Phenylacetonitriles, reaction with

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

Hydroxyimino-2-phenylacetonitrile has been prepared from benzyl cyanide by reaction with nitrous acid, with isoamyl nitrite and sodium ethoxide, and with butyl nitrite and hydrogen chloride." ... 

Phenylacetone, 54, 50 Phenylacetonitrile, 50, 20 Phenylacetylene, reaction with ethyl magnesium bromide,... 

In the reaction of the phenylacetonitrile carbanion with thiocyanates, a major side reaction leads to the formation of the dialkyl disulphides, as a result of the base-catalysed decomposition of the thiocyanate. This side reaction is reported to be insignificant in the reactions of the other carbanions. Phenylacetonitrile reacts with 1,2-ethanyl bisthiocyanate to produce 2-cyano-2-phenyl-1,3-thiolanes [52] under conditions analogous to those used for the synthesis of the thioethers (Scheme 4.12). 

Phenylacetonitriles can be induced to undergo Michael reactions with unactivated alkenes. For example, propenylarenes, formed in situ from allylarenes, react with phenylacetonitriles to form 3-aryl-l-cyano-2-methyl-l-phenylpropanes (70-98%) [3] by a procedure analogous to 6.4.1.B, Similarly, the nitriles react with alkynes giving allyl cyanides (80-95%) [38]. 

Although not a Michael acceptor, vinyl acetate reacts with a range of carbanions under phase-transfer catalytic conditions [61]. 1 1 Adducts are obtained from 1-cyano-l-phenylalkanes, but phenylacetonitrile produces a 2 1 adduct with loss of acetic acid (Scheme 6.28). The major product (40%) isolated from the reaction with diphenylmethyl cyanide is l,2-dicyano-l,l,2,2-tetraphenylethane. 

If di(tcrt-butyl)nitroxide (a radical trap) is present, the reaction with phenylacetonitrile-potassium does not proceed entirely. Acetonitrile-potassium (which is in equilibrium with potassium amide) forms only aminopyridine in the presence of the trap (Moon et al. 1983). Consequently, amination is a classical nucleophile reaction, and the formation of pyridyl acetonitrile is a reaction of the typs- These two reactions are quite different. A stronger CH acid leads to a well-defined synthesis. 

If di(terf-butyl)nitroxidc (a radical trap) is present, the reaction with phenylacetonitrile-potassium does not proceed entirely. Acetonitrile-potassium (which is in equilibrium... 

In addition to phenylacetonitrile and fluorene, various active methylene compounds such as indene, propiophenone, phenyl propionate, benzyl phenylacetate afforded the corresponding carboxylated products by the carboxylation reaction with La(0 Pr)3-Ph-N=C=0-C02 system. Of fundamental and practical importance is that S-benzyl thiopropionate was effectively carboxylated into a thioester of 2-methylmalonate in a good yield, since this reaction is related to the biological carboxylation of propionyl coenzyme A with a biotin enzyme. Other thioesters were also carboxylated similarly, where successful examples were thioesters of phenylacetic, acetic, and isovaleric acids carrying active methylene and methyne groups, respectively. 

C-Cyanation. The reagent is obtained (70%) in two steps from benzotriazole /V-chlorination with 5% NaOCl and reaction with NaCN in MeCN, Phenylacetonitrile gives phenylmalononitrile after lithiation and exposure to 1 -cyanobenzotriazole. 

Reaction with phenylacetonitrile.s Sodium naphthalenide reacts with phenylaceto-nitrile to give products of electron or proton transfer, depending on the solvent. Electron transfer is particularly favored in THF-tetraglyme. 

Photo-stimulated reactions of di halopyridines with pinacolone potassium enolate in liquid ammonia lead to facile replacement of both halogens via a modified Sr I mechanism. The potassium salt of phenylacetonitrile reacts with 2,6-dibromopyridine (182) under similar conditions to give a mixture of mono- and disubstituted products 183 and 184 (83JOC1180). The photo-stimulated reaction of 2-bromopyridine (185) and potassioacetonitrile in... 

Wolfe and co-workers have found that the photo-induced reaction of the enolate of phenylacetonitrile (221) with 2,4-dichloropyrimidine (222) gives substitution products 223 and 224 via the mechanism (83JOC1180). 

In a related reaction with the anion of phenylacetonitrile, the initial addition is followed by an internal alkylation, generating a cyclopropane-containing product. ... 

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