Benzyl alcoholate

It is readily oxidized by air to benzoic acid. With aqueous KOH gives benzyl alcohol and benzoic acid. Gives addition products with hydrogen cyanide and sodium hydrogen sulphite. 

It is prepared by the direct chlorination of toluene in the presence of PClj. It is purified by fractionation from the unchanged toluene and the higher chlorinated products. It is used for benzylating amines and for preparing benzyl alcohol. 

Cannizzaro reaction Two molecules of many aldehydes, under the influence of dilute alkalis, will interact, so that one is reduced to the corresponding alcohol, while the other is oxidized to the acid. Benzaldehyde gives benzyl alcohol and benzoic acid. Compare the aldol condensation. 

Benzyl Alcohol, CeH5CH20H, and Benzoic Acid, CaHsCOOH. (Cannizzaro s Reaction). 

A crystalline derivative of benzyl alcohol cannot be obtained by using benzoyl chloride, because the benzyl benzoate, C HiCOOCHiCaHj, so obtained has m.p. 18°, and is thus usually liquid the present preparation illustrates therefore the use of a substituted benzoyl chloride (p-nitrobenzoyl chloride, m.p. 75°) in order to obtain a crystalline derivative of suitably high m.p. 

Place I ml. of benzyl alcohol in a boiling-tube and add 6 ml. of 10% sodium hydroxide solution add also 6 ml. of water to moderate the subsequent reaction, otherwise the rise in temperature may cause hydrolysis of some of the ester produced. Now add r-q g. of finely powdered />-nitrobenzoyl chloride, and shake the well-corked tube vigorously. The mixture becomes warm, and the solid ester rapidly... 

Alcohols. Methanol, ethanol, n propanol, propan-i-ol.n-butanol, glycol, glycerol, benzyl alcohol, cyclohexanol. 

Undergoes Cannizzaro s reaction, giving benzyl alcohol and benzoic acid (p. 229). Warm gently for several minutes, cool, add a few ml. of water and then cone. HCl, and cool again. Crystals of benzoic acid separate out on scratching the sides of the tube with a glass rod. 

Physical Properties. All colourless liquids, completely miscible with water, except benzyl alcohol and cyclohexanol, which are slightly soluble. Pure glycol and glycerol have high viscosity, which falls as the hygroscopic liquids absorb water from the air. 

Glycol and glycerol are odourless the other alcohols have faint odours, that of benzyl alcohol being characteristic. 

Example. Add a solution of 0 5 ml. of benzyl alcohol in 5 ml. of petroleum (b.p. 100-120 ) to a similar solution of 0 5 ml. of phenylisocyanate, and boil the mixture gently under reflux for 20 minutes. Filter hot if necessary from any insoluble diphenylurea, and cool. Filter off the crystalline urethane, and recrystallise from the petroleum colourless crystals, m.p. 76 . 

C) Carboxylic adds For aryl-substituted alcohols, such as benzyl alcohol, oxidation readily gives the corresponding add (c/. p. 336). 

Almost insoluble in cold water. Higher alcohols (including benzyl alcohol), higher phenols (e.g., naphthols), metaformaldehyde, paraldehyde, aromatic aldehydes, higher ketones (including acetophenone), aromatic acids, most esters, ethers, oxamide and domatic amides, sulphonamides, aromatic imides, aromatic nitriles, aromatic acid anhydrides, aromatic acid chlorides, sulphonyl chlorides, starch, aromatic amines, anilides, tyrosine, cystine, nitrocompounds, uric acid, halogeno-hydrocarbons, hydrocarbons. 

CH3COOH + C.HsCHjOH Acetic acid Benzyl alcohol... 

Mix 31 g. (29-5 ml.) of benzyl alcohol (Section IV, 123 and Section IV,200) and 45 g. (43 ml.) of glacial acetic acid in a 500 ml. round-bottomed flask introduce 1 ml. of concentrated sulphuric acid and a few fragments of porous pot. Attach a reflux condenser to the flask and boil the mixture gently for 9 hours. Pour the reaction mixture into about 200 ml. of water contained in a separatory funnel, add 10 ml. of carbon tetrachloride (to eliminate emulsion formation owing to the slight difference in density of the ester and water, compare Methyl Benzoate, Section IV,176) and shake. Separate the lower layer (solution of benzyl acetate in carbon tetrachloride) and discard the upper aqueous layer. Return the lower layer to the funnel, and wash it successively with water, concentrated sodium bicarbonate solution (until effervescence ceases) and water. Dry over 5 g. of anhydrous magnesium sulphate, and distil under normal pressure (Fig. II, 13, 2) with the aid of an air bath (Fig. II, 5, 3). Collect the benzyl acetate a (colourless liquid) at 213-215°. The yield is 16 g. 

Benzyl alcohol. This alcohol, b.p. 205-5°, may be similarly prepared from benzaldehyde in approximately the same yield (compare Section IV, 123.)... 

The catalyst is inactive for the hydrogenation of the (isolated) benzene nucleus and so may bo used for the hydrogenation of aromatic compounds containing aldehyde, keto, carbalkoxy or amide groups to the corresponding alcohols, amines, etc., e.g., ethyl benzoate to benzyl alcohol methyl p-toluate to p-methylbenzyl alcohol ethyl cinnamate to 3 phenyl 1-propanol. 

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