DE2228334A1 - Anthraquinone alpha phenyl ethers prepn - from alpha nitro anthraquione and phenol - Google Patents

Abstract

The process effected with heating, is improved by using a water miscible aprotic solvent (I) for the reaction, 1.0-1.9 moles phenol and 0.5-2 moles acid binder being used per NO2 gp. Use of (I) as solvent decreases the amts. of phenol and acid binder required, and gives higher space-time yields. Products are intermediates for dyes. EXAMPLE 50 pbw 1-nitroanthraquinone (90%), 100 pbw DMF, 40 pbw phenol and 30 pbw K2CO3 were stirred at 140 degrees C for 2.5 hrs. After cooling to 100 degrees C, 250 pbw isopropanol were added, and cooling to room temp., filtration, washing with warm water and drying at 100 degrees C gave 40 pbw yellow 1-phenoxyanthraquinone, m.pt. 126 degrees C.

Description

Process for the preparation of a-phenyl ethers of anthraquinone Die The invention relates to a process for the preparation of α-phenyl ethers of anthraquinone from a-nitroanthraquinones.

x-aryl ethers of anthraquinone are according to the German patent 158 551 by reacting the corresponding Moho- or Dinitroanthraquinones with aromatic hydroxy compounds obtained in the presence of potassium or sodium hydroxide. However, this process has the disadvantage that a large excess of the hydroxy compound, which serves as a solvent at the same time, and is required on the alkali hydroxides is why the mother liquors are worked up after isolation of the reaction product Need to become. Because of the content of alkali hydroxide, phenolate and nitrite, this is Work-up is very costly and with great losses of the aromatic hydroxy compound tied together.

The object of the present invention was to provide an easy-to-use one To find a method that also has the disadvantages of the method of the prior art does not have.

It has now been found that a-phenyl ether of anthraquinone in technically and economically advantageous manner by reacting a-nitroanthraquinones obtained with phenols in the presence of alkali metal hydroxides if the implementation of the a-Nitroanthraquinones in the presence of 1.0 to 1.9 moles of a phenol and 0.5 to 2 moles of an acid-binding agent per mole of nitro group-in water-miscible aprotic Solvents.

The process of the invention gives a high space-time yield pure a-phenyl ether of anthraquinone.

Aprotic solvents are understood to mean those solvents who are not capable under normal conditions To give up protons. Water-miscible aprotic solvents are, for example, the X, N-dialkyl-substituted Carboxamides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N, XJ it, N'-tetramethylurea and N-methylpyrrolidone. aliphatic sulfoxides or sulfones such as dimethyl sulfoxide, Tetramethylene sulfone, hexamethylene sulfone or dialkyl ethers of glycols and polyglycols such as ethylene glycol dimethyl ether, trimethylene glycol dimethyl ether or diethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl or diethyl ether and mixtures to name this solvent.

For economic reasons, the N, N-dialkylcarboxamides are the main ones to call. Of these, N, N-dimethylformamide and N-methylpyrrolidone are very special preferred.

As acid-binding agents, for example, the alkali carbonates, Alkali hydroxides and the alkali salts of weak carboxylic acids should be mentioned. In detail for example sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate 'potassium acetate, sodium benzoate, potassium benzoate, Sodium propionate, potassium propionate or their mixtures can be considered.

Potassium hydroxide is preferred for the method according to the invention and potassium carbonate are used as acid-binding agents, since these are the highest Space-time yields and the purest reaction products obtained.

In addition to the unsubstituted phenol, the im Nuclear phenols substituted by alkyl or halogen such as o-cresol, p-cresol, m-cresol, p-tert-butylphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, 2,4-dichlorophenol, 4-chloro-okresol, 3,5-dimethylphenol into consideration.

Has particular technical importance for economic reasons especially the unsubstituted phenol.

The reaction is carried out in such a way that one leads to the Suspension or solution of a-nitroanthraquinone in dimethylformamide and the acid-binding agent is added to the phenol and the mixture is poured onto the warmed desired reaction temperature. The implementation is expedient at temperatures between 90 and 180 ° C, preferably between 110 and 150 ° C. the The duration of the reaction depends on the temperature and is generally between 1 and 5 hours. If the reaction is carried out, for example, in the temperature range between 120 and 150 ° C., the reaction is complete after 2 to 5 hours.

