KR102254089B1 - Method for producing cyclobutane tetracarboxylic acid derivative - Google Patents

Abstract

(식 중, R 은 수소 원자 또는 탄소수 1 ∼ 20 의 알킬기를 나타낸다.)Provision of an efficient method for producing 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivatives useful as raw materials for polyimide and the like. By subjecting the maleic anhydride compound represented by formula (1) to a light dimerization reaction in the presence of benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, or benzaldehyde substituted with an electron withdrawing group, A method for producing a 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivative represented by formula (2).
[Formula 1]

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

Description

Method for producing a cyclobutanetetracarboxylic acid derivative {METHOD FOR PRODUCING CYCLOBUTANE TETRACARBOXYLIC ACID DERIVATIVE}

The present invention relates to a novel method for producing a cyclobutanetetracarboxylic acid derivative useful as a raw material such as polyimide.

Cyclobutanetetracarboxylic acid derivatives are compounds useful as raw materials for polyimides and the like. As a method for producing the compound, a light dimerization reaction of a maleic anhydride derivative is known (Patent Documents 1 to 5).

Among them, in Patent Document 1, as a method for producing 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride (CBDA), in a solvent having a carbonyl group such as ketones The photo dimerization reaction of maleic anhydride is disclosed. However, in the reaction, there is a description that the use of acetophenone, benzophenone, anthraquinone, etc., which are usually used as photosensitizers, has no effect, and rather does not exist gives good results ((2) ) Last row of the lower right column of the page ∼ (3) 4 rows of the upper left column of the page).

The method for producing 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride (CBDA) by photodimerization reaction of maleic anhydride described in Patent Document 1 is a raw material Phosphorus maleic anhydride is relatively inexpensive and is useful because it is simple as a production method, but the photoreaction efficiency is not sufficient, and thus it has a problem in the yield of the target product.

Japanese Patent Laid-Open Publication No. 59-212495 Japanese Laid-Open Patent Publication No. Hei 4-106127 Japanese Unexamined Patent Publication No. 2003-192685 Japanese Unexamined Patent Publication No. 2006-347931 Japanese Patent Application Laid-Open No. 2008-69081

An object of the present invention is to perform a light dimerization reaction of a specific maleic anhydride derivative, resulting in high light reaction efficiency and high yield, and the target 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3 ,4-2 to provide a method for producing an anhydride derivative.

The present inventors, as a result of conducting intensive research in order to solve the above-described problems, resulted in the presence of a compound in which acetophenone, benzophenone or benzaldehyde with an electron withdrawing group was substituted in the reaction system, contrary to the disclosure of Patent Document 1, The photoreaction efficiency of the maleic anhydride compound is improved, and as a result, the target 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivative can be prepared in high yield. Finding out what can be done, the present invention was completed.

The present invention makes the following a summary.

1.A light dimerization reaction of a maleic anhydride compound represented by the following formula (1) in the presence of benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, or benzaldehyde substituted with an electron withdrawing group A method for producing a 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivative represented by formula (2), characterized in that.

[Formula 1]

(In formula, R represents a hydrogen atom or a C1-C20 alkyl group.).

2. The production method according to 1 above, wherein R is a methyl group.

3. The production method according to 1 above, wherein R is a hydrogen atom.

4. The electron withdrawing group described in any one of 1 to 3 above, wherein the electron withdrawing group is at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodine group, a nitro group, a cyano group, and a trifluoromethyl group. Manufacturing method.

5. The number of electron withdrawing groups is 1-5, and the manufacturing method in any one of said 1-4.

6. Any of the above 1 to 5, wherein the electron withdrawing group substituted benzophenone, the electron withdrawing group substituted acetophenone, or the electron withdrawing group substituted benzaldehyde is 0.1 to 20 mol% based on the maleic anhydride compound. The manufacturing method according to one.

7. The production method according to any one of the above 1 to 6, wherein the light dimerization reaction is carried out in a reaction solvent.

8. The production method according to 7 above, wherein the reaction solvent is an ester of an organic carboxylic acid, an anhydride, or a carbonate ester.

9. The production method according to 7 or 8 above, wherein the reaction solvent is ethyl acetate or dimethyl carbonate.

10. The production method according to any one of 7 to 9, wherein the reaction solvent is used in an amount of 3 to 300 times by mass based on the maleic anhydride compound.

11. The production method according to any one of 7 to 9, wherein the amount of the reaction solvent is 3 to 10 times by mass relative to the maleic anhydride compound.

12. The production method according to any one of 1 to 11, wherein the reaction temperature is 0 to 20°C.

According to the present invention, the target product, 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4 is used as a raw material for an inexpensive maleic anhydride compound and reacted with light dimerization at a photoreaction rate. The -2 anhydride derivative can be prepared with high light reaction efficiency and high yield.

1 is a 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride obtained in Reference Example 1 (hereinafter, 1,3-DM-CBDA It is a molecular model assembled based on the X-ray structure analysis of a single crystal of.
Fig. 2 is a molecular model assembled based on an X-ray structure analysis of a 1,3-DM-CBDA single crystal obtained in Example 20 of the present invention.

1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivative represented by formula (2) by photodimerization reaction of maleic anhydride compound represented by formula (1) The manufacturing method of is represented by the following reaction scheme.

