JPS6141338B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [In the formula, X and Y independently represent hydrogen, halogen, alkyl, trifluoromethyl or alkoxy, R ₁ represents hydrogen or an alkyl group, R ₂ and R ₃ independently represent hydrogen, optionally represents an alkyl or cycloalkyl, or alkenyl or aralkyl group optionally substituted by hydroxyl, halogen or alkoxy, or R ₂ and R ₃ together with the nitrogen atom form a multicyclic ring, R ₄ represents hydrogen or alkyl, and n represents 0 or 1]. The method uses the general formula sulfuric acid half-esters, their alkali metal salts, such as sodium, potassium or lithium salts or their alkaline earth metal salts, such as calcium or barium salts, of It consists of reacting with an amine. Amines of formula () are used as coupling components in the production of dyes. Dyes of this type are used, for example, in German Patent Specifications 1011396, 1644175 and
2059945. The alkyl and alkoxy groups mentioned in X, Y, R ₁ and R ₄ and the alkoxy groups mentioned in R ₂ and R ₃ preferably have 1 to 4 carbon atoms and R ₂ The alkyl groups mentioned in and R ₃ preferably have 1 to 18 carbon atoms. Alkenyl is to be understood in particular as alkyl and methyl-allyl. Aralkyl preferably represents benzyl and phenylethyl and their derivatives substituted by methyl in the phenyl ring. Cycloalkyl preferably represents cyclopentyl and cyclohexyl. R ₂ and R ₃ together with the nitrogen atom, especially 5
Forms a 7- to 7-membered ring, such as a pyrrolidine, piperidine, piperazine, N-methylpiperazine, morpholine or hexamethyleneimine ring. By halogen is meant in particular fluorine, chlorine and bromine. _{Suitable amines include : _ _ _} - alkyl, and R ₂ and R ₃ independently of each other represent hydrogen, C ₁ -C ₄ -alkyl, cyclohexyl, allyl or benzyl, optionally substituted by hydroxyl, chlorine, methoxy or ethoxy; , or of formula (), in which R ₂ and R ₃ together form a piperidine or morpholine ring, R ₄ represents hydrogen or C ₁ -C ₄ -alkyl and n represents 0. Among these suitable amines, the formula Special mention is made of the following formulas: where X' represents hydrogen or methyl, R ₁ ' represents methyl or ethyl, and R ₂ ' and R ₃ ' represent methyl, ethyl or benzyl. The reaction between the sulfuric ester () and the amine () can be carried out continuously or discontinuously. Generally, the temperature range is 80-250°C, preferably 140-220°C. The reaction takes place at pressures up to 90 bar, especially between 5 and
Performed at 25 bar. A preferred molar ratio of sulfate ester () to amine () is from 1:1 to 50, especially from 1:2 to 10. The process is preferably carried out in aqueous solution, but can also be carried out in the presence of organic solvents. Examples of suitable organic solvents are benzene, toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, quinoline, cyclohexane, anisole, decalin and mixtures of these solvents. The sulfuric esters () are obtained in a manner known per se by reacting the corresponding hydroxy compounds with sulfuric acid or chlorosulfuric acid. Sulfuric esters and their production are described, for example, in KHS Saunders, Journal of the Chemical Society, 121.
(1922), pp. 2667-2675. Examples of starting materials for the production of sulfuric acid half-esters () include N-hydroxyethyl compounds of the following aromatic amines: aniline, m-toluidine, m-chloroaniline, M-trifluoromethylaniline, N-methylaniline, N-methyl-m-toluidine, N-ethylaniline,
N-ethyl-m-toluidine, N-propyl-aniline, N-propyl-m-toluidine, m-chloro-N-ethyl-aniline and m-trifluoromethyl-N-ethylaniline. Among the amines of the formula () the following may be mentioned in particular: ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, secondary butylamine, isobutyl. Amine, diisobutylamine, tertiary-butylamine, 1,1-dimethylpropylamine, 1-aminohexane, 2-ethylhexylamine, dodecylamine (1-amino-dodecane), methylstearylamine, allylamine,
diallylamine, ethanolamine, 2-methoxyethylamine, N-methylethanolamine,
Diethanolamine, 3-amino-1-propanol, isopropanolamine, diisopropanolamine, cyclohexylamine, N-methyl-cyclohexylamine, dicyclohexylamine, aminomethylcyclohexane, benzylamine, N-methyl-benzylamine, pyrrolidine,
Piperidine, hexamethyleneimine, N-methyl-piperazine, morpholine and N-amino-morpholine. The advantage of the new process over the known process for the preparation of amines (), which is carried out by reacting the corresponding halogen compounds, is that it is an economical process with less environmental pollution. The compounds of formula () in the inner salt form are essentially solid and are soluble in dilute aqueous alkali metal hydroxide solutions. This means that the reaction with the amine of formula () can be carried out in a homogeneous aqueous phase, compared to the above-mentioned production method using a halogen compound. As a result, amines () can be obtained in surprisingly high purity and in good yields in short reaction times. Example 1 245 parts of the sulfuric acid half ester of N-hydroxyethyl-N-ethylaniline are dissolved in a solution containing 40 parts of sodium hydroxide in 400 parts of water and the mixture is placed in an agitated autoclave. Moved to. After adding 135 parts of dimethylamine, the reaction mixture was heated to 180° C. for 2 hours. When the mixture was allowed to cool, the phases separated and the product phase was distilled in vacuo over an 80 cm pat column. Collecting the fraction between 139 and 141 °C/22 mbar yields 172.7, which corresponds to 89.9% of the theoretical value.
Part of N-dimethylaminoethyl-N-ethylaniline was obtained with a purity of 99.4%. 7.7 parts remained as distillation residue. Example 2 40 parts of sodium hydroxide were dissolved in 400 parts of water. 259 parts of N-hydroxyethyl-N-ethyl-m-toluidine sulfuric acid half ester were added to this solution. After transferring the mixture to a stirred autoclave, 140 parts of dimethylamine were added and the reaction mixture was heated to 160-170°C for 3 hours. Processing was carried out as described in Example 1. The fraction boiling at 173 DEG-175 DEG C./30 mm Hg was collected, yielding 175 parts of N.N-dimethyl-N'-m-tolyl-ethylenediamine of excellent purity. Example 3 123 parts of N-ethyl-N-hydroxyethyl-
The sulfuric acid half ester of aniline and 380 parts of a 25% strength ammonia solution in water were heated to 180° for 2 hours in a high grade steel autoclave. This increased the pressure to 25 bar. After cooling the reaction mixture to room temperature, separating the organic phase and fractionally distilling it,
45 parts of N-ethyl-N-aminoethyl-aniline (boiling point 136-142°C/18 mmHg) were obtained with a purity of 98-99%. Example 4 245 parts of N-ethyl-N-hydroxyethyl-
Sulfuric acid half ester of aniline and 525 parts of diethanolamine are heated in a stirred apparatus for 2 to 3 hours.
Heated to 175-180°C. After cooling the reaction mixture to room temperature, 1000 parts of water were added and the amine phase was separated by adding 100 parts of sodium hydroxide. The amine was purified by vacuum distillation on a 30 cm silver coated column. After removing 35 parts of the first fraction, a fraction boiling at 194-196° C./2 mbar was collected. 204 parts of N-, corresponding to 81% of the theoretical value
Ethyl-N-(bis-hydroxyethyl-aminoethyl)-aniline was obtained. Example 5 890 parts of 45% strength sodium hydroxide solution were
A suspension containing 2450 parts of the sulfuric acid half ester of N-ethyl-N-hydroxyethyl-aniline in 6000 parts of water was added in such a way that the temperature did not exceed 20°C. After adding 2520 parts of 53.6% strength dimethylamine solution, a clear solution was obtained. This solution was continuously fed from a water reservoir to a reaction tube having a diameter of 7 mm and a length of 28 m, heated to 180-200 DEG C., using a metering pump. After passing through a needle valve which allowed the pressure to be adjusted to 20 bar, the reaction mixture was cooled to room temperature in a downflow condenser and collected in a receiver, where the phases separated. The organic phase was examined by gas chromatography. The following results were obtained by varying the residence time and reaction temperature.

