Benzonitrile, hydrolysis preparation

Prepared by the action of ammonia on benzoyl chloride or benzoic esters, or by partial hydrolysis of benzonitrile. 

Aromatic nitriles differ from their aliphatic cousins in that they bear no H-atoms at C(a) and, hence, cannot undergo oxidative denitrilation. Here, hydrolysis of the CN group depends on the substrate properties and on the relative efficiency of competitive reactions such as ring hydroxylation. Thus, the CN group of benzonitrile (11.87, R = H), 2- and 4-hydroxybenzonitriles (11.87, R = 2-OH or 4-OH), and 4-nitrobenzonitrile (11.87, R = 4-N02) was not hydrolyzed by rat liver subcellular preparations [124],... 

A cyclization reaction involving the sulfonamide 267 finalized an efficient synthetic approach to the COX-inhihitor 268 after subsequent simultaneous ester hydrolysis and detosylation (Equation 82) <2003JOC4104>. Indoles have also been prepared by reaction of (2-aminobenzyl)triphenylphosphonium salts with carboxylic acid anhydrides in the presence of a base <2002TL2885>. Exposure of o-(benzoylamino)benzonitriles to a-bromoketones under basic conditions gives 3-aminoindole derivatives <2001BML2169>. 

Roberts and Whiting developed a method for effecting the anhydrous hydrolysis of esters and nitriles in DMSO. A solution of sodium methylsulfinylmethide is prepared from sodium hydride and DMSO and titrated with a solution of an appropriate amount of water in DMSO, using triphenylmethane as indicator. This produces a fine suspension of sodium hydroxide which hydrolyzes ethyl benzoate very rapidly at room temperature. As compared with reactions in hydroxylic solvents, rates are enhanced by a factor of 10 -10 . Benzonitrile is hydrolyzed to benzamide. Methyl and ethyl mesitoates are hydrolyzed readily at 25°. 

Benzonitrile acts in a similar way to form benzoic acid but requires sulfuric acid in the reacting mixture. Nicotinic acid amide (nicotinamide) has been prepared by the mild hydrolysis of 3-cyanopyridine, and acrylamide by the partial hydrolysis of acrylonitrile. Acrylonitrile may also be hydrolyzed to acrylic acid with mineral acids or with alkalies. Polyacrylonitrile is partially converted to the amide by nitric acid, and the nitrile oups of a number of polymers and copolymers have been hydrolyzed to amide and carboxylic acid groups to produce water-soluble polyelectrolytes. Isooyanides are stable toward alkalies but hydrolyze in the presence of acids to form an acid and an amine ... 

Preparation by reaction of benzonitrile with phloroglucinol in the presence of zinc chloride and hydrochloric acid in ethyl ether at r.t. for overnight, followed by hydrolysis of the ketimine salt formed with dilute sulfuric acid [370], (65%) [371] (Hoesch reaction). 

Preparation by adding phenylmagnesium bromide to 2-methoxy-5-(trifluoromethyl)benzonitrile,followed by hydrolysis of the intermediate imino compound formed, then demethylation of 2-methoxy-5-(trifluoromethyl)-benzophenone so obtained [568]. - Preparation by demethylation of 2-methoxy-5-(trifluoromethyl)benzophenone with boron trichloride in methylene chloride at -60° for 1 h, then at r.t. [569]. 

PrqKiration by reaction of m-(trifluOTCMnethyl) benzoyl chloride with resorcinol dimethyl ether in the presence of aluminium chloride or titanium tetrachloride in refluxing n-hexane for 8 h [239]. - Preparation by reaction of m-(trifluoromethyl)benzonitrile with m-methoxyphe-nol in the presence of aluminium chloride for 8 h at 190°, followed by hydrolysis of the ketimine so formed [77]. 

Moreover, an aerobic oxidative decarboxylative ammoxidation of phenylacetic acids and a-hydroxyphenylacetic acids to primary benzamides was realized with CU2O catalyst [28] (Scheme 3.10). The C(C=0)-N bond was formed with NH3 as nitrogen source and O2 as the sole terminal oxidant. Benzonitrile which is generated from phenylacetic acid through decarboxylation and ammoxidation with ammonia is the key intermediate for this transformation. It could convert into benzamide through ammonolysis and hydrolysis. A variety of primary benzamides could be prepared in 36-85 % yields form the corresponding acid. 

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