CS268011B1 - Acid ammonium salts of polyhydric carboxyl aliphatic acids and method of their preparation - Google Patents

Abstract

Acid salts formed by polybasic carboxylic acids aliphatic acids and aminoalkylbenzenes of formula I wherein R 1 is hydrogen, R ' is hydrogen, hydroxyl, or hydrogen; hence R ^ a forms a double bond between the carbons, to which R is bound is hydrogen, hydroxyl, methyl, CHL COOH, R is hydrogen, hydroxyl, R 8 is free, methyl, ethyl, R- denotes methyl, ethyl, wherein R_ and R- may be the same or different or together they form an annealed alicyclic the ring is prepared by the reaction of amines. of formula II with polyhydric aliphatic acids of Formula III wherein the substituents R 9, R 9, R 8 are as defined above.

Description

The invention relates to acidic ammonium salts of polybasic carboxylic aliphatic acids and to a process for their preparation which consists in the interaction of aminoalkylbenzenes and polybasic carboxylic aliphatic acids in the presence of a polar organic solvent, optionally in the presence of water.

Acid ammonium salts of polybasic carboxylic aliphatic acids have not yet been technically used and are not described in the available literature. The invention relates to acidic ammonium salts formed by polybasic carboxylic aliphatic acids and aminoalkylbenzenes of the general formula I ^R 2 Z ¹

HOOC-C-C-CCxP (I),

I \ ^'J N ^R 3 ^R 4 ⁵ wherein denotes hydrogen, R ₂ is hydrogen or hydroxyl, or on site R, and R ₂ is a double bond between carbons, R ₃ is hydrogen, hydroxyl, methyl or CH ₂ COOH, R _{R 8} is hydrogen or hydroxyl, R 5 is hydrogen, methyl or ethyl, R 8 is methyl or ethyl, wherein R 8 and R 8 may be the same or different, or together form a fused alicyclic ring of 5 to 6 carbons, preparation, which consists in applying to the amines of the general formula II.

^h ₂ N - (II) acts with polybasic carboxylic aliphatic acids of general formula III ^R 2 fx

HOOC-C-C-COOH (III),

II ^R 3 ^R 4 · _ wherein only R $ are as defined above, in a medium of water or polar organic solvents or in aqueous mixtures thereof. The invention also relates to a mixture of constitutively different compounds of the formula I which can be prepared from a mixture of two or more polyhydric carboxylic aliphatic acids and a selected amine of the formula II or from one selected polybasic carboxylic aliphatic acid and a mixture of amines of the formula II. Among the aminoalkylbenzenes capable of forming said acid salts, mention may be made, for example: toluidines, sylidines, aminotetralins and aminoindans from polyhydric carboxylic aliphatic acids suitable for the preparation of acid salts: succinic, fumaric, maleic acid, malic, citric, tartaric, but also less common acids. 2-hydroxy-2-methyl-succinate and the like.

The process for the preparation of the ammonium acid salts according to the invention can be carried out in water or organic polar solvents or in a mixture of both. Suitable organic polar solvents are alcohols, in particular methanol, athanol, aliphatic esters, nitriles, for example acetonitrile, formamide, acetamide, 1-methyl-2-pyrrolidone, dimethylacetamide, etc. The process can be carried out by preferably heated, alkylaminobenzene is added and then some of the polyhydric carboxylic aliphatic acids, as a rule the crystalline acid salt soon precipitates. The procedure can be reversed, i.e. the acid is dissolved first and then the aminoalkylbenzene. A variant is also suitable in which solutions of both aminoalkylbenzenes and acids are prepared, preferably at elevated temperatures, after which the two solutions are mixed.

In cases where the acid salts of the formula I precipitate rapidly during the preparation, the reaction mixture can be heated, optionally to the boiling point of the mixture, optionally with the addition of a solvent, and the solution obtained is brought to controlled crystallization by slow cooling. A suitable combination of water and organic solvents can affect the solubility and, if appropriate, the crystallization ability of the acid salts in such mixtures. The subject substances are intermediates for a number of organic syntheses.

CS 268011 Bl

The examples below illustrate the process for the preparation of the salts according to the invention.

