DE2415662A1 - 1-Nitro-anthraquinone separation from reaction mixt - by reduction of dinitro-anthraquinones in solvents in opt presence of water - Google Patents

Abstract

Separation of 1-nitroanthraquinone (I) from crude mixt. obtd. in mono-nitration of anthraquinone, takes place by (i) treatment with 2-30 (2-20) equiv. reducing agent, w.r.t., dinitro cpds. present in mixt., in organic soln., in opt. presence of water, pref. at 10-180 (40-150) degrees C, and (ii) suction of suspension and washing to remove reaction products. (I) is used in dye prodn. via 1-aminoanthraquinone. (I) is obtd. in good yields and sufficient purity for further processing to dyes. Only by-prods of nitration, i.e. the dinitro-anthraquinones, are reduced, and not (I). Purification and separation may take place in presence of water, allowing use of nitroanthraquinone mixture press-cakes.

Description

Procedure for the isolation of 1-nitroanthraquinone from nitroanthraquinone mixtures The invention relates to a method for isolating pure 1-nitroanthraquinone from MitroantbrachinongemlsebenO In the nitration of anthraquinone one always obtains Gemisebe of various nitro compounds. The mononitration is not uniform drive through, so that 1-nitroanthraquinone is only contaminated with 2-nitroanthraobinone and dinitroanthraquinones. For monitoring in concentrated sulfuric acid one obtains products that have a maximum of 80 to 85 percent by weight, usually 60 to 75 percent by weight of 1-nitroanthraquinone is therefore obtained from durob Reduction from this raw nitroanthraquinone mixture a 1-aminoanthraquinone, which the contains aminoanthraquinones corresponding to the nitration byproducts. Since the coloristic Properties of the dyes made from 1-aminoanthraquinone differ from those in the starting material existing impurities are often adversely affected, it is desirable from an i-aminoantbraobinone that is as pure as possible and thus from one as well as possible starting from pure 1-nitroantbracbinone.

The object of the present invention was to produce 1-nitroantbraebinone to isolate the nitroanthraquinone mixtures obtained in the mononitration, the be obtained according to known nitriding processes.

It has been found that 1-nitroanthraquinone in good yield and in a purity from 1-nitroanthraquinone which is sufficient for further processing into dyes containing nitroanthraquinone mixtures obtained when one on the nitroanthraquinone mixture in organic solvents in the presence or absence of water 2 to 30 Equivalent of a reducing agent, based on those present in the mixture Dinitro compounds, lets act, the suspension is suctioned off and then the reaction products by washing removed.

When treating with reducing agents, the undesirable ones suffer Dinitro compounds a conversion through which they are converted into a more soluble form will. It was surprising that the by-products of nitration, the dinitroanthraquinones, and not, or only to a very small extent, the concentration present in bober and reducing desired 1-nitro compound.

The procedure according to the invention is usually carried out in such a way that that the 1-nitroantbraobinone-containing nitroanthraquinone mixture in the solvent enters and then adds the required amount of reducing agent. The mixture will warmed to reaction temperature and after completion of the reaction, what was consumed of the reducing agent can be determined, the 1nNitroanthrachlnon from the Reaction mixture isolated by filtration. The filter residue becomes with solution medium and then washed with water.

Nitroantbracbinone mixtures are used for the process according to the invention in particular, the known nitriding processes are obtained. These mixtures contain a maximum of 80 to 85 percent by weight, but usually only 65 to 75 percent by weight 1-nitroanthraquinone. Mixtures with a higher proportion of 1-nitroantbrachinone can be sieved Of course, cleaning is even easier.

The reducing agent used for the method according to the invention e.g. catalytically excited hydrogen, metals such as zinc, tin, iron, magnesium and aluminum, reducing salts such as tin (II) compounds, iron (II) compounds, soluble sulfides, soluble sulfites, soluble dithionites, thiosulfates, citrates, Tartrates, hypophosphites, hydrogen sulfites, boron hydrides, salts of α-hydroxyalkylsulfinic acids into consideration. Hydroxylamine and its N-alkyl- and N-phenyl compounds, mercaptans and their salts, aldoses, pyrogallol, phloroglucinol, Gallic acid, α-hydroxyacetone, ascorbic acid, p-toluenesulfonic acid hydrazide, Hydroquinone, Resorcinol and tetralin effective.

