Sodium acetate acid formate

The azlactones of a-benzoylaminocinnamic acids have traditionally been prepared by the action of hippuric acid (1, Ri = Ph) and acetic anhydride upon aromatic aldehydes, usually in the presence of sodium acetate. The formation of the oxazolone (2) in Erlenmeyer-Plochl synthesis is supported by good evidence. The method is a way to important intermediate products used in the synthesis of a-amino acids, peptides and related compounds. The aldol condensation reaction of azlactones (2) with carbonyl compounds is often followed by hydrolysis to provide unsaturated a-acylamino acid (4). Reduction yields the corresponding amino acid (6), while drastic hydrolysis gives the a-0X0 acid (5). ... 

Solubility op Cinnamic Acid in Aqueous Solutions of Sodium Acetate, Butyrate, Formate, and Salicylate at 26.4 . 

Phenylhydrazine is usually dissolved in acetic acid for hydrazone formation if a salt of phenylhydrazine with an inorganic acid is used, it must be mixed with an excess of sodium acetate (see preparation of osazones, p. 137). 

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. 

The metals are impregnated together or separately from soluble species, eg, Na2PdCl4 and HAuCl or acetates (159), and are fixed by drying or precipitation prior to reduction. In some instances sodium or potassium acetate is added as a promoter (160). The reaction of acetic acid, ethylene, and oxygen over these catalysts at ca 180°C and 618—791 kPa (75—100 psig) results in the formation of vinyl acetate with 92—94% selectivity the only other... 

Examples are given of common operations such as absorption of ammonia to make fertihzers and of carbon dioxide to make soda ash. Also of recoveiy of phosphine from offgases of phosphorous plants recoveiy of HE oxidation, halogenation, and hydrogenation of various organics hydration of olefins to alcohols oxo reaction for higher aldehydes and alcohols ozonolysis of oleic acid absorption of carbon monoxide to make sodium formate alkylation of acetic acid with isobutylene to make teti-h ty acetate, absorption of olefins to make various products HCl and HBr plus higher alcohols to make alkyl hahdes and so on. 

Acids that are solids can be purified in this way, except that distillation is replaced by repeated crystallisation (preferable from at least two different solvents such as water, alcohol or aqueous alcohol, toluene, toluene/petroleum ether or acetic acid.) Water-insoluble acids can be partially purified by dissolution in N sodium hydroxide solution and precipitation with dilute mineral acid. If the acid is required to be free from sodium ions, then it is better to dissolve the acid in hot N ammonia, heat to ca 80°, adding slightly more than an equal volume of N formic acid and allowing to cool slowly for crystallisation. Any ammonia, formic acid or ammonium formate that adhere to the acid are removed when the acid is dried in a vacuum — they are volatile. The separation and purification of naturally occurring fatty acids, based on distillation, salt solubility and low temperature crystallisation, are described by K.S.Markley (Ed.), Fatty Acids, 2nd Edn, part 3, Chap. 20, Interscience, New York, 1964. 

When bicyclo[2.2.2]octyl brosylate was solvolyzed in acetic acid containing sodium acetate, the products were a mixture of bicyclo[2.2.2]octyl acetate and bicyclo[3.2.1]octyl acetate, each of which was optically active. The formation of bicyclo[2.2.2]octyl acetate was found to proceed with 82 15% retention of configuration, a result which is in... 

Steroidal 17-cyanohydrins are relatively stable towards chromium trioxide in acetic acid (thus permitting oxidation of a 3-hydroxyl group ) and towards ethyl orthoformate in ethanolic hydrogen chloride (thus permitting enol ether formation of a 3-keto-A system ). Sodium and K-propanol reduction produces the 17j -hydroxy steroid, presumably by formation of the 17-ketone prior to reduction. ... 

Clearly, the presence of sodium hydroxide has mostly neutralized the acidity of the acetic acid through formation of acetate ion. 

In 1897, Reissert reported the synthesis of a variety of substituted indoles from o-nitrotoluene derivatives. Condensation of o-nitrotoluene (5) with diethyl oxalate (2) in the presense of sodium ethoxide afforded ethyl o-nitrophenylpyruvate (6). After hydrolysis of the ester, the free acid, o-nitrophenylpyruvic acid (7), was reduced with zinc in acetic acid to the intermediate, o-aminophenylpyruvic acid (8), which underwent cyclization with loss of water under the conditions of reduction to furnish the indole-2-carboxylic acid (9). When the indole-2-carboxylic acid (9) was heated above its melting point, carbon dioxide was evolved with concomitant formation of the indole (10). 

Support for this suggestion comes from many quarters. Reduction of the jS-carboline anhydro-bases with sodium and alcohol or with tin and hydrochloric acid gives the 1,2,3,4-tetrahydro derivatives, as does catalytic reduction over platinum oxide in an alkaline medium. On the other hand, catalytic reduction with platinum oxide in acetic acid results in the formation of the 5,6,7,8-tetrahydro-j3-carbolinium derivatives (see Section III,A,2,a). It should be noted, however, that reduction of pyrido[l,2-6]indazole, in which the dipolar structure 211 is the main contributor to the resonance hybrid, could not be effected with hydrogen in the presence of Adams catalyst. 

Carbethoxycyclooctanone (40 g, 0.2 mole) dissolved in 50 ml of dry benzene is added to the stirred sodium hydride over about 30 minutes at room temperature. The mixture is stirred an additional hour at room temperature to complete the formation of the sodium salt. Methyl iodide (284 g, 2.0 mole, a 10-fold excess) is added to the stirred solution over 1 hour and the stirring at room temperature is continued for 20-24 hours. The reaction mixture is poured cautiously into 500 ml of 3 aqueous acetic acid, and the aqueous solution is extracted three times with 100-ml portions of benzene. The combined benzene extracts are washed three times with water and dried over anhydrous magnesium sulfate. Benzene and excess methyl iodide are removed under reduced pressure (rotary evaporator) and the residue is distilled. 

Amyl Acetate.—This is, with the exception of amyl formate, which is not of practical importance, the simplest possible ester of amyl alcohol, and has the formula CHj. COO. CsHjj. It is a fruity oil, with a strong odour resembling that of the pear, and is known as art ficial oil of pear. It is prepared on a very large scale by, for example, treating 100 parts of dry sodium acetate, 100 parts of amyl alcohol, and 130 parts of sulphuric acid for twelve hours at ordinary temperature, and then distilling off the ester. It has a specific gravity 0-876, and boils at 138°. The alcohol in this ester is not normal amyl alcohol, but isoamyl alcohol. 

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