TWI767955B - Method for producing alyclic tetracaeboxylic dianhydride - Google Patents

Abstract

The present invention relates to a method for producing an acid dianhydride in which at least one of the following two operations (A) and (B) is performed when reacting an olefin compound with carbon monoxide. (A) After mixing a palladium compound, a copper compound and an alcohol compound in a reaction vessel, the substitution operation (C-2) described below and the stirring operation (C-1) described below are performed in that order, and the resulting product is mixed with the olefin compound. (B) After mixing a palladium compound, a copper compound, an alcohol compound and an orthoester compound in a reaction vessel, the substitution operation (C-2) described below is performed, and the resulting product is mixed with the olefin compound. (C-1) Stirring is performed under a carbon monoxide atmosphere. (C-2) After reducing the pressure inside the reaction vessel, an operation of introducingcarbon monoxide gas is performed at least once.

Description

The production method of alicyclic tetracarboxylic dianhydride

The present invention relates to a method for producing an alicyclic tetracarboxylic dianhydride and a method for producing an ester compound which is an intermediate thereof. Among them, alicyclic tetracarboxylic dianhydrides are useful compounds as monomers for the production of polyimide.

Alicyclic carbonyl compounds are conventionally used in various fields, and alicyclic tetracarboxylic dianhydrides are useful compounds as monomers for producing polyimide. Among them, (3aR,4R,5R,5aR,8aS,9S,10S,10aS)-decahydro-1H,3H-4,10:5,9-dimethylnaphtho[2,3-c:6,7 -c']difuran-1,3,6,8-tetraone (hereinafter sometimes referred to as DNDA) is one of useful compounds. A method for producing DNDA, for example, (1R,4S,5S,8R)-1,4,4a,5,8,8a-hexahydro-1, which is obtained from norbornadiene and cyclopentadiene, is known. 4: 5,8-Dimethylnaphthalene (hereinafter also referred to as BNDE) reacts with carbon monoxide in the presence of palladium catalyst to form (1R,2R,3S,4S,5S,6S,7R,8R)-decahydro- After 1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid tetramethyl ester (hereinafter sometimes referred to as DNME), it is subjected to anhydrous reaction in the presence of acid to obtain A method of producing DNDA (for example, refer to Patent Documents 1 and 2, and Non-Patent Document 1).

In Patent Document 1, a method for producing DNDA and a polyimide using DNDA are reported. For the production method of DNDA, specifically, BNDE, methanol, palladium carbon, and copper chloride are put into a reaction vessel, and then reacted with carbon monoxide to obtain DNME as an ester compound, and hydrochloric acid is used to prepare a tetracarboxylic acid compound , followed by cyclization with acetic anhydride.

Patent Document 2 describes a method for producing a carboxylic acid anhydride from a carboxylate compound. Specifically, DNDA is produced by reacting the ester compound DNME in acetic acid in the presence of an acid such as an ion exchange resin and p-toluenesulfonic acid. In this reaction, since DNDA was obtained as a solid, acetic acid was distilled off under reduced pressure, and the precipitate was filtered.

Non-Patent Document 1 reports that DNDA and diamine are reacted to synthesize a soluble and transparent polyimide. For the production method of DNDA, cyclopentadiene and norbornadiene are reacted under heating to obtain BNDE, then BNDE, methanol, palladium carbon, and copper chloride are charged, and they are reacted with carbon monoxide to obtain ester compound DNME, Then, in the presence of an acid (p-toluenesulfonic acid), the transesterification reaction is carried out in formic acid, and the dehydration reaction (cyclization reaction) is carried out in acetic anhydride. The obtained DNDA was crystallized from acetic anhydride, but there is no description of its purity. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-235842 [Patent Document 2] Japanese Patent Application Laid-Open No. 5-140141 [Non-Patent Document]

[Non-Patent Document 1] Macromolecules 1994, 27, 1117

(Problems to be Solved by the Invention) Regarding Patent Document 1, the inventors of the present application repeated the experiment, and as a result, BNDE was insoluble in methanol, so the reaction was not reproducible and the yield was very low. Moreover, as a result of retesting the production method of Patent Document 2, acetic anhydride remained in DNDA, and it was found out that it is not suitable as a production method of an acid dianhydride used in the synthesis of polyimide. Furthermore, the same crystallization method as in Non-Patent Document 1 was carried out. As a result, acetic anhydride and acetic acid remained in DNDA in several wt %. Since acetic anhydride reacts with diamine, it was found that this crystallization method is not suitable as a method for producing an acid dianhydride for synthesizing polyimide.