[Formula 2]

In the formula, R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be a linear or branched saturated alkyl group, or a linear or branched unsaturated alkyl group. Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl- n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n- Butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-ecosyl, 1- Methylvinyl, 2-allyl, 1-ethylvinyl, 2-methylallyl, 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 2 -Hexenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 2,3-dimethyl-2-butenyl, 1-ethyl-2-pentenyl, 3-dodecenyl, propargyl , 3-butynyl, 3-methyl-2-propynyl, and 9-decynyl.

In addition, n represents normal, i represents iso, s represents secondary, and t represents tertiary, respectively.

Examples of the maleic anhydride compound represented by formula (1) include citraconic anhydride, 2-ethyl maleic anhydride, 2-isopropyl maleic anhydride, 2-n-butyl maleic anhydride, and 2-t-butyl anhydride. Maleic acid, 2-n-pentylmaleic anhydride, 2-n-hexylmaleic anhydride, 2-n-heptylmaleic anhydride, 2-n-octylmaleic anhydride, 2-n-nonylmaleic anhydride, 2- n-decylmaleic anhydride, 2-n-dodecylmaleic anhydride, 2-n-eicosylmaleic anhydride, 2-(1-methylvinyl)maleic anhydride, 2-(2-allyl)maleic anhydride, 2-(1-ethylvinyl)maleic anhydride, 2-(2-methylallyl)maleic anhydride, 2-(2-butenyl)maleic anhydride, 2-(2-hexenyl)maleic anhydride, 2- (1-ethyl-2-pentenyl)maleic anhydride, 2-(3-dodecenyl)maleic anhydride, 2-propargylmaleic anhydride, 2-(3-butynyl)maleic anhydride, 2-( 3-methyl-2-propynyl)maleic anhydride, 2-(9-decynyl)maleic anhydride, and the like.

From the viewpoint of high photoreaction efficiency, among these, citraconic anhydride, 2-ethyl maleic anhydride, 2-isopropyl maleic anhydride, 2-n-butyl maleic anhydride, 2-t-butyl maleic anhydride, 2-n-pentylmaleic anhydride, 2-n-hexylmaleic anhydride, 2-n-heptylmaleic anhydride, 2-n-octylmaleic anhydride, 2-n-nonylmaleic anhydride, 2-n-decyl Maleic anhydride, or 2-n-dodecylmaleic anhydride is preferred, and citraconic anhydride, 2-ethyl maleic anhydride, 2-isopropyl maleic anhydride, 2-n-butyl maleic anhydride, 2-t -Butyl maleic anhydride, 2-n-pentylmaleic anhydride, or 2-n-hexylmaleic anhydride is more preferred.

In the present invention, benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, or benzaldehyde substituted with an electron withdrawing group acts as a sensitizer.

Examples of the electron withdrawing group include at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodine group, a nitro group, a cyano group, and a trifluoromethyl group, and a fluoro group, a chloro group , A bromo group, a cyano group, or a trifluoromethyl group, and the like are preferable. A particularly preferable electron withdrawing group is a fluoro group or a chloro group.

The number of electron withdrawing groups is 1 to 10, but 1 to 5 are preferable, and in particular, 1 to 3 are preferable.

Examples of the substitution position of the electron withdrawing group include an ortho position, a meta position, and a para position with respect to the carbonyl group, but the ortho position or the para position is preferable, and in particular, the para position is preferable.

When the number of electron withdrawing groups is 2 or more, the electron withdrawing groups may be the same or may be different from each other. Moreover, an anthraquinone crosslinked at the ortho position may be sufficient as the carbonyl group having the effect of electron withdrawing property.

Specific examples of the benzophenone substituted by the electron withdrawing group include 2-fluorobenzophenone, 3-fluorobenzophenone, 4-fluorobenzophenone, 2-chlorobenzophenone, 3-chlorobenzophenone, and 4-chloro Benzophenone, 2-cyanobenzophenone, 3-cyanobenzophenone, 4-cyanobenzophenone, 2-nitrobenzophenone, 3-nitrobenzophenone, 4-nitrobenzophenone, 2,4'-dichlorobenzophenone , 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 3,3'-bis(trifluoromethyl)benzophenone, 3,4 '-Dinitrobenzophenone, 3,3'-dinitrobenzophenone, 4,4'-dinitrobenzophenone, 2-chloro-5-nitrobenzophenone, 1,3-bis(4-fluorobenzoyl)benzene , 1,3-bis(4-chlorobenzoyl)benzene, 2,6-dibenzoylbenzonitrile, 1,3-dibenzoyl-4,6-dinitrobenzene, anthraquinone, and the like. Among them, 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone is preferable.

Examples of the acetophenone substituted by the electron withdrawing group include 2'-fluoroacetophenone, 3'-fluoroacetophenone, 4'-fluoroacetophenone, 2'-chloroacetophenone, 3'-chloroacetophenone, 4 '-Chloroacetophenone, 2'-cyanoacetophenone, 3'-cyanoacetophenone, 4'-cyanoacetophenone, 2'-nitroacetophenone, 3'-nitroacetophenone, 4'-nitroacetophenone , 2',4'-difluoroacetophenone, 3',4'-difluoroacetophenone, 2',4'-dichloroacetophenone, 3',4'-dichloroacetophenone, 4'-chloro- 3'-nitroacetophenone, 4'-bromo-3'-nitroacetophenone, 4'-fluoro-3'-nitroacetophenone, etc. are mentioned. Among them, 4'-fluoroacetophenone, 4'-chloroacetophenone, 2',4'-difluoroacetophenone, 3',4'-difluoroacetophenone, 2',4'-dichloroaceto Phenone, or 3',4'-dichloroacetophenone is preferred.

