Hydrolysis from alcohols

Hydrolysis of p-tolunitrile to p-toluic acid. Boil a mixture of 5 g. of p-tolunitrile, 80 ml. of 10 per cent, aqueous sodium hydroxide solution and 15 ml. of alcohol under a reflux condenser. (The alcohol is added to prevent the nitrile, which volatUises in the steam, from crystalhsing in the condenser it also increases the speed of hydrolysis. The alcohol may be omitted in the hydrolysis of nitriles which are hquid at the ordinary temperature, e.g., benzo-nitrUe.) The solution becomes clear after heating for about 1 hour, but continue the boiling for a total period of 1 - 5 hours to ensure complete hydrolysis. Detach the condenser and boil the solution for a few minutes in the open flask to remove dissolved ammonia and incidentally some of the alcohol CAUTION /). Cool, and add concentrated hydrochloric acid until precipitation of the p-toluic acid is complete. When cold, filter off the p-toluic acid with suction and wash with a little cold water. Recrystallise from a mixture of equal volumes of water and alcohol (methylated spirit) or from benzene. The yield of p-toluic acid, m.p. 178°, is 5-5 g. 

It may be converted into dibromofluorescein diacetate as follows. Reflux a mixture of 10 g. of dibromofluorescein, 40 ml. of redistilled acetic anhydride and 1 drop of concentrated sulphuric acid for 1 hour, pour into water, filter, wash, and dry the resulting diacetate (95 per cent, yield) has m.p. 210°. Upon recrystallisation from acetic anhydride or nitrobenzene, the pure diacetate (colourless or pale yellow plates), m.p. 211°, is obtained. Hydrolysis with alcoholic sulphuric acid gives a quantitative yield of pure dibromofluorescein, m.p. 285°. 

Glycine ethyl ester hydrochloride has been prepared by the action of absolute alcohol and hydrogen chloride on glycine from glycyl chloride and alcohol by the action of ammonia or hexamethylenetetramine on chloroacetic acid, and subsequent hydrolysis with alcoholic hydrochloric acid and by the action of hydrogen chloride and alcohol on methyleneamino-acetonitrile. ... 

Hydrolysis of alkyl halides (Section 8.1) A reaction useful only with substrates that do not undergo E2 elimination readily. It is rarely used for the synthesis of alcohols, since alkyl halides are normally prepared from alcohols. 

Genvresse and Langlois isolated an alcohol of the sesquiterpene group of the formula GijH.j O from oil of vetiver, which they named vetivenol. This alcohol has been examined by Semmler, Risso, and Schroeter. From the fraction boiling at 260° to 298° at 13 mm. they obtained an ester of vetivenol, C 5H,240, with an acid of the formula. CijHj.jO,. On hydrolysis the alcohol was obtained, which had the following characters —... 

Protection of Alcohols. Trimethylsilyl ethers, readily prepared from alcohols by treatment with a variety of silylating agents have found considerable use for the protection of alcohols. They are thermally stable and reasonably stable to many organometallic reagents and they are easily cleaved by hydrolysis in acid or base or by treatment with fluoride ion. t, Butyl dimethylsilyl ethers have considerably greater hydrolytic stability and are easier to work with than trimethylsilyl ethers. They are prepared from alcohols by treatment with t. butyl dimethylsilyl chloride. 

In a 2-1. round-bottom flask, fitted with a stopper holding a dropping funnel and a mechanical stirrer, is placed a mixture of 275 cc. of concentrated nitric acid (sp. gr. 1.42) and 275 cc. of concentrated sulfuric acid (sp. gr. 1.84). This is cooled to io° in a freezing mixture, and 100 g. of benzyl cyanide (free from alcohol and water) are run in slowly, at such a rate that the temperature remains at about io° and does not exceed 20°. After all the benzyl cyanide has been added (about one hour), the ice bath is removed, the mixture is stirred for an hour and then poured on to 1200 g. of crushed ice. A pasty mass slowly separates more than half of this mass is -nitrobenzyl cyanide, the other constituents being o-nitrobenzyl cyanide, and a variable amount of an oil which resists hydrolysis apparently no dinitro compounds are formed. The mass is filtered on a porcelain funnel with suction, pressed well to remove as much oil as possible, and dissolved in 500 cc. of boiling alcohol (95 per cent). On cooling, -nitrobenzyl cyanide crystallizes the mother liquor, on distillation, gives an impure alcohol which can be used for the next run. Recrystallization from 550 cc. of 80 per cent alcohol (sp. gr. 0.86 to 0.87) yields 70 to 75 g. (50-54 per cent) of a product which melts at 115-116°. 

Kozikowski and Li (268) also made use of this protocol for the construction of the hexahydronaphthalene portion of the hypocholesteremic agent compactin (256) (see Section 6.4.2.2). The oxime derived by from alcohol 253 (via y-lactone 252) was heated with aqueous sodium hypochlorite in the presence of triethylamine to give the tricyclic isoxazoline adduct 254 (Scheme 6.96). Reductive hydrolysis and dehydration afforded enone 255, which in several further steps led to compactin (256) (268). 

The particle characteristics such as particle size, crg, yield, and particle number density were independent on the reaction time and temperature examined in the formation of Fe203 particles from an emulsion state. However, the particle characteristics are generally influenced by the reaction time and temperature in the particle formation from the hydrolysis in alcohol solution, because the reaction time and temperature promote the hydrolysis reaction. 

Usually, after hydrolysis, the alcohol is the product, but sometimes (especially with aryl aldehydes) elimination follows directly and the product is an olefin. By the use of Bu,P along with Zn, the olefin can be made the main product,454 making this an alternative to the Wittig reaction (6-47). Since Grignard reagents cannot be formed from a-halo esters, the method is quite useful, though there are competing reactions and yields are sometimes low. A similar reaction (called the Blaise reaction) has been carried out on nitriles 455... 

Oxygen abstraction reactions from alcohols, ketones, acyl halides and other oxygen-containing compounds by MCI or related derivatives also afforded a route to relatively simple complexes of the oxo halides (Table 24). Thus Nb2Cli0 was found to abstract oxygen from higher ketones to yield, after hydrolysis, alkanes, chloroalkanes or arylalkanes.414... 

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