JP2011162449A - Method for producing biphenyltetracarboxylic acid tetraester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an improved economical method for producing an asymmetric biphenyltetracarboxylic acid tetraester. <P>SOLUTION: The method for producing an asymmetric biphenyltetracarboxylic acid tetraester as a main product, comprising oxidation-coupling a phthalic acid diester in the presence of a catalyst comprising at least a Pd salt and a copper salt in the presence of molecular oxygen, is characterized by comprising a process (process 1) for reacting a reaction mixture in a temperature range of ≥150°C and <200°C for at least ≥0.5 hr, and a process (process 2) for reacting the reaction mixture in a temperature range of ≥200°C for ≥1 hr. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  In the present invention, phthalic acid diester is oxidatively coupled with a catalyst containing palladium in the presence of molecular oxygen to form biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetra The present invention relates to a more economical production method for producing an asymmetric biphenyltetracarboxylic acid tetraester such as an ester as the main product.

  Phthalic acid diester is oxidatively coupled with a catalyst containing palladium in the presence of molecular oxygen to form an asymmetric 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetraester (hereinafter abbreviated as a-BPTT). There are already some examples of the production method for producing the main product.

  For example, Patent Document 1 discloses a production method for producing a-BPTT by causing an organic palladium salt and an organic copper salt to be present in a reaction solution in the presence of molecular oxygen and oxidatively coupling a phthalic acid diester. ing. Specifically, in Example 16, by reaction at 140 ° C. for 7 hours, 20.4 g of a-BPTT was obtained with respect to the usage amount of bisacetylacetonate palladium chelate salt of 3.0 mmol. Here, focusing on the catalyst rotation speed (hereinafter sometimes abbreviated as TON) represented by [product (mole number) / catalyst palladium (mole number)] with respect to the production of a-BPTT, TON is very low, about 18, and has a problem that it is economically disadvantageous because it consumes a large amount of expensive noble metal palladium.

In Patent Document 2, phthalic acid diester is oxidatively coupled using palladium salt and copper salt at high temperature in the presence of molecular oxygen while continuously or intermittently replenishing β-diketone to the reaction system. A method for producing a-BPTT is disclosed.
Here, it is disclosed in Example 1 that TON related to the generation of a-BPTT has been improved to about 129, but the utilization efficiency of palladium, which is an expensive noble metal, is not sufficient, and further improvement is possible. There was room.

JP 55-141417 A JP 61-106541 A

  The object of the present invention is to oxidatively couple a phthalic acid diester using a catalyst containing palladium in the presence of molecular oxygen to produce a biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetra. It is to provide an improved and economical process for producing asymmetric biphenyltetracarboxylic acid tetraesters such as carboxylic acid tetraesters as the main product.

That is, the present invention relates to the following items.
(1) A method for producing an asymmetric biphenyltetracarboxylic acid tetraester as a main product by oxidatively coupling a phthalic acid diester using a catalyst comprising at least a palladium salt and a copper salt in the presence of molecular oxygen, A step of reacting the reaction mixture by maintaining it in a temperature range of 150 ° C. or more and less than 200 ° C. for at least 0.5 hour or more (Step 1), and then a step of reacting the reaction mixture by maintaining in a temperature region of 200 ° C. or more for 1 hour or more (Process 2) is comprised, The manufacturing method of the biphenyl tetracarboxylic acid tetraester characterized by the above-mentioned.
(2) The method for producing a biphenyltetracarboxylic acid tetraester as described in (1) above, wherein the β-dicarbonyl compound is intermittently or continuously supplied to the reaction mixture.
(3) The biphenyltetracarboxylic acid as described in (2) above, wherein the β-dicarbonyl compound is intermittently or continuously supplied to the reaction mixture in a temperature range where the reaction mixture is 130 ° C. or higher. Method for producing tetraester.
(4) The β-dicarbonyl compound is acetylacetone or 2,2,6,6-tetramethyl-3,5-heptanedione, as described in (2) or (3) above A method for producing biphenyltetracarboxylic acid tetraester.