As described above, any of the above-mentioned methods has low yields, and the purity of each compound is unknown, and is not a satisfactory industrial method for producing monomers for polymer production such as polyimide.

From the above, an object of the present invention is to provide an industrially suitable production of alicyclic tetracarboxylic dianhydride, which can produce alicyclic tetracarboxylic dianhydride or ester compounds such as DNDA with high yield and high purity by a simple method under mild conditions. or ester compound method. Moreover, alicyclic tetracarboxylic dianhydrides and ester compounds suitable as monomers for polymer production, such as polyimide, are provided. (the way to solve the problem)

The present invention relates to the following matters.

1. a manufacture method of alicyclic tetracarboxylic dianhydride, comprising the following steps: Step 1, the norbornadiene represented by the following formula (1) is reacted with the cyclopentadiene represented by the following formula (2) to obtain the following: The olefin compound represented by the formula (3); Step 2, in the presence of a palladium compound and a copper compound, the olefin compound represented by the formula (3), the alcohol compound, and carbon monoxide are reacted to obtain an ester compound represented by the following formula (4) and step 3, the ester compound represented by the formula (4) is reacted in an organic solvent in the presence of an acid to obtain an alicyclic tetracarboxylic dianhydride represented by the following formula (5); In step 2, the following 2 At least one of the operations (A) and (B); (A) After mixing the palladium compound, the copper compound, and the alcohol compound in the reaction vessel, the following (C-2) substitution operations and the following ( C-1) Stirring operation to mix with the olefin compound represented by the formula (3); (B) After mixing a palladium compound, a copper compound, an alcohol compound, and an orthoester compound in a reaction vessel, the following (C) -2) The substitution operation is carried out to mix it with the olefin compound represented by the formula (3); (C-1) Stirring in a carbon monoxide gas atmosphere; (C-2) The reaction vessel is depressurized and then sealed with carbon monoxide gas operation more than once;

【Change 1】

【Change 2】

【Change 3】

式中，R表示碳數1~10之烷基；【Chemical 4】

In the formula, R represents an alkyl group with 1 to 10 carbon atoms;

。【Chemical 5】

.

2. The production method of the acid dianhydride according to 1., wherein, in the step 2, in the olefin compound represented by the formula (3) used, the content of the compound represented by the following formula (6) is 50-99% by weight;

。【Chemical 6】

.

3. The production method of the acid dianhydride according to 1. or 2., wherein, in the operations (A) and (B) of this step 2, when mixing with an olefin compound, it is for a compound containing a palladium compound, a copper compound, and an alcohol. The olefin compound represented by the formula (3) is added dropwise to the mixture of the compounds or to the mixture containing the palladium compound, the copper compound, the alcohol compound, and the orthoester compound.

4. A method for producing an ester compound, comprising in the presence of a palladium compound and a copper compound, reacting an olefin compound, an alcohol compound and carbon monoxide represented by the following general formula (7) to obtain an ester represented by the following general formula (7-1) The compound step, in which at least one of the following two operations (A) and (B) is performed: (A) After mixing the palladium compound, the copper compound, and the alcohol compound in the reaction vessel, the following ( The substitution operation of C-2) and the stirring operation of the following (C-1) are mixed with the olefin compound; (B) After mixing the palladium compound, the copper compound, the alcohol compound, and the orthoester compound in the reaction vessel , implement the substitution operation of the following (C-2) to mix it with the olefin compound; (C-1) stir in a gaseous environment of carbon monoxide; (C-2) implement a process of decompressing the reaction vessel and encapsulating the carbon monoxide gas operate more than 1 time;