As the benzaldehyde substituted by the electron withdrawing group, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-cyanobenzaldehyde, 3-cyanobenzaldehyde, 4-cyanobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2,4-difluorobenzaldehyde, 3 ,4-difluorobenzaldehyde, 2,4-dichlorobenzaldehyde, 3,4-dichlorobenzaldehyde, 2-chloro-5-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 4-chloro-3 -Nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 2-fluoro-5-nitrobenzaldehyde, 4-fluoro-3-nitrobenzaldehyde, 5-fluoro-2-nitrobenzaldehyde, etc. I can. Among them, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, 2,4-difluorobenzaldehyde, 3,4-difluorobenzaldehyde, 2,4-dichlorobenzaldehyde, or 3,4-dichloro Benzaldehyde is preferred.

The amount of the sensitizer to be used may be an amount at which the photoreaction rate accelerates, and is not particularly limited, but is preferably 0.1 to 20 mol%, more preferably 0.1 to 5 mol% with respect to the maleic anhydride compound. The sensitizer is preferably used alone from the easiness of processing after the reaction.

As the reaction solvent, an organic solvent generally used in photochemical reactions is used. On the other hand, requirements for a solvent that can be employed industrially include (1) a carbonyl compound having a high photosensitization effect, (2) a high solubility of the maleic anhydride compound as a raw material, and the resulting CBDA derivative compound In order to suppress the decomposition reaction, the solubility of the CBDA derivative compound should be low, (3) the solubility of by-products should be high, and the CBDA derivative compound should be able to be purified only by washing with the same solvent, and (4) the risk of flammability. It is not a low boiling point, and should be a compound having a boiling point of around 100°C in order not to remain in the CBDA derivative compound, (5) it should be safe for the environment, (6) it should be stable even during photoreaction, (7) it should be inexpensive, etc. It should be satisfying. From these points, as the reaction solvent, an ester of an organic carboxylic acid, an anhydride, or a carbonate ester is preferable. As the reaction solvent, n-hexane, n-heptane, cyclohexane, acetonitrile, acetone, dichloromethane, chloroform, tetrahydrofuran, and the like can also be used.

As an ester of an organic carboxylic acid, the formula: R ¹ COOR ² (however, R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably 1 or 2 ^{carbon atoms, and R 2} is a carbon number 1 A fatty acid alkyl ester represented by -4, more preferably 1-3 alkyl groups) is preferable.

Preferred examples of esters of organic carboxylic acids include methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, i-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i acetic acid -Propyl, n-butyl acetate, i-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, and i-butyl propionate. Further, ethylene glycol diformate, ethylene glycol diacetate, ethylene glycol dipropionate, and the like can also be used.

In addition, as an anhydride of an organic carboxylic acid ^{, it is preferable to represent with the formula: (R 1} CO) ₂ O (however, R ¹ has the same meaning as above including a preferred embodiment). A preferred specific example thereof is propionic anhydride, butyric anhydride, trifluoroacetic anhydride, or acetic anhydride. Among them, acetic anhydride is preferred from the viewpoint of obtaining 1,3-DACBDA with a higher recovery rate.

Further, as the carbonate ester, a dialkyl carbonate having an alkyl carbon number of preferably 1 to 3, more preferably 1 or 2 is preferable. Preferred examples thereof include dimethyl carbonate, diethyl carbonate, or a mixture thereof.

When the reaction solvent contains ethyl acetate, dimethyl carbonate, diethyl carbonate, or ethylene glycol diacetate, although the solubility of the maleic anhydride compound as a raw material is high, the solubility of the resulting CBDA derivative compound is low, and the target compound Since these crystals precipitate during the reaction, side reactions such as the reverse reaction of the CBDA derivative compound to the maleic anhydride compound and the formation of oligomers can be suppressed.

The amount of the reaction solvent used is 3 to 300 times by mass, more preferably 4 to 250 times by mass based on the maleic anhydride compound. Although the use of a solvent may be used alone or in combination, it is preferable to use it alone from the easiness of processing after the reaction.

In addition, it is preferable that the amount of the reaction solvent is small, and in this case, the concentration of the maleic anhydride compound is increased, the reaction is fast, and the yield of the resulting product increases. Therefore, when the reaction is to be accelerated or the quantity of the product is to be increased, the amount of the solvent is preferably 3 to 10 times the mass of the maleic anhydride compound.

In this photoreaction, the wavelength of light is 200 to 400 nm, more preferably 250 to 350 nm, and particularly preferably 280 to 330 nm. As the light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, an electrodeless lamp, a light-emitting diode, etc. are preferable in that a CBDA derivative compound is specifically provided with a high yield. Among them, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a light emitting diode is preferable.

In addition, as the reaction device, by changing the light source cooling tube from quartz glass to Pyrex (registered trademark) glass, adhesion of colored polymers and impurities to the light source cooling tube are reduced, so that the yield of the CBDA derivative compound can be improved. Do.