  According to the present invention, a phthalic acid diester is oxidatively coupled with a catalyst containing palladium in the presence of molecular oxygen to form a biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetracarboxylic acid. It is possible to provide a more economical production method for producing an asymmetric biphenyltetracarboxylic acid tetraester such as a tetraester as a main product.

3 is a diagram schematically showing a reaction apparatus used in Example 3. FIG.

Hereinafter, the present invention will be described in detail.
Preferred examples of the phthalic acid diester that can be used in the present invention include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, and diphenyl phthalate. be able to. These phthalic acid diesters can be easily obtained by reacting phthalic acid, phthalic anhydride, phthalic acid halide, and the like with a compound having a hydroxyl group, such as lower aliphatic alcohols, aromatic alcohols, and phenols. it can.

  Examples of the palladium salt used as a catalyst in the present invention include palladium chloride, palladium bromide, palladium nitrate, palladium sulfate, palladium hydroxide, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium pivalate, trifluoromethanesulfonic acid. Specific examples include palladium, bis (acetylacetonato) palladium, and bis (1,1,1-5,5,5-hexafluoroacetylacetonato) palladium. In particular, palladium acetate, palladium propionate, palladium pivalate, palladium trifluoroacetate, palladium hydroxide, and palladium nitrate are preferable because they exhibit high catalytic activity.

The amount of the palladium salt used is 1 × 10 ⁻⁵ to 1 × 10 ⁻² times mol, preferably 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ times mol, with respect to 1 mol of phthalic acid diester as a reaction raw material. The amount is preferably 8 × 10 ^{−5 to} 3 × 10 ⁻⁴ times mol, more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻⁴ times mol. If palladium is used in an amount greater than the specified range, the TON improvement effect may not be sufficient. On the other hand, if less palladium is used than this specified range, the yield of product per reaction batch may be low and impractical.

  Examples of the copper salt used as a catalyst in the present invention include copper acetate, copper propionate, copper normal butyrate, copper 2-methylpropionate, copper pivalate, copper lactate, copper butyrate, copper benzoate, and copper trifluoroacetate. Bis (acetylacetonato) copper, bis (1,1,1-5,5,5-hexafluoroacetylacetonato) copper, copper chloride, copper bromide, copper iodide, copper nitrate, copper nitrite, sulfuric acid Specific examples include copper, copper phosphate, copper oxide, copper hydroxide, copper trifluoromethanesulfonate, copper paratoluenesulfonate, and copper cyanide. In particular, copper acetate, copper propionate, normal butyrate, copper pivalate, and bis (acetylacetonato) copper are preferable because they have a high effect of promoting the oxidative coupling reaction. These copper salts can be suitably used in the form of anhydrides or hydrates.

  The amount of the copper salt used is preferably 1 to 10 times mol, more preferably 3 to 8 times mol, and still more preferably 4 to 6 times mol based on the palladium salt.

  The β-dicarbonyl compound preferably used in the present invention may be either an aliphatic or aromatic β-dicarbonyl compound. Specific examples include acetylacetone, benzoylacetone, trifluoroacetylacetone, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, 1,3-diphenyl-1,3-propanedione, 1, 1,3-diketones such as 1,1-trifluoro-2,4-hexanedione, acylacetates such as methyl acetoacetate, ethyl acetoacetate and methyl 3-oxovalerate, alcoylacetic acid such as ethyl benzoylacetate Preferable examples include esters, malonic acid esters such as diethyl malonate and Meldrum's acid. Among these, 1,3-diketones are preferable.

