Ethyl 3- benzoate

Uses of hydrogen chloride—Hydrogen chloride is sometimes used in the preparation of an ester, for example ethyl benzoate, where it acts as both an acid catalyst and a dehydrating agent. Hydrochloric acid is used primarily to produce chlorides, for example ammonium chloride. It is extensively used in the manufacture of anilme dyes, and for cleaning iron before galvanising and tin-plating. 

Ethyl Benzoate. CeHsCOOCaHs- (Method 2 The Fischer-Speler Method, p. 96.)... 

As a general rule esterification by the Fischer-Speier method should be carried out using absolute cthanob in the following preparation of ethyl benzoate, however, the yield is not sensibly affected by the use of the cheaper rectified spirit. 

When the solution has been boiling for hours, remove A, cool the contents, and then pour the ethanolic solution of the ester into a separating-funnel containing about 200 ml. of water, finally rinsing out the flask with a few ml. of water which are also doured into the funnel. Since the pensity of ethyl benzoate is only... 

Ethyl benzoate is a colourless liquid, of b.p. 213° and dy 1 05 almost insoluble in water it has a characteristic odour. 

Cinnamic acid can be readily esterified by the Fischer-Speier method without any risk of the addition of hydrogen chloride at the double bond. Proceed precisely as for the preparation of ethyl benzoate (p. 104), using 20 g. of cinnamic acid and 20 ml. of rectified spirit. When the crude product is poured into water, a sharp separation of the ester is not readily obtained, and hence the addition of about 10 ml. of carbon tetrachloride is particularly desirable. Finally distil off the carbon... 

Ethyl benzoate Ethyl acetate Ethyl benzoylacetate. 

Triphenyl-carbinol, (C6H5)3COHy from Ethyl Benzoate and Phenyl Magnesium Bromide. (Grignard Reaction 6 (a).)... 

Now remove the flask from the water-bath, and slowly add a solution of 5 ml. (5-2 g.) of dry ethyl benzoate in 15 ml. of anhydrous ether down the condenser in small quantities at a time, mixing the contents of the flask thoroughly between each addition. When the boiling of the ether again subsides, return the flask to the water-bath and reheat for a further 15 minutes. Then cool the mixture in ice-water, and carefully pour off the ethereal solution into a mixture of about 60 ml. of dilute sulphuric acid. and 100 g. of crushed ice contained in a flask of about 500 ml. capacity fitted for stearn-distillation, taking care to leave behind any unchanged magnesium. 

Fit securely to the lower end of the condenser (as a receiver) a Buchner flask, the side-tube carrying a piece of rubber tubing which falls well below the level of the bench. Steam-distil the ethereal mixture for about 30 minutes discard the distillate, which contains the ether, possibly a trace of unchanged ethyl benzoate, and also any biphenyl, CeHs CgHs, which has been formed. The residue in the flask contains the triphenyl carbinol, which solidifies when the liquid is cooled. Filter this residual product at the pump, wash the triphenyl-carbinol thoroughly with water, drain, and then dry by pressing between several layers of thick drying-paper. Yield of crude dry product, 8 g. The triphenyl-carbinol can be recrystallised from methylated spirit (yield, 6 g.), or, if quite dry, from benzene, and so obtained as colourless crystals, m.p. 162. ... 

As a general guide, however, it may be noted that the following have fairly easily recognisable odours methyl and ethyl formate methyl and ethyl acetate (apples) methyl and ethyl benzoate methyl salicylate (oil of winter-green) and ethyl salicylate methyl and ethyl cinnamate. (It is however usually impracticable to distinguish by odour alone between the methyl and ethyl esters of a particular acid.) Methyl and ethyl o. alate, and methyl and ethyl phthalate are almost odourless. Succinic and tartaric esters have faint odours. 

