DE1769591A1 - Process for the preparation of 1-alkyl-amino-4-chloroanthraquinones - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG _{Λ η η η Γ η} "

Our reference: Ο, Ζ »25 624 Ste / Th Ludwigshafen (Rhine), June 10, 1968

Process for the preparation of 1-alkylamino-4-chloroanthraquinones

The present invention relates to a process for the preparation of l-alkylamino - ^ - chloranthraquinones with tertiary amino groups in the alkylr.es f .. ■

l-Alkylamlno-4-chloranthraquinones with tertiary amino groups in the Alkyl radicals are valuable intermediates for the production of dyes, especially polyacrylonitrile dyes. These intermediates are known to be produced by first anthraquinones with exchangeable groups / such as nitro, sulfonic acid, Chlorine or bromine group, with alkylamines with a tertiary Reacts amino group and then the 1-alkylaminoanthraehinones obtained by chlorination into the l-alkylamino-4-chloroanthraquinones convicted.

Attempts have also been made to 1-alkylamino-4-chloroanthraquinones without tertiary amino groups, in the alkyl radical by exchanging one Chlorine atom in the technically more advantageously accessible 1,4-dichloro-anthraquinone by reaction with corresponding primary alkylamines (see e.g. German Patent 1 205 550,

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Example 5, and French patent specification 1,082-4-9, example 6).

According to this known procedure, 1.4 dichloro is obtained from 1.4 anthraquinone and twice the molar amount of alkylamine, half of which is used to bind the hydrogen chloride formed in the reaction is used, difficult to separate equipment from 1-alkylainino-4-chloro-anthraquinone and unreacted starting material. If the amount of amine is increased, mixtures of 1-alkylamino-4-chloro-anthraquinone are obtained and 1,4-bisalkylamino-anthraquinone. The same mixtures are obtained if one uses molar amounts of alkylamine used and the reaction in the presence of alkaline substances, such as alkali acetate or alkali carbonate, while 1,4-Bisalkylamino-anthraquinones arise when one is in the presence the alkaline substances and works with a larger excess of alkylamine.

It has now been found that l-alkylamino-4-chloroanthraquinones of the general formula I.

0 NH-X-Nf ι

ir

It I ^ »T-vl

(D,

in which X is an aliphatic divalent hydrocarbon radical having 2 to 6 carbon atoms or a phenylene group and R denotes an aliphatic hydrocarbon radical having 1 to 4 carbon atoms and R has the same meaning as R or a aromatic hydrocarbon radical of the benzene series can mean

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or R and R together with the tertiary nitrogen atom for one can stand heterocyclic ring, can advantageously be produced, if you have a 1,4-Dichloraufhrachinon with amines of the general Formula HpN-X-N ^, (II), in which X, R and R are those given above Have meaning, optionally in solvents, at temperatures between 70 and 220 C. : ■

According to the process of the invention, 1-alkylamino-4-ehloranthraquinones are obtained in a simple manner I in great purity and high yield. Surprisingly, the exchange of the second chlorine occurs atoms do not enter even if there is a large excess of amine used.

The 1,4- to be used as starting materials for the new process

Dichloroanthraquinones can be in one or more ß-positions of the anthraquinone nucleus or substituents such as chlorine atoms, methyl groups, tert-butyl groups, carboxyl groups, carbonamide groups, Benzoyl groups, benzoxazole groups contain. Suitable 1,4-dichloroanthraquinones are for example 1,4-dichloroanthraquinone, 1,4,6-trichloroanthraquinone, 1,2,5,4-tetrachloranthraquinone, 1,4,6,7-tetrachloranthraquinone, 1,4-dichloro-6-methylanthraquinone, 1,4-dichloroanthraquinone-6-carboxylic acid, l, 4-dichloro-6-benzoyl anthraquinone, 1,4-dichloro-6- (2'-benzoxazolo) -anthraquinone, 1,4-dichloroanthraquinone-6,7-dicarboxylic acid and 1,4-diehloranthraquinone-6,7-dicarbonimide. '

In the amines of the formula HgN-XN ^ ^ , X is an aliphatic divalent hydrocarbon radical with 2 to 6, preferably 2 to

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4 carbon atoms, which can be branched, or a phenylene group. R and optionally R denote an aliphatic hydrocarbon radical having 1 to 4, preferably 1 to 2 carbon atoms, such as a saturated straight-chain, branched or ring-shaped hydrocarbon radical, this radical still having inert substituents, such as halogen atoms, e.g. chlorine or bromine atoms, hydroxyl groups, alkoxy groups such as those with 1 to 4 carbon atoms, nitrile groups, May contain carbon ester or carbon amide groups. Around R together with the nitrogen atom can also form a preferably 5- to 7-membered ring, for example the remainder of the piperidine, Morpholins, Pyrrolidins, Imidazoles, form. If R is an aromatic hydrocarbon radical, this can still be inert Substituents such as methyl groups, methoxy groups or halogen atoms, e.g. chlorine or bromine atoms. The following amines may be mentioned as examples: l-dimethylamino-2-amino-ethane, l-dimethylamino-5-amino-propane, l-diethylamino-3-aminopropane, l-diethylamino-4-aminon-pentane, N - ^ - aminopropylJ-imidazole, N - (^ - aminoethyl) -piperidine, N- (γ-aminopropyl) morpholine, N-methyl-N-phenyl-ethylenediamine, 1-amino-4-dimethylaminobenzene.

