Nitriles reaction with hydrogen

The pharmacological versatility of this general substitution strategy is further illustrated by diazonium coupling of 14 with 2-nitrobenzenediazonium chloride to produce biarylal-dehyde 18. Formation of the oxime with hydroxylamine is followed by dehydration to the nitrile. Reaction with anhydrous methanolic hydrogen chloride leads to imino ether and addition-elimination of ammonia leads to the antidepressant amid-ine, nitrafudam (20). ... 

Acrylonitrile (2-propenonitrile, propene nitrile, vinyl cyanide, CH2=CHCN freezing point -83.5°C, boiling point 77.3°C, density 0.806) used to be manufactured completely from acetylene by reaction with hydrogen cyanide. 

When the bifunctional reactant is aldehyde (glutaraldehyde), cyanopiperidines 119 (Fig. 43) are obtained by reaction with hydrogen cyanide and primary amine, although one of the nitrile groups may be partially hydrolyzed to amide during the synthesis. ... 

Hydration of attenic nitriles. 4,4-Dialkyl-substitutcd allenic nitriles (1) are converted into allenic amides (2) in 60 70% yield by reaction with hydrogen peroxide in alcoholic sodium hydroxide. 

By the reaction with hydrogen cyanide, HCN, forming cyan-hydrines, which are acid nitriles, with hydroxyl amine, H2NOH, forming oximes, and with phenyl hydrazine, H2N—NH—CeHs, forming hydrazones, all of which reactions are characteristic of the carbonyl group, carbohydrates in water solution are aldehyde or ketone compounds. 

Aromatic aldehydes react with sodium hydrogen sulfite to yield bisulfite compounds. Further reaction with sodium cyanide forms the hydroxy nitrile (cyanohydrin), which can sometimes be formed directly from the aldehyde by reaction with hydrogen cyanide (Scheme 6.11). 

Imidoyl chlorides are also intermediates in the Gattermann aldehyde synthesis and in the Houben-Hoesch ketone synthesis. The former reaction uses hydrocyanic acid, hydrogen chloride, and aluminum chloride as the catalyst, while in the latter reaction nitriles, hydrogen chloride, and zinc chloride are used. Hoesch in 1915 assumed that the nitriles combine with hydrogen chloride to form imidoyl chlorides, which undergo electrophilic substitution reaction with a wide variety of substrates. Stephen verified Hoesch s hypothesis by reacting phenylbenzimidoyl chloride with resorcinol, and he obtained the intermediate anil CLIX, which can be hydrolyzed to the corresponding ketone (CLX). 

From nitriles by treatment with anhydrous Stannous chloride dissolved in ether saturated with hydrogen chloride the resulting crystaUine aldimine stannichloride, [(RCH=NHj)2] SnCl, or (RCH=NH,HCl)2SnCl4, is hydrolysed by warm water, and the aldehyde is isolated by distillation with steam or by extraction with a solvent (Stephen reaction), for example, for R = CH3(CH2)4, i.e., n-amyl ... 

Weak to moderate chemiluminescence has been reported from a large number of other Hquid-phase oxidation reactions (1,128,136). The Hst includes reactions of carbenes with oxygen (137), phenanthrene quinone with oxygen in alkaline ethanol (138), coumarin derivatives with hydrogen peroxide in acetic acid (139), nitriles with alkaline hydrogen peroxide (140), and reactions that produce electron-accepting radicals such as HO in the presence of carbonate ions (141). In the latter, exemplified by the reaction of h on(II) with H2O2 and KHCO, the carbonate radical anion is probably a key intermediate and may account for many observations of weak chemiluminescence in oxidation reactions. 

Method 5. Nitrile reduction reaction of a nitrile with hydrogen over a hydrogenation catalyst. 

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 ... 

Nitriles. Nitriles can be prepared by a number of methods, including ( /) the reaction of alkyl haHdes with alkaH metal cyanides, (2) addition of hydrogen cyanide to a carbon—carbon, carbon—oxygen, or carbon—nitrogen multiple bond, (2) reaction of hydrogen cyanide with a carboxyHc acid over a dehydration catalyst, and (4) ammoxidation of hydrocarbons containing an activated methyl group. For reviews on the preparation of nitriles see references 14 and 15. 

Other modifications of the polyamines include limited addition of alkylene oxide to yield the corresponding hydroxyalkyl derivatives (225) and cyanoethylation of DETA or TETA, usuaHy by reaction with acrylonitrile [107-13-1/, to give derivatives providing longer pot Hfe and better wetting of glass (226). Also included are ketimines, made by the reaction of EDA with acetone for example. These derivatives can also be hydrogenated, as in the case of the equimolar adducts of DETA and methyl isobutyl ketone [108-10-1] or methyl isoamyl ketone [110-12-3] (221 or used as is to provide moisture cure performance. Mannich bases prepared from a phenol, formaldehyde and a polyamine are also used, such as the hardener prepared from cresol, DETA, and formaldehyde (228). Other modifications of polyamines for use as epoxy hardeners include reaction with aldehydes (229), epoxidized fatty nitriles (230), aromatic monoisocyanates (231), or propylene sulfide [1072-43-1] (232). 

The comparatively ready accessibility of selenocarboxamides has encouraged the use of this procedure for the synthesis of selenazoles (1889LA(250)294). Reaction of the a-chloro-carbonyl compound (73) with the selenocarboxamide (74) provided a ready synthesis of a variety of substituted selenazoles (75). Useful variations of this general procedure are described in detail in Chapter 4.20, and particularly attractive is the reaction of hydrogen selenide with a mixture of a nitrile and the a-halogenoketone to afford the selenazole (48YZ191, 79S66). 

A similar reaction is probably involved in the reaction of 4-nitrophthalodi-nitrile (27) with dimedone (28), which provided under milder condition compound 29 and at a higher temperature tricyclic compound 30 (87ZOR2629). Similarly as in the vicarious nucleophilic reactions, intermediate 29 is formed by nucleophilic displacement of the ort/io-hydrogen atom in 27 (Scheme 3). 

---