Table: The yield was quantitative in nature.
Valuable intermediates for dyeing purposes were obtained in the same way when the esters and amines shown in Examples 1 to 5 were replaced by the components shown in the table below.

【table】

【table】

[Table] Example 6 245 parts of N-ethyl-N-hydroxyethyl-
Sulfuric acid half ester of aniline and 435 parts of morpholine in a stirred apparatus over a period of 6 hours.
Heated to 130°C. After the reaction mixture had cooled to room temperature, 300 parts of water were added and the amine phase was separated by adding 200 ml of 45% strength sodium hydroxide solution. The amine was purified by vacuum distillation on a 30 cm silver coated column. After removing 34 parts of the first fraction, 155
The fraction boiling at °C/4 mbar was collected. 130 parts of N-(N'-ethyl-N'-phenyl)-aminoethyl-morpholine were obtained, corresponding to 55.6% of theory.

Claims (1)

[Claims] 1. General formula [In the formula, X and Y independently represent hydrogen, halogen, alkyl, trifluoromethyl or alkoxy; R ₁ represents hydrogen or alkyl; R ₂ and R ₃ each independently represent hydrogen, optionally hydroxyl; , alkyl or cycloalkyl optionally substituted by halogen or alkoxy, or alkenyl or aralkyl, or R ₂ and R ₃ together with the nitrogen atom form a heterocyclic ring, and R ₄ is hydrogen or alkyl, and n represents 0 or 1] In the method for producing a compound of the general formula [wherein _, A process characterized in that it is reacted with an amine of the following formula: [wherein R ₂ , R ₃ , R ₄ and n have the meanings given above]. 2 formulas [In the formula, X′ represents a hydrogen atom or a methyl group, and R ₁ ′ represents a methyl or ethyl group] The process according to claim 1, characterized in that the reaction is carried out with an amine of the following formula: wherein R ₂ ' and R ₃ ' represent methyl, ethyl or benzyl. 3 Reaction at 80-250°C, preferably 140°C-
The method according to claim 1, characterized in that it is carried out at 220°C. 4. Process according to claim 1, characterized in that the reaction is carried out at between 1 and 100 bar, preferably between 2 and 25 bar. 5. Process according to claim 1, characterized in that the components are reacted in a molar ratio of from 1:1 to 50, preferably from 1:2 to 10. 6. The method according to claim 1, characterized in that an alkali metal salt of a sulfuric acid half-ester is used. 7 As amines, ammonia, methylamine,
characterized in that dimethylamine, diethylamine and N-methyl-benzylamine are used,
A method according to claim 1.