Sodium alcohols and

Transesterification, an equiUbrium reaction, is practical only when the alcohol to be esterified has a high boiling point and the leaving alcohol can be removed by distillation. The most widely used catalysts are sodium alcoholates and organic titanates, although amines are also used (30,31). 

Ethylmalonic Acid.—Like acetoacetic ester (see p. 83), diethylmalonate contains the gioup CO.CHj.CO. By the action of sodium or sodium alroholate, the hydrogen atoms of the methylene group are successively replaceable by sodium. The sodium atoms are in turn replaceable by alkyl or acyl groups. Thus, in the present preparation, ethyl malonic ester is obtained by the action of ethyl iodide on the monosodium compound. If this substance be treated with a second molecule of sodium alcoholate and a second molecule of alkyl iodide, a second radical would be in roduced, and a compound formed of the general formula... 

TABLE 7 Krafft Temperatures of Sodium Alcohol and Alcohol Ether Sulfates... 

The bicyclic lactam acetal (40) was formed when pyrido[2,l-b][l,3]-oxazinium perchlorate (38) was treated with sodium methylate [70JCS(CC)900]. Treatment of 38 with sodium alcoholate and then with an alkyl halide gave quaternary salts 35, presumably as a mixtures of two stereoisomers (79TL809). 

Of.B., 18,173 B., 12,10 9. 0.8., ,820 Ann., 29. 129 Perkin showed that the ester would not react with sodium alcoholate and benzoyl chloride,thus prov lng the absence of a replaceable hydrogen atom. 

Nitroso-/ -phenylhydroxylamine, of which cupferron is the ammonium salt, has been made by the action of sodium nitrite and hydrochloric acid on /3-phenylhydroxylamine,1 of hydrogen peroxide on normal phenyldiazotates,2 of sodium alcoholate and hydroxylamine on nitrobenzene,3 of nitric oxide on phenyl magnesium bromide,4 and by the action of permonosulfuric acid on aniline in the presence of amyl nitrite.5... 

It should be noted that owing to the great affinity of the phenol for sodium, no sodium alcoholate remains to react with the ethyl iodide. Diethyl ether, however, may be prepared in a similar manner, using the same quantities of sodium, alcohol and ethyl iodide as above. The ether and excess of alcohol are distilled off and the ether separated from the alcohol by the addition of salt solution. Anisole (phenylmethyl ether, B.P. 154°, see p. 218) can also be prepared in a similar way, using corresponding quantities of methyl alcohol and methyl iodide. The alkyl iodides give the best yields, but alkyl chlorides can also be employed. 

Using Alfin catalysts, butadiene polymers were already obtained in the 1940s. The Alfin catalytic system consists of three components (formed in statu nascendi from alkyl chloride, metallic sodium, alcohol and olefin) sodium salt of secondary alcohol (e.g. sodium isopropoxide), alkenylsodium (e.g. allyl-sodium) and finely dispersed sodium chloride (the name Alfin originates from a/cohol + olefin) [2,3], Since the molecular weight of polybutadiene obtained with Alfin catalysts is very high (it can reach a value of a few millions), 1,4-dihydronaphthalene is often added to the polymerisation system for the regulation of molecular weight [1],... 

T. Urbanski and Pawlowski [89] investigated the salts formed on treating trinitrotoluene in acetone-alcohol solution with sodium alcoholate and also with an alcoholic solution of Ba(OH)2. Various addition products were obtained, according to the proportion of the alcoholate or hydroxide, e.g. ... 

Allylic chlorides, e.g., allyl, methallyl, and crotyl chlorides, are very reactive and are employed in the synthesis of unsaturaled ethers Besides the usual coupling of the sodium alcoholate and halide in alcohol solutions other conditions have been described, including reaction of the alcohol and unsaturated halide in the presence of potassium carbonate or sodium hydroxide in acetone or water. The combination of anhydrous potassium carbonate and acetone is widely used in the preparation of allyl aryl ethers the reaction is aided by the addition of finely powdered potassium iodide. ... 

