DE1263951B - Process for the preparation of 2-aminoanthraquinones - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C 09b

German class: 22 b -3/01

Number: 1263 951

File number: B 59146IV c / 22 b

Filing date: August 27, 1960

Open date: March 21, 1968

The introduction of amino groups in the / i position of anthraquinone derivatives is known by replacement of hydroxyl, sulfonic acid groups or halogen versus ammonia possible, but these are generally stringent conditions necessary.

It has already been proposed an anthraquinone compound of the formula

Process for the production of
2-aminoanthraquinones

O OH

Shark

O OH
with a diamine of the formula

N —A —N:

, R ₁

to condense, where in the given formulas A is an aliphatic or aromatic radical, Ri and R2 are hydrogen atoms or alkyl radicals, η is an integer not exceeding 5, Hal is a halogen atom and in which the ring B can still have substituents. The compounds obtained can be used as free bases (cf. column 3, lines 40, 41, of German patent 1,186,161).

It has now been found that in 1,4-dihydroxyanthraquinone derivatives (Quinizarine derivatives), which contain interchangeable radicals in the 2-position, the 2-position substituents very easily by am Nitrogen not aromatically substituted residues of primary or secondary amines and the starting compounds can be converted into 2-amino compounds in this way and thus valuable, new dyes are available. In the 2-position interchangeable residues are z. B. Ethereal, Thioether, sulfonic acid groups or their salts or halogen. The implementations are excluded from this according to patent 1,186,161.

The 2-position ether group can, for example, be an alkyl ether, e.g. B. methyl ether, an aryl ether, z. B. Phenyl, p-chlorophenyl, chlorosulfonylphynyl applicants:

Aniline & Soda Factory in Baden
Aktiengesellschaft, 6700 Ludwigshafen

Named as inventor:

Dr. Karl Maier, 6700 Ludwigshafen

ether or sulfonated phenyl ether, an aralkyl ether, e.g. B. benzyl, / 9-phenylethyl ether, or a Thioethers, e.g. B. phenylthioether. The preferred halogen in the 2-position is bromine.

Amines which are non-aromatic on the nitrogen and with which the 2-position substituents of the 1,4-dihydroxyanthraquinones can be exchanged are primary and secondary aliphatic amines, such as methylamine, ethylamine, n-butylamine, n-hexylamine, 2-ethylhexylamine, dimethylamine. In the alkyl radical further substituents can be present, as in y-methoxy-, y-ethoxy-, y-butoxy-, y-dimethylamino-, y-pyrrolidino-, y-piperidino-, y-hexamethyleneimino-, y-morpholino-, y-cyclohexylaminopropylamine, ß-diethylaminoethylamine, aminoethanol, 3-aminopropanol- (l), «j-aminocapronitrile, ethylenediamine, 1,6-hexamethylenediamine, 1,2-diaminocyclohexane. The aliphatic substituents of the amines can also be substituted by aromatic radicals, as in benzylamine and / i-phenylethylamine. Cycloaliphatic amines, such as cyclohexylamine, and cyclic amines, such as ethyleneimine, Pyrrolidine, piperidine, morpholine and thiomorpholine are also suitable amines. the Amines show certain differences in reactivity due to basicity and steric relationships and solvency are likely to be conditional. In the implementation according to the invention with primary 1,2-diamines, such as 1,2-ethylenediamine and 1,2-diaminocyclohexane, the second amino group takes the place of the neighboring hydroxyl group in the nucleus with the formation of a tetrahydropyrazine ring system.

The reaction is advantageously carried out in excess amine as a solvent and diluent, but other solvents, such as water, alcohol, dioxane, can also be used.

809 519/575

be turned. It generally proceeds at temperatures between room temperature and 8O ⁰ C, in some cases immediately, in other maximum within a few hours.

The products of the process can be isolated in a customary manner, by filtration, if appropriate after dilution with alcohols, water, dilute acids, or after steam distillation.

The new process products are valuable dyes for synthetic fibers and plastics. For example, some of them give colorations with excellent thermal properties on polyester material Properties. Some of the new dyes are also valuable intermediates for the Manufacture of other dyes. Compared to dyes that are known from US Pat. No. 2,737,517 are known, the dyes prepared according to the invention have a considerably better drawability on polyester fibers.

The parts mentioned in the exemplary embodiments are parts by weight.

example 1

15 parts of 2-phenoxyquinizarin are heated to 50 ° C. with 80 parts of methylamine in a RuhräüTöklav for 1 hour. After the excess amine has evaporated, the residue is rubbed with water, filtered off with suction and washed neutral. 12 parts of the dye are obtained with a ^{temperature of approximately 300 to 302 °} C. (from chlorobenzene). He dyes polyester and acetate fabrics in strong red tones. Color reaction with concentrated sulfuric acid-formaldehyde: red - * ■ bluish green.

