Benzyl nitrile

Condensation of 165 with ethoxymethylenemalononitrile gave 171, and with ethyl ethoxymethylenecyanoacetate or methyl bis(methylmercapto)-methylene cyanoacetate it yielded 172 (80AP108). The reaction of 172 with urea, thiourea, and benzyl nitrile afforded 173 (91PHA98). Treatment of hydrazino derivatives 165 with alkyl, aryl, or aralkyl isothiocyanates yielded (86JHC1731) 3-(/V-substituted-thiocarbamoyl)-hydrazino[l,2,4]triazino[5,6-b]indoles which have been evaluated for in vitro antimicrobial activity (Scheme 36). 

Hydroxy-2-athyI-3,3-diphenyl- -nitril 115 3-Hydroxy-3-aryl- -nitril 604 3-Hydroxy-2-benzyl- -nitril 206... 

Oxo-3-(2-nitro-phenyl)- -methylester 477 3-Oxo-3-phenyl-2-benzyl- -nitril 562 3-Oxo-3-phenyl- -nitril 562 Pentafluor- 147... 

Figure 11.11 Pyrogram of a paint sample collected from a decorative frame of the Universal Judgement by Bonamico Buffalmacco (fourteenth century, Monumental Cemetery of Pisa, Italy). Pyrolysis was performed with a microfurnace pyrolyser, at 600°C, in the presence of HMDS. 1, Benzene 2, ethyl acrylate 3, methyl methacrylate 4, acetic acid, trimethyl silyl ester 5, pyrrole 6, toluene 7, 2 methylpyrrole 8, 3 methylpyrrole 9, crotonic acid 10, ben zaldehyde 11, phenol 12, 2 methylphenol 13, 4 methylphenol 14, 2,4 dimethyl phenol 15, benzyl nitrile 16, 3 phenylpropionitrile 17, indole 18, phthalate 19, phthalate 20, ben zyl benzoate HMDS pyrolysis products [27]...

The Bulfington group [17] at Johnson and Johnson Pharmaceutical have also developed a very efficient and concise synthesis (Scheme 5) of the Furst-ner intermediate (6) to lukianol A. The synthesis relies on the condensation of benzyl nitriles with aromatic aldehydes under basic conditions to give the corresponding electron deficient alkenes (23). 

Although the hydride reduction of nitriles frequently requires the use of vigorous conditions (LiAlH4, B2H6), aryl nitriles and benzyl nitriles are reduced to the... 

Tertiary benzylic nitriles are useful synthetic intermediates, and have been used for the preparation of amidines, lactones, primary amines, pyridines, aldehydes, carboxylic acids, and esters. The general synthetic pathway to this class of compounds relies on the displacement of an activated benzylic alcohol or benzylic halide with a cyanide source followed by double alkylation under basic conditions. For instance, 2-(2-methoxyphenyl)-2-methylpropionitrile has been prepared by methylation of (2-methoxyphenyl)acetonitrile using sodium amide and iodomethane. In the course of the preparation of a drug candidate, the submitters discovered that the nucleophilic aromatic substitution of aryl fluorides with the anion of a secondary nitrile is an effective method for the preparation of these compounds. The reaction was studied using isobutyronitrile and 2-fluoroanisole. The submitters first showed that KHMDS was the superior base for the process when carried out in either THF or toluene (Table I). For example, they found that the preparation of 2-(2-methoxyphenyl)-2-methylpropionitrile could be accomplished h... 

In this approach the C(2)-N(3) and C(6)-N(l) components are usually the same. Formamide or nitriles are common C-N components. A classical example is the trimerization of acetonitrile to give 2,6-dimethyW-pyrimidinamine <1994HC(52)1 >, while a modern example involves a similar trimerization of a variety of alkyl and benzylic nitriles 707 under microwave conditions <2005JC0483>. 

Further, by using Et3N.3HF in acetonitrile as solvent, they have demonstrated that electrolysis of benzyl nitriles, carboxylic acid esters, sulphonic acid esters and ketones give the corresponding monofluoro- or difluoro-compounds, depending on anode potential in yields of 30 - 70 %. 

In connection with the substituent effects, the kinetic stability of benzyne is suggested to be increased by electron withdrawal (-/) and decreased by electron release (+/).73 However, the inference cannot be extrapolated to selectivity of substituted arynes in general. For example, in additions involving competition between phenyllithium and lithium piperidide, the methyl substituents (+/) on benzyne increase its selectivity, whereas methoxy groups (-/) decrease it (Scheme 6). On the other hand, in reactions of car-banions derived from acetonitrile in alkylamine solvents both +/ and -/ benzyne substituents lower selectivity and cause predominant amination. Thus, the method was found unsuitable for preparation of many substituted benzyl nitriles.74 In symmetrically disubstituted arynes there is partial cancellation of polarization, and in fact acceptable yields of acetonitrile adducts could be obtained from 3,6-dimethoxy-benzyne.75 The selectivity of substituted arynes varies with the set of nucleophiles in the competition and no comprehensive theory or simple generalization is available on this point. 

