JPS59205376A - Manufacture of 3,4,9,10-perylene tetracarbonic acid diimide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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. Thus, according to German Patent No. 384057, 3.71, 9.1
0-perylenetetracarboxylic acid diimide is 3,4,9.
It can be produced by reacting 10-perylenetetracarboxylic acid dianhydride with ammonia. Although the products obtained by this method are very pure, the method has the disadvantage of being very expensive; this is because (3) the 3,4,9.10-perylenetetra used as reaction component The carboxylic acid dianhydride itself is 3.4,
This is because it is obtained by hydrolyzing 9.10-perylenetetracarboxylic acid diimide with concentrated sulfuric acid. This process therefore does not serve as a solution to the industrial problem of producing 3,1,9,10-perylenetetracarboxylic acid diimide from naphthalene derivatives that are readily available on a large industrial scale.

According to German Patent No. 274357, 3.4,
9.10-Helentitracarboxylic acid diimide can be prepared by heating a mixture of naphthalene-1,8-dicarboxylic imide, potassium hydroxide and a small amount of water to a temperature of 280-300°C. However, the patent specification does not describe the yield and purity of the reaction product. In the method described there! 1, 4, 9.
1[]-Perylenetetracarboxylic acid diimide is obtained with insufficient purity and yield.

According to Chemical Abstracts 1948, 5892 (
4) For example, 3,4,9.10-perylenetetracarboxylic acid diimide can be prepared by melting naphthalene-1,8-dicarboxylic acid imide with an alkali metal hydroxide under the addition of water. % yield and the product is described by spectroscopic studies to be nearly pure. In a follow-up test described in Chemical Abstracts, 1948, 5892, in which the batch size was increased tenfold, a solution of 3.4,9.10-perylenetetracarboxylic acid diimide was obtained by acidification. It was not possible to confirm the claim that this occurs.

Using sodium hydroxide as a melting agent, the crude #!
5,4,9.10-perylenetetracarboxylic acid diimide is obtained in a yield of 46.1% of theory. Conventional methods for determining purity yield only 57.8% of pure 3,4,9.10-perylenetetracarboxylic diimide for crude 3,4,9.10-perylenetetracarboxylic diimide. Obtained in stages. When using potassium hydroxide, the crude yield was 81.2% of theory, and the purity was determined to be 81.2% of theory.
A value of 9.7% is obtained (5).

European patent application no.
3.4,9.10-
A method for making perylenetetracarboxylic acid diimide is described. Yields of up to 93.4% are stated and the purity of the product obtained is stated to be high. However, the measurement method is not described.

As follows, naphthalene-1,8-dicarboxylic acid imide is melted with potassium hydroxide and sodium acetate to form the alkali metal salt of the leuco compound of 3,4,9,10-perylenetetracarboxylic acid diimide, and the reaction is carried out. After that, the melt is diluted with water and the leuco form is oxidized to 3
, 4,9.10-Perylenetetracarboxylic acid diimide can be produced with high purity and high yield (6). (a) A vacuum of less than 100 torr (100 mHg) was applied to the naphthalene-1,8-dicarboxylic imide before it was introduced into the potassium hydroxide/sodium acetate melt and the potassium hydroxide/sodium acetate mixture was heated to 1 mHg. 200~3
00 DEG C., in particular 250 DEG -300 DEG C., and thereby the mixture is heated so that the melt obtained under industrial conditions
Dehydrated at 220° C. while still stirring, and then introducing naphthalene-1,8-dicarboxylic imide or its sodium or potassium salt into the melt at 200-220° C. under normal pressure and The melt is removed from atmospheric oxygen for 2
751 or (b) 1.8-naphthalene dicarboxylic acid imide or its sodium or potassium salt is heated to 200-200° C. until the formation of the alkali metal salt of the leuco compound is completed.
After charging into the potassium hydroxide/sodium acetate melt at 20°C and normal pressure, (7) reduce the pressure to below 100 torr (100 Ht) and heat the mixture to 200-250°C and This allows the mixture to have a melt of 200-220% under industrial conditions.
dehydrated so that it can still be stirred at 0.degree. C. and then heating the melt to 250-300.degree. C. without atmospheric oxygen until the formation of the alkali metal salts of the leuco compounds has ended, or (C) naphthalene- The sodium or potassium salt of the 1,8-dicarboxylic acid imide is introduced into a potassium hydroxide/sodium acetate melt at 200 DEG to 220 DEG C. under normal pressure and the melt is heated at 250 DEG C. to 220 DEG C. without atmospheric oxygen. 300
C. until the formation of the alkali metal salt of the roy compound is completed.

