CS225021B1 - The 2-amine -6-acylamine-1,3,5-trimethylbenzene-4-sulphonic acid,its salts and their preparation - Google Patents

Description

(54) 2-Amino-6-acylamino-1,3,5-trimethylbenzene-4-sulfonic acids, their salts and processes for their preparation

The invention relates to compounds of formulas Ie and Ib,

SOJIVIe (la)

wherein Ac denotes an acyl having 1 to 11 carbon atoms, Me denotes hydrogen or an alkali metal, caustic earth, ammonium, magnesium or aluminum cation, and a process for their preparation by partial acylation of the corresponding diaminosulfonic acid, respectively. sulfonates.

The nitrogen compounds of the above formulas represent a group of novel substances not previously described in the available literature.

The present invention provides 2-amino-6-ecylamino-1,3,5-triraethylbenzene-4-sulfonic acids and their salts, characterized by the formulas Ia and Ib,

wherein Ac denotes an acyl having 1 to 1 carbon atoms, Me denotes hydrogen or an alkali metal, caustic earth, ammonium, magnesium or aluminum cation, and a process for the preparation thereof according to the present invention comprising interacting with the corresponding diamino compounds represented by the general formula XX

wherein Me is as defined above, and acylating agents employing 100-150% of the theory, based on one amino group, in aqueous or organic solvents, preferably in the presence of acylating aids such as e.g. alkali metal oxides, carbonates, hydroxides, acidic carbonates, phosphates, octenates, formates, citrates, oxalates or tartrates, caustic soils, ammonium, magnesium or aluminum, optionally in the presence of sulfur or phosphorus halides.

2,6-Diemino-1,3,5-trimethylbenzene-4-sulfonic acid, respectively. salts thereof, are obtained by reduction of the corresponding dinitro compound, which can be readily prepared by sulfonating with mesitylene splitting.

Of the ecylating agents, all of the hitherto commonly used for known ecylecids, such as carboxylic acid anhydrides or halides or mixed anhydrides, but also acid esters such as ethyl acetate or ethyl trichloride, ketene and diketene can be applied. Along with the acyl, the molecule of the compounds Xa, respectively. Ib, to introduce a nitro group, for example, by treating the starting amine with nitro- or dinitrobenzoyl chlorides and the like.

By way of illustration, it is desirable to list some important representatives of the above groups, for example »anhydrides and acid halides: acetic, propionic, chloroacetic, bromopropionic, maleic, benzoic, phthalic, nitro- and dinitrobenzoic, naphthoic; esters of acids: acetic, oxalic, oxaloacetic; Alternatively, ketene, diketene, etc. may be used.

The compounds of formulas Ia and Ia, respectively. Ib, may conveniently be obtained by reacting with the selected reagents in an aqueous medium or in an organic solvent medium such as acetic acid, acetic anhydride, dimethylsulfoxide, formemide and the like. Sodium carbonate, Sodium bicarbonate, Potassium carbonate, Sodium hydroxide, Potassium hydroxide, Venetian carbonate, Magnesium carbonate, Sodium acetate, Potassium vinegar, Aluminum acetate, Aluminum oxide, Tartrate and all similar salts of weak acids, released by strong acids, released reactions, converting them to strong acid salts and releasing weak acids or sulfur or phosphorus halogens, for example, in acylcation with methyl acetootan, ethyl acetate, oxalacetate and ethyl.

The novel compounds can serve as blanks for the preparation of tar dyestuffs or as starting materials for the synthesis of more complex blanks.

A 13q-NMR record of the N-acetylderivative (sodium salt solution in D 2 O, external standard CMS) was used to characterize the new compounds. The measured data, including the carbon designation and substitution pattern, are shown in the following overview.

CH ₃ ^H 2 ^{N 4} - k ( ^NHCOCH 3)

SO ^ Na *

CH ₃

Designation carbons Chemical shift (with internal standard correction) 1 125.1 2 132.5 3 124.7 4 139.7 5 122.5 6 141.9 7 12.6 8 15.9 9 15.6 10 21.7 11 173.8

He did

0.2 mol of 2,6-diamino-1,3,5-trimethylbenzane-4-sulfoacid is mixed with 400 ml of water and the resulting suspension is basified by the addition of 80 ml of sodium hydroxide at a concentration of c (NaOH) = 2.5 mol / l. converted into a solution; The pH is both 8 and 0.5. The resulting solution was heated to 60 ° C with stirring and at this temperature a total of 12.5 g of CO 2 calcined and 25% of acetic anhydride (0.24 mol) were added simultaneously in three portions (at 15 minute intervals); The pH of the reaction mixture was maintained at 5.5 and 0.5 during acetyl. The resulting reaction mixture was then heated at 55 ° C for 30 minutes, then 30 ml of concentrated hydrochloric acid was added, the suspension was stirred for minutes, then the precipitated product was filtered off and washed with 200 ml of water. 75% of theory of 2-amino-6-acetylamino-1,3,5-trimethylbenzene-4-sulfonic acid are obtained in the form of a colorless crystalline substance.

Example

Selective monoacetylation was carried out in the same manner as in Example 1, but 0.24 mol of acetyl chloride was used in place of acetic anhydride.

The yield of 2-amino-6-ethyl-araino-1,3,5-trimethylbenzene-4-sulfonic acid was 79.3% of theory.

Example 3

0.1 mol of 2,6-diamino-1,3,5-trimethylbenzene-4-sulfoacid is stirred in 200 ml of water, the pH of the mixture is adjusted by adding 40 ml of sodium hydroxide with a concentration of c (NaOH) = 2.5 mol / l. not a value of 8 1 0.5, but the resulting solution of the vigorous stirring is heated to a temperature of 60 ° C and a total of 8.5 g of NegCO 2 calcined and 27.6 g of 3,5-dinitrobenzoyl chloride (0.12) are added simultaneously at this temperature. mol) within 30 minutes; The pH of the reaction mixture is maintained at 5.5 ± 0.5. At 60 ° C, the reaction mixture is then stirred for 30 minutes.

The reaction mixture contains 80% of the theory of 2-amino-6- (3 ', 5'-dinitrobenzoylamino) -1,3,5-trimethylbenzene-4-sulfonic acid; chromatographic analysis showed that the major impurity is unreacted 2,6-diamino-1,3,5-trimethylbenzene-4-sulfonic acid with a small amount of 3,5-dinitrobenzoic acid.

Claims (3)

SUBJECT OF THE INVENTION CLAIMS 1. 2-Amino-6-ecylemino-1,3,5-trimethylbenzene-4-sulfonic acids and their sele, cherekterized by the formulas Ia and Ib, wherein Ac pollutes acyl with 1 to 11 carbon atoms and Me pollutes hydrogen or an alkali cation metals, caustic soils, ammonium, magnesium or aluminum. 2. A process for the preparation of the compounds of the formulas (Ia) and (1b) by reacting with the appropriate diemino compounds characterized by the formula (II) and acylating agents using 100-150% of the theory, based on one amino group, in an aqueous medium; in organic solvents, preferably in the presence of acylating agents, such as, for example, oxides, carbonates, hydroxides, acidic carbonates, phosphates, acetates, foals, citrates, oxolates or tartrates of alkali metals, caustic earths, ammonium, magnesium or aluminum, optionally sulfur or phosphorus halides. 3. A process according to claim 2, characterized in that the anhydrides or halides of nitrated or dinitrated aromatic carboxylic acids are used for acylation.