The reaction temperature is preferably -20 to 80°C, more preferably -10 to -from the point of view that the polymerization product is by-produced when the temperature is high, and the solubility of the maleic anhydride compound decreases when the temperature is low, resulting in a decrease in production efficiency. It is 50 degrees Celsius. In particular, at a temperature of 0 to 20°C, generation of by-products is greatly suppressed, and a CBDA derivative compound is obtained with a high selectivity and yield.

The reaction time varies depending on the injection amount of the maleic anhydride compound, the type of the light source, the irradiation amount, etc., but until the unreacted maleic anhydride compound reaches preferably 0 to 40%, more preferably 0 to 10%. Can be carried out during the time.

The reaction time is specifically, usually 1 to 200 hours, preferably 1 to 100 hours, more preferably 1 to 60 hours.

In addition, the conversion rate can be determined by analyzing the reaction solution by gas chromatography or the like.

When the reaction time increases, the conversion rate of the maleic anhydride compound increases, and the precipitation amount of the CBDA derivative compound increases, the produced CBDA derivative compound begins to adhere to the outer wall (reaction liquid side) of the light source cooling tube, and the decomposition reaction occurs. The resulting crystal coloration and light efficiency (unit power x yield per hour) were decreased. Therefore, in order to increase the conversion rate of the maleic anhydride compound, it is not preferable to apply it in one batch for a long time due to a decrease in production efficiency in practical use.

Moreover, although it is possible to carry out the reaction in a batch type or a flow type, a batch type is preferable. In addition, although the pressure at the time of reaction may be normal pressure or pressurization may be sufficient, it is preferable that it is normal pressure.

The target compound, 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivative, after photoreaction, the precipitate in the reaction solution is filtered, and the filtered product is used in an organic solvent. After washing with, it is obtained by drying under reduced pressure.

The amount of the organic solvent used for washing the filtered sample may be an amount capable of transferring the precipitate remaining in the reaction tank to the filter. When the amount of the organic solvent is large, the target compound migrates to the filtrate, and the recovery rate decreases. For this reason, the amount of the organic solvent used for washing of the filtrate is preferably 0.5 to 10 times by weight, more preferably 1 to 2 times by weight, based on the maleic anhydride compound used in the reaction.

Although it does not specifically limit as an organic solvent used for washing|cleaning of the filtrate, the use of a solvent with high product solubility is not preferable because the target compound migrates to the filtrate and the recovery rate decreases. For this reason, preferable organic solvents used for washing of the filtrate are methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, and i- formic acid, which are reaction solvents used in the light dimerization reaction. Butyl, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, propionic acid i-butyl, ethylene glycol diformate, ethylene glycol diacetate, ethylene glycol dipropionate, dimethyl carbonate, diethyl carbonate, etc., and a solvent that does not dissolve the product and does not react with the product, such as toluene, Hexane, heptane, acetonitrile, acetone, chloroform, acetic anhydride, and mixed solvents thereof. Especially, ethyl acetate, dimethyl carbonate, or acetic anhydride is preferable, and ethyl acetate or dimethyl carbonate is more preferable.

Further, the compound after washing the filtered sample is further stirred and washed at room temperature or heating in an organic solvent, and the precipitate is collected by filtration to obtain 1,2,3,4-cyclobutanetetracarboxylic acid-1 represented by formula (2). ,2: It can improve the purity of 3,4-2 anhydride derivatives. In the case of using 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivatives represented by formula (2) of high purity, it is higher than that of polymers prepared using low purity products. Since it is possible to obtain a polymer having a molecular weight and low dispersion, 1,2,3,4-cyclobutanetetracarboxylic acid-1,2 represented by formula (2) of high purity from the viewpoint of obtaining a polymer having a high molecular weight and low dispersion. : 3,4-2 Anhydride derivatives are preferred.

The organic solvent used for washing at this time is not particularly limited, but the use of a solvent having high product solubility is not preferable because the target compound migrates to the filtrate and the recovery rate decreases. For this reason, a preferable organic solvent used for washing after washing|cleaning of the filtration sample mentioned above is mentioned. Among them, ethyl acetate, dimethyl carbonate, acetonitrile, or acetic anhydride is preferable, and acetic anhydride is more preferable because the hydrolyzate can be closed.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In addition, the analysis method used in Examples is as follows.

<GC analysis conditions>

Device: GC-2010 Plus (manufactured by SHIMADZU),

Column: DB-1 (manufactured by Agilent Technology Co., Ltd.) 0.25 mm in diameter x 30 m in length,

Film thickness 0.25 um,

Carrier gas: He, detector: FID, sample injection amount: 1 um, inlet temperature: 160 ℃, detector temperature: 220 ℃, column temperature: 70 ℃ (20 min) -40 ℃/min -220 ℃ (15 min), split Ratio: 1:50, internal standard substance: butyl lactate.

< ¹ H NMR analysis conditions>

Device: Fourier variable-sensitized superconducting nuclear magnetic resonance device (FT-NMR) INOVA-400 (manufactured by Varian) 400 ㎒,

Solvent: DMSO-d6, internal standard substance: tetramethylsilane (TMS).

