Succinonitrile, hydrogenation

Putrescine dihydrochloride has been prepared by the Hofmann degradation of adipamide 3.. s by the Curtius degradation of adipyl hydrazide through the urethane by the Curtius degradation of adipyl azide obtained from adipyl chloride and sodium azide by the Schmidt degradation of adipic acid with hydrogen azide by the reduction of succinonitrile, succinaldoxime, or 7-phthalimidobutyronitrile with sodium and from N-ben-zoyl-7-iodobutylamine ... 

It has been known that the electrolysis in an MeCN- NaClO system generates an acid The hydrogen has to originate from the solvent. A mechanism for hydrogen abstraction from acetonitrile by the electrooxidatively generated radical 104- to produce perchloric acid has been proposed, but no evidence for the succinonitrile formation appeared (Eq. (5)). The detection of the 104- radical by the aid of HSR was tried But it was found to be difficult to differentiate between the perchlorate radical and the radical from chlorine dioxide The electrolysis in a CH Clj—... 

Pyrrolines and Tetrahydropyridines Biltz91 first examined the action of concentrated hydriodic acid on succinonitrile and obtained a product which was claimed to contain four equivalents of hydrogen iodide. The analytical data, however, agree better with the empirical formula C4H4N2 3HI, and undoubtedly this material has the structure 114 in accordance with the recent work of Howard,92 Osborn,93 and Johnson.94 These investigators found that hydrogen bromide causes an immediate precipitation of 115 from a solution of succinonitrile in ether, benzene, or acetic... 

Substituted succinonitriles behave similarly, giving the corresponding 2-bromo-92, 93 or 2-iodo-5-imino-l-pyrroline94,95 hydrohalides. Where the substitution is unsymmetrical, the products must be regarded as mixtures, since substituents do not appear to affect the direction of cyclization. Fumaronitrile affords 117 when treated with hydrogen bromide,92 and the structure of the salt obtained96 by the action of hydrogen bromide on 118 is probably 119. 

The reaction of hydrogen chloride with succinonitrile does not lead to the expected pyrroline but takes a different course and affords 120 as the product.97... 

Hydrogenation of phthalonitrile over Raney Ni does not give the corresponding diamine, but isoindoline in 91-98% yields due to extensive occurrence of cyclization (eq. 7.59).110 Likewise, hydrogenation of succinonitrile and glutaronitrile leads to the formation of pyrrolidines and piperidines, respectively. 

Hydrogenation in a dilute solution is also effective to suppress the cyclization. Thus, when succinonitrile was hydrogenated in THF-NH3 over Raney Co and CaO at 120°C and 20 MPa H2, an 88% yield of 1,4-butanediamine was obtained by adding a THF solution of succinonitrile drop by drop during a 100-min period.113 When hydrogenation was carried out in usual way, the yield of the 1,4-diamine decreased to 72.7%. 

The addition of hydrogen cyanide to olefins and acetylenes has been the subject of many patents. An important application is the addition of hydrogen cyanide to acetylene under special catalytic conditions leading to acrylonitrile or succinonitrile, as illustrated above. 

The selective hydrogenation of aliphatic dinitriles to amino nitriles appears to be best accomplished using rhodium catalysts. Succinonitrile (45) was... 

In the hydrogenation of aliphatic dinitriles, cyclization can also be an important reaction pathway.92 Saturation of succinonitrile, 45, (Eqn. 19.45) over Raney nickel gave pyrrolidine, 49, as the primary product even in the presence of ammonia. 24 Intramolecular condensation of the imine-amine intermediate is apparently a very facile reaction, taking place in preference to imine hydrogenation and the intermolecular ammonia-imine condensation. The... 

Cyclization of o,cu-dinitriles in the presence of anhydrous hydrogen halides affords cyclic imidoyl chlorides. For example, addition of hydrogen bromide to succinonitrile causes an immediate precipitation of the imidoyl bromide XL, ... 

While substituted succinonitriles also add hydrogen bromide to produce the corresponding imidoyl halides addition of hydrogen chloride to succinonitrile gives rise to the formation of different reaction products ( ). 

Further work related to the reaction of succinonitrile and glutaro-nitrile and some of its derivatives with hydrogen halide has been reported and the cyclic amidinium structures XLIV and XLV were verified by NMR studies... 

Cyclic and secondary amides, such as 2-pyrrolidinone, can be amidocarbony-lated only with formaldehyde (12). Lin and Knifton reported on the catalytic performance of various cobalt/ligand systems in the synthesis of iV-acetylglycine. Basic phosphines, such as PBus, allowed low pressure conditions (55 bar). The addition of Ph2SO or succinonitrile resulted in improved selectivity and facilitated the catalyst recovery (13-15). The addition of acid cocatalysts (plfa < 3 e.g., trifluoroacetic acid) allowed for low temperature conditions and the absence of hydrogen (16) (Scheme 3). 

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