An example of this class of condensation with elimination of water is the formation of a-phenyl-cinnamic nitrile, from benzaldehyde and benzyl nitrile ... 

It wit.M shown by V. Meyer, that solid sodium hydroxide m better than sodium ethylate for condensing1 benzyl nitrile with methyl iodide 36... 

SYNS BENZENEACETONITRILE BENZYL CYANIDE BENZYLKYANID BENZYL NITRILE (CYANOMETHYL)BENZENE a-CYANOTOLUENE O-CYANOTOLUENE 2-PHENYLACETONITRILE PHENYLACETONITRILE, Uquid POT PHENYL ACETYL NITRILE a-TOLUNITRILE USAF KF-21... 

Nitriles can act as nitrogen nucleophiles in aziridine ring-opening reactions. Two examples are shown in Scheme 25 in which a formal [3-1-2] cycloadduct is the final product. Tosylaziridine 147 was reacted with benzoni-trile and BF3 OEt2 catalysis to produce the r-fused imidazoline 148 <2004TL1137>. The utility of the reaction is limited in the case of cyclic aziridines to benzofused aziridines and either aryl or benzyl nitriles. It was also found that the reaction required stoichiometric BF3. Lesser amounts of Lewis acid reduced the chemical yield drastically. 

Ultra-violet light irradiation of tetramethylphenylene diamine (152) in aqueous or methanolic solutions of alkyl nitriles yields the ortho-amino substituted product (153). ° With benzyl nitriles the ortho-benzyl product (154) is obtained. It is proposed that both products are produced by electron transfer from the excited state of the diamine to the nitrile. With alkyl nitriles the products are derived from solvolysis of the adduct formed by attack of the nitrile nitrogen on the arene radical cation, while with benzyl nitrile electron transfer from the excited amine gives the benzyl nitrile radical anion which ionises by loss of cyanide the resulting benzyl radical then attacks the diamine. 

O-Benzylidene-D-gIucose, 159, 160 Benzyl ketones, 268 Benzyl mercaptan, 27 Benzyl nitrile, 209... 

Chelated bis(silyl)iron complexes react photochemically with nitriles, providing routes to A/,N-bis(silyl) enamines229,230 A variety of aliphatic and benzylic nitriles may be employed (equation 85). The proposed mechanism (Scheme 6) involves addition of an... 

BENZYL NITRILE (140-29-4) Combustible oily liquid (flash point 215°F/102°C). Violent reaction with acids, forming hydrogen cyanide. Violent reaction with sodium hypochlorite. 

Benzyl nitriles. Tertiary benzyl nitriles are prepared by substitution of aryl fluorides. 

Nitriles nitro compounds. Benzylic chlorides or bromides react in acetonitrile or methylene chloride with dry KCN in the presence of 18-crown-6 to give benzyl nitriles in 85-95% yield. This procedure has been used to convert tri-methylchlorosilane into trimethylsilyl cyanide (4, 542-543) in about 45% yield. 

Phenylacetonitrile (benzeneacetonitrile, benzyl cyanide, benzyl nitrile, (cyanomethyl) benzene, a-cyano-toluene, a-tolunitrile) [140-29-4]... 

Usually, the aqueous salt could be too hydrophilic to allow the quaternary salt to dissolve in the organic phase, and resided exclusively in the aqueous phase anion exchange occured at or near the interface. The mechanism is applied to carbanion reactions, carbene reactions, condensation of polymerization, and C-alkylation of active methylene compounds such as activated benzylic nitriles, activated hydrocarbons, and activated ketones under PTC/OH. In most cases, the reaction involves the Q OH complex because QOH is highly hydrophilic and has extremely low solubility in the organic phase. 

Alkylation of Nitrile Derivatives. Tertiary benzylic nitriles were prepared from aryl fluorides and secondary nitrile anion. In the presence of 4 equiv of nitrile and 1.5 equiv of a base, the nucleophilic aromatic substitution of fluoroarenes led to tertiary benzylic nitriles (eq 36). KHMDS was the best base for this reaction, as LiHMDS and NaHMDS provided lower yields. The desired product was not observed when CS2CO3, LDA, or f-BuOK were used. "With KHMDS, the reaction proceeded in high yields with a variety of substrates. 

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