In order to carry out the method at each point, naphthalene-1,
3 to 100, in particular 5 to 6 parts by weight of potassium hydroxide and 0.1 to 100 parts by weight, in particular 5 to 6 parts by weight, per part by weight of 8-dicarboxylic acid imide or the corresponding amount of its sodium or potassium salt.
Preference is given to using from 2 to 2 (8) parts by weight, in particular from 0.3 to 0.8 parts by weight, of sodium acetate.

The oxidation of the leuco compound of 5,4,9,10-perylenetetracarboxylic acid intermediately obtained according to the invention by one of the routes (a), (b) or (c) above can be carried out in known manner, e.g. By passing air (B engineering O81'1na
l Report, 1484. page 21) or European patent application cylinder 54. hypochlorite solutions, adducts of hydrogen peroxide and borates as described in EI 06;
It is carried out with chlorates, nitrates and beloxonisulfates.

Regarding the compounds used in the process according to the invention, potassium hydroxide and sodium acetate, the sodium acetate is used in anhydrous form, whereas the potassium hydroxide used is industrially obtained with 10-15 % water content of potassium hydroxide.

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 (9), (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 may seem 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. Yes, because European Patent Application No. 54.806 states that high yields and high purity can be achieved by keeping the reaction time as short as possible and the reaction temperature as low as possible.

Content determination shows that the 3,4,9.10-perylenetetracarboxylic acid diimide produced by the method of the said European patent application has a purity content of 81%.
nt@nt ), whereas the 3,4,9.10-perylenetetracarboxylic acid diimide prepared by the method according to the invention had a pure content of 90-95% (puri
ty contentB).

(10) The 3,4,9.10-perylenetetracarboxylic acid diimide obtained by the route according to the invention is 3.4,9.10-perylenetetracarboxylic acid diimide in the form of a pigment.
For the production of 4,9.10-perylenetetracarboxylic acid diimide and for alkylation products and! 1,
It is outstandingly suitable as a starting material for producing 4,9.10-perylenetetracarboxylic acid dianhydride.

Example 1 Potassium hydroxide 2659 (85% purity) and acetic acid (anhydrous) in a stainless steel container equipped with a stirrer
Insert IJum 22.59.

Then apply vacuum (3 Torr 1-HP) to the mixture for 2 hours 3
Heat to 00°C: 259 water escapes during this time. It was then cooled to 200°C and then 509°C for 1 hour at this temperature.
of 1,8-naphthalene dicarboxylic acid imide (98,1%
of purity) while passing nitrogen through it. then 30
Heat to 0° C. and stir at this temperature for 6 hours. After cooling to 200° C., 300 ml of water was added at this temperature, and the melt thus diluted was then poured into 1,500 (11) ml of water, and air was passed through for 6 hours at room temperature to leucorate. After the oxidation of the compound is completed, the precipitate is suctioned off, and the residue on the filter is washed with water and placed in dilute hydrochloric acid. 7 of the mixture
After stirring for 1 hour at 5°C, the product is vacuumed, washed in a neutral trench and dried at 80°C. 44.90 g of crude 314?9T10-perylenetetracarboxylic acid diimide are obtained.

3. Measurement of pure content (pure contθnt) of 4,9.10-perylenetetracarboxylic acid diimide: The crude 3,4,9.10-perylenetetracarboxylic acid diimide of 209 produced through the above procedure was added to 4009 of concentrated sulfuric acid. put it inside. After heating this mixture to 80 °C to dissolve the above crude product, 150 g of sulfuric acid (of 50% strength)
is completed in one hour; during that time the temperature can rise to 100°C. It is then cooled to 25° C., the precipitate is suctioned off, washed with 78% strength sulfuric acid until the drained liquid becomes clear, then washed until neutral and finally dried in SO'C. 1
8.489 pure 3,4,9.10-perylene (12
) Tetracarboxylic acid diimide is obtained. The crude 3.4,q,1o-perylenetetracarboxylic acid obtained is thus 92.4% pure. this is,
Pure yield of 85.5% of theory for 100% O pure naphthalene-1,8-dicarboxylic imide.
d).