<melting point analysis conditions>

Apparatus: DSC1 (made by METTLER TOLEDO),

Temperature: 35 ℃-5 ℃/min-400 ℃, Fan: Au (closed).

<Single crystal X-ray crystal structure analysis conditions>

Device: APEX2 (manufactured by Bruker),

Temperature: 298 K, X-ray: Cu.

Comparative Example 1

[Formula 3]

In a nitrogen atmosphere, in a 30 ml Pyrex (registered trademark) glass test tube, 0.10 g (0.89 mmol) of citraconic anhydride (CA), and 20 g (222 mmol, citraconic anhydride (CA)) of dimethyl carbonate 200 Mass times) was injected, and stirred with a magnetic stirrer to dissolve. Next, a 100 W high-pressure mercury lamp was irradiated for 4 hours while stirring at 10-15°C. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and as a result, the residual ratio of citraconic anhydride (CA) was 26.2%. Further, 2 g of the reaction liquid in the reactor was collected, and the solvent was distilled off at 70-80 Torr with an evaporator. The resulting crude is ¹ mixture of (1,3-DM-CBDA which by H NMR analysis, including 1,3-DM-CBDA and 1,2-DM-CBDA: 1,2- DM-CBDA = 48.3: 51.7).

¹ H NMR (DMSO-d6, δ ppm) (1,3-DM-CBDA): 1.38 (s, 6H), 3.89 (s, 2H).

¹ H NMR (DMSO-d6, δ ppm) (1,2-DM-CBDA): 1.37 (s, 6H), 3.72 (s, 2H).

Comparative Example 2

[Formula 4]

In a nitrogen atmosphere, in a 30 ml Pyrex (registered trademark) glass test tube, citraconic anhydride (CA) 0.10 g (0.89 mmol), benzophenone (BP) 0.020 g (0.11 mmol, citraconic anhydride (CA)) Relative to 20% by mass) and 20 g of dimethyl carbonate (222 mmol, 200% by mass relative to citraconic anhydride (CA)) were poured, and stirred with a magnetic stirrer to dissolve. Then, a 100 W high-pressure mercury lamp was irradiated for 4 hours, stirring at 10-15°C. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and as a result, the residual ratio of citraconic anhydride (CA) was 3.9%. Further, 2 g of the reaction liquid in the reactor was collected, and the solvent was distilled off at 70-80 Torr with an evaporator. The obtained crude product was ^{a mixture containing 1,3-DM-CBDA and 1,2-DM-CBDA by 1} H NMR analysis (1,3-DM-CBDA: 1,2-DM-CBDA = 48.3: 51.7 ).

Comparative Examples 3 to 10 and Examples 1 to 9

A series of operations was carried out in the same manner as in Comparative Example 2, by adding 20 wt% of a sensitizer to citraconic anhydride (CA). And, in the same manner as in Comparative Example 2, the residual ratio of citraconic anhydride (CA), and the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA (1,3-DM-CBDA: 1 ,2-DM-CBDA) was calculated.

The types and results of the added sensitizer are shown in the table below. In addition, the residual ratio of citraconic anhydride in the reaction solution obtained here, the reaction rate, and the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA were calculated, and the results obtained in Comparative Examples 1 and 2 Shown in the table together with. In addition, the reaction rate in the table was calculated from the number of moles of citraconic acid used and the residual ratio of citraconic acid at the time of reaction for 4 hours. Therefore, when the residual ratio of citraconic acid is 0, the reaction rate becomes 0.22, but there is a possibility that the actual reaction rate is faster than that.

Example 10

[Formula 5]

In a nitrogen atmosphere, in a 300 ml Pyrex (registered trademark) glass five-neck flask, citraconic anhydride (CA) 3.5 g (31.2 mmol), 4-chlorobenzophenone (ClBP) 0.70 g (3.23 mmol, citraconic acid) 10 mol% with respect to anhydride (CA)) and 136.5 g of dimethyl carbonate (1515 mmol, 39.0 wt. times with respect to citraconic anhydride (CA)) were poured, followed by stirring with a magnetic stirrer to dissolve.

Next, a 100 W high-pressure mercury lamp was irradiated for 1 hour, stirring at 10-15°C. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and as a result, the residual ratio of citraconic anhydride (CA) was 69.1%. Further, 0.2 g of the reaction solution in the reactor was collected, and the solvent was distilled off at 70 to 80 Torr with an evaporator. The resulting crude is ¹ mixture of (1,3-DM-CBDA which by H NMR analysis, including 1,3-DM-CBDA and 1,2-DM-CBDA: 1,2- DM-CBDA = 44.6: 55.4).

Examples 11 to 13

In the same manner as in Example 10, a series of operations were performed with the values shown in the following table for the type of sensitizer. In addition, the residual ratio of citraconic anhydride in the reaction solution obtained here, the reaction rate, and the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA were calculated, and the table together with the results obtained in Example 10 Shown in. In addition, the reaction rate in the table was calculated from the number of moles of citraconic acid used and the residual ratio of citraconic acid at the time of reaction for 1 hour.

