Nitriles from alkyl chlorides

Cyanotrimethylsilane and Lewis acids have been shown to be effective in the cyanation of alkyl halides. Use of this silane and tin tetrachloride in refluxing dichloromethane allowed synthesis of bridge-head adamantoid nitriles from the chlorides and/or 292... 

Reactions with Secondary Amides. Treatment of AT-alkyl or A -aryl secondary amides with thionyl chloride in an inert solvent such as methylene chloride results in the formation of imidoyl chlorides (eq Q)." Upon heating, the imidoyl chlorides from N-alkylamides undergo scission to generate nitriles and alkyl chlorides via the von Braun degradation (eq 10). ... 

The synthesis of alkylnitriles from alkyl chlorides, shown in the scheme below, is an important industrial pathway to organic nitriles and subsequent derivatives ... 

Ketenimines are usually prepared from carboxyHc acid derivatives such as amides and imino chlorides via elimination and from nitriles via alkylation with alkyl haHdes under strong basic conditions (21,64). 

Cross coupling between an aryl halide and an activated alkyl halide, catalysed by the nickel system, is achieved by controlling the rate of addition of the alkyl halide to the reaction mixture. When the aryl halide is present in excess, it reacts preferentially with the Ni(o) intermediate whereas the Ni(l) intermediate reacts more rapidly with an activated alkyl halide. Thus continuous slow addition of the alkyl halide to the electrochemical cell already charged with the aryl halide ensures that the alkyl-aryl coupled compound becomes the major product. Activated alkyl halides include benzyl chloride, a-chloroketones, a-chloroesters and amides, a-chloro-nitriles and vinyl chlorides [202, 203, 204], Asymmetric induction during the coupling step occurs with over 90 % distereomeric excess from reactions with amides such as 62, derived from enantiomerically pure (-)-ephedrine, even when 62 is a mixture of diastereoisomcrs prepared from a racemic a-chloroacid. Metiha-nolysis of the amide product affords the chiral ester 63 and chiral ephedrine is recoverable [205]. 

Functional Group Transformations Functional group transformations help us in the conversion of a functional group to an aldehyde or a ketone without affecting the carbon skeleton of the molecule. Aldehydes can be synthesised by the oxidation of primary alcohols, or by the reduction of esters, acid chlorides, or nitriles. Since nitriles can be obtained from alkyl halides, this a way of adding an aldehyde unit (CHO) to an alkyl halide ... 

Alkylation of metallated a-(dialkylamino)nitriles with alkyl halides, epichlorohydrin, allyl halides or ethyl bromoacetate followed by hydrolysis furnishes an array of ketones in good yield. - For example, reaction of (42) with benzyl chloride leads to the formation of deoxybenzoins. Alkylation of a-(dialkyl-amino)nitriles is also possible if the latter are derived from aliphatic aldehydes. - ... 

A still unresolved problem is the structure of the often used adducts from phosphorus trihalides and carboxylic acid amides, which might be described by the formulae (8) or (9). With the aid of in situ generated adducts of acid amides and PX3 amidines, isonitriles, quinazolinones, alkyl chlorides, aminomethylenediphosphonic acids, carbamoyl halides, triformylaminomethane, 1,3,4-oxadia-zoles, sulfides (from sulfoxides), nitriles (from primary nitro compounds)" and bromoqui-nolines (from methoxyquinolines)" have been prepared. 

Alkylation of benzene by tu-chloroalkanoic acids Cl(CH2)nC02H and their methyl esters and nitriles has also been studied. It was found that introduction of electron-acceptor substituents such as —CO2H, —CChMe and —CN into n-alkyl chlorides decreased the extent of isomerization of the alkyl chain below that of the corresponding 1-chloroalkanes, as seen from the examples in equations (18) and (19). 

An improved method for the preparation of nitriles and thiocyanates from halides with benzyltrimethylammonium salts and a convenient preparation of both aliphatic and aromatic nitriles from aldehydes through N,N,N-trimethylhydrazonium salts have been reported. Nitriles can be easily converted into amidines with ammonium halides . Acylisocyanates can be conveniently prepared from amides with oxalyl chloride . A simple preparation of alkyl and aryl carbamates with N-carbonylsulfamic acid... 

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