式中，R¹ 為碳數1~15之烷基、或碳數1~15之烯基；3個R¹ 可彼此相同也可不同，也可2個以上之R¹ 互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；烷基上之氫原子也可取代為碳數1~5之烯基、-COOR^a 表示之酯基、碳數6~15之芳基、-OR^b 表示之烷氧基、氰基、或-OSO₂ R^c 表示之基，烷基中之碳原子也可形成羰基；此芳基上之氫原子也可取代為苯基、碳數1~10之烷基、或碳數1~10之烯基；又，R^a 、R^b 、R^c 各為碳數1~10之烷基、或碳數6~10之芳基；【Chemical 7】

In the formula, R ¹ is an alkyl group with 1 to 15 carbon atoms, or an alkenyl group with a carbon number of 1 to 15; 3 R ¹ can be the same or different from each other, or two or more R ¹ can be bonded to each other and combined with them. The bonded carbon atoms together form one or more rings; the hydrogen atom on the alkyl group can also be substituted with an alkenyl group with 1 to 5 carbon atoms, an ester group represented by -COOR ^a , and an aryl group with 6 to 15 carbon atoms. , -OR ^b represents the alkoxy group, cyano group, or -OSO ₂ R ^c represents the group, the carbon atom in the alkyl group can also form a carbonyl group; the hydrogen atom on the aryl group can also be substituted with phenyl, carbon number 1-10 alkyl group, or carbon number 1-10 alkenyl group; and, R ^a , R ^b , R ^c are each carbon number 1-10 alkyl group, or carbon number 6-10 aryl group;

式中，R¹ 同前述意義，R表示碳數1~10之烷基。【Chemical 8】

In the formula, R ¹ has the same meaning as above, and R represents an alkyl group having 1 to 10 carbon atoms.

5. The production method of the ester compound according to 4., wherein, in the operations (A) and (B), when mixing with the olefin compound, it is for a mixture containing a palladium compound, a copper compound, and an alcohol compound, or for a mixture containing a palladium compound, a copper compound, and an alcohol compound. The olefin compound is added dropwise to a mixture of a palladium compound, a copper compound, an alcohol compound, and an orthoester compound.

6. The production method of the ester compound according to 4. or 5., wherein the olefin compound and the ester compound are each of the following formulae (8) and (8-1), the following formulae (9) and (9-1), the following Formulas (10) and (10-1), the following formulae (11) and (11-1), the following formulae (11-2) and (11-3), the following formulae (12) and (12-1), the following formulae Formulas (13) and (13-1), the following formulae (14) and (14-1), the following formulae (15) and (15-1), the following formulae (16) and (16-1), or the following formulae The compound represented by any one of (17) and (17-1);

式中，R² 為氫原子、碳數1~10之烷基、-COOR^d 表示之酯基、或氰基；烷基上之氫原子也可取代為-COOR^a 表示之酯基、或碳數6~10之芳基；2個R² 可彼此相同也可不同，也可互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；酯基中之R^d 及R^a 表示碳數1~10之烷基、或碳數6~10之芳基；式中，R表示碳數1~10之烷基；【Chemical 9】

In the formula, R ² is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an ester group represented by -COOR ^d , or a cyano group; the hydrogen atom on the alkyl group can also be substituted with an ester group represented by -COOR ^a , or a carbon group. Aryl groups of 6 to 10; 2 R ² can be the same or different from each other, or can be bonded to each other and form 1 or more rings together with the carbon atoms to which they are bonded; R ^d and R in the ester group ^a represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R³ 表示氫原子、碳數1~10之烷基、氰基、或-COOR^d 表示之酯基；烷基上之氫原子也可以取代為-COOR^a 表示之酯基、或碳數6~10之芳基；2個R³ 可彼此相同也可不同，也可以互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；酯基中之R^d 及R^a 表示碳數1~10之烷基、或碳數6~10之芳基；式中，R表示碳數1~10之烷基；【Chemical 10】