  The reaction of the present invention is carried out in the presence of molecular oxygen. The molecular oxygen may be pure oxygen gas, but considering the risk of explosion, the oxygen content is diluted to about 5% to 50% by volume with an inert gas such as nitrogen gas or carbon dioxide. A mixed gas or air can be suitably used. Specific supply methods include, for example, a method in which a molecular oxygen-containing gas is circulated along the liquid surface of the reaction mixture and brought into gas-liquid contact, and the gas is ejected from a nozzle provided at the top of the reaction mixture. A method of blowing, a method of supplying the gas in the form of bubbles from a nozzle provided at the bottom of the reaction mixture, and causing the bubbles to flow into the reaction mixture and bringing them into gas-liquid contact, from a perforated plate provided at the bottom of the reaction mixture Preferred examples include a method of supplying the gas in the form of bubbles, or a method in which the reaction mixture is flowed into the conduit and the gas is ejected into the reaction mixture from the side of the conduit. The supply amount varies depending on the type and supply method. For example, when air is used, it is uniform in the reaction mixture at a supply rate of about 1 to 20000 ml / min, particularly 10 to 10000 ml / min per 1000 ml of the reaction solution. It is preferable to supply so that it may spread.

  In the present invention, a reaction solvent may be used, but may not be used when the reaction raw material is liquid under the reaction conditions. Industrially, it is preferable to use substantially no reaction solvent. In the case of using a reaction solvent, for example, organic ester compounds such as ethylene glycol diacetate and dimethyl adipate, and ketone compounds such as n-butyl methyl ketone, methyl ethyl ketone, and isopropyl ethyl ketone can be preferably exemplified.

  The first feature of the production method of the present invention is that a catalyst composed of at least a palladium salt and a copper salt is used in the presence of molecular oxygen to oxidatively couple a phthalic acid diester, and the main product is an asymmetric biphenyltetracarboxylic acid tetrachloride. In the method for producing an ester, when the reaction mixture is heated to carry out an oxidative coupling reaction, the step (1), that is, the reaction mixture is maintained in a temperature range of 150 ° C. or higher and lower than 200 ° C. for at least 0.5 hour or longer. And then the step (2), that is, the step of reacting the reaction mixture while maintaining the reaction mixture in a temperature range of 200 ° C. or higher for 1 hour or longer. That is, in the present invention, before the step (2), which is the main reaction step in which the reaction mixture is kept in the temperature region of 200 ° C. or higher for 1 hour or more and reacted, the reaction mixture is heated to a temperature region of 150 ° C. or higher and lower than 200 ° C. The step (1) of reacting by holding for 0.5 hour or longer is performed. By performing this step (1), it can be estimated that the active species of the catalyst is sufficiently generated in the reaction mixture, but as a result, the reaction efficiency in step (2) which is the main reaction step is improved. As a whole reaction step, the catalyst rotation speed (TON) related to the production of a-BPTT can be remarkably improved.

  In the present invention, the reaction mixture may be reacted at a high temperature of 200 ° C. or higher directly without passing through the step (1) in which the reaction mixture is kept in a temperature range of 150 ° C. or higher and lower than 200 ° C. for at least 0.5 hour. If the time of (1) is too short or the temperature of step (1) is too low, the precursor is exposed to a high temperature of 200 ° C. or more without sufficiently producing active species of the catalyst in the reaction mixture. In the process (2), which is the main reaction process thereafter, it is difficult to increase the reaction efficiency. The reaction temperature region in step (1) is 150 ° C. or higher and lower than 200 ° C., and more preferably 150 ° C. to 190 ° C.

  In the present invention, the reaction temperature region in the step (2) in which the reaction mixture is allowed to react for 1 hour or more in a temperature region of 200 ° C. or higher is preferably 200 to 250 ° C., more preferably 200 to 240 ° C. If the reaction temperature is too low, the reaction rate is slow even when the generation of active species is sufficient, and it is difficult to increase the reaction efficiency. On the other hand, if the reaction temperature is too high, the catalyst is deactivated.