NOTE. Many esters reduce Fehling s solution on warming. This reduction occurs rapidly with the alkyl esters of many aliphatic acids, but scarcely at all with similar esters of aromatic acids (f.g., ethyl oxalate reduces, but ethyl benzoate does not). Note also that this is a property of the ester itself thus both methyl and ethyl oxalate reduce Fehling s solution very rapidly, whereas neither oxalic acid, nor sodium oxalate, nor a mixture of the alcohol and oxalic acid (or sodium oxalate), reduces the solution. 

Ester formation. Add carefully 1 ml. of the liquid to i ml. of ethanol and then warm gently for i minute. Pour into water, make alkaline with aqueous Na2C03 solution (to remove HCl and other acid fumes), and note the odour of ethyl acetate or ethyl benzoate. 

The following liquids may be used (boiling points are given in parentheses) — chlorobenzene (132-3°) bromobenzene (155°) p cymene (176°) o-dichloro-benzene (180°) aniline (184°) methyl benzoate (200°) teti-alin (207°) ethyl benzoate (212°) 1 2 4-trichlorobenzene (213°) iaopropyl benzoate (218°) methyl salicylate (223°) n-propyl benzoate (231°) diethyleneglycol (244°) n-butyl benzoate (250°) diphenyl (255°) diphenyl ether (259°) dimethyl phth ate (282°) diethyl phthalate (296°) diphenylamine (302°) benzophenone (305)° benzyl benzoate (316°). 

Successful results have been obtained (Renfrew and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl and iso-amyl acetat ethyleneglycol diacetate ethyl monochloro- and trichloro-acetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyl adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, ieri.-butyl acetate, n-octadecyl propionate, ethyl and >i-butyl stearate, phenyl, benzyl- and guaicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

Ethyl benzoate sulphuric acid as a catalyst). Use 30 g. of benzoic acid, 115 g. (146 ml.) of absolute ethyl alcohol and 5 g. (2 7 ml.) of concentrated sulphuric acid. Reflux the mixture for 4 hours and work up as for Methyl Benzoate. The yield of ethyl benzoate, b.p. 212-214°, is 32 g. 

C,H,MgBr + C.H COOCjH, — (CeHj)3COMgBr + MgBrOCjHj Plienyl magnesium bromide Ethyl benzoate... 

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. 

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. 

Alcohols, esters (but not ethyl benzoate, ethyl malonate or ethyl oxalate), aldehydes, methyl ketones and cyclic ketones containing less than nine carbon atoms as well as ethers containing less than seven carbon atoms are soluble in 85 p>er cent, phosphoric acid. 

Esters. re-Butyl acetate Ethyl acetate Ethyl benzoate. 

In acetic acid the rates of nitration of chlorobenzene and bromo-benzene were fairly close to being first order in the concentration of aromatic, and nitration fully according to a first-order law was observed with O, m-, and/i-dichlorobenzene, ethyl benzoate and 1,2,4-trichloro-benzene. 

Ingold and his co-workers used the competitive method in their experiments, in which nitration was brought about in acetic anhydride. Typically, the reaction solutions in these experiments contained o-8-I 4 mol of nitric acid, and the reaction time, depending on the reactivities of the compounds and the temperature, was 0-5-10 h. Results were obtained for the reactivities of toluene, > ethyl benzoate, the halogenobenzenes, ethyl phenyl acetate and benzyl chloride. Some of these and some later results are summarized in table 5.2. Results for the halogenobenzenes and nitrobiphenyls are discussed later ( 9.1.4, lo.i), and those for a series of benzylic compounds in 5,3.4. 

On the basis of the general mechanism for acid catalyzed ester hydrolysis shown in Figure 20 4 write an analogous sequence of steps for the spe cific case of ethyl benzoate hydrolysis... 

The two OH groups m the tetrahedral intermediate are equivalent and so either the labeled or the unlabeled one can be lost when the tetrahedral intermediate reverts to ethyl benzoate Both are retained when the tetrahedral intermediate goes on to form benzoic acid... 

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