DE2742174A1 - Process for the preparation of amines - Google Patents

Description

Bayer Aktiengesellschaft

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5090 Leverkusen, Bayerwerk Mi-kl

Sep

Process for the production of amines

The present invention relates to a process for the preparation of amines of the general formula

γ 2 ^Ca 2 \

R ₄ ^R 3

wherein

X and Y independently represent hydrogen, halogen, alkyl, trifluoromethyl or alkoxy,

R _{1 represents} hydrogen or alkyl and

R ₂ and R ₃ independently of one another represent hydrogen, alkyl or cycloalkyl optionally substituted by hydroxy, halogen or alkoxy, represent alkenyl or aralkyl, or

R ₂ and R ₃ together with the nitrogen atom form a heterocyclic ring,

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for hydrogen or alkyl and

stand for 0 or 1.

The procedure consists in making sulfuric acid esters the general formula

(H)

ClL-CH ₉ -OSO H

their alkali salts, e.g. sodium, potassium, lithium salts, or their alkaline earth salts, e.g. calcium or barium salts, with amines of the general formula

H- (N) -N ^{1 n}

(III)

implements.

The amines of the formula (I) serve as coupling components in the preparation of dyes. Dyes of this type are known from German Patents 1,011,396, 1,644,175 and 2,059,945 known.

The alkyl and alkoxy radicals mentioned under X, Y, R ₁ and R _{4 and the alkoxy radicals mentioned under R 1 and R 3} are preferred

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1-4 carbon atoms, and those under R and R mentioned Alkyl radicals preferably have 1-18 carbon atoms.

Alkenyl is understood to mean, in particular, alkyl and methyl-allyl.

Aralkyl preferably represents benzyl and phenylethyl and their derivatives substituted by methyl in the phenyl ring.

Cycloalkyl is preferably cyclopentyl and cyclohexyl.

R_ and R together with the nitrogen atom form in particular a 5- to 7-membered ring, e.g. the pyrrolidine, piperidine, piperazine, N-methylpiperazine, morpholine or Hexamethyleneimine ring.

Halogen is understood in particular to mean fluorine, chlorine and bromine.

Preferred amines are those of the formula (I) in which

X for hydrogen, chlorine, Cj-C ₄ -AlJCyI, trifluoromethyl or C.-C.-alkoxy,

Y for hydrogen,

R _{1 represents} hydrogen or Cj-C.-alkyl and

R_ and R, independently of one another for hydrogen, optionally substituted by hydroxy, chlorine, methoxy or ethoxy

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C -C -alkyl, cyclohexyl, allyl or benzyl, or

R ₀ and R .. together form a piperidine or morpholine ring,

R. for hydrogen or C.-C.-alkyl and η stand for 0.

Of these preferred amines, there are in turn those of the formula X ¹
- NR ₂ '(IV)

^ CH ₀ -CH ₀ -N

highlight where

X ¹ for hydrogen or methyl,

R ₁ 'for methyl or ethyl and

R- 'and R, ^{1 represent} methyl, ethyl or benzyl.

The reaction of the sulfuric acid esters (II) with the amines (III) can be carried out continuously and discontinuously. The temperature range is generally 80-250 C, preferably 140-220 C.

The reaction takes place at pressures up to 90 bar, in particular at 5-25 bar.

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The preferred molar ratio of sulfuric acid ester (II) to amine (III) is 1: 1-50 and in particular 1: 2-10.

The process is preferably carried out in aqueous solution, but can also be carried out in the presence of organic solvents take place. Suitable organic solvents are, for example, the following: benzene, toluene, xylenes, chlorobenzene, dichlorobenzenes, Nitrobenzene, quinoline, cyclohexane, anisole, decalin and mixtures of such solvents.

The sulfuric acid esters (II) can be prepared in a manner known per se by reacting the corresponding hydroxy compounds can be obtained with sulfuric acid or chlorosulfonic acid. The sulfuric acid esters and their production are for example by K.H. Saunders in "Journal of the Chemical Society" 121 (1922) pp. 2667-2675.

As starting products for the production of sulfuric acid half esters (II) are, for example, the N-hydroxyethyl compounds the following aromatic amines called: aniline, m-toluidine, m-chloroaniline, M-trifluoromethyl-aniline, N-methyl-aniline, N-methyl-m-toluidine, N-ethyl-aniline, N-ethyl-m-toluidine, N-propyl-aniline, N-propyl-m-toluidine, m-chloro-N-ethyl-aniline, m-Trifluoromethyl-N-ethylaniline.

