DE2334991C3 - Process for the preparation of α-amino-β'-nitro-anthraquinones - Google Patents

Description

In the German Offenlegungsschrift 22 11 411 described that in the implementation of a, j3'-Dinitroanthrathinoncn with ammonia in acid amides «, j3'-diamino-anthraquinones develop.

Surprisingly, it has now been found that when Λ, / Γ-dinitro-anthraquinones are reacted with ammonia when using certain molar ratios of ammonia and dinitroamhraquinones and certain Temperatures in water, ether, aliphatic or cycloaliphatic or optionally alkyl-substituted hydrocarbons or, if appropriate, mixtures of these compounds ot-Amino-ji'-nitro-anthraquinones in good yields receives.

The invention therefore relates to a process for the preparation of α-amino-β'-nitro-anthraquinone, which is characterized in that \, j3'-dinitro-anthraquinones with ammonia at a molar ratio of ammonia to α, / 3'-dinitroanthraquinone of at least 3: 1, in particular from 10: 1 to 40: 1 and especially of 15: 1 to 30: 1, at temperatures from 100 to 220 ⁰ C, preferably 140 to 200 ° C, optionally under pressure, ir ethers, aliphatic , cycloaliphatic or optionally alkyl-substituted aromatic hydrocarbons in water or in mixtures of these compounds.

You can use both pure 1,6- and 1,7-DinitiO-anthraquinone - e.g. B. available from HeIv. Chim. acta, 14.1404 - Use as well as mixtures of these compounds.

Suitable ethers are in particular aliphatic, cycloaliphatic and aromatic ethers, such as
Dibenzyl ether, di-sec-butyl ether,
Diisopentyl ether, ethylene glycol dimethyl ether,
Diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether,
Methoxycyclohexane, ethoxycyclohexane,
Dicyclohexyl ether, anisole, phenetole, diphenyl ether, 2-methoxynaphthalene, tetrahydrofuran, dioxane,
Amylphenyl ether, benzyl isoamyl ether, dibenzyl ether, diglycol di-n-butyl ether, glycol methyl ether, methylbenzyl ether.

Suitable aliphatic and cycloaliphatic hydrocarbons are, for example

n-pentane, η-hexane, n-heptane, cyclohexane, methylcyclohexane, cyclododecane, decalin, ι ο cycloheptane, cyclopentane, n-decane, 1,2-dimethylcyclohexane,
1,3-dimethylcyclohexane,
M-dimethylcyclohexane ^^ - dimethylpentane, 2 _r 3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, isopropylhexane, methylcyclohexane, 2-methyl-heptane, 3-methyl-heptane, 4-methyl-heptane, 2- Methylhexane, 3-methylhexane, 2-methyl-octane, 3-methyl-octane, 4-methyl-octane, 2-methyl-pentane, 3-methyl-pentane, n-octane, penta-isobutane, triethyl methane, 2, 2,3-trimethylpentane, 2,2,4-trimethylpentane,
2,2,3-trimethylpentane.

Suitable aromatic hydrocarbons are, for example

Benzene, toluene, o-, m-, p-xylene,
Isopropylbenzene, trimethylbenzene, diethylbenzene, tetramethylbenzene, di-iso-propylbenzene, isododecylbenzene, tetralin, naphthalene, methylnaphthalene, diphenyl, diphenylmethane, o-, m-, p-cymene, dibenzyl, dihydronaphthalene,
2,2'-dimethyl-diphenyl,
2,3'-dimethyl-diphenyl,
2,4'-dimethyl diphenyl,
3,3'-dimethyl-diphenyl,
1,2-dimethylnaphthalene,
1,4-dimethylnaphthalene,
«Ο 1,6-diniethylnaphthalene,

1,7-dimethylnaphthalene,
1,1-diphenylethane, hexamethylbenzene, isoamylbenzene, pentamethylbenzene, 1,2,3,4-tetramethylbenzene,
1,2,3,5-tetramethylbenzene,

1,2.7 -trimethylnaphthalene,
1,2,5-trimethylnaphthalene.

The process according to the invention is generally carried out under pressure. The reaction time depends on the temperature, the pressure and the molar ratio, and the rate of reaction increases with increasing temperature and increasing molar ratio. Reaction is carried out for example at pressures greater than 30 atm and at a molar ratio of 10: 1 at 200 ° C (150 ° C and 13O ⁰ C), the reaction after 0.5 (3 or 5 hours) is completed hours, while, for example at a molar ratio of 50: 1 and a temperature of 100 ° C (30: 1 at 13O ⁰ C and 20: 1 at 150 ° C) with a reaction time of less than 5 hours (less than 4 or 0 , 5 hours).