The reaction can e.g. B. chromatographically on the decrease in the a-nitroanthraquinone compound followed and the end of the implementation can be determined.

The reaction products are inherited from the reaction mixture Usually precipitated by dilution with water or with water-miscible alcohols and'precipitation by filtering, centrifuging or decanting from the alkaline Separated mother liquor. The filter material is then washed neutral with water and dried.

A particularly advantageous and therefore preferred variant of the work-up of the reaction mixture, however, is that the reaction mixture with isopropanol is diluted, the reaction product contained in the reaction mixture together precipitated with the salts present in the mixture and then separated from the mother liquor will. A largely salt-free mother liquor is obtained without any difficulty can be worked up again by fractional distillation.

The separation of the nitrite-containing salts from the reaction products takes place z. B., by washing with warm water.

The advantage bes method of the present invention over the The prior art method is that when using with water Miscible aprotic solvents, the amount of acid-binding agents and the amount of phenol can be greatly reduced and that the reaction takes place in a high space-time yield he follows.

According to the process, pure aryl ethers of anthraquinone are obtained obtain. These are valuable intermediates for the synthesis of dyes.

The following examples are intended to further the process of the invention explain. The parts and percentages given below relate to the weight.

Example 1 l-phenoxyanthraquinone 50 parts of l-nitroanthraquinone (90 % in), 100 parts of dimethylformamide, 40 parts of phenol and 30 parts of potassium carbonate Stirred for 2.5 hours at 140.degree. After cooling to 100 cc, the reaction mixture is diluted with 250 parts of isopropanol.

After cooling to room temperature, the precipitate is filtered off with suction and washed neutral with warm water and dried at 100 cc. Yield: t40 parts of a yellow product which melts at 126 cc.

Example 2 1,5-Diphenoxyanthraquinone 55th parts of 1,5-Dinitroanthraquinone, 40 parts of dimethylformamide, 30 parts of phenol and 50 parts of potassium carbonate are 2 Stirred at 140 to 150 ° C. for hours. After cooling to 100 ° C., the reaction mixture becomes diluted with 200 parts of isopropanol and cooled. The precipitate is sucked off, with Washed in warm water and dried at 100 OC.

Yield: 36 parts of a yellow product with a melting point of 222 ° C.

Example 3 Mixture of 1,5- and 1,8-diphenoxyanthraquinone 50 parts of a mixture, as it is obtained in the dinitration of anthraquinone and the 49.4 1,5-dinitranthraquinone and 36.6 ffi 1,8-dinitroanthraquinone are used in 80 Parts of N-methylpyrrolidone, 30 parts of phenol and 20 parts of potassium hydroxide at 110 Stirred to 130 ° C for 2 hours. After cooling, the reaction mixture is 300 Diluted parts of methanol and stirred for 1 hour. The precipitate is sucked off, with washed in warm water and dried.

Yield: 50 parts of a yellow product.

Example 4 Mixture of 1,5- and 1,8-diphenoxyanthraquinone 6 parts of a mixture of 1,5- and 1,8-dinitroanthraquinone (see Example 3), 4.8 parts Phenol, 4.8 parts of anhydrous potassium carbonate and 6 parts of dimethylformamide Stirred for 1.5 hours at 140 to 150 ° C., with about 0.9 parts of water distilling off. It is then cooled to 100 ° C., 14 parts of isopropanol are added and the mixture is cooled to 20 ° C. away. The precipitate is filtered off with suction, first with 25 parts of isopropanol and then with Washed neutral in warm water.

After drying, 62 parts of a yellow powder are obtained.

The mother liquors containing isopropanol can pass through without difficulty fractional distillation are worked up.

