Anisol

Preparation and Properties of Anisol (SECTION 541).— (a) Add to 50 cc. of methyl alcohol, contained in a 250-cc. flask, 2.5 grams of sodium the metal should be cut into about half a 

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HYOCML 0.50 WATER 1.30 HYOSUL 0.30 AMMNlA 1.10 SULDIO 0.30 ANISOL 0.60 ACRNTR 1.40... 

CioHi O. White leaflets, with a strong smell and sweet taste, m.p. 22 C, b.p. 235 C. The chief constituent of anise and fennel oils and other essential oils, from which it is manufactured. It can also be prepared from anisole (meihoxybenzene). It is widely used for flavouring pharmaceuticals and dentifrices, and in perfumery. 

When a solution of a diazonium compound in absolute methanol is boiled, the chief product is the corresponding methyl ether, henzenediiizonium hydrogen sulphate thus giying methyl phenyl etlier or anisole ... 

Anisole (Methyl Phenyl Ether). CeHjOCHa. (Method i.)... 

Anisole is a colourless and almost odourless liquid, having b.p. 154°, and dy 0-99. Like the aliphatic ethers, it is chemically inert, although of course the phenyl group shows the normal aromatic reactions. 

In view of the high cost of methyl iodide in the above preparation of anisole, and the fact that, unless absolute methanol is used, the ready hydrolysis of the methyl iodide may cause a low yield of the ether, the preparation of anisole may be ad antageously replaced by that of phenetole. I he reaction is not of course a methylation, but is nevertheless of the same type as that used in the preparation of anisole. 

Dissolve 3-8 g. of sodium in 75 mi. of rectified spirit, using otherwise the same conditions as in the preparation of anisole. Then add 15 g. of phenol, and to the clear solution add 13 2 ml. (19-1 g., n mois.) of ethyl bromide. Continue precisely as in the preparation of anisole, shaking the ethereal extract with sodium hydroxide solution as before in order to eliminate any unchanged phenol. Finally collect the fraction boiling at 168-172°. Yield, 14 g. 

Heat under reflux i g. of anisole and 10 ml. of constant-boiling hydrogen iodide for 30 minutes. Now distil off the volatile methyl iodide and identify it in the distillate (see pp. 390-391). 

Add the dimethyl sulphate dropwise during 1 hour whilst stirring the mixture vigorously. Then reflux for 2 hours, with stirring, in order to complete the methylation. Allow to cool, add water, transfer to a separatory funnel, remove the lower layer, and wash once with water, twice with dilute sulphuric acid, and then with water until the washings are neutral to litmus. Add some sodium chloride to each washing as this will facilitate the separation of the two layers for anisole is 0- 996). Dry over anhydrous calcium chloride or magnesium sulphate, and distil from an air bath. Collect the anisole at 151-154°. The yield is 40 g. 

An additional useful test is to distil the acid or its sodium salt with soda lime. Heat 0.5 g. of the acid or its sodium salt with 0 2 g. of soda lime in an ignition tube to make certain that there is no explosion. Then grind together 0-5 g. of the acid with 3 g. of soda hme, place the mixture in a Pyrex test-tube and cover it with an equal bulk of soda hme. Fit a wide dehvery tube dipping into an empty test-tube. Clamp the tube near the mouth. Heat the soda lime first and then the mixture gradually to a dull-red heat. Examine the product this may consist of aromatic hydrocarbons or derivatives, e.g., phenol from sahcyUc acid, anisole from anisic acid, toluene from toluic acid, etc. 

Compounds which dissolve in concentrated sulphuric acid may be further subdivided into those which are soluble in syrupy phosphoric acid (A) and those which are insoluble in this solvent (B) in general, dissolution takes place without the production of appreciable heat or colour. Those in class A include alcohols, esters, aldehydes, methyl ketones and cyclic ketones provided that they contain less than nine carbon atoms. The solubility limit is somewhat lower than this for ethers thus re-propyl ether dissolves in 85 per cent, phosphoric acid but re-butyl ether and anisole do not. Ethyl benzoate and ethyl malonate are insoluble. 

Ethers. Di-re-butyl ether Anisole Diphenyl ether. 

Sulphinic acids. Aromatic sulphinic acids are found in Solubility Group II. They may be detected by dissolving in cold concentrated sulphuric acid and adding one drop of phenetole or anisole when a blue colour is produced (Smiles s test), due to the formation of a para-substituted aromatic sulphoxide. Thus the reaction with benzenesulphinic acid is ... 

The nitration of anisole in 40% aq. nitric acid in the presence of some nitrous acid yielded 2,4-dinitrophenol as the main product. In more concentrated solutions of nitric acid 0- and />-nitroanisoles were the main products, less than o-1 % of the weta-isomer being formed. " The isomeric ratios for nitration imder a variety of conditions are given later ( 5.3.4). 

The kinetics of nitration of anisole in solutions of nitric acid in acetic acid were complicated, for both autocatalysis and autoretardation could be observed under suitable conditions. However, it was concluded from these results that two mechanisms of nitration were operating, namely the general mechanism involving the nitronium ion and the reaction catalysed by nitrous acid. It was not possible to isolate these mechanisms completely, although by varying the conditions either could be made dominant. 

It was shown that in preparative experiments sulphuric acid markedly catalysed, and acetate ions markedly anticatalysed the nitration of anisole. ... 

The authors of this work were concerned chiefly with additions to alkenes, and evidence about the mechanism of aromatic nitration arises by analogy. Certain aspects of their work have been repeated to investigate whether the nitration of aromatic compounds shows the same phenomena ( 5-3-6). It was shown that solutions of acetyl nitrate in acetic anhydride were more powerful nitrating media for anisole and biphenyl than the corresponding solutions of nitric acid in which acetyl nitrate had not been formed furthermore, it appeared that the formation of acetyl nitrate was faster when 95-98% nitric acid was used than when 70 % nitric acid was used. 

Zeroth-order nitrations. The rates of nitration at 25 °C in solutions of acetyl nitrate (6xio —0-22 mol 1 ) in acetic anhydride of 0- and jw-xylene, and anisole and mesitylene were independent of the concentration and nature of the aromatic compound provided that... 

Acetoxylation and nitration. It has already been mentioned that 0- and m-xylene are acetoxylated as well as nitrated by solutions of acetyl nitrate in acetic anhydride. This occurs with some other homologues of benzene, and with methyl phenethyl ether,ii but not with anisole, mesitylene or naphthalene. Results are given in table 5.4. 

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