Some of the reducing agents can also be used in the form of Gemiseben e.g. sulphide / ditbionite, sulphide / thiosulphate, sulphite / ditbionite, sulphite / biosulphate and sulfide / sulfite. In the case of reducing agents which release acidic hydrogen, is it is advantageous to use bases such as sodium hydroxide, potassium hydronide, Add soda, potash and / or amines. In the case of the use of metals and It is useful to use metal compounds as reducing agents in an acidic medium, zeBe in the presence of hydrochloric acid, dilute sulfuric acid, acetic acid, propionic acid, Formic acid or mixtures thereof to work.

The reducing agents mentioned are for economic reasons especially hydrogen, the alkali metal sulfides, the alkali metal sulfites, the alkali metal hydrogen sulfites, the alkali metal dithionites, the alkali metal thiosulfates, hydroxylamine, M-hydroxyacetone, Ascorbic acid, p-toluenesulfonic acid hydrazide and hydroquinone are preferred.

The amount of reducing agent depends mainly on the content of the nitroanthraquinone mixture of dinitroanthraquinones and also to the solvents used. Appropriately, one turns per mole in the nitroanthraquinone mixture pre-existing dinitro compound 2 to 30, preferably 2 to 20 equivalents of reducing agent at.

The organic solvents used for the method according to the invention solobe in subjects in which 1-nitroantbrachinone is largely insoluble, in which however, the products which form in the course of the reaction are soluble. It asked siob Exaggerated that such solvents are particularly balanced, aliphatic and aromatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1- or 1,2-dichloroethane, trichloroethane, Tetracblorätban, letrachlorethylene, dichloropropane, Dibromoethane, chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, chloronaphthalene or aliphatic carboxamides, especially the dialkylamides of Propionic acid, of acetic acid and in particular that of formic acid, as well as N methylpyrrolídon. Also suitable as solvents are alcohols such as ethanol, propanol, isopropanol, n-butanol, isobutanol, n-pentanol, secondary and tertiary amyl alcohol and ethylene glycol monomethyl ether, Ketones such as acetone, methyl ethyl ketone, dietbyl ketone, cyclopentanone or cyclohexanone. In addition, there are also aliphatic carboxylic acids such as formic acid, acetic acid and propionic acid can be used as a solvent. Furthermore, there are also anisole and hexamethylphosphoric acid triamide well suited. These solvents can also be used in a mixture.

For economic reasons, N, N-dimethylformamide, N-methylpyrrolidone, 1,1- and 1,2-dichloroethane, dichloropropane, anisole, acetic acid, Propionic acid, propanol, isobutanol, n-pentanol, ethylene glycol monomethyl ether, acetone, Cyclohenanone and hexamethylphosphoric acid triamide are preferred, since these are a sebr pure 1-nitroanthraquinone can be isolated. Achieved particularly good results one in N, N-dimethylformamide, isobutanol, isobutanol / water mixtures and hexamethylphosphoric acid triamide, which is why these solvents are particularly preferably used Solvent can be varied within a wide range. The amount of Solvent primarily depends on the solubility of the reaction products and also on the solubility of the 1-nitroantbracbinone in the solvent to be used away. As a rule, one becomes the same, based on the nitroantbracbinone mixture up to about 20 times the weight of the solvent or solvent mixture use.

The reducing agent is expediently left at temperatures between 10 and 180 ° C, preferably between 40 and 1500C on the nitroanth rachinongemi act scb. If you work at temperatures below 40 to 20 ° O, then extend the response times are usually considerable; at temperatures above 1500C, But above all above 18000 the Gefabr insists that undesirable by-products are formed.

An advantage of the method according to the invention is that the Purification operation and the isolation of the pure 1-Nitroantbracbinons also by Presence of significant amounts of water is not disturbed. This makes it possible also 1-nitroanthraquinone-containing nitroanthraquinone mixtures in the form of the press cake to use.