Example 1

12.1 g of pure 4-amino-1,2-dimethylbenzene are dissolved in 45 ml of methanol and 11.8 g of succinic acid are added. The mixture is heated to dissolution with stirring, then allowed to cool freely, the crystalline product is filtered off, washed with 10 ml of methanol cooled to 5 DEG C. and freely dried. To identify the product, a sample of the crystalline product was dissolved in DgO and the NMR spectrum was recorded at 70 ° C (OSS internal standard). The interpretation of the measured values is in accordance with the above constitution

7.24 I CH ₃

7.01 [7.06 ®OOCCH ₂ CH ₂ COOH cT (CH ₃ ) = 2.25 and 2.27

Z (CH ₂ ) = 2.59

Similar results are obtained when methanol is replaced by ethanol, propanol or butanol.

Example 2

12.1 g of pure 3-amino-1,2-dimethylbenzene are treated in the same manner as in Example 1. Before isolation, the suspension is cooled to 0 [deg.] C., then the solid is filtered off and dried. The product was identified by NMR spectra as in Example 1. Comparing the measured values with those of Example 1 revealed an overlap of most signals except for one methyl, 18), which is consistent with the constitution below.

ch ₃

COCCH, CH_COOH © ^{J 22} ·

-Example 3

12.1 g of pure 4-amino-1,2-dimethylbenzene are dissolved in 50 ml of ethanol and 15.0 g of pure tartaric acid are added, the mixture is heated to dissolution and then allowed to cool freely for 2 hours. The filtered crystalline product is washed with 10 ml of ethanol at 2 DEG C. and dried freely.

The recorded 1 H NMR spectrum corresponds to the constitution of OH.

NH- θΟΟΟΟΗ (OH) CH (OH) COOH © ^J. (CH ₃ ) = 2.08 and 2.10% / (CH) = 4.36

Example 4

12.1 g of pure 4-amino-1,2-dimethylbenzene are dissolved according to Example 3, treated with 21 g of crystalline citric acid hydrate.

The recorded NMR spectrum is consistent with constitution

CS 268011 Bl c.

NH, 0000-CH_-C-CH, COOH ® COOH

2.08 and 2.10 2.72 and 2.83 (AB system) if (CH ₃ ) = </ ( ^c H ₂ ) =

Example 5

12.1 g of pure 4-amino-1,2-dimethylbenzene are reacted with 11.6 g of maleic acid according to the procedure of Example 3. The isolated product is subjected to analysis. The measured NMR spectrum corresponds to the constitution

CH,

J ^ (CH) = 6.68 ·

Note: During the preparation, the initial configuration of cis was converted to trans, as the signals recorded are identical to the spectrum of the product obtained from 4-amino-1,2-dimethylbenzene and fumaric acid (d (CH) = 6.68).

Example 6

13.4 g of pure 5-aminoindan are dissolved in 400 ml of methanol, 15 g of pure tartaric acid are added, the mixture is heated, after which the solution is freely cooled to 15 DEG C. for 3 hours, the solid is filtered off and washed with 15 ml of methanol. at a temperature of 10 ° C and dried. The 1 H NMR spectrum of the sample dissolved in 0 DEG C. at 70 DEG C. (internal DSS standard) corresponds to the constitution

2.74 6.91 ^6.39 '- NH ₃ © DOCCH (OH) CH (OH) COOH

2.74 6.50 © (CG) = 4.36

Example 7

13.4 g of 5-aminoindan are dissolved in 200 ml of methanol. In addition, an aqueous solution is prepared from 15 g of tartaric acid and 80 ml of water. The two solutions are mixed and, after two hours, the solid crystalline fraction is filtered off and dried freely. The NMR recorded is identical to that recorded in Example 6.

Claims (2)

OBJECT OF THE INVENTION Acid ammonium salts of polybasic carboxylic aliphatic acids of the general formula I f ² f ¹ HOOC - C - C - C0 (© H, řP- / cl ·) (I), II ^"3 4» wherein R is hydrogen, is hydrogen, hydroxyl, or R ^ and R ^ form a double bond between the carbons to which they are attached form R ₃ is hydrogen, hydroxy, methyl, or CH ₂ COOH, R ₄ is hydrogen, hydroxyl, R ₅ denotes hydrogen, methyl, ethyl, R ₆ denotes methyl, ethyl, wherein CS 268011 B1 ^R 6 may be the same or different and together form an alicyclic ring with 5 to 6 carbons. 2. A process for the preparation of acid ammonium salts according to claim 1, characterized in that na 1 molar part of aminoalkylbenzene of general formula II (II) is treated with 0.8 to 1.5 molar parts of polybasic carboxylic aliphatic acids of formula III R— Rq I Γ HOOC - C - C - COOH (III), _{where R 3 and} R ₄ are as defined above, in an environment of water or polar organic solvents such as methanol, ethanol.