Sodium Alcoholate or Phenate. Sodium alcoholate and phenate react with diphenyl chloroarsine as follows ... 

With sodium hydroxide or better with sodium, alcohol forms sodium alcoholate, a salt in which the ethyl radical plays the part of a non-metal, while with hydrochloric acid it forms ethyl chloride, a salt in which the ethyl radical plays the part of a metal. Now while alcohol acts as an acid toward only the strong bases it acts as a base toward practically all acids. We may say then that the basic character of alcohol is more pronounced than the acid. In both of these cases we have reactions that are simply the neutralization of an acid or a base by a base or an acid, the products being the same as in all neutralizations, viz., a salt and water. Both sodium alcoholate and ethyl chloride are to be looked upon then as salts. 

From sodium alcoholates and carbon monoxide. This is analogous to the above, the carboxyl group being formed by the direct entrance of the carbon monoxide. 

But the mechanism of the reaction is much more complicated than here indicated. According to the views of Claisen, the sodium first acts on the alcohol, which, as above mentioned, must be present in small quantities, forming sodium alcoholate, and this unites with the acetic ester as follows ... 

V) The ester of malonic acid, like acetacetic ester, possesses the property in virtue of which one of the two methylene hydrogen atoms can be replaced by sodium, in consequence of the acid properties imparted by the two neighbouring carbonyl (CO) groups. When the sodium compound is treated with organic halides, like alkyl halides, halogen derivatives of add-esters, acid-chlorides, etc., the sodium is replaced by alkyl residues, add residues, etc-, just as in the case of the dosely related acetacetic ester. In the above-mentioned examples, the sodium salt of the malonic ester is first formed from sodium alcoholate and the ester ... 

Certain electrocatalytic, or at very least electrochemical, processes correspond to classical preparative techniques in organic chemistry such preparations as those involving sodium-alcohol and zinc-dust-acid reductions, or indeed the many processes using different heterogeneous reductive agents... 

Sodium alcohol and sodium carbonate NaOR and Na2COg... 

Sodium/alcohol and sodium hydroxide NaOR and NaOH... 

It is readily oxidized by air to benzoic acid. With aqueous KOH gives benzyl alcohol and benzoic acid. Gives addition products with hydrogen cyanide and sodium hydrogen sulphite. 

CCls CHO. A colourless oily liquid with a pungent odour b.p. 98°C. Manut actured by the action of chlorine on ethanol it is also made by the chlorination of ethanal. When allowed to stand, it changes slowly to a white solid. Addition compounds are formed with water see chloral hydrate), ammonia, sodium hydrogen sulphite, alcohols, and some amines and amides. Oxidized by nitric acid to tri-chloroethanoic acid. Decomposed by alkalis to chloroform and a methanoate a convenient method of obtaining pure CHCI3. It is used for the manufacture of DDT. It is also used as a hypnotic. 

Fig. XIV-3. Steric effects in the penetration of sodium cetyl sulfate monolayers by cetyl alcohol and oleyl alcohol.

Although the acetylation of alcohols and amines by acetic anhydride is almost invariably carried out under anhydrous conditions owing to the ready hydrolysis of the anhydride, it has been shown by Chattaway (1931) that phenols, when dissolved in aqueous sodium hydroxide solution and shaken with acetic anhydride, undergo rapid and almost quantitative acetylation if ice is present to keep the temperature low throughout the reaction. The success of this method is due primarily to the acidic nature of the phenols, which enables them to form soluble sodium derivatives, capable of reacting with the acetic... 

The cost of this preparation (particularly for large classes) can be appreciably reduced by using a solution of 20 g. of sodium hydroxide in 25 ml. of water, in place of the potassium hydroxide solution. In this case, however, the product on standing overnight forms a very hard mass, which should be dissolved in tcarm water. The yields of alcohol and acid are unchanged. 

All esters are hydrolysed by sodium hydroxide to the alcohol (or sodium phenoxide) and the sodium salt of the acid from which they are derived. 

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. 

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