine and 23% of dicyclohexylamine over platinum dioxide in acetic acid at 25° and 125 atm [5]. A better yield (90%) of cyclohexylamine was obtained by hydrogenation over nickel at 175° and 180... 

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 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. 

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

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... 

In the Bnchamp process, nitro compounds are reduced to amines in the presence of iron and an acid. This is the oldest commercial process for preparing amines, but in more recent years it has been largely replaced by catalytic hydrogenation. Nevertheless, the Bnchamp reduction is still used in the dyestuff industry for the production of small volume amines and for the manufacture of iron oxide pigments aniline is produced as a by-product. The Bnchamp reduction is generally mn as a batch process however, it can also be mn as a continuous (48) or semicontinuous process (49). 

Isocyanates. The commodity isocyanates TDI and PMDI ate most widely used in the manufacture of urethane polymers (see also Isocyanates, organic). The former is an 80 20 mixture of 2,4- and 2,6-isomers, respectively the latter a polymeric isocyanate obtained by phosgenation of aniline—formaldehyde-derived polyamines. A coproduct in the manufacture of PMDI is 4,4 -methylenebis(phenyHsocyanate) (MDI). A 65 35 mixture of 2,4- and 2,6-TDI, pure 2,4-TDI and MDI enriched in the 2,4 -isomer are also available. The manufacture of TDI involves the dinitration of toluene, catalytic hydrogenation to the diamines, and phosgenation. Separation of the undesired 2,3-isomer is necessary because its presence interferes with polymerization (13). 

The N,]S -dialkyl-/)-PDAs are manufactured by reductively alkylating -PDA with ketones. Alternatively, these compounds can be prepared from the ketone and -lutroaruline with catalytic hydrogenation. The /V-alkyl-/V-aryl- -PDAs are made by reductively alkylating -nitro-, -nitroso-, or /)-aminodipheny1 amine with ketones. The AijAT-dialkyl- PDAs are made by condensing various anilines with hydroquinone in the presence of an acid catalyst (see Amines-aromatic,phenylenediamines). 

Aniline 77 was converted into its diazonium salt with nitrous acid and this was followed by reduction with stannous chloride to afford the corresponding arylhydrazine 78. Condensation of 78 with 3-cyanopropanal dimethylacetal 79 gave the arylhydrazone 80. Treatment of 80 with PPE resulted in cyclization to indole 81. The nitrile group was then reduced to the primary amine by catalytic hydrogenation. Reaction of the amine with excess formalin and sodium borohydride resulted in Imitrex (82). 

Catalytic hydrogenation of azo compounds over Pt or Ra-Ni often leads to hydrogenolysis. 551 Catalytic transfer hydrogenolysis using cyclohexene and Pd is also used for the conversion of azobenzenes to anilines.552... 

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... 

Catalytic hydrogenation over palladium in acetic acid and sulfuric acid at room temperature and 2.5 atm reduced nitroacetophenones and their homologs and derivatives all the way through the alkyl anilines in yields of 78.5-95% [904]. 

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... 

Menendez et al. reported the synthesis of murrayafoline A (7) by palladium(II)-mediated oxidative double C-H activation of a diarylamine assisted by microwave irradiation (585). The aniline derivative 598 was obtained by O-methylation of 5-methyl-2-nitrophenol (625) followed by catalytic hydrogenation. The required diarylamine 654 was obtained by N-arylation of the aniline derivative 598 with phenyllead triacetate (653) in the presence of copper(II) acetate. Under microwave-assisted conditions, in the presence of more than the stoichiometric amount of palladium(II) acetate and a trace of dimethylformamide, the diarylamine 654 was cyclodehydrogenated to murrayafoline A (7) (585) (Scheme 5.47). 

A double reduction was achieved under catalytic hydrogenation conditions to open the epoxide and reduce the nitro group to an amino group in 90% yield. The aniline thus afforded was reacted with diethylethoxymethylenemalonate to give 92. 92 was next cyclized to the 1,4-benzoxazine 93 via a Mitsunobu reaction in the absence of a Lewis acid, unlike Kim s approach (Kang et al., 1996). Completion of the tricycle core was ultimately achieved in PPE at 140-145°C to furnish the LVX core in 85% yield. The core was converted to LVX (1) in two precedented steps. 

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