The to be used according to the method of the invention as a starting material Amine is generally used in at least an equimolar amount used. If the reaction is carried out in an inert solvent, the amine is expediently used in amounts of 1 to 4, preferably 1.05 to 2 moles per mole of 1,4-dichloroanthraquinone. However, the amine can also be used in a large excess, e.g. by using it at the same time as a diluent. This procedure is expediently used when the amine is technically

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NiSGh is easily accessible.

Inert solvents, for example, alcohols, ketones * Ethers, amides, aromatic and aliphatic, optionally nitrated or halogenated hydrocarbons or tertiary amines are suitable. Let us mention here, for example, ethanol, '- isobutane ©! " n-butanol, ethyl glycol, n-butyl glycol, methyl ethyl ketone, dioxane, n-methylpyrrolidone, toluene, xylene, chlorobenzene, o-dichlorobenzene, Nitrobenzene, pyridine.

The method of the invention is performed at temperatures between 70 and 22'0 ° C, preferably 100-170 ⁰ C is performed. In general, atmospheric pressure is used. It is also possible, however, to work at elevated pressure, for example if the boiling point of the solvent is below the reaction temperature, or to use reduced pressure, for example 500 mm Hg. Depending on the reaction temperature, the reaction generally takes from 0.5 to 10 hours.

The new method is carried out, for example, in such a way that the 1,4-dichloroanthraquinone with 1.1 to 2 times the molar amount of primary amine heated to the reaction temperature in one of the solvents mentioned, advantageously at the boiling point the solvent works under reflux.

To accelerate the reaction, it is often advantageous if small amounts, preferably between 0.01 and 1.0% by weight , based on the 1,4-dichioranthraquinone derivative, are added to the reaction mixture.

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Copper or copper compounds, such as copper (II) acetate, copper (II) carbonate, Copper (II) chloride, copper (I) chloride, adds.

After the reaction has ended, the end product is in the form of 1-alkylamino-4-chloroanthraquinone and / or its hydrochloride, depending on the amount of amine used. The work-up is carried out, for example, by separating the end product quantitatively as the hydrochloride from the reaction mixture with the inert solvent by adding an alcoholic hydrogen chloride solution and isolating W as such. However, the reaction mixture can also be freed from the solvent, for example by steam distillation, and the free base can be isolated from the residue, if appropriate after adding basic substances such as aqueous ammonia, aqueous sodium or potassium hydroxide solution.

The l-alkylamino-4-chloroanthraquinones are obtained according to the new process in high yield and in chromatographically pure form. If unsymmetrical 1,4-dichloroanthraquinones are used as starting materials fe used, so can in the reaction depending on the exchange of 1- or 4-position chlorine atom isomer mixtures are formed.

The parts mentioned in the examples are parts by weight. Room parts relate to parts by weight as liters to kilograms.

example 1

400 parts by volume of chlorobenzene, 66 parts of 1-dimethylamine-2-aminoethane, 138.5 parts of 1,4-dichloroanthraquinone and 0.5 part of copper acetate are

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30 parts by volume of saturated ethanolic hydrogen chloride solution are then added, which is heated under reflux for 8 hours. After cooling, the precipitated hydrochloride is filtered off with suction, washed with cold alcohol and stirred into a mixture of ice and excess ammonia. After several hours, the deposited base has solidified. It is filtered off with suction and washed with water. After drying, 121 parts (74 % of theory) of 1- (2'-dimethylaminoethyl) -4-chloroanthraquinone are obtained. A sample recrystallized from ethanol melts at 115 to 116 ° C. C ₁₈ H ₁₇ ClN ₂ O ₂ calcd. T Cl 10.8 N 8.5

Gef .: Cl 10.4 N 8.8

Example 2

300 parts by volume of chlorobenzene, 70 parts of l-dimethyiamino-3-aminopropane and 138.5 parts of 1,4-dichloro-anthraquinone are refluxed for ΐβ hours. The chlorobenzene is then distilled off with steam and the remaining aqueous solution is filtered. The piltrate is poured into a mixture of ice and excess ammonia, the reaction product separating out. After filtering off with suction, washing with water and drying, 142.5 parts (83 % of theory) of 1- (3'-dimethylaminopropyl) -4-chloroanthraquinone are obtained. A sample recrystallized from ethanol melts at 85 to 86 ^° C.

