JPH053470B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing highly pure 3,4,9,10-perylenetetracarboxylic acid diimide in high yields.

3,4,9,10-perylenetetracarboxylic acid diimide and its production method are already known. According to German Patent No. 386057, 3.
4,9,10-perylenetetracarboxylic diimide can be produced by reacting 3,4,9,10-perylenetetracarboxylic dianhydride with ammonia. Although the products obtained by this method are very pure, the method has the disadvantage of being very expensive; The anhydride itself is 3, 4, 9, 10
- It is obtained by hydrolyzing perylenetetracarboxylic acid diimide with concentrated sulfuric acid. Therefore, this method can be used to prepare 3,4,
It is excluded as a solution to the industrial problem of producing 9,10-perylenetetracarboxylic acid diimide.

According to German Patent No. 276357, 3.
4,9,10-perylenetetracarboxylic acid diimide is prepared by preparing a mixture of naphthalene-1,8-dicarboxylic imide, potassium hydroxide, and a small amount of water.
It can be produced by heating to a temperature of 280-300°C. However, the patent specification does not describe the yield and purity of the reaction product. In the process described therein, 3,4,9,10-perylenetetracarboxylic acid diimide is obtained with insufficient purity and yield.

According to Chemical Abstracts 1948, 5892,
3,4,9,10-perylenetetracarboxylic acid diimide is prepared by melting naphthalene-1,8-dicarboxylic acid imide with an alkali metal hydroxide with the addition of water. The product is described as nearly pure by spectroscopic analysis. In a follow-up test described in Chemical Apstracts 1948, 5892, in which the batch size was increased by 10 times, 3, 4,
The claim that a solution of 9,10-perylenetetracarboxylic acid diimide is produced such that a solution of said diimide is obtained could not be confirmed.

Using sodium hydroxide as a melting agent,
Crude 3,4,9,10-perylenetetracarboxylic acid diimide is obtained in a yield of 46.1% of theory. Conventional methods for measuring purity show that the crude 3,4,9,10-perylenetetracarboxylic acid diimide contains only
% yield of pure 3,4,9,10-perylenetetracarboxylic acid diimide is obtained at the stage. When using potassium hydroxide, the crude yield is
81.2%, and the purity measurement gives a value of 89.7%.

European Patent Application No. 54806 discloses that naphthalene-1,8-dicarboxylic imide is melted in a mixture consisting of potassium hydroxide, sodium hydroxide and sodium acetate at a temperature of 190-220°C and then, inter alia, the melt is A method is described for producing 3,4,9,10-perylenetetracarboxylic acid diimide by oxidizing it in the following state. 93.4%
It is stated that the purity of the product obtained is high. However, the measurement method is not described.

Now, naphthalene-1,8-dicarboxylic acid imide is melted with potassium hydroxide and sodium acetate to form the alkali metal salt of the Leuko compound of 3,4,9,10-perylenetetracarboxylic acid diimide, and the reaction is completed. Afterwards, the melt is diluted with water,
Then, 3,4,9,10-perylenetetracarboxylic acid diimide is produced with high purity and high yield by oxidizing the leuco form to 3,4,9,10-perylenetetracarboxylic acid diimide. We have found that it is possible to: (a) apply a vacuum of less than 100 torr (100 mm Hg) before introducing the naphthalene-1,8-dicarboxylic imide into the potassium hydroxide/sodium acetate melt; , the potassium hydroxide/sodium acetate mixture is heated to 200-300°C, in particular 250-300°C, and the resulting melt is heated under industrial conditions at 200-220°C. Dehydrated and then heated under normal pressure so that it can still be stirred.
Naphthalene-1,8-dicarboxylic imide or its sodium- or potassium-salt is introduced into the melt at 200-220°C and the melt is exposed to atmospheric oxygen until the formation of the alkali metal salt of the leuco compound is completed. 250 in the absence of
(b) naphthalene-1 at 200-220°C under normal pressure;
After introducing the 8-dicarboxylic acid imide or its sodium- or potassium-salt into the potassium hydroxide/sodium acetate melt, a vacuum of up to 100 torr (100 mmHg) is applied and the mixture is heated to 200-250°C. and thereby the mixture is dehydrated such that the resulting melt can still be stirred at 200-220° C. under industrial conditions, and the subsequent formation of the alkali metal salt of the leuco compound is completed. or (c) heating the melt to 250-300°C in the absence of atmospheric oxygen until
The sodium or potassium salt of the 8-dicarboxylic acid imide is introduced into the potassium hydroxide/sodium acetate melt and the melt is heated in the absence of atmospheric oxygen until the formation of the alkali metal salt of the leuco compound is complete. Heat to 250-300℃.