An advantageous variant of the process consists in the fact that 1-nitroantbracbinone is used developing nitroanthraquinone mixture in the form of the Preßkucbens, as it is from the nitration After the bag is isolated, enters the solvent and drives, if necessary the amount of acid or base necessary for the reduction to take place is added and finally the reducing agent is added dissolved or in pure form and until the end of the The reaction is stirred at the desired temperature.

Depending on the solvent used, the 1-nitroanthraquinone is filtered from the hot or from the disconnected suspension abO The filter residue, the after washing with a solvent in which the reaction products as possible should be well soluble, and optionally water is obtained, consists of practically pure 1-nitroantbracbinone.

The 1-nitroanthraquinone obtained after the procedure according to the invention can be reduced to 1-aminoantbrachinone by known processes because of its The 1-Aminoantbracbinon thus inherited is ideally suited for the production of purity of dyes and dye precursors.

The following examples are intended to further the process according to the invention explain. The parts and percentages mentioned relate to weight. The parts of space relate to parts by weight like the liter to the kilogram. The temperature is given in degrees Celsius that is used in the working examples Nitroanthraquinone mixture - also known as robnitroanthracbinon - reveals if not stated otherwise, approx. 74 percent by weight of 1-nitroanthraquinone.

Example 1 50 parts of robes 1-nitroanthraquinone were in 50 parts by volume Dimethylformamide with the addition of palladium on carbon at 100 ° with 2.24 parts by volume Partially reduced hydrogen.

The red colored suspension is suctioned off and then with 20 parts by volume of dimethylformamide washed with methanol and finally with water. After drying, one obtains 36.1 parts of 1-nitroanthraquinone with a content of 97.4.

Example 2 A suspension of 50 parts of 9Rohnitroanthraquinone in 400 parts of glacial acetic acid are given as in Example 1 with the addition of Raney nickel reduced.

Yield: 36 parts; 1-nitroantbracbinone content: 96.8%.

Example 3 A suspension of 50 parts of crude 1-nitroantbracbinone isobutanol in 400 parts by volume is stirred at 1000 for 15 minutes, then innerbalb 7.8 parts of 60 percent sodium sulfide in 20 parts of water were added over a period of 20 minutes. The mixture is then stirred at 1000 for 1 hour. The suspension sucked hot and washed with isobutanol, methanol and water.

Yield: 36.2 parts; 1 Kitroantbrachinon content: 96.2%.

Example 4 A suspension of 50 parts of robem 1-nitroantbracbinone in 50 parts by volume of dimethylformamide is stirred at 1000 for 15 minutes, then added dropwise within 20 minutes a solution of 12.6 parts of sodium sulfite (anhydrous) in 100 parts of water and stir for 1 hour at 1000. It will be like under example 1 indicated worked up.

Yield: 36.3 parts; 1-nitroantbracbinone content: 97.8%.

Example 5 To a suspension of 50 parts of crude nitroanthraquinone, Parts by volume of ethylene glycol monomethyl ether, 100 parts of water, 100 parts of sodium hydroxide 10 parts of sodium ditbionite are added at 20.degree and stirred for 3 hours at this temperature. The suspension is suctioned off, with Glykolmonometbylätber and finally washed with water.

Yield: 36 parts; 1-nitroanthraquinone content: 96.5%.

Example 6 To a suspension of 50 parts of crude nitroanthraquinone, 150 parts by volume of ethylene glycol monomethyl ether, 35 parts by volume of 2N sodium hydroxide solution at 500, 9.1 parts of α-hydroxyacetone were added dropwise within 1 to 2 hours. The suspension turns red in the process. The mixture is kept at 400 for 5 hours.

The procedure is then as indicated in Example 5, with a yield: 36 parts; 1-nitroantbracbinone content: 97.5%.

Example 7 A suspension of 50 parts of robnitroanthine brachinone, 80 Parts of dimethylformamide, 20 parts of water, 5 parts of sodium hydroxide and 8 parts Ascorbic acid is stirred for 3 hours at 1000 and then as indicated in Example 1 worked up.

Yield 35 parts; Content of 1-nitroanthraquinone: 95.4% o.

Example 8 The procedure is as indicated in Example 4, but the mixture is turned as a reducing agent, a solution of 3.4 parts of 60 percent sodium sulfide and 6.2 parts of sodium ditbionite in 50 liters of water.