In the present invention, the reaction time is not limited as long as the conditions of the step (1) and the step (2) are satisfied, and may be appropriately determined. Usually, the entire reaction time is 1.5 to 30 hours, preferably 5 to 5 hours. It is about 20 hours, more preferably about 5 to 10 hours. Of these, the time for maintaining in the temperature range of 150 ° C. or more and less than 200 ° C. in step (1) is 0.5 hour or more, preferably 1 hour or more, more preferably 2 hours or more, preferably the entire reaction time. 70% or less, more preferably 60% or less, and still more preferably 40% or less. If the time for holding in the temperature range of 150 ° C. or higher and lower than 200 ° C. is too short, the generation of the active species of the catalyst is not sufficient, and it becomes difficult to increase the reaction efficiency in the subsequent step (2). The time for maintaining the temperature in the temperature range of 150 ° C. or more and less than 200 ° C. may be long, but performing the reaction for a long time in a temperature region where the reaction rate is relatively low leads to a decrease in reaction efficiency as a whole reaction time. It might be. For this reason, it is usually 20 hours or less, preferably 10 hours or less, more preferably 5 hours or less.
Here, the reaction time is a time during which the reaction mixture is in a temperature range of 150 ° C. or higher and the reaction is considered to occur substantially. Although it does not react even if it is less than 150 ° C., it is not included in the reaction time because the reaction rate is extremely low.

  In the present invention, the method of controlling the temperature of the reaction mixture after the start of the reaction is not particularly limited as long as the conditions of step (1) and step (2) are satisfied. That is, the temperature may be raised after being held at a certain temperature for a certain time, and the subsequent reaction may be carried out at a certain temperature, or the temperature of the reaction mixture may be continuously increased by heating or cooling gradually. You may go while lowering.

In carrying out the present invention industrially, it is not limited by the reaction method, and can be carried out either batchwise or continuously. When the reaction is carried out continuously, a reaction apparatus in which a plurality of reaction tanks are connected in series is used, the temperature of the first tank is set in the temperature range of step (1), and the temperature of the reaction tanks after the second tank is set. Set the temperature higher than the first tank to the temperature range of step (2), or use a multistage blade tank reactor or tube reactor, and change the temperature of the inlet of the raw material mixture to the temperature range of step (1) It is preferable to set the temperature on the outlet side to be higher than that on the inlet side and set the temperature range in the step (2) in order to heat the reaction mixture stepwise in the steady operation state.
The reaction apparatus used in the present invention is not particularly limited as long as it has a heating function, a stirring function, a gas supply / discharge function, and the like, and a conventionally known reaction apparatus can be suitably used. Absent.

A further feature of the production process of the present invention is that during the production, the β-dicarbonyl compound is preferably fed intermittently or continuously to the reaction mixture.
Here, “intermittent or continuous” means intermittent supply or continuous supply across a supply stop period of a predetermined interval. That is, the present invention relates to a method for producing a biphenyltetracarboxylic acid tetraester in which a phthalic acid ester is oxidatively coupled using a catalyst comprising at least a palladium salt, a copper salt, and a β-dicarbonyl compound in the presence of molecular oxygen. During the oxidative coupling reaction, a β-dicarbonyl compound is supplied to the reaction mixture preferably in less than 30 minutes, more preferably in less than 10 minutes (intermittent supply) to 0 minute (continuous supply). And
When the supply interval of β-dicarbonyl compound (supply stop period) is 30 minutes or more, it becomes difficult to suppress the consumption of palladium, which is an expensive noble metal, and [product (number of moles) / catalyst palladium ( The TON indicated by the number of moles)] may become low and it may be difficult to obtain a more economical production method.

Further, the β-dicarbonyl compound is preferably supplied to the reaction mixture intermittently or continuously at a temperature of the reaction mixture of 130 ° C. or higher. In order to start the reaction, the temperature of the reaction mixture is increased. At this time, if the supply is started in a state where the temperature of the reaction mixture is low, the β-dicarbonyl compound does not evaporate or decompose. -It is not preferable because a dicarbonyl compound is likely to be present, which becomes a reaction inhibiting factor. In particular, supplying the palladium salt together with a palladium salt at a temperature of less than 130 ° C. at the start of the reaction and then heating to a high temperature to start the reaction may lead to deactivation of the catalyst.
Accordingly, in the present invention, the supply start temperature of the β-dicarbonyl compound is such that the temperature of the reaction mixture is 130 ° C. or higher, preferably 140 ° C. or higher, more preferably 150 ° C. or higher.