To carry out the process, 3 to 10 parts by weight, in particular 3 to 10 parts by weight of naphthalene-1,8-dicarboxylic imide or the corresponding amount of its sodium or potassium salt, are used in order to carry out the process. Preference is given to using 3 to 6 parts by weight of potassium hydroxide and 0.1 to 2 parts by weight, especially 0.3 to 0.8 parts by weight of sodium acetate.

The oxidation of the leuco compound of 3,4,9,10-perylenetetracarboxylic acid intermediately obtained according to the invention according to one of the above processes (a), (b) or (c) can be carried out by methods known per se. by passing air through (BIOS Final Report, 1484, page 21) or hypochlorite solutions, adducts of hydrogen peroxide and borates, chloric acid as described in European Patent Application No. 54806. It is carried out with salts, nitrates and peroxodisulfates.

Regarding the compounds used in the method according to the invention, potassium hydroxide and sodium acetate, sodium acetate is used in anhydrous form, whereas
The potassium hydroxide used is obtained industrially 10
Can be interpreted to mean potassium hydroxide with a moisture content of ~15%.

Naphthalene-1,8-dicarboxylic imide or its sodium- or potassium-salt used in the present invention can always be interpreted as meaning an anhydrous compound (KOH and naphthalene-1,8
Preference is given to using sodium or potassium salts (in order to avoid the formation of water in the melt by reaction with dicarboxylic acid imides).

It is considered surprising that 3,4,9,10-perylenetetracarboxylic acid diimides can be obtained according to the invention, i.e. at relatively high reaction temperatures and/or at relatively long reaction times. It will be done. ; is European Patent Application No. 54806
This is because it is stated in No. 1 that a high yield and high purity can be achieved by making the reaction time as short as possible and the reaction temperature as low as possible. According to the content measurements, the 3,4,9,10-perylenetetracarboxylic diimide produced by the method of the European patent application has a purity of 81%.
3,4,9,10-perylenetetracarboxylic acid diimide prepared by the process according to the invention has a purity content of 90-95%.

3,4,9,10− obtained by the route according to the invention
Perylenetetracarboxylic acid diimide is used for the production of 3,4,9,10-perylenetetracarboxylic acid diimide in the form of pigments and for alkylation products and for the production of 3,4,9,10-perylenetetracarboxylic acid diimide. It is outstandingly suitable as a starting material for the production of dianhydrides.

Example 1 Into a stainless steel container equipped with a stirrer (85
235 g of potassium hydroxide (of % purity) and (anhydrous)
Add 22.5g of sodium acetate. Vacuum pressure (3 torr (3 mmHg)) was then applied and the mixture was heated to 300°C for 2 hours.
Heat to; 25g of water will escape during this time. next
Cool to 200°C and then 50°C for 1 hour at this temperature.
g of naphthalene-1,8-dicarboxylic imide (98.1% purity) are introduced while bubbling with nitrogen. Then heat to 300°C and stir at this temperature for 6 hours. After cooling to 200 °C, at this temperature 300 ml of water was started to be added dropwise, the melt thus diluted was then poured into 1500 ml of water, and air was passed for 6 hours at room temperature to terminate the oxidation of the leuco compounds. , suction off the precipitate, wash the residue on the filter with water, and place it in dilute hydrochloric acid. After stirring the mixture at 75°C for 1 hour,
Aspirate the product, wash until neutral, and store at 80°C.
Dry with. 44.90g of crude 3,4,9,10−
Perylenetetracarboxylic acid diimide is obtained.

Determination of the pure content of 3,4,9,10-perylenetetracarboxylic acid diimide: 20 g of crude 3,4,9,10-perylenetetracarboxylic acid diimide prepared as above was dissolved in 400 g of concentrated sulfuric acid. Let it go inside. After heating the mixture to 80.degree. C. to dissolve the crude product, 150 g of sulfuric acid (50% strength) are added dropwise over the course of 1 hour; during this time the temperature can rise to 100.degree. It is then cooled to 25° C., the precipitate is suctioned off, washed with 78% strength sulfuric acid until the effluent becomes clear, then washed until neutral and finally dried at 80° C. 18.48g pure 3,
4,9,10-perylenetetracarboxylic acid diimide is obtained. The crude 3,4,9,10-perylenetetracarboxylic acid thus obtained was 92.4%
purity. This is 100% pure naphthalene
Theoretical 85.5 for 1,8-dicarboxylic acid imide
% pure yield.

