DE833811C - Process for the production of pellets of sulfonamides of the aromatic series - Google Patents

Description

Process for the preparation of derivatives of sulfonamides of the aromatic Series Aromatic sulfonamides acylated on the sulfonamide group, which are in the p-position to the sulfonamide group contain an amino group or a group which can be converted into it, have so far been prepared by direct acylation of the sulfonamide group. @ (cf. z. B`. the French patent, 868 714).

It has now been found that such connections can be made more easily Wise fret in good yield, loot can also be obtained if one of the aromatic sulfonic acids Series or their reactive derivatives, in particular benzenesulfonic acid halides, those in the p-position to the sulfonic acid halides, an amino group or one therein Contain convertible groups, reacts with acylimido ethers and for the purpose of splitting the Im: idoether compound hydrolyzes the sales product and either at the same time or then the p-position core substituent is converted into an amino group.

The reaction is explained in more detail by the following equation and examples: EXAMPLE 1 26.4 g of carbethoxysulfanilic acid chloride are heated with 12.4 g of acetimidoether hydrochloride in 25 cc of dried pyridine for one hour on the water heater. The clear, light brown colored solution is then mixed with five times the amount of water and acidified with hydrochloric acid. The initially oily nut separation soon solidifies in crystalline form, the melting point of the carbethoxysulfanilic acid acetirnidoether after being converted from dilute alcohol is 113 °. After briefly heating the ether in excess alcoholic potassium hydroxide solution, the potassium compound of the carbethoxysulfanilic acid acetamide separates out. To saponify the carbethoxy group, the precipitated potassium set is heated for a short time in 150 ccm of 2N potassium hydroxide solution on the water bath until a sample is clearly soluble in hydrochloric acid. When the al) cooled solution is acidified with acetic acid, the sulfanilic acid acetamide then precipitates. F. i81 to 182 ° (from water). : \ usl) 17.5 g, i.e. over 80% of the theory.

_ \ n Place of the Acetimidoärherhydrochlori-ds can also the free Acetimidoärlier and in place of the carbethoxysulfatiilic acid chloride, sulfonic acid halides can also be used with other groups which can be converted into the amino group, e.g. 13. the. \ Cetylamino-. Nitro. Nitroso group, etc. can be used. Ilei use of z. B.: '\ cetylsulfanilic acid chloride The starting material is an intermediate product: \ cetvlsulfanilsäureacetanii-d from the F. 252 °.

Instead of the stepwise saponification of the ether and the acyl group, it is also possible, in which case aqueous potassium hydroxide solution is expediently used, to saponify both groups at the same time. EXAMPLE 2 26.4 g of Carbärhoxysulfanilsäurechlori (l are heated with 13.8 g of Propionimidoäthethydrochlori.d in 60 ccm of dry PVC for 2 hours on the water bath. After diluting the clear, light yellow solution with five times the amount of water and acidifying with hydrochloric acid, a precipitate of Carbethoxysulfanilic acid propionylimido ether (m.p. 115 to 117 ° from alcohol). When the ether is heated with alcoholic potassium hydroxide, the potassium content of carbethoxysulfanilic acid-1) ropionyl amide separates, which is saponified to sulphanilic acid by heating with 2 n-latige. After being converted from dilute alcohol, the amide melts at 134his 135 °. Yield 18 g (79% of theory). lieisl) ie1 3 26.49 carbethoxysulfanilic acid clilori (1 with 18.6 g 13enzimi (loätl) erv.droclilorid in 6o ccm dry pyridine on the water bath for one hour heated. Precipitation with water provides the carb ethoxysulfanilic acidel) enzovliniidoätliei- (F. 153 °, from Alcohol dissolved). The saponification takes place through Warming ether with 2N lye. From the alka- The mixture solution is made by acidification with acetic acid the stilfanilic acid benzovlafni (1 allgeschieden, which recrystallized from alcohol at 181 to 182 ° melts. . \ trsl) etite 23.5 g (850o of theory). lieisl) iel4 4-aminot) enzenesulfous acid - N- (1 ', 2' - (liinethyl- benzoyl) amide. 26.4g Carl) ätlioxvsulfanilic acid- chloride with 21.1 g of T, 2-dimethyl-4-benzimi- doether hydrochloride (obtained from 1,2-dimethyl 4, benzonitrile in alcoholic solution by a conducting gaseous hydrochloric acid) in 25 ccm dry pyridine on the water bath for one hour warmed up. The clear solution is to (learning waste cool with dilute hydrochloric acid up to the Congo acidic reaction and the deposited 4-Carbethoxyaminobetizol sulfone-4 '-, \ -'- (1'. 2 '-diine- thyl, benz) imido ether, which after a short time becomes solidified in line, for cleaning. crystallized. After briefly heating the ether in over- Liquid alcoholic potassium hydroxide separates (read 4-cart potassium set) ätlioxyaminobenzolsul- fonsäure-.1'-N- (i ', 2'-dimethylbenzovl) -amids from, which is sucked off and in r 50 ccm 2N potassium hydroxide solution warmed up on the water bath for a short time, his a sample is clearly soluble in hydrochloric acid. 13 as soon as acidify the cooled solution with acetic acid the 4-aminobenzenesulfonate-4'-N- (1 ', 2' -. di- met'livll) efizovl) -amici. F.211 to S 2T2 ° (from : \ lkohol). . Example 4 - aminobenzenesulfonic acid dimetliylacroylamide. 26.4 g of Carbäthoxvsulfanilsätirechlorid are heated with 16.4 9 Dimethvlacrvlimidoätherhvdrochlorid (obtained from Dimethylacrylsäurenitril in alcoholic solution by introducing gaseous hydrochloric acid) in 25 ccm of anhydrous pyridine for one hour on a water bath. After cooling, the clear solution is treated with dilute hydrochloric acid until it has a Congo-acidic reaction and the precipitated 4-carbethoxyaminobenzene sulfone dimethylacroylimidoether is purified by recrystallization from alcohol.

After briefly heating the ether in an excess of alcoholic potassium hydroxide to the potassium salt of 4-Carbäthoxyaminobenzolsulfonsäuredimethylacroylamids separates which is heated by sucking in your 1 50 cc of 2N potassium hydroxide solution short time on a water bath until a sample in hydrochloric acid gives a clear solution. When the cooled solution is acidified with acetic acid, the 4-aminobenzenesulphonic acid dimethylacrovlamide precipitates. F. iSi up to 18z ° (from dilute alcohol).

Claims (1)

PATENT CLAIM: A process for the preparation of derivatives of sulfonamides of the aromatic series which contain an amino group in the p-position to the sulfonamide group or a group which can be converted into it and which are acylated on the sulfonamide group, characterized in that sulfonic acids of the aromatic series or their reactive derivatives, in particular benzenesulfonic acid halides, which carry an amino group or a group which can be converted into it in the p-position to the sulfonamide group, reacts with acylimidoethers and, for the purpose of splitting the imidoether compound, hydrolyzes the reaction product, and if necessary either simultaneously or afterwards the p- permanent core substituents converted into an amino group.