The supply amount of the β-dicarbonyl compound needs to be determined appropriately in consideration of the influence of the pressure during the reaction, the reaction temperature, etc., but is usually 0.1 to 50 times per hour with respect to the palladium salt used. It is suitable to supply intermittently or continuously at a mole ratio, preferably 1 to 10 moles, more preferably 2 to 9 moles, and even more preferably 3 to 8 moles.
The state and form of the β-dicarbonyl compound at the time of supply are not particularly limited. If the β-dicarbonyl compound is a liquid, it may be supplied intermittently or continuously by a liquid feed pump or the like. The liquid feed pump may be a solution in which the β-dicarbonyl compound is dissolved in, for example, a phthalate ester as a reaction raw material. It may be supplied intermittently or continuously to the reaction system.

  In the production method of the present invention, the reaction pressure is not particularly limited. If the catalyst, molecular oxygen, and β-dicarbonyl compound can stay in the reaction system within a predetermined concentration range, any conditions of reduced pressure, normal pressure, and increased pressure are used. But it doesn't matter. Usually, normal pressure is preferred because facilities and operations become simple.

  Next, the manufacturing method of this invention is demonstrated using an Example etc. In addition, this invention is not limited to a following example.

  In the following examples, dimethyl phthalate (hereinafter sometimes abbreviated as DMP) is used as a reaction raw material, and biphenyltetracarboxylic acid tetramethyl ester (hereinafter abbreviated as BPTT), which is a product of an oxidative coupling reaction. Sometimes manufactured). Here, 3,4,3 ′, 4′-biphenyltetracarboxylic acid tetramethyl ester (hereinafter sometimes abbreviated as s-BPTT) which is an isomer in the oxidative coupling reaction product, Production ratio of 3 ′, 4′-biphenyltetracarboxylic acid tetramethyl ester (hereinafter also abbreviated as a-BPTT) (hereinafter also abbreviated as S / A), and main product The catalyst rotation speed for a certain a-BPTT (hereinafter also abbreviated as TON) was calculated according to the following calculation formula.

[Example 1]
Using an SUS reactor having an internal volume of 0.5 liter equipped with a stirrer and an air supply conduit, an oxidative coupling reaction was performed as follows.
After adding 2.40 mol of dimethyl phthalate, 0.36 mmol of palladium acetate and 2.0 mmol of acetylacetone copper to the reactor, air was bubbled through the reaction mixture at 260 ml / min, and at a rotational speed of 400 rpm. The reaction mixture was heated to 165 ° C. at a rate of temperature increase of about 2 ° C./min while rotating the stirrer and stirring. The oxidative coupling reaction was carried out at a temperature of 165 ° C. until 3 hours after reaching 165 ° C. Thereafter, the reaction solution was heated to 200 ° C. at a rate of temperature increase of about 1 ° C./min, and reacted at a temperature of 200 ° C. until 3 hours after reaching 200 ° C. Further, the reaction solution was heated to 235 ° C. at a rate of temperature increase of about 2 ° C./min, and the reaction was performed at a temperature of 235 ° C. until 1 hour after reaching 235 ° C. The reaction time was about 8 hours.
The reaction mixture was sampled, diluted with 10 mM Na phosphate buffer solution and acetonitrile, and each product was quantified by high performance liquid chromatography (hereinafter sometimes abbreviated as HPLC).
The results are shown in Table 1. The TON was 176.

[Comparative Example 1]
Using an SUS reactor having an internal volume of 0.5 liter equipped with a stirrer and an air supply conduit, an oxidative coupling reaction was performed as follows.
After adding 2.40 mol of dimethyl phthalate, 0.36 mmol of palladium acetate and 2.0 mmol of acetylacetone copper to the reactor, air was bubbled through the reaction mixture at 260 ml / min, and at a rotational speed of 400 rpm. While rotating the stirrer and stirring, the reaction mixture was heated to 165 ° C. at a temperature increase rate of about 2.5 ° C./min, and an oxidative coupling reaction was performed at a temperature of 165 ° C. The reaction time was about 8 hours.
The reaction mixture was sampled, diluted with 10 mM Na phosphate buffer solution and acetonitrile, and each product was quantified by high performance liquid chromatography.
The results are shown in Table 1. The TON was 81.

