Aryl acetonitriles

By the action of concentrated hydrochloric acid at about 40° upon aryl-acetonitriles hydrolysis is arrested at the arylacetamide stage (see Section IV, 160 for the preparation of phenylacetamide by this method) ... 

The reaction of 2-isothiocyanato benzonitrile with aryl acetonitrile anions was used to prepare quinazoline thione derivatives 53 <06S3067>. 

Auch Amino-acetonitril selbst (Rl = H) bzw. 2-Amino-alkansaure-nitrile sowie Amino-aryl-acetonitrile (R1 = Alkyl, Aryl) konnen eingesetzt werden196,197. 

Die Kondensation von zwei Aquivalenten Alkylimino-aryl-acetonitril liefert 4,5-Diaryl-imi-dazole304,305 ... 

A somewhat different type of coupling is observed when salts of p-keto esters, aryl-acetonitriles ArCH2CN, and other compounds of the form ZCH2Z are treated with an... 

Michael reactions (10, 82). In the presence of equimolar amounts of CsF and SifOCHj), or Si(OC2H5)4, ketones and aryl acetonitriles undergo Michael addition to ot,p-... 

Aryl acetonitriles. The aryl cyanophosphatcs obtained by reaction of aryl ketones or aldehydes (80-100% yield) are converted into ar 1 acetonitriles by hydrogcnolysis using Pd/C. This method was used to convert the ketone 1 to ibuprofen (2) in 81% overall yield. 

MON O-C-M ETHYLATION OF ARYL ACETONITRILES AND METHYL ARYLACETATES BY DIMETHYL CARBONATE ... 

Recently a further method of alkaline nitration has been developed. It involves acetone cyanohydrin nitrate, which is readily obtained from acetone cyanohydrin and fuming nitric acid, and applies to compounds such as aryl-acetonitriles and malonic and acetoacetic esters that contain active methylene groups.130... 

Dehydration. Reagent (1) has been used for the dehydration of various substrates, including aldoximes (to give nitriles), /3-hydroxy amino acids, and /3-hydroxy sulfones. 3-Aryl-2-hydroxyiminopropionic acids undergo dehydration and decarboxylation, to give 2-aryl acetonitriles, upon reaction with (1). ... 

Several methods exist for the synthesis of substituted 3-phenyl 1,2-benzisoxazoles or hetero-benzisoxazoles varying from heating of substituted benzophenone azides (Example 1), triethyl phosphite reduction of ortho-nitro benzophenone or heterophenone compounds (Example 2), even to nucleophilic substitution of nitro compounds with aryl acetonitriles (Example 3). °... 

Janier-Dubry, J. L. Devin, C. Perrot, R. Addition compounds obtained by the action of tin(IV) chloride on acetonitrile and several aryl acetonitriles. I. Preparation and analysis of the solid compounds formed. Bull. Soc. Chim. Fr. 1971, 2816-2819. 

Another unusual route to 1-phenylisoquinolines is the condensation of an aromatic aldehyde such as benzaldehyde with two equivalents of an aryl-acetonitrile, e.g., phenylacetonitrile, to a l,4-dihydro-l-phenyl-3(2//)-isoquino-line. The reaction is run in polyphosphoric acid, and proceeds through the intermediacy of a benzylidenebisphenylacetamideY ... 

Nitrile enolates can also react with carbonyl derivatives such as oxalate, which serves as a carboxyl surrogate. Reaction of 2-phenylacetonitrile and diethyl oxalate, in the presence of sodium amide, gave 4.99. " Catalytic hydrogenation of the cyano group and hydrolysis led to ethyl 2-phenyl-3-aminopropanoate, 4.100. In this case also, the nitrile moiety was an amine surrogate. Other a-aryl acetonitrile derivatives... 

This osmium catalyst system was also found to be effective for the a-alkylation of aryl acetonitrile, where it exhibited a high turnover frequency of up to 675 h ... 

Makosza has applied the phase-transfer alkylation method to the preparation of 1-aryl-l-cyanocyclobutanes from aryl acetonitriles and 1,3-dihalogenopropanes. Cyclization of the 6-chloro-ester (24) with lithium di-isopropylamide gave a mixture of epimeric esters (25). The major component (25a) of the mixture was converted by a standard series of reactions into ( )-grandisol (26). 

A diastereoselective synthesis of cyclopropanes combines an aryl acetonitrile, ArCH2CN, with an aldehyde, RCHO, to give 100% cis-product (116) as a racemic mixture of enantiomers. " The one-pot reaction shows yields of 45-93% covering a wide range of substrates Ar includes 3-pyridyl and 2-thiophenyl, and the aldehyde can be aromatic or aliphatic. The reaction sequence consists of a Knoevenagel condensation followed by a Corey/Chaykovsky cyclopropanation. 

The cyanovinylene moiety is constructed by the Knoevenagel condensation of a suitable aldehyde with an aryl acetonitrile derivative using potassium r-butoxide. EDOT carboxaldehyde was prepared by the Vilsmeier formylation of EDOT with POC1.J and DMF while EDOT acetonitrile was prepared by the Ni(acac)2 catalyzed coupling of EDOT-ZnCl with bromoacetonitrile as shown below 8). 

The condensation of benzaldehyde with aryl acetonitriles does not occur in... 

Later, Cid and Ruano reported that aryl-acetonitriles bearing an electron-withdrawing group at the ortho- or poro-position could serve as suitable nucleophiles in organocatalytic Michael reactions with enals [39]. The reaction proceeded with good yields and good enantioselectivities, albeit with low... 

The same group in their subsequent paper discussed a carbonate-catalyzed synthesis of 5-amino-l,2,3-triazoles 9 and 74-75 from substituted acetonitriles 73 and azides 2/7 in the presence of 10 mol% of CS2CO3 in DMSO -I- H2O (7 3) at room temperature for 0.5-2 h (Scheme 4.25) [29]. The 5-amino-l,2,3-triazoles 9 and 74-75 were obtained with very high regioselectivity. The reaction was found to tolerate various substituents on the phenyl ring of the aryl acetonitriles 73. Various substituted aryl azides generated the products in good to excellent yields. 

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