Ethyl salicylate, reactions

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). 

Methyl-3-phosphorylchroman-4-one 1106 is accessible via a tandem allyl-vinyl migration and cyclization reaction of the allylic phosphonate 1105 and ethyl salicylate (Equation 435) <2001SC2613>. 

Mono- and bis(2-hydroxyphenyl)-l,3,5-triazines 23 can be prepared by the reaction of 477-1,3-benzoxazin-4-oncs 22 with amidines. The first examples of this synthesis were described in 1911428-429 as an extension to Pinner s condensation of ethyl salicylate with two equivalents of benzimidamide.430... 

Addition of a suspension of lithioenolate 8 in diethyl ether to ethyl salicylate affords c/.s-ketone 9 with very high diastereoselectivity in a kinetically controlled reaction (at equilibrium, cisjtrans 19 81 )183. 

Benzo[b]xanthone formation in 74% yield occurred readily in the reaction of ethyl salicylate and 1-naphthol at elevated temperature in refluxing diphenyl ether during 8 hours (ref.93). 

Salicylaldehyde, 188 Salicylic acid, 190 Sa tdnieycr s reaction, 165, 167 Saponification of ethyl acetate, 82 palm oil, 104 Sthlff s azotometer, 14 reaction, 67... 

Reaction of salicylamide 185 (obtainable from a suitable activated derivative of salicylic acid and N,N-diethylethylenediamine) with ethyl chloroformate... 

A seemingly complex heterocycle which on close examination is in fact a latentiated derivative of a salicylic acid shows antiinflammatory activity. It might be speculated that this compound could quite easily undergo metabolic transformation to a salicylate and that this product is in fact the active drug. Condensation of acid 134 with hydroxylamine leads to the hydroxamic acid 135. Reaction of that with the ethyl acetal from 4-chlorobutyraldehyde then leads to the cyclic carbinolamine derivative 136. Treatment... 

In the reaction of salicylic acid thioamide 419 with 2-cyano-3,3-bis(methylsulfanyl)acrylate under acidic conditions, a 2-(o-hydroxyphenyl)-6-imino-l,3-thiazine derivative was obtained as a perchlorate salt 420 on treatment with phenacyl bromide, this underwent a ring transformation to yield 4-benzoylmethylthio-27/-l,3-benzoxazin-2-ylidene-substituted ethyl cyanoacetate 421 (Scheme 81) <2003H(60)2273, 2004H(63)2319>. 

As with inorganic solid catalysts, the most extensively studied system was acetic acid—ethanol [428,432,434,444—448]. Other alcohols used in kinetic studies were methanol [430,449,450], 2-propanol [438], 1-bu-tanol [429,431,433,451—458], allyl alcohol [459], 1-pentanol [434] and ethyleneglycol [460] besides acetic acid, the reactions of formic [450], propionic [443,461], salicylic [430,449], benzoic [453—457] and oleic acids [430,451—453] and of phthalic anhydride [462] have been reported. Investigation of a greater variety of reactants is reported in only one paper [463] six alcohols (C4, Cs and C8) and five acids (mainly dicarboxylic were studied. Transesterification kinetic studies were performed with ethyl formate [437,439,441], isobutyrate [437,439—441] acetate [402, 435—437,439—442], methoxyacetate [441] and acrylate [403,404,464, 465] the alcohols used were methanol [402,435,437,439—442,450],... 

A mixture of 20 g. (0.1 mole) of o-bromobenzoic add, 63 cc. of 10% potassium hydroxide solution, 20 cc. of ethyl alcohol, 40 cc. of 50% tripotassium arsenite solution, and a little freshly reduced copper is refluxed at 90-95° for twelve hours with constant stirring. The reaction mixture is filtered hot to remove copper, made add to Congo red paper with 20 cc. of concentrated hydrochloric add, and evaporated to dryness on a steam cone. The resulting residue is extracted with absolute methanol the methanol extract is evaporated to dryness, and the residue is washed with ether to remove salicylic acid and unchanged o-bromo-... 

Lipoic acid uses its S-S bond in redox reactions (Chapter 50), while shikimic acid is an intermediate in the formation of compounds with benzene rings, such as phenylalanine, in living things (Chapter 49). Salicylic acid s ethyl ester is aspirin, which is, of course, like the last example ibuprofen, a painkiller. 

Acetoxymercuri-salicylic methyl ester — Fifteen grams of mercuric acetate, an equal weight of the ester, and 2 5 grams of acetic acid are boiled under reflux for about forty minutes, until the reaction is complete. On cooling, needles separate, and after standing overnight these are filtered off. Yield 9 grams, 52 per cent. It melts at 202° C. (corr.) and is readily soluble in warm alcohols, ethyl acetate, acetone, or chloroform, but with difficulty in water or petroleum ether. In alkali it is soluble, but the ester is saponified,... 

Acetoxymercuri-salicylic ethyl ester,— This product is not so readily formed as the methyl ester, but if the reaction is carried out at 180° C. the yield is almost quantitative. It crystallises from ethyl... 

Hydroxyglutaric acid forms a ternary anionic complex with Fe and The complexes TiCl2L2 (L = ethyl-4-nitrobenzoylpyruvate, ethyl-4-phenylbenzoyl-pyruvate, ethyl-2,4-dimethoxybenzoylpyruvate, or ethyl-2-naphthylpyruvate) have been prepared.There has been a spectroscopic study of complex formation in the Ti -salicylate-aa-bipyridyl system,and a reinvestigation of the reaction between Ti and salicylic acid in concentrated sulphuric acid. The coloured TiO salicylic acid complex formed in the latter system is formulated as a 7t-compIex rather than a chelate. 

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