Example 2 235g potassium hydroxide (90% purity)
and 22.5 g of sodium acetate (anhydrous) in a stainless steel container equipped with a stirrer. After heating this mixture to 200℃, naphthalene-1,8-
Potassium salt of dicarboxylic acid imide 62.5g (100%
Pure naphthalene-1,8-dicarboxylic acid imide 50
g) in 1 hour while passing in nitrogen. After heating to 300° C. and stirring at this temperature for 6 hours, it is allowed to cool to 200° C. and 300 ml of water are gradually added dropwise at this temperature. The diluted melt is then
Pour into 1500 ml of water, blow air at room temperature for 6 hours to terminate oxidation of the leuco compound, suction off the precipitate, wash with water, put the residue on the filter into dilute hydrochloric acid, stir at 75°C for 1 hour, The precipitate is suctioned off, washed until neutral and finally dried at 80°C.

46.22 g of 3,4,9,10-perylenetetracarboxylic acid diimide (95.0% purity) are obtained;
This corresponds to a pure yield of 88.7% of theory for 100% pure naphthalene-1,8-dicarboxylic imide (determination of the pure content of 3,4,9,10-perylenetetracarboxylic diimide , carried out by the method described in Example 1).

Example 3 155g potassium hydroxide (90% purity)
and 25 g of sodium acetate (anhydrous) in a stainless steel container equipped with a stirrer. After heating this mixture to 200°C, 60.6 g of potassium salt of naphthalene-1,8-dicarboxylic imide (50 g of 100% pure naphthalene-1,8-dicarboxylic imide)
) at the above temperature for 1 hour while passing nitrogen through. Then reduce the pressure (40-50 Torr (40-50mm
Hg)) is applied and dehydrated for 2 hours at temperatures up to 250°C; during this time 6.9 g of water escapes. The mixture was then heated to 260° C. under normal pressure and stirred at this temperature for 4 hours while passing nitrogen through. After cooling to 200 °C, start adding 300 ml of water dropwise at this temperature, and then add the diluted melt to
Pour into 1500 ml of water, blow in air for 6 hours at room temperature to terminate the oxidation of the leuco compound, suction off the precipitate, wash with water and then into dilute hydrochloric acid. 75
After stirring for 1 hour at 0.degree. C., the product is sucked off, washed to neutrality and dried at 80.degree.

45.5 g of 3,4,9,10-perylenetetracarboxylic diimide (91.0%) is obtained; this is 83.3% of theory for 100% pure naphthalene-1,8-dicarboxylic imide. Corresponds to the pure yield (determination of the pure content of 3,4,9,10-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 4 235g potassium hydroxide (90% purity)
and 22.5 g of sodium acetate (anhydrous) in a stainless steel container equipped with a stirrer. Vacuum pressure (40-50 torr (40-50 mmHg)) was then applied for 2 hours.
Heat to 300°C; 12.4g of water escapes during this time.
It was then cooled to 200°C and then heated at this temperature for 1 hour to obtain 62.5 g of the potassium salt of naphthalene-1,8-dicarboxylic imide (100% pure naphthalene-1,8-dicarboxylic acid imide).
(equivalent to 50 g of dicarboxylic acid imide) are introduced while passing in nitrogen. Then heat to 300°C and stir at this temperature for 6 hours. After cooling to 200 °C, start adding 300 ml of water dropwise at this temperature, and then add the diluted melt to
Pour into 1500 ml of water, blow in air for 6 hours at room temperature to terminate the oxidation, suction off the precipitate, wash with water and then into dilute hydrochloric acid. After stirring at 75°C for 1 hour, the product was sucked off and washed until neutral.
Dry at 80℃. 48.0 g of 3,4,9,10-perylenetetracarboxylic acid diimide (of 95% purity) is obtained;
This corresponds to a pure yield of 94.1% (determination of the pure content of 3,4,9,10-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 5 235g potassium hydroxide (85% purity)
and 22.5 g of sodium acetate (anhydrous) in a stainless steel container equipped with a stirrer. Vacuum pressure (3 torr (3 mmHg)) is then applied and heated to 300°C for 2 hours; during this time 24.8 g of water escapes. then 200
℃ and then for 1 hour at this temperature the potassium salt of naphthalene-1,8-dicarboxylic acid imide.
62.5 g (corresponding to 50 g of 100% pure naphthalene-1,8-dicarboxylic imide) are introduced while passing in nitrogen. Next, heat to 250℃, and at this temperature 6
Stir for an hour. After cooling to 200 °C, start adding 300 ml of water dropwise at this temperature, pour the diluted melt into 1500 ml of water, separate the resulting leuco compound from the mother liquor by filtration, and reduce the residue on the filter by 5 times. Stir with a certain amount of water and let the air pass through to terminate the oxidation,
Adjust the pH to 3 with dilute hydrochloric acid, suck out the product,
Wash until neutral and dry at 80℃.