Example 2 235 g of potassium hydroxide (90% purity) and 22.59 g of sodium acetate (anhydrous) are placed in a stainless steel container equipped with a stirrer. 200% of this mixture
62.5 g of the potassium salt of naphthalene-1,8-dicarboxylic imide (corresponding to 50 g of 100% pure naphthalene-1,8-dicarboxylic imide) were heated to
Put it in for 1 hour while passing nitrogen through it. After heating to 300°C and stirring at this temperature for 6 hours, cool to 200°C,
Gradually start pouring 300ml of water at this temperature. The diluted melt was then poured into 1,500 ml of water, air was passed for 6 hours at room temperature to terminate the oxidation of the leuco compound, the precipitate was washed with water under suction (13), and the residue on the filter was washed with dilute hydrochloric acid. The mixture was stirred at 75°C for 1 hour, the precipitate was washed with suction until it became neutral, and finally dried at 80°C.

46.229 of 3.4,9.10-perylenetetracarboxylic acid diimide (95.0% purity) is obtained; Corresponding to a net yield of 88.7% (
Determination of the pure content of 3,4,9.10-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 3 155 g of potassium hydroxide (90% pure) and 259 g of sodium acetate (anhydrous) are placed in a stainless steel container with a stirrer.

After heating this mixture to 200'C, naphthalene-1
, 8-dicarboxylic acid imide potassium salt + So, 6g
(corresponding to 50 g of 100% pure naphthalene-1,8-dicarboxylic imide) are charged at the above temperature for 1 hour while passing in nitrogen. Next (14) Reduce pressure (A o ~ 50 mHf)
) and dehydrated for 2 hours at a temperature 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 for 4 hours through nitrogen gas. 2
After cooling to 00 °C, start adding 300 ml of water dropwise at this temperature, the diluted melt is then poured into t500y+t of water, air is passed for 6 hours at room temperature to terminate the oxidation of the leuco compound, and the precipitate is sucked out. Wash with water and then place in dilute hydrochloric acid. After stirring for 1 hour at 75°C, the product is taken off with suction F, washed to neutrality and dried at 80°C.

45.59 of 3.4,9.10-perylenetetracarboxylic acid diimide (91.0%) is obtained; Corresponding to a net yield of 83.3% (K
, 4,9. Determination of the pure content of 10-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 4 (15) 255 g of potassium hydroxide (90% pure) and 22.59 g of acetic acid (anhydrous) are placed in a stainless steel container with a stirrer. Next, reduce the pressure (ao~
50 Torr (40-50wH+r)) and 300°C for 2 hours.
Heat to °C: during this time i2.4 g of water escapes. It was then cooled to 200°C, and then at this temperature for 1 hour 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.

It is then heated to 300 DEG C., poured into 1.501 d of water, oxidized by passing air through it at room temperature for 6 hours, and the precipitate is suctioned, washed with water and placed in dilute hydrochloric acid.

After stirring for 1 hour at 75°C, the product is vacuumed, washed until neutral and dried at 80°C. 48.09 (D 3
, 4,9,10-helentitracarboxylic acid diimide (
(16) of 95% purity is obtained; this corresponds to a pure yield of 94.1% of theory based on 100% pure naphthalene-1,8-dicarboxylic acid imide. (!+
The determination of the pure content of t4,9,1o-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 5 235 g of potassium hydroxide (85% purity) and 22.59 g of acetic acid (anhydrous) are placed in a stainless steel container with a stirrer. Next, reduce pressure (5) #
(3 hours H?)) and heated to 300 °C for 2 hours; during which time the water of 24.8.9 escapes. Then cool to 200 °C, and then at this temperature for 1 hour naphthalene-1,8- 62.5 g of the potassium salt of dicarboxylic imide (corresponding to 50 g of 10% pure naphthalene-1,8-dicarboxylic imide) are introduced while passing in nitrogen. Then, the mixture was heated to 250° C. and stirred for 6 hours at a temperature of . After cooling to 200°C, dropwise addition of 300ml of water was started at this temperature, the diluted melt was poured into 150ml of water, and the resulting leuco compound was separated from the mother liquor by filtration (17). The residue on the filter was stirred with 5 times the amount of water, air was passed through to terminate the oxidation, the temperature was adjusted to 3 with dilute hydrochloric acid, the product was sucked out, washed until neutral, and heated at 80℃. dry.

