Ether salicylic acid

Ullmann, F. A new path for preparing phenyl ether salicylic acid. Ber. 1904, 37, 853-854. 

Bis(salicylic acids) have been polymerized with metal salts to yield the chelate polymers (lX-26). Metal acetylacetonates (72), and metal chlorides and acetates have been used. Aqueous (9, 99,131) or organic (72) media are suitable. Data indicating that high molecular weight products were obtained have not been presented. The insolubility of the products is the main reason. A comparative study of the polymerization of a free bis(salicylic acid), the corresponding bis(methyl salicylate), and the corresponding bis(methyl ether salicylic acid) has been reported (72). 

In the following experiment, salicylic acid is reduced to o-hydroxybenzyl alcohol (or saligenin), which being crystalline is readily isolated the excess of hydride is destroyed by the addition of undried ether, and the aluminium hydroxide then brought into solution by the addition of sulphuric acid. 

Required Salicylic acid, 6 0 g. lithium aluminium hydride, 2 5 g. dry ether, 165 ml. 

Now cool the mixture thoroughly in ice-water, and run in over a period of 45 minutes a solution of 6 o g. of dry salicylic acid in 75 ml. of dry ether. When the addition of the acid to the stirred solution is complete, heat the mixture under reflux on the water-bath for 15 minutes to ensure completion of the reduction. Then thoroughly chill the mixture in ice-water, and hydrolyse any unused hydride by the slow addition of 50 ml. of ordinary undried ether, followed similarly by 75 ml. of dilute sulphuric acid. 

Xanthone (Coll. Vol. i, 537) In nearly quantitative yields by distillation in vacuo of the acid chloride formed by the action of thionyl chloride on the phenyl ether of salicylic acid. Lock and Kempter, Monatsh. 67, 24 (1936). 

In the first total synthesis of thromboxane A2, lactone 340 is opened by potassium trimethylsilanolate 97 to give the potassium salt 341 [120]. The potassium salt of the methoxymethyl ether of salicylic acid is prepared likewise [121], as are... 

Dinitrofluorobenzene (DNFB) reacts with phenols and, which is not of interest here, with amino groups. Hydrogen fluoride is eliminated. DNFB does not react w ith carboxylic acids. Alcohols, if they react at all, form dinitrophenyl ethers very slowly. Very weakly dissociated phenolic hydroxyl groups, e.g., in salicylic acid (pK = 13.4), are inert towards DNFB. 

Silica gel Petrol ether / acetic acid (9/1) UV 223 and 295 nm Benzoic acid. Salicylic acid 18... 

Silica gel Hexane / ether / acetic acid (81/5/4) Bromphenol blue Benzoic acid. Sorbic acid. Salicylic acid 22... 

Long introduces ether as an anesthetic Locock accidentally discovers bromides as anticonvulsants Lister pioneers use of phenol as a surgical antiseptic Liebreich discovers hypnotic effects of chloral hydrate Strieker uncovers analgesic properties of salicylic acid Guthzeit and Conrad synthesize a series of barbiturates Erlich pioneers concepts of receptor and chemotherapy ... 

Alkylation involving formaldehyde in the presence of hydrogen chloride is known as chloromethylation (eq. 3). The reagent may be a mixture of formalin and hydrochloric acid, paraformaldehyde and hydrochloric acid, a chloromethyl ether, or a formal. Zinc chloride is commonly employed as a catalyst, although many other Lewis acids can be used. Chloromethylation of salicylic acids yields primarily the 5-substituted product 5-chloromethylsalicylic... 

