DE640064C - Process for the preparation of oxyarylcarboxylic acid esters - Google Patents

Description

Process for the preparation of oxyaryl carboxylic acid esters Subject of the main patent 638.07; 2 and the additional patent 638 824 is the implementation of mono- or polyoxyarylcarboxylic acid chlorides or their esterified in the hydroxyl group Descendants with the salts of mono- or polyoxyaryl-, -alkyl-, -cycloalkyl = or -aralkylsulfonic acids or their derivatives in aqueous solution. Thereby finds a Esterification of the carboxyl groups of the oxyarylcarboxylic acids with one or more of the hydroxyl groups of the sulfonic acids instead:.

This method arguably delivers in a number of cases in a very smooth manner Reaction the said ester, but in other cases, especially there; where the carboxylic acid chlorides are very sensitive to water, more or less large losses always occur, in that part of the carboxylic acid chloride used is decomposed by the water.

It would be obvious to determine the amount of - water used, which causes the incorrect reaction of the chlorides to be greatly reduced. Of the. related However, the experiment shows just the opposite: the more the amount of water is reduced, all the more unfavorable. are the yields. Surprisingly, however, it could be a smooth one Implementation can be achieved when working with the complete exclusion of water, and it would thereby be made possible, with ease also those after the one mentioned Method to produce ester sulfonic acids that are difficult to obtain in very good yield.

According to the present process, those in the main or additional patent named components, of which the oxysulfonic acids as salts or in free form can be used with. or without the addition of an organic solvent mixed and optionally heated until the reaction occurs. Under strong The esterification occurs which in most cases, without having to fear decomposition, can be completed by heating to temperatures above roo °.

With the addition of anhydrous, inorganic or organic, in particular tertiary organic bases; in theoretical amount or in excess carry out the esterification as well. This can be done at the same time the annoying foaming of the reaction mass can be avoided by using in large quantities Hydrochloric acid released is absorbed by the base. Sometimes it is not necessary it is often downright harmful to heat up the real mixture. With enough If the reaction time is selected to be long, the esterifications can also occur at low temperatures be performed.

In addition to those mentioned in the main patent and additional patent 638o72 and 638824 The higher molecular weight ester sulfonic acids in particular have pronounced properties Substantivity to animal fibers.

Example i ig, 9 g of acetylsalicylic acid chloride are mixed with 17.4 g of phenolsulfonic acid mixed. The temperature is gradually increased to 100 °, in the course of which they escape under excessive foaming of the mass large amounts of hydrogen chloride. After about 1/2 hour it is the reaction ended. The tough, glassy reaction mass in the cold is in water clearly soluble. Acidification with strong hydrochloric acid can remove the aqueous solution the free o-acetoxybenzoyl-p-phenolsulfonic acid C H3. - C O - O - Ca H4 - C O -. O -C6 H4 - S O3 H as hydrous. viscous oil can be separated.

Example 2 2 mol of the condensation product of p-oxybenzoic acid and Phosphorus pentachloride is treated with 1 mol of potassium resorcinol for 2 hours i2o ° heated. The reaction product is dissolved in 2.5 1 of water and, if necessary p-oxybenzoic acid formed as a small by-product is extracted with ether. The condensation product, bis (oxybenzoyl) resorcinol sulfonic acid (HO-C, H4-CO- O) 2CQHg - SO, H, is located. in the aqueous solution.

EXAMPLE 3 30 g of o-oxybenzoyl-o-oxybenzoic acid chloride, 12 g of cresol sulfonic acid and 40 cc of benzene are heated to 80 ° for an hour. When the reaction has ended, the mass is mixed with 300 cc of water and 100 cc of strong hydrochloric acid and the mixture is brought to 8011. Three layers form in the separating funnel. The top, benzene layer contains traces of o-oxybeizoyl-o-oxybenzoic acid in addition to some dissolved condensation product. In addition to hydrochloric acid, the aqueous layer contains a small amount of the condensation product in solution, while the main amount of the condensation product is deposited as the lowest layer. This lowest oily layer is a colorless, @@ tvva 40% aqueous solution of o-oxy - @@ f @ iizoyl-o-oxybenzoylcresolsulfonic acid HO-'r'H4 # CO-O-CIH4-CO-O-ClH3 ( CH $) - "p.03 H.

Example 4 2o3-g of the Krist. Condensation product from o-oxybenzoic acid and phosphorus trichloride are added together with 126 g of oxyethanesulphonic acid per hour ioo ° held. The reaction product H O - Cg H4 - C O - O - C, H4 -S O3 H is in Very easily and clearly soluble in water.

Example 5 In a mixture of 1 part pyrogallol, 4 parts dimethylaniline and 6 parts of the condensation product of o-oxybenzoic acid and phosphorus trichloride gradually added dropwise with cooling i part of chlorosulfonic acid. After standing for 2 days at room temperature, the reaction mass is mixed with 120 parts of water and with 30 parts 39 ° Joiger hydrochloric acid boiled. This separates the reaction product, which consists of a mixture of pyrgallolsulfonic acids with different degrees of esterification, as heavy oil.

Example 6 34.4 g of i- (o-oxybenzoyl) -oxynaphthalene-4-sulfonic acid are mixed with 27.7 g of o-oxybenzoyl 1-oxybenzoic acid chloride and left to stand for ½ hour at room temperature. The reaction is then brought to an end at 80 ° for 1/2 hour. The reaction mass, which consists of i- (o-Oxybenzoyl-o-oxybeitzoyl-o-oxybenzoyl) -oxynaphthalene-4-sulfonic acid HO -CaH4-CO-OC, H4-CO-O-CsH4-C O - O - Clo HB # S 0, H is an almost colorless viscous mass which is easily soluble in water, apparently in colloidal form, since it gives the solution opalescence. i

Claims (1)

PATENT CLAIM: Process for the production of oxyaryl carboxylic acid esters according to patent 638o72 and additional patent 638 824, characterized in that the Starting materials mentioned there, of which the oxysulfonic acids also in the free state Can be used with or without the addition of organic solvents or of anhydrous inorganic or organic bases here in the absence of water can act on each other at normal or elevated temperature.