Comparative Example 11

In a nitrogen atmosphere, in a 300 ml Pyrex (registered trademark) glass five-neck flask, citraconic anhydride (CA) 35.0 g (312 mmol), and dimethyl carbonate 152 g (1682 mmol, citraconic anhydride (CA)) 4.33 wt times) was injected, and the mixture was stirred with a magnetic stirrer to dissolve. Then, a 100 W high-pressure mercury lamp was irradiated for 6 hours, stirring at 10-15°C. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and as a result, the residual ratio of citraconic anhydride (CA) was 88.5%. Further, 0.2 g of the reaction solution in the reactor was collected, and the solvent was distilled off at 70 to 80 Torr with an evaporator. The resulting crude is ¹ mixture by H NMR analysis, including 1,3-DM-CBDA and 1,2-DM-CBDA (1,3- DM-CBDA: 1,2-DM-CBDA = 41.7: 58.3).

Example 14

[Formula 6]

In a nitrogen atmosphere, a 300 ml Pyrex (registered trademark) glass five-neck flask, citraconic anhydride (CA) 35.0 g (312 mmol), 4,4'-dichlorobenzophenone (DClBP) 0.0784 g (0.31 mmol, 0.1 mol% with respect to citraconic anhydride (CA)), and 152 g of dimethyl carbonate (1682 mmol, 4.33 wt. times with respect to citraconic anhydride (CA)) were poured, followed by stirring with a magnetic stirrer to dissolve. Then, a 100 W high-pressure mercury lamp was irradiated for 2 hours, stirring at 10-15°C. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and as a result, the residual ratio of citraconic anhydride (CA) was 88.2%. Further, 0.2 g of the reaction solution in the reactor was collected, and the solvent was distilled off at 70 to 80 Torr with an evaporator. The resulting crude is ¹ mixture of (1,3-DM-CBDA which by H NMR analysis, including 1,3-DM-CBDA and 1,2-DM-CBDA: 1,2- DM-CBDA = 43.3: 56.7).

Examples 15 and 16

A series of operations was carried out in the same manner as in Example 14, with the added amount of 4,4'-dichlorobenzophenone (DClBP) as the value shown in the following table. In addition, the residual ratio of citraconic anhydride in the reaction solution obtained here, the reaction rate, and the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA were calculated, and in Comparative Examples 11 and 14 It is shown in the table together with the obtained result. In addition, the reaction rate of Comparative Example 11 in the table was the number of moles of citraconic acid used and the time when the reaction was performed for 6 hours, and the reaction rate of Examples 14-16 was the number of moles of citraconic acid used and the time when the reaction was performed for 2 hours. It was calculated from the residual ratio of citraconic acid.

Example 17

In a nitrogen atmosphere, a 300 ml Pyrex (registered trademark) glass five-neck flask, citraconic anhydride (CA) 28.0 g (250 mmol), 4,4'-dichlorobenzophenone (DClBP) 0.313 g (1.25 mmol, 0.5 mol% with respect to citraconic anhydride (CA)) and 158 g of dimethyl carbonate (1799 mmol, 5.66 wt times with respect to citraconic anhydride (CA)) were poured, and the mixture was stirred with a magnetic stirrer to dissolve. Then, a 100 W high-pressure mercury lamp was irradiated for 2 hours, stirring at 10-15°C. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and as a result, the residual ratio of citraconic anhydride (CA) was 79.7%. Further, 0.2 g of the reaction solution in the reactor was collected, and the solvent was distilled off at 70 to 80 Torr with an evaporator. The resulting crude is ¹ mixture of (1,3-DM-CBDA which by H NMR analysis, including 1,3-DM-CBDA and 1,2-DM-CBDA: 1,2- DM-CBDA = 43.9: 56.1).

Example 18

A series of operations was carried out in the same manner as in Example 17, with the added amount of 4,4'-dichlorobenzophenone (DClBP) as the value shown in the following table. In addition, the residual ratio of citraconic anhydride in the reaction solution obtained here, the reaction rate, and the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA were calculated, and the table together with the results obtained in Example 17 Shown in. In addition, the reaction rate in the table was calculated from the number of moles of citraconic acid used and the residual ratio of citraconic acid at the time of reaction for 2 hours.

Comparative Example 12

In a nitrogen atmosphere, in a 300 ml Pyrex (registered trademark) glass five-neck flask, citraconic anhydride (CA) 35.0 g (312 mmol), and dimethyl carbonate 152 g (1682 mmol, citraconic anhydride (CA)) 4.33 wt times) was injected, and the mixture was stirred with a magnetic stirrer to dissolve. Then, a 100 W high-pressure mercury lamp was irradiated for 48 hours, stirring at 10-15°C. The reaction liquid confirmed that the residual ratio of raw materials was 23.7% by gas chromatography analysis. Thereafter, the precipitated white crystals were taken out by filtration at 10-15°C, and the crystals were washed twice with 43.8 g of ethyl acetate (497 mmol, 1.25 wt times of citraconic anhydride (CA)). Subsequently, this was dried under reduced pressure, and 8.1 g of white crystals (yield 23.2%) were obtained. This crystal was determined by ¹ H NMR analysis, and a mixture containing 1,3-DM-CBDA and 1,2-DM-CBDA (1,3-DM-CBDA: 1,2-DM-CBDA = 90.3: 9.7 ). Further, the obtained crystal, filtrate, and washing liquid ^{were quantitatively analyzed by 1} H NMR analysis and gas chromatography, respectively. The mass balance with respect to the injection amount was 88.9%.

