Nitriles reactions with hydrogen halides

Zil berman, E. N. Reactions of nitriles with hydrogen halides and nucleophilic reagents. Russ. Chem. Rev. 1962, 31, 615-633. 

Examples include high-pressure hydrolysis of a nitrile paraffin autoxidation homogeneous aldehyde hydrogenation olefin hydroformylation to alcohol with paraffin by-product formation, aldehyde condensation to heavy ends, and olefin isomerization cyclo-addition reactions and hydrogen-halide reactions. 

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... 

Lazaris AY, Zil berman EN, Strizhakov OD (1962) Products of interaction of haloaceto-nitriles with hydrogen halides and it s reaction with nucleophiles. J Gen Chem USSR 32 890-893... 

Alpha hydrogen atoms of carbonyl compounds are weakly acidic and can be removed by strong bases, such as lithium diisopropylamide (LDA), to yield nucleophilic enolate ions. The most important reaction of enolate ions is their Sn2 alkylation with alkyl halides. The malonic ester synthesis converts an alkyl halide into a carboxylic acid with the addition of two carbon atoms. Similarly, the acetoacetic ester synthesis converts an alkyl halide into a methyl ketone. In addition, many carbonyl compounds, including ketones, esters, and nitriles, can be directly alkylated by treatment with LDA and an alkyl halide. 

As esters the alkyl halides are hydrolysed by alkalis to alcohols and salts of halogen acids. They are converted by nascent hydrogen into hydrocarbons, by ammonia into amines, by alkoxides into ethers, by alkali hydrogen sulphides into mercaptans, by potassium cyanide into nitriles, and by sodium acetate into acetic esters. (Formulate these reactions.) The alkyl halides are practically insoluble in water but are, on the other hand, miscible with organic solvents. As a consequence of the great affinity of iodine for silver, the alkyl iodides are almost instantaneously decomposed by aqueous-alcoholic silver nitrate solution, and so yield silver iodide and alcohol. The important method of Ziesel for the quantitative determination of alkyl groups combined in the form of ethers, depends on this property (cf. p. 80). 

The cycloaddition of 1-halogeno-l-nitroethene with nitrile /V-oxides leads to the nitro derivatives of isoxazole [520-524], Thus, for example, the reaction of equimolar amounts of 1-chloro- or 1-bromonitroethene with benzonitrile /V-oxidc gave 5-nitro-3-phenylisoxazole [520], The same compound is formed in the reaction of nitrile /V-oxides with ra .s-2-chloro-1 -nitrocthcnc [485], The formation of nitroisoxazoles in these reactions can be explained by the fact that the initial products from the cycloaddition of halogenonitro-A2-isoxazolines more readily eliminate a molecule of hydrogen halide and not HNOr... 

Alkylmercaptomethyleneiminium salts (267 Scheme 39), which are accessible either by addition of thiols to the nitrile function in the presence of hydrogen halides or by reaction of chloroformic acid thioethyl ester with thioamides, can also be transformed to the corresponding thioimidates (268). 

The course of the reaction between halogenoboranes and the aminoben-zonitriles depends upon the position of the NH2 group.169 With the 3- and 4-amino-derivatives the products are the corresponding amine-boranes and compounds obtained by loss of hydrogen halide, (25) and (26). With the 2-amino-benzonitrile, however, the nitrile group is inserted into a B-halogen... 

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