Formation from nitrile hydrogenation

Xie X, Liotta CL, Eckert CA (2004) C02-protected amine formation from nitrile and imine hydrogenation in gas-expanded liquids. Ind Eng Chem Res 43 7907-7911... 

The value of AG° at various reaction temperatures and corresponding Kp values are reported in Table 2. It can be understood from Table 2 that the formation of hydrogenated nitrile rubber from nitrile rubber is thermodynamically feasible. 

The selectivity of RNH2 on M/A1203 and Raney catalysts decreased in the order Co Ni Ru>Rh>Pd>Pt. This order corresponds to the opposite sequence of reducibility of metal-oxides [8] and standard reduction potentials of metalions [9], The difference between Group VIII metals in selectivity to amines can probably been explained by the difference in the electronic properties of d-bands of metals [3], It is interacting to note that the formation of secondary amine, i.e. the nucleophilic addition of primary amine on the intermediate imine can also take place on the Group VIII metal itself. Therefore, the properties of the metal d-band could affect the reactivity of the imine and its interaction with the amine. One could expect that an electron enrichment of the metal d-band will decrease the electron donation from the unsaturated -C=NH system, and the nucleophilic attack at the C atom by the amine [3], Correlation between selectivity of metals in nitrile hydrogenation and their electronic properties will be published elsewhere. 

Thus, hydrogen peroxide has found application in the implementation of the well-known organic reactions in the gas phase—dehydrogenation, epoxidation, hydrogenolysis, nitrile formation from /V-alkylbcnzcne, nitrogen fixation, etc. 

The formation of amide chlorides from nitriles and hydrogen halides under anhydrous conditions is a well-known reaction of wide scope7- There has been some confusion on the nature of the reaction products, but it has turned out that the isolable species are amide chlorides. The thermal stability of the addition products strongly depends on the acidity of the hydrogen halide used. Iodides are more stable than bromides, which in turn are more stable than the chlorides. As a consequence, thermally stable HQ adducts (38 equation 22) can be prepared if Lewis acids ate present, which incorporate the chlorine anion to give a less basic anion (39). 

In addition to comonomers, nylons are frequently used in blends. The pyrolysis of blends typically shows little interaction between the compounds generated from the individual blend components. However, a study on the co-pyrolysis of several polyamides in the presence of PVC showed interactions [40]. The study was done on nylon-12, nylon-6,6 and poly(1,4-phenylene terephthalamide) (Kevlar) in the presence of poly(vinyl chloride). Polyamide-PVC mixtures (typical mass ratio 1 1) were pyrolyzed at 700 and 900°C. It was found that the presence of PVC promoted the hydrol ic decomposition routes of amide groups and volatile nitrile formation from all examined polyamides due to the hydrogen chloride eliminated from PVC under pyrolysis. In the presence of PVC, an elevated yield of alkenenitriles was observed from nylon-12. For Kevlar in the presence of PVC, it was noticed the evolution of benzeneamine, benzoic acid, benzenenitrile and benzeneisocyanate. At 900°C in the presence of PVC, an enhanced evolution of HCN from nylon-12 and nylon-6,6 was noticed. 

Other methods for the synthesis of l,4-dihydro-l,2,4,5-tetrazines 9 which can be explained by intermediate formation of nitrile imines 8 are the photolysis of 1,2,3-triazoles 2181 and sydnones 3,182 reaction of tetrazoles 4180 with tosyl chloride, elimination of pyridine from the pyridinium compounds 5,189-190 of hydrogen chloride from the hydrazonic acid chlorides 1 s.3-i88 or elimination 0f sulfinate from the a-sulfonyl hydrazone 7.189... 

The generation of imidoyl chlorides from nitriles and hydrogen halides in the presence of a suitable Lewis acid accounts for the formation of ketones in the Houben-Hoesch reaction (see Section IVD). 

Like the triple bond of alkynes (Section 13-6), the nitrile group is hydrogenated by catalytically activated hydrogen. The result is the same as that of reduction by lithium aluminum hydride—amine formation. All four hydrogens are from the hydrogen gas. 

The tertiary amine is formed in a similar manner from the imine and a secondary amine. This side reaction can be minimized by carrying out the hydrogenation in the presence of ammonia, which tends to shift the equiHbrium back towards the imine. When a compound with two or more nitrile groups is hydrogenated, the formation of both cycHc and acycHc secondary and tertiary amines is possible, depending on whether the side reaction is intramolecular or intermolecular. For example, for the hydrogenation of adiponitfile ... 

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