The following amines of the formula (III) may be mentioned in particular: ammonia, methylamine, dimethylamine, ethylamine, diethylamine, Propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, sec-butylamine, iso-butylamine, Diisobutylamine, tert-butylamine, 1,1-dimethylpropylamine, 1-aminohexane, 2-ethylhexylamine, dodecylamine

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(1-amino-dodecane), methy lstearylanii η, allylamine, diallylarain, Ethanolamine, 2-Methoxyätliy lamLn, N-Methy la'thanolamin, Diethano lamin, i-Ami.no- 1 -propanol, isopropanolaniin, DL isopropanolamine, cyclohexylamine, N-methyl-cyclohexylamine, I) icyclohexy lamin, Aminoinethy Icyclohexan, Benzy lamin, N-Methy1-benzylamine, Pyrrolidine, piperidine, hexamethyleneimine, N-methy 1-piperazine, morpholine, N-A-Juino-morphol in.

The advantage of the new process over the known processes for the preparation of the amines (I), which are obtained by reacting the corresponding halogen compounds of the F ¹ Orme I.

(V)

CH_-CH ,, - halogen Y II

take place lies in the economic and more environmentally friendly Way of working.

The compounds of the formula (II) present as internal salts are as a rule solid and can be used in dilute aqueous Alkali solutions can be dissolved. This leads to the fact that, in contrast to the above manufacturing process via the halogen compounds - can react in a homogeneous aqueous phase with the amines of the formula (III).

The amines (I) are obtained in surprisingly high purity and good yield in short reaction times.

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example 1

245 parts of the sulfuric acid half-ester are dissolved in a solution of 40 parts of caustic soda in 400 parts of water of N-hydroxyethyl-N-ethylaniline and transferred the mixture in a stirrer autoclave. After 135 parts of dimethylamine have been pressed in, the mixture is heated Reaction mixture at 180 ° C. for 2 hours.

After cooling and releasing the pressure, the phases are separated and distilled in an 80 cm packed column Vacuum. One collects the fraction between 139 - 141 C / 22 nibar and receives 172.7 parts of N-dimethylaminoethyl-N-ethylaniline, corresponding to 89.9% d. Th., In 99.4% purity. 7.7 parts remain as the distillation residue return.

Example 2

40 parts of caustic soda are dissolved in 400 parts of water. In this solution nan carries 259 parts of the sulfuric acid half-ester of N-hydroxyethyl-N-ethyl-m-toluidine. To Transfer to a stirrer autoclave is pressed 140 Split up dimethylamine and heat the reaction mixture to 160-170 ° C. for hours.

Working up is carried out as described in Example 1. The fraction which boils at 173-175 ° / 3O Torr is collected and 175 parts of Ν, Ν-dimethyl-N ¹ -m-tolyl-ethylenediamine of excellent purity are obtained.

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Example 3

123 parts of the sulfuric acid half ester of N-ethyl-N-hydroxyethyl-aniline and 380 parts of 25% strength aqueous ammonia solution are in a 1.3 l stainless steel autoclave for 2 hours heated to 180 for a long time. The pressure rises to 25 bar at. After the reaction mixture has cooled to room temperature, the organic phase and its fractionated phase are separated off Distillation is obtained at 136-142 ° C / 18 now boiling Hg 45 parts of N-ethyl-N-aminoethyl-aniline in 98-99% strength Purity.

Example 4

245 parts of the sulfuric acid half ester of N-ethyl-N-hydroxyethyl-aniline and 525 parts of diethanolamine are stirred for 2-3 hours at 175-180 ° C heated. After the reaction mixture has cooled to room temperature, 1000 parts of water are added and the mixture is separated off the amine phase by adding 100 parts of caustic soda. The amine is purified by vacuum distillation on a 30 cm silver jacketed column. After taking off a first run of 35 parts, they are collected at 194-196 ° / 2 mbar boiling fraction. 204 parts of N-ethyl-N- (bis-hydroxyethyl-aminoethyl) -aniline are obtained, corresponding to 81% d. Th.

Example 5

A suspension of 2450 parts of the sulfuric acid half ester of N-ethyl-N-hydroxyethyl-aniline in 6000 parts of water 890 parts of 4 5% caustic soda solution are added, so

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Al

that the temperature does not exceed 20 C. After adding 2520 parts of 53.6% strength dimothylamine solution are obtained clear solution.