The same compound is obtained from 2-bromoquinizarin under these conditions; F. 311 bis 312 ° C (also anisole), mixed melting point 302 to 3O3 ° C.

Example- 2

15 parts of 2-bromoquinizarin are heated to 80 ° C. with 80 parts of ethylamine in an autoclave for 1 hour. In the work up, as indicated in the preceding example, is obtained .12 parts of the dye, mp 265 to 265.5 ⁰ C, the red dyeings on acetate and polyester fabrics results; Color reaction as with the dye according to Example 1.

Example3

15 parts of 2-phenoxyquinizarin are heated to 45 ^° C. with 80 parts of n-butylamine for ^{1 ^ hour.} After dilution with 100 parts of methanol, left to stand for a few hours and the addition of highly dilute hydrochloric acid, 13.5 parts of the dye with a melting point of 159 to 160 ^° C. (from propanol) can be isolated, which gives strong colors on acetate and polyester fabrics; Color reaction as with the dye according to Example 1.

Example 4

20 parts of 2-Bromchinizarin be 2-ÄthyJhexylamin heated with 50 parts of 75 minutes to 70 to 75 ⁰ C. After dilution with 100 parts of methanol and cooling, 20 parts of the dye with a melting point of 137.degree. To 138.degree. C. are obtained. With it, red dyeings are obtained on polyester fabric; Color reaction as above.

Example 5

20 parts of 2-Bromchinizarin are heated with 50 parts of cyclohexylamine 1 hour at 70 ⁰ C, the reaction initially is exothermic. After dilution with methanol, 16 parts of the dye with a melting point of 189 to 190 ^° C. (from benzene-ethane) are obtained: strong red colorations on polyester fabric.

Example 6

15 parts of 2-bromoquinizarin are heated to 50 ° C. for 1 hour with 100 parts of dimethylamine in a stirred autoclave. After working up, as indicated in Example 1, 12.5 parts of the dye with a ^{temperature of 201 to 203 °} C. are obtained: cherry-red dyeings on polyester fabric, negative color reaction.

Example 7

13 parts of 2-phenoxyquinizarin are mixed with 50 parts Piperidine heated to 45 ° C. for 30 minutes with stirring. After dilution with 100 parts of methanol is suctioned off cold and washed out with methanol and acidified water. 10.5 parts of the Dye with a temperature of 188 to 189 ° C: strong cherry-red colorations on polyester fabric, color reaction negative.

Example 8

10 parts of 2-bromoquinizarin are introduced into 50 parts of pyrrolidine with gentle cooling (exothermic reaction), whereupon the reaction mixture is stirred for 0.5 hours at room temperature. After dilution with methanol, it is suctioned off. 7.5 parts of the dye with a melting point of 232 to 233 ^° C. are obtained, which dyes polyester fabric in a strong burgundy red; Color reaction negative.

15 parts of 2-phenoxyquinizarin are introduced into 50 parts of pyrrolidine. After ¹ yo. Hour stirring at 35 to 40 ⁰ C is diluted with 100 parts of methanol and suction filtered; Yield 13.5 parts of the dye which is identical to that obtained in paragraph 1.

Example 9

15 parts of 2-bromoquinizarin are introduced into 80 parts of morpholine (slightly exothermic reaction). After stirring for one hour at 50 ^° C., it is diluted with methanol, filtered off with suction and washed; Yield 14 parts of the dye with a melting point of 239 to 241 ^° C.: medium-strong, opaque pink colorations on polyester fabric.

Example 10

20 parts of 2-phenoxyquinizarin in 50 parts of methanol are mixed with 50 parts. Ethylenimine heated to about 70 ° C for 6 hours. After cooling, it is filtered off with suction and washed with methanol; Yield 9.5 parts of the dye; Discoloration and decomposition from about 220 ^° C.: strong red colorations on polyester fabric are obtained; Color reaction red -> bluish green.

Eg game 11

15 parts of 2-Bromchinizarin are heated with 70 parts of 4-aminocapronitrile 1 hour Stickstoffatmo sphere at 6O ⁰ C. After dilution with methanol, 14 parts of the dye with a mp of 184 ° C. can be isolated: medium pink dyeings on polyester fabric.

Example 12

13 parts of 2-Phenoxychinizarin be diluted ^l k in 80 parts of aminoethanol hour at 60 ⁰ C heated the reaction mixture with 100 parts of methanol and filtered off with suction, the reaction product; Yield 10.5 parts of the dye with a melting point of 264 ° to 266 ° C.: bluish red dyeings on polyester fabric.

Example 13

Of 15 parts of 2-Phenoxychinizarin in 80 parts of 3-Aminopropanol- (l) gives 13 parts of dye, mp 177-178 ° C (/ ₂ hour 80 ^{0 C!):} On polyester and acetate fabric bluish red colorations.