Example 19

In a nitrogen atmosphere, a 300 ml Pyrex (registered trademark) glass five-neck flask, citraconic anhydride (CA) 28.0 g (250 mmol), 4,4'-dichlorobenzophenone (DClBP) 0.628 g (2.50 mmol, 1.0 mol% with respect to citraconic anhydride (CA)), and 158 g of dimethyl carbonate (1799 mmol, 5.66 wt times with respect to citraconic anhydride (CA)) were poured, followed by stirring with a magnetic stirrer to dissolve. Then, a 100 W high-pressure mercury lamp was irradiated for 14 hours, stirring at 10-15°C. The reaction liquid confirmed that the residual ratio of raw materials was 3.8% by gas chromatography analysis. Thereafter, the precipitated white crystals were taken out by filtration at 10-15°C, and the crystals were washed twice with 35.0 g of ethyl acetate (397 mmol, 1.25 wt times of citraconic anhydride (CA)). Subsequently, this was dried under reduced pressure, and 6.9 g of white crystals (yield 24.7%) were obtained. This crystal was determined by ¹ H NMR analysis, and a mixture containing 1,3-DM-CBDA and 1,2-DM-CBDA (1,3-DM-CBDA: 1,2-DM-CBDA = 91.8: 8.2 ). Further, the obtained crystal, filtrate, and washing liquid ^{were quantitatively analyzed by 1} H NMR analysis and gas chromatography, respectively. The mass balance with respect to the injection amount was 90.2%.

Reference Example 1

[Formula 7]

A mixture containing 1,3-DM-CBDA and 1,2-DM-CBDA obtained in the same manner as in Comparative Example 12 in a 5-L 4-neck flask under a nitrogen stream (1,3-DM-CBDA: 1,2-DM-CBDA = 92: 8) 700 g and 3500 g of acetic anhydride were poured and suspended at 25°C under magnetic stirrer stirring. Then, it was heated and refluxed (130 degreeC) for 4 hours. Then, it cooled until internal temperature became 25 degreeC or less, and it stirred at 25 degreeC or less for 1 hour. Then, the precipitated white crystal was filtered, and the obtained crystal was washed twice with 700 g of ethyl acetate. Then, the obtained white crystal was dried under reduced pressure to obtain 634 g of high purity 1,3-DM-CBDA (91% recovery). By ¹ H NMR analysis of the crystal, it was confirmed that the ratio of 1,3-DM-CBDA and 1,2-DM-CBDA was 1,3-DM-CBDA: 1,2-DM-CBDA = 99.5: 0.5 I did.

¹ H NMR (DMSO-d6, δ ppm) (1,3-DM-CBDA): 1.38 (s, 6H), 3.89 (s, 2H).

¹ H NMR (DMSO-d6, δ ppm) (1,2-DM-CBDA): 1.37 (s, 6H), 3.72 (s, 2H).

mp. (1,3-DM-CBDA): 316.45 ℃

X-ray structure analysis of single crystal (1,3-DM-CBDA): Fig. 1 shows a molecular model assembled based on the X-ray structure analysis of a single crystal. The single crystal for X-ray structure analysis was prepared by dissolving 1,3-DM-CBDA obtained by the above method in ethyl acetate, and dropping n-hexane as a poor solvent.

Molecular formula; C ₁₀ H ₈ O ₆ , molecular weight; 224.16, political system; Orthorhombic, space group; Pbca, lattice constant; a = 11.2988 (3) A, b = 6.9330 (2) A, c = 12.1220 (4) A, α = 90°, β = 90°, γ = 90°, Z value = 4, R (gt) = 0.11 , wR (gt) = 0.32.

Example 20

[Formula 8]

A mixture containing 1,3-DM-CBDA and 1,2-DM-CBDA obtained in the same manner as in Example 19 (1,3-DM-CBDA: 1,2-DM-CBDA = 85:15) 18.3 g and 92 g of acetic anhydride were poured and suspended at 25°C under magnetic stirrer stirring. Then, it was heated and refluxed (130 degreeC) for 4 hours. Then, it cooled until internal temperature became 25 degreeC or less, and it stirred at 25 degreeC or less for 1 hour. Then, the precipitated white crystal was filtered, and the obtained crystal was washed twice with 18 g of ethyl acetate. Then, the obtained white crystal was dried under reduced pressure to obtain 14.4 g of high purity 1,3-DM-CBDA (92% recovery rate). By ¹ H NMR analysis of the crystal, it was confirmed that the ratio of 1,3-DM-CBDA and 1,2-DM-CBDA was 1,3-DM-CBDA: 1,2-DM-CBDA = 99.5: 0.5 I did.

¹ H NMR (DMSO-d6, δ ppm) (1,3-DM-CBDA): 1.38 (s, 6H), 3.89 (s, 2H).

¹ H NMR (DMSO-d6, δ ppm) (1,2-DM-CBDA): 1.37 (s, 6H), 3.72 (s, 2H).

mp. (1,3-DM-CBDA): 316.82 ℃

Single crystal X-ray structure analysis (1,3-DM-CBDA): Fig. 2 shows a molecular model assembled based on the X-ray structure analysis of a single crystal. The single crystal for X-ray structure analysis was prepared by dissolving 1,3-DM-CBDA obtained by the above method in ethyl acetate, and dropping n-hexane as a poor solvent.