In the formula, R ³ represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cyano group, or an ester group represented by -COOR ^d ; the hydrogen atom on the alkyl group can also be substituted with an ester group represented by -COOR ^a , or a carbon Aryl groups of 6 to 10; 2 R ³ can be the same or different from each other, or can be bonded to each other and form 1 or more rings together with the carbon atoms to which they are bonded; R ^d and R in the ester group ^a represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R⁴ 表示氫原子、或碳數1~10之烷基；2個R⁴ 可彼此相同也可不同，也可互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；式中，R表示碳數1~10之烷基；【Chemical 11】

In the formula, R ⁴ represents a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms; two R ⁴ can be the same or different from each other, and can also be bonded to each other and form one or more carbon atoms together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R⁵ 表示氫原子、碳數1~10之烷基、-OR^b 表示之烷氧基、或-OSO₂ R^c 表示之基；R^b 表示碳數1~10之烷基、或碳數6~10之芳基，R^c 表示碳數1~10之烷基、或碳數6~10之芳基；2個R⁵ 可彼此相同也可不同，也可互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；式中，R表示碳數1~10之烷基；【Chemical 12】

In the formula, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group represented by -OR ^b , or a group represented by -OSO ₂ R ^c ; R ^b represents an alkyl group having 1 to 10 carbon atoms, or Aryl with carbon number 6~10, R ^c represents alkyl group with carbon number 1~10, or aryl group with carbon number 6~10; 2 R ⁵ can be the same or different from each other, or can be bonded to each other and combined with them The bonded carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R表示碳數1~10之烷基；【Chemical 13】

In the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R⁶ 表示氫原子、苯基、或碳數1~10之烷基；6個R⁶ 可彼此相同也可不同，也可2個以上之R⁶ 互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；式中，R表示碳數1~10之烷基；【Chemical 14】

In the formula, R ⁶ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; 6 R ⁶ may be the same or different from each other, or two or more R ⁶ may be bonded to each other and to which they are bonded. The carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R⁷ 表示氫原子、苯基、或碳數1~10之烷基；3個R⁷ 可彼此相同也可不同，也可2個以上之R⁷ 互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；式中，R表示碳數1~10之烷基；【Chemical 15】

In the formula, R ⁷ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; 3 R ⁷ may be the same or different from each other, or two or more R ⁷ may be bonded to each other and to which they are bonded. The carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R⁸ 表示氫原子、或碳數1~10之烷基；4個R⁸ 可彼此相同也可不同，也可2個以上之R⁸ 互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；式中，R表示碳數1~10之烷基；【Chemical 16】

In the formula, R ⁸ represents a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms; 4 R ⁸ may be the same or different from each other, or two or more R ⁸ may be bonded to each other and to the carbon atom to which they are bonded. form one or more rings together; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R⁹ 表示氫原子、苯基、或碳數1~10之烷基；3個R⁹ 可彼此相同也可不同，也可2個以上之R⁹ 互相鍵結並和它們所鍵結之碳原子一起形成1個或多個環；式中，R表示碳數1~10之烷基；【Chemical 17】

In the formula, R ⁹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; 3 R ⁹ may be the same or different from each other, or two or more R ⁹ may be bonded to each other and to which they are bonded. The carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

式中，R表示碳數1~10之烷基；【Chemical 18】

In the formula, R represents an alkyl group having 1 to 10 carbon atoms;

式中，R表示碳數1~10之烷基。【Chemical 19】

In the formula, R represents an alkyl group having 1 to 10 carbon atoms.

7. An alicyclic tetracarboxylic dianhydride represented by the following formula (5), containing N,N-dimethylformamide, N,N-acetamide, N-methylpyrrolidone, and N, At least one solvent molecule in the group consisting of N-dimethylbutanamide;

。【Chemistry 20】

.