Numerous methods for the synthesis of salicyl alcohol exist. These involve the reduction of salicylaldehyde or of salicylic acid and its derivatives. The alcohol can be prepared in almost theoretical yield by the reduction of salicylaldehyde with sodium amalgam, sodium borohydride, or lithium aluminum hydride by catalytic hydrogenation over platinum black or Raney nickel or by hydrogenation over platinum and ferrous chloride in alcohol. The electrolytic reduction of salicylaldehyde in sodium bicarbonate solution at a mercury cathode with carbon dioxide passed into the mixture also yields saligenin. It is formed by the electrolytic reduction at lead electrodes of salicylic acids in aqueous alcoholic solution or sodium salicylate in the presence of boric acid and sodium sulfate. Salicylamide in aqueous alcohol solution acidified with acetic acid is reduced to salicyl alcohol by sodium amalgam in 63% yield. Salicyl alcohol forms along with -hydroxybenzyl alcohol by the action of formaldehyde on phenol in the presence of sodium hydroxide or calcium oxide. High yields of salicyl alcohol from phenol and formaldehyde in the presence of a molar equivalent of ether additives have been reported (60). Phenyl metaborate prepared from phenol and boric acid yields salicyl alcohol after treatment with formaldehyde and hydrolysis (61). 

SALICYLIC ACID AND RELATED COMPOUNDS. [CAS 69-72-7], Salicylic acid or C H4(OH)(COOH) is a white solid, melting points 159°C, sublimes at 76°C, insoluble in cold water, soluble in hot water, alcohol, or ether. With ferric chloride solution, salicylic acid solutions are colored violet (distinction from benzoic acid). 

The crude material, which is a mixture of pimelic acid and unchanged salicylic acid, is esterified by boiling for four hours with 260 cc. of absolute ethyl alcohol and 3 cc. of concentrated sulfuric acid. Two-thirds of the alcohol is then removed by distillation. To the residue, 300 cc. of water and 200 cc. of ether are added, the mixture is shaken and the aqueous layer is removed. The ether solution is washed with two 100-cc. portions of 2 N sodium hydroxide solution to remove the ethyl salicylate (Note 7) and then with water until the disappearance of an alkaline reaction. The ether is evaporated and the residue is distilled under reduced pressure. The ethyl pimelate boils at i53-i56°/24 mm. i48-i52°/22 mm. The yield is 27-30 g. (35-38 per cent of the theoretical amount based upon the salicylic acid used). 

Salicylic Acid, ioo c.c. of the milk are shaken with ioo c.c. of hot water (6o°), 8 drops of acetic acid and 8 drops of mercurous nitrate solution and filtered, the filtrate being shaken with 50 c.c. of a mixture of ether and petroleum ether in equal volumes. The ethereal layer is then separated and the solvent evaporated, the residue being dissolved in a little water and treated with a few drops of a recently prepared 005% ferric chloride solution a violet coloration indicates salicylic add. 

Salicylic Acid.—100 c.c. of the beer, acidified with 5 c.c. of dilute sulphuric acid, are shaken in a separating funnel twice with 50 c.c. of a mixture of ether and petroleum ether in equal volumes, a few drops of alcohol being added to facilitate the clarification of the solvent. The ethereal liquids are filtered into a flask and the solvent distilled off on a water-bath, the small amount of hot residue bdng treated with 4 or 5 c.c. of water and, with shaking, a few drops of dilute ferric chloride solution. The liquid is filtered through a moist filter and if the filtrate is violet, the presence of salicylic acid is indicated. 

This coloration may, however, be due to maltol derived from torrefied malt. If, then, the reaction with ferric chloride is obtained, a portion of the aqueous solution of the residue from the ethereal extract should be tested with Millon s reagent2 a red coloration indicates salicylic acid, whilst no coloration shows that the reaction with ferric chloride is due to maltol. 

On this basis a silicon therapy was developed in France. Two silicon containing preparations, DNR (60) [complex of potassium methylsiliconate with salicylic acid (or with other oxycarbonic acids)] and RDN (61) (cyclic ether of dimethylsilanediol and glycerol), are used in the treatment of cardiovascular diseases, cancer and virus infections. Investigations in this field have been carried out by N. Duffaut,... 

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