DE360491C - Process for the preparation of haloalkyl esters of aromatic o-oxycarboxylic acids - Google Patents

Description

Process for the preparation of haloalkyl esters of aromatic o-oxycarboxylic acids. It has in drug synthesis no lack request to '#', 'display Salicylsäureverbilndungen with iodine content for internal as external applicatio g. Jedocli adheres to the well-known products that either the iodine is difficult to split off in the organism, as is the case with the iodine salicylic acids. Because iodine is in the nucleus, or the entire side complex that carries the iodine, can easily be split off, as in iodoacetylsal, icylic acid, which gives rise to the strongly irritating iodoacetic acid. So far no iodine-containing salicylic salicylic acid has been described which is easily absorbed by the skin as well as from the stomach without irritation and which is then able to develop an iodine and salicylic acid effect in a productive manner.

It has now been found that compounds with a high iodine and salicylic acid activity are obtained if iodine is introduced into the alkyl groups of the salicylic acid esters. Products are then obtained which are extremely favorably absorbed by the skin and the stomach , without irritating in the slightest, and develop a high effect of sodium and iodine. These compounds can be obtained by adding salicic acid or its o-acyl compounds or their homologues and derivatives in a known manner with iodihydrins . esterified or the esters chlorinated or brominated in the alcohol group are not reacted with iodine salts. Example 1. 5 parts of chloroethyl salicylate (patent specification 1885715, 5 parts of iodine sodium and 25 parts of alcohol are boiled for 5 hours Water, ether and a small amount of Bistilfit treated. The ether extract consists of a-LisSalicvläurjodäthviest he. ET sie, -Ict at i.8o this I 93 ', tinter 2o in:' n pressure and represents a colorless liquid. By, #, cetyliierti: ng with acetic acid hydride one obtains the acetyl compound # tn # -, the can also be represented as follows.

Example 2.

To 17.2 parts of ethyl-1, iodohydrin, 16 parts of pyridine and 50 parts of benzene add 19.85 parts of acetvisalic acid chloride, dissolved in 25 parts, of benzene. The next day it is washed successively with hydrochloric acid and bicarbonate solution. The benzene extract solidifies to crystals in the cold: that sniff out of alcohol UnIgelÖst at 37 to 38 ' .

The acetylsalic acid chlorethyl ester can be prepared in the same way, which, when dissolved in benzene, melts at 62 ° and can be converted into the above iodine ester by boiling with sodium iodine.

By saponifying the acetylated iodine ester with alikabgliscli-water, the hydrochloric acid is obtained. Salicylic acid iodoethyl ester (Example i). Example 3.

17.2 parts of eth #, lenjodh #, - drill, 16 parts of pyridine, 3o parts of Relizol are combined 'with 1 5.6 parts', salicylic acid cli # ld # id in 25 parts of benzene, while cooling.

The work-up is carried out as in Example 2. The salicvl.sätirejodätbylester is obtained.

Example 4.

16 parts of salicylic acid sodium are mixed with 2o parts of ethylene chloroiodine # d 6 hours heated to i4o '. The reaction product is washed with water and a little Bistilfit and deng fractionated salicylic iodoethyl ester.

Example 5.

19.85 parts of acetylsalic acid chloride in 25 parts of ether are added to a solution of: 2 parts of aiodioxypropane, 60 parts of ether and 16 parts of pyridine. The next day it is washed with dilute hydrochloric acid, then with bicarbonate and evaporated. The residue, a yellowish thick oil which dissolves easily in most organic solvents and decomposes on heating, is AcetvlsaJiey # l # acid glycerol-r, .- iodide-drine ester.

Example 6.

Dry hydrogen chloride is introduced into a mixture of 10 parts of salicylic acid and 30 parts of ethylene iodohydrin while heating it in a water bath until all the salicylic acid is dissolved. The reaction product is washed with water and Bistilfit and the Salicvl # säurejodät # hylest-er is fractionated. Example 7.

10 parts of p-cresotinic acid lorethyl ester, 10 parts of sodium hydroxide and 60 parts of amyl alcohol are boiled for 5 hours. The amyl alcohol is distilled off in the Vaktium and the residue is purified successively with Bistilfit and sodium bicarbonate. The p-cresotinic iodoethyl ester thus obtained boils at 166 to 169 ° under 10 mm pressure.

By, # £ cetylieren with Acetylchlchrid and vridiii 1) gives the acetyl-p-kresotinsäurejodäth # "lest he, a yellowish 01, which decomposes on Destilfieren largely.

The chloroethyl p-cresotinate used as the starting material is obtained by heating 45 parts of p-cresotinic acid with 48 parts of ethylene chlorohydrin and 4 parts of concentrated sulfuric acid for less days, washing the reaction product with soda and distilling it as a boiling oil that is liquid at summer temperature and solidifies in ice 136 to 139 ' preserved in print under io.

Example 8.

To 29.8 parts, (xy-diiodopropyl alcohol, 16 parts of pyridine and 50 parts of benzene, 19.8 parts of acetylsalicylic acid chloride in 25 parts of benzene are added, with cooling. The next day, it is washed with hydrochloric acid and bistillite, then with bicarbonate. After drying and chasing - The acetylsalicylic acid iodopropyl ester remains behind the solvent as a yellowish, viscous oil that cannot be distilled.

Claims (1)

PATENT-A # xSPRU CII: Procedure! 7 "LiT representation of haloalkyl esters aromatic o-oxy-carboxylic acids, characterized by the fact that one o-oxy-enzoic acid or their o-acidyl compounds or their homologues and derivatives in a known manner Way with iodohydrin # en, verestext or those chlorinated in the alcohol group or Reacts brominated esters with iodized salts.