This solution is continuously transferred from a storage vessel to one heated to 180 - 200 ° C. using a metering pump Reaction tube, the diameter of which is 7 mm and length 28 m and which is provided with a pressure indicator, promoted. After passing through a needle valve with which the pressure is regulated to 20 bar, the reaction mixture becomes cooled to room temperature in a downstream cooler and collected in a template in which the Separate phases. The organic phase is examined by gas chromatography. With variation of residence time and reaction temperature the following result is obtained:

Dwell time

Reaction temperature

composition

N-ethyl-N- dimethylaminoethylaniline

of the raw product

N-ethyl-N-hy-

hydroxyethyl

aniline

1 H.

1 H. 0.5 hours 0.5 hours

200 ° C 180 ° C 200 ° C 180 ° C

98.7%

98.9%

98.7%

98.6%

1.3%

1.1%

1.3%

1.4%

The yields are practically quantitative.

Likewise valuable intermediates for dye purposes are obtained if, instead of the esters and amines given in Examples 1-5, the components given in the following table are used:

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ORIGINAL INSPECTED

Shelfelic acid half-ester of Amine component N-hydroxyethyl aniline ammonia tr Methylamine f! Dimethylamine 11 Ethylamine M. Diethylamine Tl Allylamine N-methyl-N-hydroxyethyl aniline ammonia Il Mo thy lamin M. Dimethylamine M. Diethylamine Il N-methyl-benzylamine Il Cyduhexylamine Il Pyrrolidine Il flnr pholin Il N-amino-morpholine Il Diethanolamine Il Diisopropanolamine N-ethyl-N-hydroxyethyl-aniline Methylamine Il Ethylamine Il Diethylamine Il Denzylamine ff N-methyl-benzylamine ti Propylamine It I sopropylamine ft Ethanolamine " tert-butylamine Il 2-methoxyethylamine It Cyclohexylamine Il Pyrrolidine It Piperidine Il Hexamethyleneimine Il N-methyl piperazine ft Morpholine dd N-methyl-N- (0-hydroxypropyl) amine N-ethyl-N-hydroxyethyl-m-toluidine ammonia If Methylamine Il Diethylamine Il Diethanolamine Il D i ρ r ο ρ y 1 a m i η Il Butylamine M. CyclohBxylamine M. Benzylamine Il N-Me t hy1-benzy lamin N-ethyl-N-hydroxyethyl-m-chloroaniline Dimethylamine Il Diethylamine ff Dipropylamine It
ft N-methyl-benzylamine Il N-methyl- cyclohexylamine
Piperidine

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Example 6

245 parts of the Schuefelsäurehalbesters des N-Äthy1-N-hydroxyäthylanilins and 435 parts of morpholine are heated to 130 ° C. for 6 hours in a stirring apparatus. After the reaction mixture has cooled to room temperature, 300 parts of water are added and the amine phase is separated by adding 200 ml of 45% sodium hydroxide solution.

The amine is purified by vacuum distillation on a 30 cm silver-jacketed column. After taking off a first run of 34 parts, the fraction boiling at 155 C / ambar is collected. 130 parts of N- (N'-ethyl-N'-phenyl-) aminaethyl-marpholine are obtained, corresponding to 55.6 % of theory.

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Claims (7)

Claims 7, process for the preparation of compounds of general formula wherein X and Y independently represent hydrogen, halogen, alkyl, trifluoromethyl or alkoxy, R _{1 represents} hydrogen or alkyl and R ₂ and R ₃ independently of one another represent hydrogen, alkyl or cycloalkyl optionally substituted by hydroxy, halogen or alkoxy, represent alkenyl or aralkyl, or R ₂ and R ₃ together with the nitrogen atom form a heterocyclic ring, R for hydrogen or alkyl and stand for 0 or 1, Le A 18 410 - 12 - 90 9 813/0296 characterized in that one sulfuric acid half esters of the general formula R, CIU-ClU-OSO, H. where X, Y and R. have the meaning given above, odor their alkali or alkaline earth salts with amines of general formula Il - in which R and R. have the meaning given above, implements. 2. The method according to claim 1, characterized in that one compounds of the formula in which X ¹ denotes a hydrogen atom or a methyl group and R. ' stand for a methyl or ethyl radical, Le A 18 41 0 - 13 - 9098 1 3/0296 with amines of the general formula HN in which R 'and R' are methyl, ethyl or benzyl, implements. 3. The method according to claim 1, characterized in that the reaction at 80-25O ° C, preferably at 140
220 C is carried out. 4. The method according to claim 1, characterized in that the reaction at 1 - 100 bar, preferably at 2-25 is carried out in cash. 5. The method according to claim 1, characterized in that the components in a molar ratio of 1: 1-50, preferably
1: 2-10 can be implemented. 6. The method according to claim 1, characterized in that the alkali salts of the sulfuric acid half-esters are used. 7. The method according to claim 1, characterized in that the amines used are ammonia, methylamine, dimethylamine, diethylamine and N-methylbenzylamine is used. Le A 18 410 - 14 - 9098 1 3/0296