Example 5 Mixture of 1,5- and 1,8 = di- (o-chloro) -phenoxyanthraquinone 50 parts of a mixture of 1,5- and 1,8-dinitroanthraquinone (see Example 3), 50 parts of o-chlorophenol, 50 parts of potassium carbonate and 100 parts of N-methylpyrrolidone are stirred at 110 to 120 ° C for 2 hours. After cooling down, add the reaction product precipitated from 200 parts of methanol, filtered off with suction and dried.

Yield: 66 parts of a yellow powder.

Analysis: C26H1404C12 calcd. C 67.7 H 5.4 0 13 9 Cl 15.2 (460) found. 67.8 3.2 13.6 15.8 Example 6 Mixture of 1,5- and 1,8-di (p-tert-butyl) -phenoxyanthraquinone The implementation takes place according to the information in Example 5; where the o-chlorophenol is replaced by 50 parts of p-tert-butylphenol.

Yield: 26 parts of a yellow powder.

Analysis: 054H5204 calcd. C 81.0 H 6.36 0 12.7 (504) found. 80.5 6.50 13.0 Example 7 1. 5-'Diphenoxy-2-methylanthraquinone 50 parts of 1,5-dinitro-2-methylanthraquinone, 100 parts of dimethylformamide, 60 parts of potassium carbonate and 40 parts of phenol are used 3 Stirred at 140 to 150 ° C. for hours. The reaction mixture is after cooling diluted with 500 parts of isopropanol and suction filtered with isopropanol and the precipitate then washed with warm water and dried. 90 parts of an ocher color are obtained Powder with a melting point of 166 00.

Example 8 50 parts of a mixture of 1,5- and 1,8-dinitroanthraquinone (see Example 3), 35 parts of phenol, 20 parts of powdered potassium hydroxide and 300 parts of N-methylpyrrolidone are stirred at 120 ° C. for 2 to 3 hours. After this Cooling is diluted with 500 parts of water or methanol, and the precipitate is filtered off with suction and washed neutral with water. 49.5 or 53.1 parts of a yellow product are obtained.

Example 9 50 parts of a mixture of 1,8- and 1,5-dinitroanthraquinone (see Example 5), 55 parts of phenol, 15 parts of powdered sodium hydroxide and 150 parts of N-mebhylpyrrolidone are stirred at 120 to 150 ° C. for 2 to 3 hours cooling the reaction mixture to a mixture of methanol and water (1: 1 parts by weight) discharged, the precipitate sucked off and neutral with water washed.

Yield: 20.9 parts of a yellow product.

Example 10 50 parts of a mixture of 1,5- and 1,8-dinitroanthraquinone (Example 5), 55 parts of phenol, 40 parts of anhydrous sodium acetate and 150 parts of N'N-dimethylformamide are stirred at 120 to 130 ° C for 3 hours. After cooling it is made to 1000 parts Discharge water and filter off the precipitate and wash neutral.

Yield: 26.2 parts of a yellow product.

Example 11 50 parts of a 1,5 / 1,8-dinitroanthraquinone mixture (Example 3), 35 parts of phenol, 50 parts of potassium hydrogen carbonate and 100 parts of N, N-dimethylformamide are stirred at 140 to 150 ° C for 5 hours. At 100 ° C the reaction mixture TOO parts isopropanol added and the precipitation after cooling Sucked off and washed neutral with water: 56 parts of a yellow product.

Example 12 The procedure described in Example 5 is repeated, but using instead of o-chlorophenol the same amount of p-chlorophenol.

65 parts of a yellow product with a melting point of 182 ° bis are obtained 187 c.

Analysis: found C: 67.5; H: 5.5; Cl: 15.7; 0: 13.6% Example 13 Proceeds as indicated in Example 5, but using 50 instead of the o-chlorophenol Parts of p-cresol result in half of a yellow product having a melting point of 205 bis 215 cc.

Analysis: Calcd. C: 80.0; H: 4.75: 0: 15.5% found. 80.5 5.1 15.0% used instead of the p-cresol, the same amount of o- or m-cresol is obtained corresponding products.