8. The acid dianhydride of 7., wherein the content of the aforementioned solvent molecules is 0.05 to 5% by weight.

9. An ester compound represented by the following formula (18).

式中，R¹⁰ 可相同也可不同，表示甲基、乙基、正丙基、或異丙基中之任一者。【Chemical 21】

In the formula, R ¹⁰ may be the same or different, and represents any one of methyl, ethyl, n-propyl, or isopropyl.

10. An olefin compound represented by the following formula (19);

式中，Ms表示-SO₂ CH₃ 表示之甲磺醯基。【Chemical 22】

In the formula, Ms represents a methanesulfonyl group represented by -SO ₂ CH ₃ .

11. an ester compound represented by the following formula (20);

式中，Ms表示-SO₂ CH₃ 表示之甲磺醯基；R¹¹ 可相同也可不同，表示甲基、乙基、正丙基、或異丙基中之任一者。 (發明之效果)【Chemistry 23】

In the formula, Ms represents a methylsulfonyl group represented by -SO ₂ CH ₃ ; R ¹¹ may be the same or different, and represents any one of methyl, ethyl, n-propyl, or isopropyl. (effect of invention)

According to the present invention, it is possible to provide a method for producing an alicyclic tetracarboxylic dianhydride or ester compound suitable for industrialization such as DNDA and other alicyclic tetracarboxylic dianhydride or ester compound with a simple method and high yield under mild conditions. Moreover, alicyclic tetracarboxylic dianhydrides suitable as monomers for polymer production, such as polyimide, and ester compounds can be provided.

Hereinafter, a preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<<The manufacturing method of alicyclic tetracarboxylic dianhydride (DNDA)>> As an ideal alicyclic tetracarboxylic dianhydride, (3aR, 4R, 5R, 5aR, 8aS, 9S, 10S, 10aS) are mentioned. -Decahydro-1H,3H-4,10:5,9-dimethylnaphtho[2,3-c:6,7-c']difuran-1,3,6,8-tetraone (below Also sometimes called DNDA). The manufacturing method of DNDA is shown in the figure below.

式中，R與前述為同義，表示碳數1~10之烷基。【Chemical 24】

In the formula, R is synonymous with the above, and represents an alkyl group having 1 to 10 carbon atoms.

Each step is described in detail below.

<Step 1> The step 1 of the present invention is a step of obtaining the olefin compound represented by the aforementioned formula (3) by reacting norbornadiene and cyclopentadiene.

Step 1 of reacting norbornadiene and cyclopentadiene according to the present invention, as shown in the figure below, will obtain (1R,4S,5S,8R)-1,4,4a, which has the same three-dimensional structure as the target DNDA, 5,8,8a-Hexahydro-1,4: In addition to 5,8-dimethylnaphthalene (BNDE), it also includes stereoisomers (1R,4S,4as,5R,8S,8as)-1,4, 4a,5,8,8a-hexahydro-1,4: 5,8-dimethylnaphthalene (BNDE-1) and (1R, 4S, 4ar, 5R, 8S, 8ar)-1,4,4a,5 ,8,8a-hexahydro-1,4:5,8-dimethylnaphthalene (BNDE-2) reaction mixture. Then, by distilling the obtained reaction mixture, the target BNDE can be obtained. The boiling point of the target BNDE is close to that of BNDE-1 and BNDE-2. Without rectification, only high-purity target BNDE can be obtained, but with single distillation, a mixture of these three compounds as the main components can be obtained.

【Chemical 25】

In the present invention, in the subsequent step 2, high-purity BNDE may be used, or a mixture containing BNDE and BNDE-1 may be used. As will be described later, in the production method of the present invention, even if a mixture of BNDE and BNDE-1 is used, high-purity DNME can be produced. In the present invention, in this mixture (that is, the olefin compound represented by the aforementioned formula (3)), the mass ratio of BNDE/BNDE-1 is preferably 50/50~99/1, and the content of BNDE in the mixture is preferably 50 to 99% by weight. Regarding BNDE-2, the mass ratio after the reaction is extremely small, which is not a problem in the present invention. In addition, BNDE is a compound represented by the aforementioned formula (6).

The cyclopentadiene used in the step 1 of the present invention is represented by the aforementioned formula (2).