After working up, 35.5 parts of pure 1-nitroanthraquinine are obtained: 96.9.

Example 9 A suspension of 50 parts of crude nitroanthraquinone, 200 Parts by volume of isobutanol, 100 parts by volume of water and 12.4 parts of sodium biosulfate refluxed for two hours.

It is worked up as indicated in Example 3.

Yield: 36.3 parts; 1-nitroantbracbinone content: 96.8%.

Example 10 A suspension of 50 parts of crude nitroanthraquinone, 300 Parts by volume of ethylene glycol monomethyl ether, 100 parts by volume of water and 30 parts of sodium hydrogen sulfite are stirred at 150 ° for 4 hours. It is suctioned off hot and washed with ethylene glycol monomethyl ether, Methanol and water.

Yield: 35.8 parts; 1-nitroanthraquinone content: 97.1%.

Example 11 91.8 parts of robnitroantbracbinon in the form of a compression piston, which contains 54.5% dry matter, of which 74% is 1-nitrow anthraquinone suspended in 50 parts by volume of N, N-dimethylformamide and four hours at 100 ° with Treated 30 parts of sodium sulfite. It was worked up as indicated in Example 1 Yield: 35.9 parts; Content of 1-nitroanthraquinone: 97.4.

Example 12 89.9 parts of an irrigation flask with a weight of 55.6 % Dry matter, of which 63.5 are 1-nitroantbracbinon, are as in Example 11 indicated banded.

Yield: 32.9 parts; 1-nitroanthraquinone content: 96.3.

Example 13 100 parts of crude nitroanthraquinone, 100 parts by volume of N, N-dimethylformamide, 10 parts of water, 7.5 parts of sodium hydroxide, 10 parts of hydroxylammonium chloride are used Heated to 40 ° for 3 hours.

It is worked up as described in Example 1.

Yield: 72 parts; 1-nitroantbracbinone content: 97.2%.

Example 14 50 parts of crude nitroanthraquinone, 75 parts by volume of hexamethylphosphoric acid triamide, 20 parts of sodium dithionite are carefully pickled, at 600 an exotic temperature occurs Reaction on, after it has subsided, the mixture is stirred at 800 for 4 hours, after cooling is filtered off and washed with hexamethylphosphoric triamide, methanol and water.

Yield: 36.5 parts; 1-nitroanthraquinone content: 96.9.

Example 15 50 parts of crude nitroanthracbinone, 10.5 parts of sodium ditbionite, 10 parts of cyclohexanone, 5 parts of morpholine, 300 parts by volume isobutanol, 100 parts by volume Water is refluxed for 4 hours and as indicated in Example 3, worked up0 yield. 36 parts; 1-nitroantbracbinone content: 96.8%.

Claims (6)

Claims 1. Process for the isolation of 1-nitroanthraquinone from 1-nitroanthraquinone containing nitroanthraquinone mixtures, characterized in that the Nitroanthraquinone mixture in organic solvents in the presence or absence of water 2 to 30 equivalents of reducing agent, based on those present in the mixture Dinitro compounds, allowed to act, the suspension sucks and then the reaction products removed by washing. 2. Verabren according to claim 1, characterized in that one 2 to 20 equivalent of reducing agent applied. 3. Method according to claims 1 or 2, characterized in that that the reducing agent is added to the nitroanthraquinone mixture at temperatures between 10 and 180 ° C can act. 4. The method according to claims 1 or 2, characterized in that that the reducing agent is added to the nitroanthraquinone mixture at temperatures between 40 and 1500C lets act, 5. The method according to claims 1 to 4, characterized in that that the reducing agent used is catalytically excited hydrogen, alkali metal sulfites, Alkali metal dithionites, hydroxylamine, α-hydroxyacetone or mixtures thereof applies. 6. Method according to claims 1 to 5, characterized in that that the treatment of the nitroanthraquinone mixture with the reducing agent in N, N-dimethylformamide, isobutanol, ethylene glycol monomethyl ether, acetic acid, hesamethyl phosphoric acid triamide or mixtures thereof, optionally in the presence of water.