Aryl nitriles Subject

Because cyano groups may be hydrolyzed to carboxylic acids (Section 20.19), the Sandmeyer preparation of aryl nitriles is a key step in the conversion of arylarnines to substituted benzoic acids. In the example just cited, the o-rnethylbenzonitrile that was formed was subsequently subjected to acid-catalyzed hydrolysis and gave o-rnethylbenzoic acid in 80-89% yield. 

Among the aryl-aliphatic nitriles subject to alkylation, phenylaceto-nitrile, CjHjCHjCN, is especially reactive and its methylene hydrogens are readily replaced by one or two alkyl groups. Alkylation of this substance has been performed with alkyl halides or dialkyl sulfates. ... 

Isoxazole-supported selenium resins, produced via 1,3-dipolar cycloaddition of nitrile oxides with propargyl selenium resin, were subjected to a-alkylation reactions with various electrophiles, leading to 3-aryl-5-i4-substituted ethenylisoxazoles in satisfactory yields (62-78%) and purity (90-99%). Compound 238 gave olefin 240, through selenoxide elimination from the a-alkylation product 239 (Scheme 56) <2003OL4649>. 

Trimethylsilyl cyanide. 13, 87-88 14,107 15,102-104 17,89 18,381-382 19,375 fi-Trimethylsiloxy nitriles. The TiCl -promoted epoxide opening is subject to asymmetric induction by chiral ligands. The derivatization of aryl ketones is efficiently promoted by LiClO and LiBF. For safety consideration the use of LiBF /MeCN is recommended. 

Photoreactions of aryl and alkyl oxiranes such as 79 and 81 with TEA were also reported by EpHng to give the corresponding alcohols 80 and 82 (Scheme 23). Other studies by Maruyama using derivatives such as epoxy quinone 83 and by Ishii using epoxy nitrile 86 were also subjected to PET reduction with TEA to produce the various reduction products 84, 85, 87, and 88 (Scheme 24 and Scheme 25). 

---