^C 19 ^H 19 ^C1N 2 ° 2 calc .: Cl 10.4 N 8.2

Found: Cl 10.0 N 7.9

Example 3

400 parts by volume of pyridine, 91 parts of l-diethylamino-3-amino-propan,

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138.5 parts of 1-4 dichloro-anthraquinone and 0.5 part of copper acetate are refluxed for 8 hours. The pyridine is then distilled off under reduced pressure and the residue is boiled with 200 parts by volume of ethanol. After adding 50 parts by volume of saturated ethanolic hydrogen chloride solution, the mixture is left to stand for 24 hours, a red salt separating out in crystalline form. After filtering off with suction, washing with cold ethanol and drying, 194 parts (95 % of theory) of 1- (3'-diethylaminopropylamino) -4-chloroanthraquinone hydrochloride with a melting point of 192 ° to 195 ° C. are obtained. C ₂₁ H ₂₄ Cl ₂ N ₂ O ₂ calcd .: Cl 17.4 N 6.9

Found: Cl 17.4 N 6.8

Example 4

If the procedure is as described in Example 3, using 85 parts of N- (3-aminopropyl) imidazole instead of the 1-diethylamino-3-aminopropane, 146 parts (73 % of theory) 1 are obtained with the same procedure - [3'-imidazolyl (N) -propylamine?] - 4-chloranthrachinonhydrochlorid of melting point 225-227 ⁰ C. C ₂₀ H ₁₇ Cl ₂ N ₅ O ₂ Cl Calcd .: 17.7 N 10.4

Found: Cl 17.3 N 10.1

Example 5 ^ΛΛ

400 parts by volume of amyl alcohol, 90 parts of N- (3-aminopropyl) morpholine, 138.5 parts of 1,4-dichloroanthraquinone and 0.5 part of copper carbonate are refluxed for 8 hours. After that, the amyl alcohol distilled off with steam and the distillation residue in the cold until the alkaline reaction with aqueous ammonia

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puts. The deposited base is filtered off with suction and washed with water. After drying, 194 parts (100 % of theory) of ^{1- (5 I} -morpholino- (N) -propylamino) -4-chloroanthraquinone are obtained. A sample recrystallized from ethanol melts at HO ⁰ Cp C ₂₁ H ₂₁ ClN ₂ O ₅ calc .; Cl 9.2 N 7.3

found: Cl 8.8 N 7, 1

Example 6

If the procedure described in Example 5 is followed, using 90 parts of N-methyl-N-phenylethylenediamine instead of the N- (3-aminopropyl) morpholine, 14 l parts (72 % of theory) are obtained in an analogous procedure. 2'-N-methylanilinoethylamino) -4-chloranthraquinone. The compound melts after recrystallization from amyl alcohol at 127 to 128 ° C. · C ₂ ^ H ₁₉ ClN ₂ O ₂ calcd .: Cl 9.1 N 7.2

Found: Cl 9.0 N 7.2

Example 7

1,000 parts by volume of cyclohexanol, 90 parts of Ν, Ν-dimethyl-p-phenylenediamine and 138.5 parts of 1,4-dichloroanthraquinone are refluxed for 8 hours. After cooling, the precipitated product is filtered off with suction, washed with methanol and digested with cold aqueous sodium acetate solution. After renewed suctioning off, washing with water and drying, 165 parts (88 % of theory) of 1- (p-dimethyl-aminophenylamino) -4-chloranthraquinone with a melting point of 177 to 179 ^° C. are obtained.
C ₂₂ H ₁₇ ClN ₂ O ₂ calc . : Cl 9Λ N 7Λ

Found: Cl 9.1 N 7.5

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Claims (1)

- 10 - OoZo 25 624 Claim Process for the preparation of 1-alkylamino-4-chloroanthrachinones of the general formula I. (D, 0 Cl in which X is an aliphatic divalent hydrocarbon radical with 2 to 6 carbon atoms or a phenylene group and R an |) aliphatic hydrocarbon radical with 1 to 4 carbon atoms and R can have the same meaning as R or an aromatic hydrocarbon radical of the benzene series or R and R together with the tertiary nitrogen atom can stand for a heterocyclic ring, characterized in that a 1,4-dichloroanthraquinone with amines of the general formula H ₀ NXN, (II), in which X, R and R are as defined above ^d no ¹ have reacted at temperatures between 70 and 220 ^° C., if appropriate in solvents. Badische Anilin- & Soda-Fabrik AG 1 0 9 8 A 0/1 3 7 9