48.89 of 3.4,9.10-perylenetetracarboxylic acid diimide (91.3% purity) is obtained:
This corresponds to a pure yield of 90.0% of theory for 100% pure naphthalene-1,8-dicarboxylic imide. (The determination of the pure content of 3,4,q,1o-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 6 235 g of potassium hydroxide (85% purity) and 22.59 g of acetic acid (anhydrous) are placed in a stainless steel container with a stirrer. Then apply vacuum (3 Torr (3 Hf)) and heat to 300° C. for 2 hours; during this time 24.99% of water escapes. Next, cool to 200℃,
Then at this temperature for 1 hour 62.5 g of the potassium salt of naphthalene-1,8-dicarboxylic imide (18) (corresponding to 50 g of 100% pure naphthalene-1,8-dicarboxylic imide)
is introduced while passing nitrogen through it. Next, heat to 280℃,
Stir at this temperature for 2 hours. After cooling to 200℃, 300℃
Start adding dropwise 1 ml of water at a temperature of and add 1 ml of the diluted melt.
, 500 m, air was passed for 6 hours at room temperature to terminate the oxidation of the leuco compound, the precipitate was suctioned out, and the residue on the filter was washed with water and placed in dilute hydrochloric acid. 75
After stirring for 1 hour at 0.degree. C., the product is vacuumed, washed to neutrality and dried at 80.degree.

47.99 of 3.4,9.10-perylenetetracarboxylic acid diimide (of 91.6% purity) is obtained;
This corresponds to a pure yield of 88.7% of theory for 100% pure naphthalene-1,8-dicarboxylic imide. (The determination of the pure content of s,a,q,1a-perylenetetracarboxylic acid diimide is carried out by the method described in Example 1).

Example 7 (19) 235 g of potassium hydroxide (85% pure) and 22.59 g of sodium acetate (anhydrous) are placed in a stainless steel container with a stirrer. Decompression (3 torr (3 fight H)
f)) and heated to 300°C for 2 hours;
．． 39 water is removed. 61.7 g of sodium salt of naphthalene-1,8-dicarboxylic imide (corresponding to 50 g of 100% pure naphthalene-1,8-dicarboxylic imide) then cooled to 200° C. and then heated at a temperature of 1 h for 1 hour.
is applied by force through nitrogen. Next, heat to 300℃,
Stir at this temperature for 6 hours. After cooling to 200℃, 300℃
Start adding dropwise 1 ml of water at a temperature of and add 1 ml of the diluted melt.
, 500 d of water, air was passed for 6 hours at room temperature to terminate the oxidation of the leuco compound, the precipitate was suctioned off, and the residue on the filter was washed with water and poured into dilute hydrochloric acid.

After stirring for 1 hour at 75°C, the product is vacuumed, washed to neutrality and dried at 80°C.

46.89 of 3,4,9.10-perylenetetracarboxylic acid diimide (95.0% purity) was obtained (20
) Yield: Yield corresponds to a pure yield of 89.8% of theory on 100% pure naphthalene dicarboxylic imide. (
The determination of the pure content of 3,4,9.10-perylenetetracarboxylic acid is carried out by the method described in Example 1).

Agent Mitsuyoshi Ezaki Agent Mitsufumi Ezaki (21)

Claims (1)

[Claims] By melting naphthalene-1,8-dicarboxylic acid imide with potassium hydroxide and sodium acetate! 1, 4, 9.1
After the reaction is completed, the melt is diluted with water and the leuco form is oxidized to form 3,4,9.10-
A method for producing 3.4,9.1 perylenetetracarboxylic acid diimide with high purity and high yield by converting it into perylenetetracarboxylic acid diimide, (a) Naphthalene-1,8-dicarboxylic acid imide Potassium hydroxide/sodium acetate - vacuum below 100 torr (ID omHy) before entering the melt;
Potassium hydroxide/sodium acetate - mix 200-3
00° C., in particular 250-300° C. and dehydration thereby obtaining the mixture (1) so that the resulting melt is still stirrable at 200-220° C. in industrial conditions, and then dehydrated with naphthalene. -1,8
- dicarboxylic acid imide or its sodium or potassium salt is introduced into the melt at 200-220° C. and normal pressure and the melt is heated to 250°-250° C. without atmospheric oxygen.
(b) 1.8-naphthalenedicarboxylic acid imide or its sodium or potassium salt is heated at 200-220°C with water at normal pressure. After entering the potassium oxide/sodium acetate melt, a vacuum of less than 100 torr is applied, the mixture is heated to 200-250° C. and the mixture is mixed by sliding into the resulting melt. is dehydrated under industrial conditions at 200-220° C. while still stirring, and then the melt is heated to 25°-300° C. without atmospheric oxygen until the formation of the alkali metal salts of the leuco compounds is completed. or (2) (c) introducing the sodium or potassium salt of naphthalene-1,8-dicarboxylic imide into the potassium hydroxide/sodium acetate melt at 200-220° C. at normal pressure. The melt was heated to 250-300 °C without atmospheric oxygen.
℃ until the formation of alkali metal salts of leuco compounds is completed.