[Comparative Example 2]
The same operation as in Comparative Example 1 was performed except that the oxidative coupling reaction was performed at a constant temperature of 200 ° C. and the reaction time was about 6 hours.
The results are shown in Table 1. The TON was 73.

[Comparative Example 3]
The same operation as in Comparative Example 1 was performed except that the oxidative coupling reaction was performed at a constant temperature of 235 ° C.
The results are shown in Table 1. The TON was 40.

[Comparative Example 4]
The same operation as in Example 1 was performed except that the reaction temperature at 165 ° C was 140 ° C and the reaction time at 200 ° C was extended from 3 hours to 4 hours.
The results are shown in Table 1. The TON was 87.

[Example 2]
Using an SUS reactor having an internal volume of 0.5 liter equipped with a stirrer and an air supply conduit, an oxidative coupling reaction was performed as follows.
After adding 2.40 mol of dimethyl phthalate, 0.36 mmol of palladium acetate and 2.0 mmol of acetylacetone copper to the reactor, air was bubbled through the reaction mixture at 260 ml / min, and at a rotational speed of 400 rpm. The reaction mixture was heated to 185 ° C. at a rate of temperature increase of about 2 ° C./min while rotating the stirrer and stirring. From this point, a DMP solution (acacH concentration: 3.0 wt%) of acetylacetone (hereinafter sometimes abbreviated as acacH) was continuously fed to the reaction mixture at about 0.1 ml / min. The oxidative coupling reaction is performed at a temperature of 185 ° C. until 2 hours after reaching 185 ° C., and then the reaction solution is heated to 200 ° C. at a rate of temperature increase of about 1 ° C./min. The reaction was carried out at a temperature of ° C. At this time, the feeding of the DMP solution of acetylacetone was stopped, and then the reaction solution was heated to 235 ° C. at a rate of temperature increase of about 2 ° C./min, and the reaction was performed at a temperature of 235 ° C. until 2 hours after reaching 235 ° C. . The reaction time was about 9 hours. The final supply amount of acetylacetone was 13.2 mmol and the supply amount of DMP was 0.18 mol.
The reaction mixture was sampled, diluted with 10 mM Na phosphate buffer solution and acetonitrile, and each product was quantified by high performance liquid chromatography.
The results are shown in Table 1. The TON was 348.

[Comparative Example 5]
The scale of the reaction was tripled, the oxidative coupling reaction was performed at a constant temperature of 185 ° C., and a solution of 30 mmol of acetylacetone dissolved in 200 ml of DMP from the time of reaching 185 ° C. to the end of the reaction was about 0 The same operation as in Example 2 was performed except that the reaction mixture was continuously supplied at 1 ml / min. The reaction time was about 8.5 hours. The final supply amount of acetylacetone was 7.4 mmol, and the supply amount of DMP was 0.30 mol.
The results are shown in Table 1. The TON was 281.

[Comparative Example 6]
The oxidative coupling reaction was performed at a constant temperature of 200 ° C., and the DMP solution of acetylacetone (acacH concentration 3.0 wt%) was continuously added to the reaction mixture at about 0.1 ml / min from the time when the temperature reached 200 ° C. until the end of the reaction. The same operation as in Example 2 was carried out except that it was supplied. The reaction time was about 8.5 hours. The final supply amount of acetylacetone was 17.0 mmol, and the supply amount of DMP was 0.23 mol.
The results are shown in Table 1. The TON was 137.

