Ethyl benzoate, nitration

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. 

This gradation is illustrated by the results obtained with the diazonium salts from the isomeric aminobenzoic adds. When the orthQ diazonium nitrate is treated with absolute ethanol only reduction occurs 23 ethyl benzoate is obtained in 63% yield.f The diazonium add sulfate derived from ra-aminobenzoic add is converted into a mixture of ethyl benzoate and ethyl m-ethoxybenzoate, the former preponderating.24 23122 Finally, with the p-diazonium salts the ether reaction is the favored one 22123 from the nitrate the yields of p-ethoxy benzoic add and ethyl benzoate are 60% and 12%, respectively. 

Baker and his co-workers [60,61] investigated the influence of the sulphuric acid concentration in nitrating mixtures on the meta- nitro derivatives of the following compounds benzaldehyde, benzophenone and ethyl benzoate. The content of a meta- nitro derivative increases with the increase in acidity of the solution. For example, in nitration with a nitrating mixture containing 80% sulphuric acid the yield of m- nitrobenzaldehyde is 83.9%. When nitrated with a mixture containing... 

Arrange the following compounds in order of their reactivity towards nitration and give the formulae of the major products of the reactions (a) benzene, benzonitrile, methoxybenzene, tri-fluoromethyObenzene (b) acetanilide, benzoic acid, chlorobenzene, acetophenone (c) phenol, ethyl benzoate, nitrobenzene, bro-mobenzene. 

The kinetics of the nitration reaction depend upon the reaction medimn. Let us consider first the reactions in strong sulfuric acid. Compounds which are nitrated at a conveniently measurable rate in this system are those which have strong —I and effects such as nitrobenzene, anthraqui-none, and ethyl benzoate. The rate of all these nitrations is proportional to the concentration of added nitric acid and of organic substrate... 

FIGURE 14.76 The nitration of ethyl benzoate gives mainly meta product. 

The distribution of partial activities of various positions of the benzene ring in the nitration reaction compared to benzene is presented below for toluene and ethyl benzoate... 

Vinyl acetate-ethyl acetate Propane-propylene Ethanol-isopropanol Hydrochloric acid-water Nitric acid-water Close-boiling Close-boihng Close-boihng Maximum-boiling azeotrope Maximum-boiling azeotrope Phenol, aromatics Acrylonitrile Methyl benzoate Sulfuric acid, calcium chloride for salt process Sulfuric acid, magnesium nitrate for salt process Alternative to simple distillation Alternative to simple distillation, adsorption Alternative to simple distillation Sulfuric acid process rehes heavily on boundary curvature Sulfuric acid process rehes heavily on boundary curvature... 

Calcium Carbonate Calcium Hydroxide Calcium Oxide Calcium Phosphate Calcium Silicate Calcium Sulfate Camphor Carbon Dioxide Carbon Monoxide Cellulose Cellulose Nitrate Cellulose Xanthate Chlorophyll Cholesterol Cinnamaldehyde Citric Acid Collagen Copper(I) Oxide Copper(II) Oxide Copper(II) Sulfate Cyanoacrylate Cyanocohalamin Denatonium Benzoate Dimethyl Ketone Ethyl Acetate Ethyl Alcohol Ethylene Glycol Ethylene Oxide... 

Classification Specially denatured alcohol Definition Ethyl alcohol (100 gal) denatured with (1) potassium iodide USP (80 g) and red mercuric iodide NF (109 g), or (2) thimerosal USP (95 g) or (3) 76 g of any of phenyl mercuric nitrate NF, phenyl mercury chloride NF, or phenyl mercury benzoate... 

Plasticisers are also used in products such as lacquers and adhesives that fall outside the definition of the plastics industry. Dicyclohexyl phthalate is used in nitrocellulose lacquers polyethylene glycol and its monostearate are compatible with cellulose nitrate. Dibutyl maleate is compatible with polyvinyl acetate, and di- -hexyl adipate, diethylene glycol di-2-ethyl butyrate or dibutyl sebacate can be used in polyvinyl butyral. Benzoates are recommended for... 

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