Cyclohexylamine nitrobenzene

The heterocyclic rings in quinoline (116) and isoquinoline are selectively reduced by Pd on carbon-catalyzed reaction of ammonium formatc[107]. Some benzene rings are also reduced. For example, nitrobenzene is reduced to cyclohexylamine (117) with formic acid. It is important to use a sevenfold excess of formic acid[108]. 

The reaction rates cannot be set as high as intrinsically possible by the kinetics, because otherwise heat removal due to the large reaction enthalpies (500-550 kj mol ) will become a major problem [17, 60, 61]. For this reason, the hydrogen supply is restricted, thereby controlling the reaction rate. Otherwise, decomposition of nitrobenzene or of partially hydrogenated intermediates can occur ]60], The reaction involves various elemental reactions with different intermediates which can react with each other ]60], At short reaction times, the intermediates can be identified, while complete conversion is achieved at long reaction times. The product aniline itself can react further to give side products such as cyclohexanol, cyclohexylamine and other species. 

Reduction of aromatic nitro group takes preference to the reduction of the aromatic ring. Under certain conditions, however, even the benzene ring was reduced. Hydrogenation of nitrobenzene over platinum oxide or rhodium-platinum oxide in ethanol yielded aniline while in acetic acid cyclohexylamine was produced [55]. Heating of nitrobenzene with formic acid in the presence of copper at 200° gave a 100% yield of aniline, whereas similar treatment in the presence of nickel afforded 67% of cyclohexylamine [71]. 

Reduction of arenes.1 Raney nickel (Mozingo type) in combination with 2-propanol (reflux) effects reduction of aromatic rings in 2-18 hours. Naphthalene is reduced in 18 hours to tetralin (90% yield) and cis- and frans-decalin (10% yield). Anisole is reduced in 110 hours to cyclohexyl methyl ether (90% yield). Nitrobenzene is reduced quickly to aniline and then further to cyclohexylamine and cyclohexylisopropylamine. 

Figure 12.14 Chromatographic analysis of aniline (a) Precolumn chromatogram (the compound represented by the shaded peak is solvent flushed) (b) main column chromatogram without cryotrapping (c) main column chromatogram with cryotrapping. Conditions DCS, two columns and two ovens, with and without cryotrapping facilities columns OV-17 (25 m X 0.32 mm i.d., 1.0 pun d.f.) and HP-1 (50 m X 0.32 mm, 1.05 pun df). Peak identification is as follows 1, benzene 2, cyclohexane 3, cyclohexylamine 4, cyclohexanol 5, phenol 6, aniline 7, toluidine 8, nitrobenzene 9, dicyclohexylamine. Reprinted with permission from Ref. (20).

In the production of aniline by the hydrogenation of nitrobenzene, the reactor products are separated from unreacted hydrogen in a condenser. The condensate, which is mainly water and aniline, together with a small amount of unreacted nitrobenzene and cyclohexylamine, is fed to a decanter to separate the water and aniline. The separation will not be complete, as aniline is slightly soluble in water, and water in aniline. A typical material balance for the decanter is as follows ... 

The major commercial nitroaromatic hydrogenation by catalysis is the hydrogenation of nitrobenzene to aniline. A Cu catalyst is generally employed since its low activity controls the vigorous exothermic reaction and prevents the formation of cyclohexylamine. The hydrogenation of... 

Nitrogen Compounds. The aqueous Oxone-acetone combination has been developed for the transformation of certain anilines to the corresponding nitrobenzene derivatives, as exemplified in eq 15. This process involves sequential oxidation steps proceeding by way of an intermediate nitroso compound. In the case of primary aliphatic amines, other reactions of the nitrosoalkane species compete with the second oxidation step (for example, dimerization and tautomerization to the isomeric oxime), thereby limiting the synthetic generality of these oxidations. An overwhelming excess of aqueous Oxone has been used to convert cyclohexylamine to nitrocyclohexane (eq 16)P... 

N,N-Dimethyl-N-cyclohexylamine JefFcat DMCHA Polycat 8 Toyocat -DMCH 98-95-3 Nitrobenzene... 

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