Example 14

19.5 parts of 2-phenoxyquinizarin are mixed with 120 parts of chlorosulfonic acid at room temperature in the Sulphonic acid chloride transferred. The moist filter material of the sulfonic acid chloride is converted into 50 parts of γ-methoxypropylamine entered, stirred for 2 hours at room temperature and allowed to stand for several hours sucked off. 15 parts of the dye with a melting point of 141 ° to 142 ° C. are obtained (from ethanol): on polyester and Acetate fabric strong red colors.

10 parts of 2-Phenoxychinizarin are heated for 1 hour at 6O ⁰ C with 50 parts of j-methoxypropylamine. After dilution with 80 parts of methanol and hot water, 9 parts of the dye according to the preceding paragraph are obtained.

10 parts of 2-p-chlorophenoxyquinizarin are heated ^{to 60 °} C. with 50 parts of γ-methoxypropylamine for 1 hour. After dilution with 100 parts of methanol and the addition of weakly acidic water, 8.5 parts of the same dye can be isolated.

10 parts of 2-Bromchinizarin are mixed with 50 parts} '- methoxypropylamine allowed to stand for 1 hour at room temperature (25 to 30 ⁰ C) (slightly exothermic reaction). 9 parts of the same dye are obtained.

15 parts quinizarin-2-sulfonic acid are heated with 40 parts of y-methoxypropylamine Va hour at 8O ⁰ C. 9.7 parts of the same dye are obtained.

10 parts of 2-Bromchinizarin and 10 parts of y-methoxypropylamine are heated for 4 hours at 8O ⁰ C in 50 parts of butanol. 6.5 parts of the same dye are obtained.

Example 15

15 parts of 2-Phenoxychinizarin be in 60 parts of y-Äthoxypropylamin heated for 1 hour at 6O ⁰ C. After dilution with 100 parts of methanol and acidified water 14.5 parts of the dye obtained, melting at 122 to 123.5 ⁰ C on polyester fabric strong bluish red colorations.

55

Example 16

15 parts of .2-phenoxyquinizarin are in 60 parts of γ-dimethylaminopropylamine at 60 ° C. for 1 hour warmed up. The reaction product becomes after the addition of 80 parts of methanol and very dilute hydrochloric acid isolated by filtration. The yield is 13 parts of dye hydrochloride with a melting point of 276 to 278 ° C. On polyacrylonitrile fabric, the dye gives strong, somewhat opaque blue-tinged red dyeings.

Example 17

15 parts of 2-Phenoxychinizarin be heated 2V2 hours at 6O ⁰ C in 80 parts of y-Cyclohexylaminopropylamin. After working up according to Example 16, 14 parts of dye with a melting point of 261 to 263 ^° C. are obtained, namely predominantly the hydrochloride. This gives strong bluish red dyeings on polyacrylonitrile fabric.

Example 18

15 parts quinizarin-2-sulfonic acid are heated (70 ° / oig) ¹ J ₂ hour at 80 ° C with 55 parts of ethylene diamine. After dilution with 100 parts of methanol 7.4 parts of the dye obtained from the approximate F. 270-280 ⁰ C (from nitrobenzene) providing on acetate fabric strong reddish violet and covered polyester fabric rotstichigviolette dyeings; Color reaction purple pure blue.

The same dye is obtained from 15 parts of purpurin (1,2,4-trihydroxyanthraquinone) and 50 parts of ethylenediamine (70 ° / oig) after one hour of heating at 8O ⁰ C: 6 parts.

Example 19

15 parts of 2-Bromchinizarin are mixed with 40 parts of 1,2-diaminocyclohexane 1 hour at 8O ⁰ C heated (exothermic reaction). After dilution with methanol, 7.7 parts of the dye with a melting point of 250 ° C. (from chlorobenzene) are obtained: violet dyeings on acetate fabric; Color reaction violet - ■> · pure blue.

Example 20

15 parts of 2-Phenoxychinizarin are heated for 1 hour at 8O ⁰ C with 50 parts of benzylamine. After dilution with methanol, 13.5 parts of the dye with a melting point of 203 ° to 204 ° C. are obtained: red dyeings on polyester fabric.

Claims (1)

Claim: Process for the preparation of 2-aminoanthraquinones, characterized in that that one 1,4-dihydroxyanthraquinones which contain exchangeable radicals in the 2-position with converts primary or secondary amines that are not aromatically substituted on nitrogen, except for the reactions according to patent 1,186,161. Considered publications:
U.S. Patent No. 2,737,517. Legacy Patents Considered:
German Patent No. 1 186 161. When the application was announced, a coloring table provided with explanations was displayed.