Molecular formula; C ₁₀ H ₈ O ₆ , molecular weight; 224.16, political system; Orthorhombic, space group; Pbca, lattice constant; a = 11.3082 (8) A, b = 6.9168 (6) A, c = 12.1479 (9) A, α = 90°, β = 90°, γ = 90°, Z value = 4, R (gt) = 0.1192 , wR (gt) = 0.3183.

Comparative Example 13

[Formula 9]

In a nitrogen atmosphere, in a 30 ml Pyrex (registered trademark) glass test tube, 0.10 g (1.02 mmol) of maleic anhydride (MA), and 20 g of ethyl acetate (227 mmol, 200 wt. of maleic anhydride (MA)) ) Was injected, and stirred with a magnetic stirrer to dissolve. Then, stirring at 5-10 degreeC, a 100 W high-pressure mercury lamp was irradiated for 1 hour. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and the residual ratio of maleic anhydride (MA) was 72.4%. Further, 2 g of the reaction liquid in the reactor was collected, and the solvent was distilled off at 70-80 Torr with an evaporator. The obtained crude product was confirmed to be a mixture containing CBDA by ^{1 H NMR analysis.}

¹ H NMR (DMSO-d6, δ ppm) (CBDA): 3.87 (s, 4H).

Comparative Example 14

[Formula 10]

In a nitrogen atmosphere, in a 30 ml Pyrex (registered trademark) glass test tube, maleic anhydride (MA) 0.10 g (1.02 mmol), benzophenone (BP) 0.0186 g (0.102 mmol, maleic anhydride (MA)) mol%), and ethyl acetate 20 g (227 mmol, 200 wt times relative to maleic anhydride (MA)) were poured, followed by stirring with a magnetic stirrer to dissolve. Then, stirring at 5-10 degreeC, a 100 W high-pressure mercury lamp was irradiated for 1 hour. After irradiation, the reaction solution was quantitatively analyzed by gas chromatography, and the residual ratio of maleic anhydride (MA) was 80.3%. Further, 2 g of the reaction liquid in the reactor was collected, and the solvent was distilled off at 70-80 Torr with an evaporator. The obtained crude product was confirmed to be a mixture containing CBDA by ^{1 H NMR analysis.}

Comparative Examples 15 to 16, and Examples 21 to 27

A series of operations was carried out in the same manner as in Comparative Example 14, by adding 10 mol% of a sensitizer to maleic anhydride (MA). The types and results of the added sensitizer are shown in the table below. Further, the residual ratio and reaction rate of maleic anhydride in the obtained reaction solution were calculated.

It shows in Table 5 together with the results obtained in Comparative Examples 13 and 14. In addition, the reaction rate in the table was calculated from the number of moles of maleic anhydride used and the residual ratio of maleic anhydride at the time of reaction for 1 hour.

As is clear from Table 5, Examples 21 to 27 using benzophenone substituted with an electron withdrawing group were Comparative Examples 13 without using a sensitizer, Comparative Examples 14 and 15 using unsubstituted benzophenone or acetophenone, And it can be seen that the reaction rate is faster in all of Comparative Example 16 using benzophenone substituted with an electron donating group.

Industrial applicability

The cyclobutanetetracarboxylic acid derivative obtained in the present invention is a compound useful as a raw material such as polyimide, and the polyimide is a resin composition used in the field of displays such as televisions using liquid crystal panels, or in the field of semiconductors. Prize, it is used.

In addition, the entire contents of the Japanese Patent Application 2014-007184, the claims, the drawings, and the abstract for which it applied on January 17, 2014 are cited here, and taken in as an indication of the specification of the present invention.

Claims (12)

In the presence of a maleic anhydride compound represented by the following formula (1) in the presence of benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, or benzaldehyde substituted with an electron withdrawing group, A method for producing a 1,2,3,4-cyclobutanetetracarboxylic acid-1,2:3,4-2 anhydride derivative represented by formula (2), characterized by.

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) The method of claim 1,
R is a methyl group, the production method. The method of claim 1,
The production method, wherein R is a hydrogen atom. The method according to any one of claims 1 to 3,
The production method, wherein the electron withdrawing group is at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodine group, a nitro group, a cyano group, and a trifluoromethyl group. The method according to any one of claims 1 to 3,
The number of electron withdrawing groups is 1-5, and the manufacturing method. The method according to any one of claims 1 to 3,
The production method, wherein the benzophenone substituted by the electron withdrawing group, acetophenone substituted by the electron withdrawing group, or the benzaldehyde substituted by the electron withdrawing group is 0.1 to 20 mol% based on the maleic anhydride compound. The method according to any one of claims 1 to 3,
A production method, wherein a light dimerization reaction is performed in a reaction solvent. The method of claim 7,
The production method in which the reaction solvent is an ester of an organic carboxylic acid, an anhydride, or a carbonate ester. The method of claim 7,
The production method, wherein the reaction solvent is ethyl acetate or dimethyl carbonate. The method of claim 7,
A production method in which a reaction solvent is used in an amount of 3 to 300 times by mass based on the maleic anhydride compound. The method of claim 7,
The production method in which the amount of the reaction solvent used is 3 to 10 times the mass of the maleic anhydride compound. The method according to any one of claims 1 to 3,
The production method, wherein the reaction temperature is 0 to 20°C.

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