The process can be carried out continuously or batchwise.

The reaction mixture can be worked up by customary methods, for example by filtering off of the product crystallized out of the organic solvent after cooling to room temperature. The resulting mother liquor can be in the

Process. The reaction mixture can also be worked up in such a way that the solvent is distilled off or with the aid of a diluent, which increases the solubility of the a-amino-ß'-nitro-anthraquinones decreases in the reaction solution (e.g. petroleum ether), the a-amino-jS'-nitroanthraquinones be precipitated. If desired, the reaction product can be obtained by treatment with acids, for example sulfuric acid, or can be further purified by distillation in vacuo. ι ο

a-Amino-ß'-nitroanthraquinones are dyes for synthetic fiber materials or intermediate products for the production of such dyes, the z. B. by acylation of the amino group or by halogenation and or or, if appropriate, by further conversions, such as those on -amino-anthraquinones are known to be obtained.

example 1

The mixture of 310 g of 1,6-dinitro-anthraquinone (96%) and 1 liter of toluene is in the autoclave with 170 g Ammonia reacted for 2 hours at 150 ° C (molar ratio 10: 1; Pressure 50 atm).

The reaction mixture is filtered off with suction after cooling to room temperature, the residue with a little Washed toluene and dried in vacuo Yield: 277 g of a 93.1% l-amino-6-nitro-anthraquinone (96% theory).

Similar yields and purities are obtained if, instead of toluene Benzene, 1,3,5-trimethylbenzene,

Isopropylbenzene, isododecylbenzene,

Diphenylmethane, η-hexane, n-heptane,

Decalin, tetralin, methylcyclohexane,

Cyclododecane, n-dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether,

Diethylene glycol diethyl ether,

Methoxycyclohexane, dicyclohexyl ether,
Anisole, phenetole, diphenyl ether,
Tetrahydrofuran, dioxane or
Mixtures of these solvents
used

Example 2

A mixture of 301 g of 1,7-dinitro-anthraquinone (99%) and 1 liter of ethylene glycol dimethyl ether is mixed with 510 g of ammonia (molar ratio 30: 1; pressure 60 atm) at 130 ° C and a reaction time of 4 hours in the autoclave. After cooling the reaction mixture is poured into 5 liters of water and the precipitate is filtered off with suction, with Washed with water and dried Yield: 264 g of a 93% 1-amino-T-nitro-anthraquinone (91% theory).

Example 3

After a 0.5 hour reaction of 310 g of 1,6-dinitroanthraquinone (96%) with 340 g of ammonia (Mo) ratio 20: 1; Pressure 80 atm) in 1 liter of n-pentane at 150 ^° C. in the autoclave, the reaction mixture obtained is freed from the solvent by distillation. Residue 269 g of a 91.5% strength 1-amino-6-nitro-anthraquinone (89% of theory).

Example 4

A suspension of 317 g of 1,7-dinitro-anthraquinone (94%) in 2 liters of water is ^{stirred with 340 g of ammonia (molar ratio 20: 1; pressure 40 atm) at 180 °} C. for 2 hours in an autoclave. After the pressure has been released, the reaction mixture is filtered off with suction at room temperature. The mother liquor is fed back into the process while the residue is dried. Yield: 274 g of a 90% strength 1-amino-7-nitroanthraquinone (92% of theory).

Claims (5)

Patent claims: 1. A process for the preparation of atroanthraquinone, characterized in that α, ^ '- dinitroanthraquinones with ammonia at a molar ratio of ammonia to οί, β'-ΌΊ- nitroanthraquinone of at least 3: 1 at 100 to 220 ° C, optionally under pressure , in ethers, aliphatic, cycloaliphatic or optionally alkyl-substituted aromatic hydrocarbons, in water or in mixtures of these compounds. 2. The method according to claim 1, characterized in that the reaction in alkylbenzenes he follows. 3. The method according to claim 1 to 2, characterized in that the reaction is carried out at a Molar ratio of ammonia to Λ, β'-dinitro-anthraquinone from 10: 1 to 40: 1. 4. The method according to claim 1 to 3, characterized in that the reaction is carried out at a Molar ratio of ammonia to <x, j? '- dinitroanthraquinone from 15: 1 to 30: 1. 5. The method according to claim 1 to 4, characterized in that the reaction at 140 to 200 ° C.