Benzamide, hydrolysis preparation

The methoxyketene 297, coordinated to Cr carbonyl, is formed from methoxy-carbene easily by insertion of CO under irradiation [90]. An ester is formed by the reaction of ketene with alcohol. The aminocarbene complex 298 was prepared from benzamide and converted to phenylalanine ester 300 under irradiation of sunlight in alcohol via ketene 299 [91]. The eight-membered lactone 304 was prepared in high yield by the reaction of the alkyne 301 having the OH group in a tether with Cr carbene without irradiation. The vinylcarbene 302 is formed at first and converted to the vinylketene intermediate 303 as expected. The keto lactone 304 is formed from 303 by intramolecular reaction with the OH group and hydrolysis [92],... 

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°. 

As the importance of primary amides, Morera and Ortar used hexamethyldi-silazane (HMDS) as a source of ammonia in the carbonylation of aryl iodides and triflates to primary amides (Scheme 2.12) [131]. The desired products were isolated in high yields after hydrolysis. In addition, Indolese et al. reported the efficient aminocarbonylation of aryl bromides with formamide at 5 bar of carbon monoxide. Here, using 4-(dimethylamino)pyridine (DMAP) as a base was the key factor for success [132]. Primary benzamides were also prepared from aryl bromides using CO and a titanium-nitrogen complex in conjunction with NaO Bu [133],... 

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. 

Diorgano-sulphoximides.—(See also Chapter 1, p. 50.) This type of compound has recently been reviewed. Interest in their pharmacological activity has led to the preparation of some novel cyclic sulphoximides. Thus 2-(alkyl-sulphinyl)benzamides were cyclized with hydrazoic acid to the benzisothiazole oxides (98). Tricyclic sulphoxides were converted into the free sulphoximides (99) either by the tosyl azide-copper method with subsequent hydrolysis, or... 

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