Example 3
As shown in FIG. 1, a raw material supply line, a gas phase part extraction line, an air supply line, and an additional additive solution supply line are provided, and when the amount of liquid in the reaction zone reaches a certain level, A coupling reaction was performed in the following manner using a reaction apparatus in which two glass reactors each having a liquid phase extraction line installed at a predetermined position inside the reactor so as to be extracted by its own weight. The internal volume of the first reactor is 100 milliliters, and the internal volume of the second reactor is 50 milliliters, and the reaction mixture extracted from the first reactor is introduced into the second reactor. The
0.613 mol of dimethyl phthalate, 0.09 mmol of palladium acetate and 0.50 mmol of acetylacetone copper were added to the first reactor, and 0.306 mmol of DMP, 0.045 mmol of palladium acetate and 0.25 mmol of acetylacetone copper were added to the first reactor. The reactor No. 2 was charged and air circulation was started at a supply rate of 100 ml / min while stirring with a rotor, and then the temperature was raised to 185 ° C. at a rate of about 2 ° C./min. After reacting at 185 ° C. for 30 minutes, a raw material mixture consisting of 0.09 mmol of palladium acetate, 0.50 mmol of acetylacetone copper and 1.6 mmol of acetylacetone was added to 0.613 mol of DMP in the first reactor. Feeding started at 42 ml / min. At the same time, an additive mixture composed of 3.0 mmol of acetylacetone relative to 0.0613 mol of DMP was started to be fed to the second reactor at about 0.01 ml / min. Further, only the second reactor was heated from 185 ° C. to 215 ° C. at a rate of about 1 ° C./min. Along with the supply of the reaction mixture, the reaction mixture is withdrawn from the liquid phase part extraction line due to overflow, the amount of the reaction mixture in the first reaction zone is always 100 ml, and the amount of the reaction mixture in the second reaction zone is Always kept at 50 ml. Thereafter, while maintaining the temperature inside the first reactor at 185 ° C. and the temperature inside the second reactor at 235 ° C., the supply of the raw material mixture and the additive mixture was continued to carry out the reaction. The average residence time of the reaction mixture in the first reaction zone was about 4 hours and the average residence time in the second reaction zone was about 2 hours, for a total of about 6 hours.
After 15 hours, the reaction mixture was sampled, diluted with 10 mM Na phosphate buffer solution and acetonitrile, and the concentration of each component of the reaction mixture was determined by high performance liquid chromatography (hereinafter sometimes abbreviated as HPLC). did. Based on the result, TON of the product a-BPTT was calculated.
The results are shown in Table 2. The TON was 145.

  According to the present invention, a phthalic acid diester is oxidatively coupled with a catalyst containing palladium in the presence of molecular oxygen to form a biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetracarboxylic acid. It is possible to provide a more economical production method for producing an asymmetric biphenyltetracarboxylic acid tetraester such as a tetraester as a main product.

1: Raw material supply line 2 (2-1, 2-2): Reaction zone 3: Stirrer 4: Gas phase part extraction line 5: Liquid phase part extraction line 6: Air supply line 7: Additional added solution supply line

Claims (4)

  A method for producing an asymmetric biphenyltetracarboxylic acid tetraester as a main product by oxidatively coupling a phthalic acid diester using a catalyst comprising at least a palladium salt and a copper salt in the presence of molecular oxygen, comprising: A step of maintaining and reacting at a temperature range of 150 ° C. or more and less than 200 ° C. for at least 0.5 hours (step 1), and a step of reacting the reaction mixture while maintaining the reaction mixture at a temperature range of 200 ° C. or more for 1 hour or more (step 2) ), And a process for producing a biphenyltetracarboxylic acid tetraester.   The method for producing a biphenyltetracarboxylic acid tetraester according to claim 1, wherein the β-dicarbonyl compound is intermittently or continuously supplied to the reaction mixture.   The production of biphenyltetracarboxylic acid tetraester according to claim 2, wherein the β-dicarbonyl compound is intermittently or continuously supplied to the reaction mixture in a temperature range of 130 ° C or higher in the reaction mixture. Method.   The biphenyltetracarboxylic acid tetraester according to claim 2 or 3, wherein the β-dicarbonyl compound is acetylacetone or 2,2,6,6-tetramethyl-3,5-heptanedione. Manufacturing method.

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