Example 14 20 parts of a 1,5 / 1,8-dinitroanthraquinone mixture (see example 3), 50 parts of N-methylpyrrolidone, 20 parts of anhydrous potassium carbonate and 50 parts 2,4-dichlorophenol is stirred for 5 hours at 120 to 130 ° C and then the reaction mixture diluted with 20Q parts isopropanol. After working up, 16.1 parts are obtained of a yellow product, which has a fixed point of 262 to 265 cc.

Example 15 50 parts of a 1,5 / 1,8-dinitroanthraquinone mixture (see Example 3), 55 parts of phenol, 50 parts of anhydrous potassium carbonate and 100 parts Dimethyl sulfoxide are stirred at 140 to 150 ° C. for 5 hours. After cooling down 500 parts of isopropanol are added to 90 cc and the mixture is added to the reaction mixture cooled, the precipitate filtered off with suction and washed neutral with water.

Yield: 49 parts of a yellow-brown product.

Example 16 The procedure is as in Example 2, but used instead of the dimethyl sulfoxide 100 parts of sulfolane. After working up, 50 parts are obtained of a yellow product.

Example 17 The procedure given in Example 15 is used however, instead of the dimethyl sulfoxide, 100 parts of N, N-dimethylacetamide are obtained 48 parts of a yellow product.

Example 18 50 parts of 1,5 / 1,8-dinitroanthraquinone mixture (Example 3), 35 parts of phenol, 30 parts of anhydrous potassium carbonate and 100 parts of triethylene glycol dimethyl ether are stirred for 3.5 hours at 140 to 150 cc. After cooling to 90 cc it will be 300 parts of isopropanol are added and, after cooling to room temperature, the precipitation is carried out separated and washed neutral with water.

Yield: 48 parts of a yellow-brown product.

Example 19 50 parts 1,5 / 1,8-dinitroanthraquinone mixture (see Example 5), 30 parts of phenol, 35 parts of anhydrous potassium carbonate and 100 parts N.N-Dimeth-ylformamide are stirred for 6 to 7 hours at 100 cc, with water slowly distilled off. After cooling, 500 parts of isopropanol are added, the precipitation Aspirated and washed neutral with water. 42 parts of a yellow product are obtained, which may still contain small amounts of starting material.

Example 20 is as given in Example 19, but used instead of N, N-dimethylformamide, the same amount of N-methylpyrrolidone as solvent and performs the reaction at 170 to 180 cc. The reaction is after an hour already finished. After working up, 45 parts of a yellow-brown product are obtained obtained that no longer contains any starting material.

Claims (6)

/ Claims Process for the production of non-phenyl ethers of anthraquinone Reaction of i-nitroanthraquinones with phenols in the presence of potassium or sodium hydroxide in the heat, characterized in that the implementation of the «-nitroanthraquinone per mole of nitro group in the presence of 1.0 to 1.9 moles of a phenol and from 0.5 to 2 moles of an acid-binding agent in water-miscible aprotic solvents carried out. 2. The method according to claim 1, characterized in that the The reaction is carried out at temperatures between 80 and 180 ° C, 3. The method according to claim 1 and 2, characterized in that the acid-binding agents used are alkali carbonates, Alkali hydroxides, alkali salts of weak carboxylic acids or mixtures thereof are used. 4. The method according to claims 1 or 2, characterized in that that one uses potassium hydroxide or potassium carbonate as an acid-binding agent. 5. The method according to claims 1 to 4, characterized in that as aprotic solvents N, N-dialkyl-substituted carboxamides, N-methylpyrrolidone, aliphatic sulfoxides, aliphatic sulfones, bis-methyl or bis-ethyl ethers of Glycols or polyglycols or mixtures thereof are used. 6. The method according to claims 1 to 4, characterized in that that N, N-dimethyiformamide, N, N-diethylformamide, N, N-dimethylaoetamide, N, N-diethylacetamide, N, N-dimethylpropionic acid amide, N, N, N ', N' -tetramethyl urea, N-methylpyrrolidone, Dimethyl sulfoxide, tetramethylene sulfone, xthylene glycol di-methyl ether, xthylene glycol di-methyl ether, Trimethylene glycol dimethyl ether, trimethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether or mixtures thereof are used.