Benzonitrile hydrolysis

Benzisoselenazol-3(2H)-one (ebselen), peroxynitrous acid reaction, 117, 17 Benzonitrile, hydrolysis, 701-2 Benzophenone, laser photolysis, 193-5 Benzoyl acetyl peroxide, stmcture, 703 a-A-Benzoyl-L-arginine ethyl ester,... 

The less reactive magnesium reagent allows the complete reductive trimethylsilyla-tion of the nitrile function of benzonitrile. Hydrolysis of the obtained silazane into the ammonium chloride followed by its neutralization afforded the a-trimethylsilylbenzyl-amine (ASMA) in good yield.174... 

Fig. 7.10. Partial benzonitrile hydrolysis of (A) accelerated by hydrogen peroxide under basic conditions. The intermediate E, a perimidic acid, is as suitable for the epoxidation of standard alkenes as MCPBA or HHPP (cf. Section 3.19), but unlike the latter two is also capable of epoxidizing keto alkenes (which would be oxidized by MCPBA or MMPP in the ketonic substructure in a Baeyer-Vil-liger reaction cf. Section 14.35).

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... 

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

Hydrolysis of Benzonitrile. Benzonitrile is moderately readily hydrolysed by 10% aqueous sodium hydroxide, but only slowly by hydrochloric acid (cf. p. 122). Ready hydrolysis is obtained by boiling the nitrile under reflux... 

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. 

Place together in a 50 ml. conical flask about 1 g. of the substance and 10 ml. of 10% NaOH solution (or use apparatus in Fig. 38, p. 63)-Add a few pieces of unglazed porcelain, fit a reflux water- condenser, and boil gently for about 20 minutes. Nitriles require longer heating than amides, usually about 30 minutes. The completion of the hydrolysis of an insoluble nitrile ( .g., benzonitrile) is indicated by the disappearance of oily drops in the liquid. Cool the flask, add an excess of dil. H2SO4 and cool thoroughly. 

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. 

Hydrolysis may be effected with 10-20 per cent, sodium hydroxide solution (see p-Tolunitrile and Benzonitrile in Section IV,66) or with 10 per cent, methyl alcoholic sodium hydroxide. For diflScult cases, e.g., a.-Naphthoniirile (Section IV,163), a mixture of 50 per cent, sulphuric acid and glacial acetic acid may be used. In alkahne hydrolysis the boiling is continued until no more ammonia is evolved. In acid hydro-lysis 2-3 hours boiling is usually sufficient the reaction product is poured into water, and the organic acid is separated from any unchanged nitrile or from amide by means of sodium carbonate solution. The resulting acid is identified as detailed in Section IV,175. 

Similarly aniline C,H jNHj is converted into benzonitrile C,HjCN. Hydrolysis of the nitrile with so um hydroxide solution, followed by acidiheation, yields the corresponding acid, for example ... 

Since the hybridization and structure of the nitrile group resemble those of alkynes, titanium carbene complexes react with nitriles in a similar fashion. Titanocene-methylidene generated from titanacyclobutane or dimethyltitanocene reacts with two equivalents of a nitrile to form a 1,3-diazatitanacyclohexadiene 81. Hydrolysis of 81 affords p-ketoena-mines 82 or 4-amino-l-azadienes 83 (Scheme 14.35) [65,78]. The formation of the azati-tanacyclobutene by the reaction of methylidene/zinc halide complex with benzonitrile has also been studied [44]. 

Capon et al., 1978. No reference bimolecular reaction is available, but o-cyanobenzoic acid is hydrolysed over 10 times faster than phthalamic acid (A.3.9), although benzonitrile is less reactive than benzamide towards acid hydrolysis. [Rate constants for hydrolysis are (1-2) x 10 s for benzonitrile in 1 M acid (Hyland and O Connor, 1973) and 3.5 x 10-4 dm3 mol-1 s 1 for benzamide (Bender et al., 1958), both measured at 100°]... 

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],... 

In contrast to the above benzonitriles, 2-methylbenzonitrile (11.88) did undergo cyano hydrolysis, but by a very indirect route involving cytochrome P450 catalyzed hydroxylation of the 2-Me group to form 2-(hydroxyme-thyl)benzonitrile (11.89), followed by intramolecular nucleophilic addition. The cyclization reaction yielded an unstable imino ether derivative (11.90), which hydrolyzes to phthalide (11.91). The conversion of 2-(hydroxyme-thyl)benzonitrile to phthalide followed first-order kinetics with a f1/2 value of 2.8 h at pH 7.4 and 37° [124],... 

Chemical/Physical. Diuron decomposes at 180 to 190 °C releasing dimethylamine and 3,4-dichlorophenyl isocyanate. Dimethylamine and 3,4-dichloroaniline are produced when hydrolyzed or when acids or bases are added at elevated temperatures (Sittig, 1985). The hydrolysis half-life of diuron in a 0.5 N NaOH solution at 20 °C is 150 d (El-Dib and Aly, 1976). When diuron was pyrolyzed in a helium atmosphere between 400 and 1,000 °C, the following products were identified dimethylamine, chlorobenzene, 1,2-dichlorobenzene, benzonitrile, a trichlorobenzene, aniline, 4-chloroaniline, 3,4-dichlorophenyl isocyanate, bis(l,3-(3,4-dichlorophenyl)urea), 3,4-dichloroaniline, and monuron [3-(4-chlorophenyl)-l,l-dimethylurea] (Gomez et al., 1982). Products reported from the combustion of diuron at 900 °C include carbon monoxide, carbon dioxide, chlorine, nitrogen oxides, and HCl (Kennedy et al., 1972a). 

An interesting method for the hydrolysis of nitriles to amides involves two redox processes with H2O2 and a peroxycarboximidic acid (236) intermediate stage, as shown in equation 84. The mechanism of hydrolysis was established for acetonitrile and benzonitrile... 

This cycloaddition-reduction-hydrolysis sequence was also used in an approach to butyrolactones related to ribonolactone (71). These compounds are inducing agents of hunger and satiety in mammalians. Here, a subsequent aldol 1,3-diol reduction was used, and the required carboxy function was established by oxidation of the aromatic ring with ruthenium tetroxide. Cycloaddition of benzonitrile oxide to allyl alcohol afforded an enantiomeric mixture of isoxazolines 55 and 56, which were treated with sodium hydride and methyl iodide to achieve separation by chromatography on cellulose triacetate (71). 0-Demethylation, followed by... 

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