Esters Potassium hydroxide

Formylcrotonic acid butyl ester Potassium hydroxide Ethyl iodide Potassium carbonate... 

Chloroacetlc acid ethyl ester Potassium hydroxide Cysteamine Carbon disulfide Dimethyl sulfate... 

The parent acid is unstable and always reverts to the lactone form shown. It is reconverted to acetoacetic ester by boiling alcoholic potassium hydroxide. Reduced by hydrogen iodide to dimethylpyrone. 

Sodium and potassium hydroxides. The use of these efficient reagents is generally confined to the drying of amines (soda lime, barium oxide and quicklime may also be employed) potassium hydroxide is somewhat superior to the sodium compound. Much of the water may be first removed by shaking with a concentrated solution of the alkali hydroxide. They react with many organic compounds (e.g., acids, phenols, esters and amides) in the presence of water, and are also soluble in certain organic liquids so that their use as desiccants is very limited... 

By hydrolysis of substituted malonic esters with 50 per cent, potassium hydroxide, followed by decarboxylation of the resulting malonic add by heating above the m.p. or, better, by rendering the aqueous solution of the potassium salt of the dibasic acid strongly acid and refluxing the mixture, for example ... 

Boil 2 g. of the ester with 30 ml. of 10 per cent, sodium or potassium hydroxide solution under reflux for at least 1 hour. If the alcohol formed is water (or alkali) soluble, the completion of the hydrolysis will be indicated by the disappearance of the ester layer. Distil ofiF the liquid through the same condenser and collect the first 3-5 ml. of distillate. If a distinct la3 er separates on standing (or upon saturation of half the distillate with potassium carbonate), remove this layer with a capillary dropper, dry it with a little anhydrous potassium carbonate or anhydrous calcium sulphate, and determine the b.p. by the SiwoloboflF method... 

It is frequently advisable in the routine examination of an ester, and before any derivatives are considered, to determine the saponification equivalent of the ester. In order to ensure that complete hydrolysis takes place in a comparatively short time, the quantitative saponi fication is conducted with a standardised alcoholic solution of caustic alkali—preferably potassium hydroxide since the potassium salts of organic acids are usuaUy more soluble than the sodium salts. A knowledge of the b.p. and the saponification equivalent of the unknown ester would provide the basis for a fairly accurate approximation of the size of the ester molecule. It must, however, be borne in mind that certain structures may effect the values of the equivalent thus aliphatic halo genated esters may consume alkali because of hydrolysis of part of the halogen during the determination, nitro esters may be reduced by the alkaline hydrolysis medium, etc. 

Into a 2-litre, three-necked flask, fitted with a separatory funnel, a mechanical stirrer and a reflux condenser, place a hot solution of 200 g. of potassium hydroxide in 200 ml. of water. Stir the solution and add slowly 200 g. of ethyl n-butylmalonate (Section 111,154). A vigorous reaction occurs and the solution refluxes. When all the ester has been added, boil the solution gently for 2-3 hours, i.e., until hydrolysis is complete a test portion should dissolve completely in water. Dilute with 200 ml. of water and distil oflF 200 ml. of liquid in order to ensure the complete removal of the alcohol formed in the hydrolysis (1) it is best to connect the flask by means of a wide delivery tube to a condenser set for downward distillation (compare Fig. II, 41, 1 but with a mercury-sealed stirrer in the centre neck). Replace the separatory funnel and the reflux condenser. 

Diethylene glycol method. Place 0-5 g. of potassium hydroxide pellets, 3 ml. of diethylene glycol and 0 5 ml. of water in a 10 or 25 ml. distilling flask heat the mixture gently until the alkali has dissolved and cool. Add 1-2 g. of the ester and mix well. Fit the flask with a thermometer and a small water-cooled condenser in the usual way. Heat the flask over a small flame whilst shaking gently to mix the contents. When only one liquid phase, or one hquid phase and one solid phase, remains in the flask, heat the mixture more strongly so that the alcohol distils. Identify the alcohol in the distillate by the preparation of the 3 5 dinitrobenzoate (Section 111,27,2). 

The determination of the saponification equivalent of an ester by the alcohohc potassium hydroxide method is described in Section 111,106 an alternative procedure using diethylene glycol is given below. This constant should be determined if possible in the prehminary examination, since a knowledge of its value together with the boihng point provides a basis for a fairly good approximation of the size of the ester molecule. 

The most widely used method for the preparation of carboxylic acids is ester hydrolysis. The esters are generally prepared by heterocyclization (cf. Chapter II), the most useful and versatile of which is the Hantzsch s synthesis, that is the condensation of an halogenated a- or /3 keto ester with a thioamide (1-20). For example ethyl 4-thiazole carboxylate (3) was prepared by Jones et al. from ethyl a-bromoacetoacetate (1) and thioformamide (2) (1). Hydrolysis of the ester with potassium hydroxide gave the corresponding acid (4) after acidification (Scheme 1). 

Titration of thioglycolate esters is also realized by iodine in alcohoHc solution. Titration of thioglycolic acid (acid number) in thioglycolate esters is effected by potentiometric titration with potassium hydroxide. 

A solution of 130 g. (0.52 mole) of this ester in 400 cc. of ethyl alcohol is placed in a two-necked 2-I. flask, carrying a dropping funnel and a reflux condenser, and is heated to boiling. Then one-third of a solution (Note 2) of 78.5 g. (1.4 moles) of potassium hydroxide in 400 cc. of alcohol is added from the dropping funnel, and the alcoholic solution is boiled until it becomes clear. Then a second third of the alkali solution is added, and the reaction mixture is again boiled until any precipitate disappears. Finally, the last third of the alcoholic potassium hydroxide solution is added. The addition of the alkali requires about twenty minutes. The reaction mixture is then boiled for forty minutes longer. 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Potassium carbonate. Solid potassium hydroxide is very rapid and efficient. Its use is limited almost entirely to the initial drying of organic bases. Alternatively, sometimes the base is shaken first with a concentrated solution of potassium hydroxide to remove most of the water present. Unsuitable for acids, aldehydes, ketones, phenols, thiols, amides and esters. Also used for drying gaseous amines and ammonia. 

Cellobiose was prepared first by Skraup and Konig by the saponification of the octaacetate with alcoholic potassium hydroxide, and the method was improved by Pringsheim and Merkatz.3 Aqueous barium hydroxide also has been employed for the purpose, and methyl alcoholic ammonia has been used extensively for the hydrolysis of carbohydrate acetates. The method of catalytic hydrolysis with a small quantity of sodium methylate was introduced by Zemplen,i who considered the action to be due to the addition of the reagent to the ester-carbonyl groups of the sugar acetate and the decomposition of the addition compound by reaction with alcohol. The present procedure, reported by Zemplen, Gerecs, and Hadacsy, is a considerable improvement over the original method (see Note 2). 

Saponification number (DIN 51 559). The saponification number is indicative of the presence of ester groups in a resin. The saponification number is defined as the consumption of potassium hydroxide in milligrams by one gram of resin under standardized conditions. 

Though the discussion above was aimed primarily at wood binders, many of the ideas carry over into foundry and glass binding applications. For example, potassium hydroxide is used extensively in foundry binders as are esters and... 

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