48.8 g of 3,4,9,10-perylenetetracarboxylic acid diimide (of 91.3% purity) are obtained; % pure yield (determination of the pure content of 3,4,9,10-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 6 235g potassium hydroxide (85% purity)
and 22.5 g of sodium acetate (anhydrous) in a stainless steel container equipped with a stirrer. Then apply vacuum (3 torr (3 mm Hg)) and heat to 300°C for 2 hours; during this time 24.9 g of water escapes. It is then cooled to 200°C, and then the naphthalene is dissolved at this temperature for 1 hour.
Potassium salt of 1,8-dicarboxylic acid imide 62.5g
(corresponding to 50 g of 100% pure naphthalene-1,8-dicarboxylic imide) are introduced while passing in nitrogen. Next, heat to 280°C and stir at this temperature for 2 hours. After cooling to 200 °C, start adding 300 ml of water dropwise at this temperature, pouring the diluted melt into 1500 ml of water, passing air for 6 hours at room temperature to terminate the oxidation of the leuco compounds, sucking off the precipitate and passing through a filter. Wash the upper residue with water and place it in dilute hydrochloric acid. After stirring for 1 hour at 75°C, the product is sucked off, washed to neutrality and dried at 80°C.

47.9 g of 3,4,9,10-perylenetetracarboxylic acid diimide (of 91.6% purity) are obtained; this is 88.7 g of theory for 100% pure naphthalene-1,8-dicarboxylic acid imide. % pure yield (determination of the pure content of 3,4,9,10-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 7 235g potassium hydroxide (85% purity)
and 22.5 g of sodium acetate (anhydrous) in a stainless steel container equipped with a stirrer. Decompression (3
(3 mmHg)) and heated to 300°C for 2 hours; during this time 26.3 g of water is removed. Then 200℃
and then at this temperature for 1 hour to form the sodium salt of naphthalene-1,8-dicarboxylic acid imide.
61.7 g (corresponding to 50 g of 100% pure naphthalene-1,8-dicarboxylic imide) are introduced while passing in nitrogen. Next, heat to 300℃, and at this temperature 6
Stir for an hour. After cooling to 200 °C, start adding 300 ml of water dropwise at this temperature, pouring the diluted melt into 1500 ml of water, passing air for 6 hours at room temperature to terminate the oxidation of the leuco compounds, sucking off the precipitate and passing through a filter. Wash the upper residue with water and place it in dilute hydrochloric acid.
After stirring for 1 hour at 75°C, the product is sucked off, washed to neutrality and dried at 80°C.

46.8 g of 3,4,9,10-perylenetetracarboxylic acid diimide (of 95.0% purity) are obtained; this is a pure yield of 89.8% of theory based on 100% pure naphthalene dicarboxylic acid imide. (The determination of the pure content of 3,4,9,10-perylenetetracarboxylic acid is carried out by the method described in Example 1).

Claims (1)

[Claims] 1. Naphthalene-1,8-dicarboxylic acid imide is melted with potassium hydroxide and sodium acetate to form an alkali metal salt of a leuco compound of 3,4,9,10-perylenetetracarboxylic acid diimide, and then reacted. After completion, the 3,4,9,
A method for producing 10-perylenetetracarboxylic acid diimide with high purity and high yield, the method comprising: (a) introducing naphthalene-1,8-dicarboxylic acid imide into a potassium hydroxide/sodium acetate melt; Apply a vacuum of less than 100 torr (100 mmHg) and remove potassium hydroxide/sodium acetate.
The mixture is heated to 200-300°C, in particular 250-300°C, and thereby dehydrated in such a way that the resulting melt is still stirrable under industrial conditions at 200-220°C. , followed by 200℃ under normal pressure.
Naphthalene-1,8-dicarboxylic imide or its sodium- or potassium-salt is introduced into the melt at ~220°C and the melt is exposed to atmospheric oxygen until the formation of the alkali metal salt of the leuco compound is complete. 250 ~ in absence
(b) naphthalene-1 at 200-220℃ under normal pressure;
After introducing the 8-dicarboxylic acid imide or its sodium- or potassium-salt into the potassium hydroxide/sodium acetate melt, a vacuum of up to 100 torr (100 mmHg) is applied and the mixture is heated to 200-250°C. and thereby the mixture is dehydrated such that the resulting melt can still be stirred at 200-220° C. under industrial conditions, and the subsequent formation of the alkali metal salt of the leuco compound is completed. or (c) heating the melt to 250-300°C in the absence of atmospheric oxygen until
The sodium or potassium salt of the 8-dicarboxylic acid imide is introduced into the potassium hydroxide/sodium acetate melt and the melt is heated in the absence of atmospheric oxygen until the formation of the alkali metal salt of the leuco compound is complete. A method characterized by heating to 250-300℃.