Benzonitrile, hydrolysis benzoic acid

Hydrolysis of benzonitrile to benzoic acid. BoU 5 -1 g. (5 ml.) of benzo-nitrUe and 80 ml. of 10 per cent, sodium hydroxide solution in a 250 ml. round-bottomed flask fitted with a reflux water condenser until the condensed liquid contains no oUy drops (about 45 minutes). Remove the condenser, and boU the solution in an open flask for a few minutes to remove free ammonia. Cool the liquid, and add concentrated hydrochloric acid, cautiously with shaking, until precipitation of benzoic acid is complete. Cool, filter the benzoic acid with suction, and wash with cold water dry upon filter paper in the air. The benzoic acid (5-8 g.) thus obtained should be pure (m.p. 121°). Recrystal-lise a small quantity from hot water and redetermine the m.p. 

Benzamide from Benzonitrile. (A) Although benzonitrile when boiled with 70% sulphuric acid undergoes ready hydrolysis to benzoic acid (see above), treatment with hot 90% sulphuric acid gives the intermediate benzamide. This difference arises partly from the difference in temperature employed, but also... 

Hydrolysis of />-Tolunitrile. As in the case of benzonitrile, alkaline h> drolysis is preferable to hydrolysis by 70% sulphuric acid. Boil a mixture of 5 g. of p-tolunitrile, 75 ml. of 10% aqueous sodium hydroxide solution and 15 ml. of ethanol under a reflux water-condenser. The ethanol is added partly to increase the speed of the hydrolysis, but in particular to prevent the nitrile (which volatilises in the steam) from actually crystallising in the condenser. The solution becomes clear after about i hour s heating, but the boiling should be continued for a total period of 1-5 hours to ensure complete hydrolysis. Then precipitate and isolate the p-toluic acid, CH3CgH4COOH, in precisely the same way as the benzoic acid in the above hydrolysis of benzonitrile. Yield 5 5 g. (almost theoretical). The p-toluic acid has m.p. 178°, and may be recrystallised from a mixture of equal volumes of water and rectified spirit. 

Benzoic acid, 706,711, 752,755,756 Benzoic anhydride, 794 Benzoin, 708,714 Benzoin condensation, 708, 714 a-Benzoin oxime, 958 Benzonitrile, 609, 803 hydrolysis of, 609 ... 

Like acetonitrile, benzonitrile is a powerful solvent fnr many inorganic and organic materials including some polymers. It can be converted to a large number and variety of derivatives by simple syntheses e.g.. by hydrolysis, it can be converted to either benzoic acid nr benzamicle. The most important reaction is with dicyandiamide to produce 2,4-diamino-6-phenyl-l,3,5-triazine (benzogunnamine) ... 

The procedure has also been applied to halobenzoic acids.3 Thus p-bromo-benzoic acid (6) was converted into the corresponding 2-oxazoline (7) as usual, and then into the Grignard derivative (8). This is, in effect, an aryl Grignard reagent with a protected carboxyl function. Reaction with an electrophile, for example benzonitrile, gives (9). The final step is hydrolysis. If carried out in 5-7% ethanolic sulfuric acid, the ester (10b) is obtained if carried out in an aqueous medium, the free acid (10a) is obtained. 

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 ... 

Benzoic acid, mercapto-lithographic printing plates, 101 Benzonitrile hydrolysis metal catalysis, 449 Benzoquinone dioximates metal complexes non-integral oxidation states, 144 Benzylamine oxidase, 700 Benzyl halides carbonylation... 

Alkyl and aryl nitriles readily hydrolyze when submitted to NCW conditions. The hydrolysis is a multistep sequence as shown in Fig. 9.26. For instance, Katritzky et al. have reported that benzonitrile is converted to benzamide and benzoic acid at 250°C over a period of 5 days, and they conclude that the amide and the acid were in equilibrium. Under these conditions some decarboxylation can also occur. An et al. have reported the product distribution for the hydrolysis of benzonitrile as a function of time and temperature. Specifically, the ratio of benzamide to benzoic acid varied as follows after 1 h at 250°C, the distribution was 5 4. However, at 280°C after 1 h, the ratio was 1 1, and became 1 25 when the reaction time was extended to 6 h. Alkylnitriles exhibit similar behaviors Siskin et ah reported that at 250°C for 2.5 days decanonitrile quantitatively yields two major products, decanoic acid and decanoamide. When octanenitrile was hydrolyzed to octanoic acid amide and octanoic acid, the reaction was slightly slower than that ofbenzonitrile. Only 29% conversion took place in 1 h at 290°C. The limited solubility of octanenitrile in water, even in NCW conditions, was suggested as a possible factor for the slow reaction. Again the product distribution was dependent on the residence time and the temperature. 

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