Cyclopentadiene is a monomer of dicyclopentadiene, and cyclopentadiene can be quantitatively obtained by heating dicyclopentadiene at 160-200°C. The cyclopentadiene used in step 1 of the present invention can be used after being generated in the system by thermal decomposition of dicyclopentadiene. Dicyclopentadiene is a compound represented by the following formula (21).

【Chemical 26】

The usage amount of the aforementioned norbornadiene, relative to 1 mol of cyclopentadiene, is preferably more than 1 mol, and more preferably 2 to 10 mol. When using dicyclopentadiene, dicyclopentadiene is a dimer of cyclopentadiene, so the usage amount of norbornadiene should be more than 2 mol relative to 1 mol of dicyclopentadiene, more preferably 4~20 moles.

烷、1,2-亞甲基二氧基苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)、苯酚類(苯酚、甲基苯酚、對氯苯酚等)等。較佳為使用脂肪族烴類、及芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。In step 1 of the present invention, an organic solvent may or may not be used. The solvent used is not particularly limited as long as it does not interfere with the reaction, such as formic acid, aliphatic carboxylic acids (eg, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (eg, methanesulfonic acid, trifluoromethanesulfonic acid, etc.) ), alcohols (for example: methanol, ethanol, isopropanol, tert-butanol, ethylene glycol, triethylene glycol, etc.), ketones (for example: acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (eg: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (eg: N,N-dimethylformamide, N,N-dimethylacetamide, N -methylpyrrolidone, etc.), urea (N,N'-dimethylimidazolidinone, etc.), ethers (for example: diethyl ether, diisopropyl ether, tetrahydrofuran, diethyl ether

alkane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (eg: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (eg: chlorobenzene, 1,2-dichlorobenzene, etc.) , 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (for example: nitrobenzene, etc.), halogenated hydrocarbons (for example: dichloromethane, chloroform, tetrachloride carbon, 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Sulfites (eg, dimethylsulfite, etc.), sulfites (eg, cyclobutane, etc.), phenols (phenol, methyl phenol, p-chlorophenol, etc.), and the like. Preferably, aliphatic hydrocarbons and aromatic hydrocarbons are used. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

When using an organic solvent, the amount of the organic solvent used can be appropriately adjusted according to the uniformity and agitation of the reaction solution, but generally, it is preferably 1 to 50 g, and more preferably 2 to 20 g, relative to 1 g of norbornadiene.

Step 1 of the present invention can be carried out, for example, by a method of mixing norbornadiene and cyclopentadiene, or norbornadiene, cyclopentadiene and an organic solvent and stirring them. The reaction temperature at this time is preferably 140 to 250°C, and more preferably 150 to 220°C.

In step 1 of the present invention, the reaction pressure of the reaction is not particularly limited. In addition, the reaction environment is not particularly limited. In step 1 of the present invention, the reaction is preferably carried out under a flow of inert gas (eg, nitrogen, argon, helium), or in an inert gas environment.

As mentioned above, in step 1 of the present invention, an equimolar amount or an excess of norbornadiene relative to cyclopentadiene is usually used for the reaction. After the reaction is completed, if necessary, excess norbornadiene is removed from the reaction mixture by distillation, etc., and the olefin compound represented by the aforementioned formula (3) containing the target BNDE is filtered, distilled, column chromatography, etc. In a general method, the subsequent steps are carried out after isolation and purification. When BNDE is distilled, it is preferable to conduct distillation at a temperature at which BNDE does not cause thermal decomposition. The distillation of BNDE is preferably carried out at 50-180°C, more preferably at 50-160°C. Excessive norbornadiene used in the reaction can be recovered and reused after being purified by general methods such as distillation and column chromatography.

<Step 2> Step 2 of the present invention is a step of obtaining an ester compound represented by the following formula (4) by reacting the olefin compound represented by the aforementioned formula (3) with an alcohol compound and carbon monoxide in the presence of a palladium compound and a copper compound.

【Hua 27】

In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl, and isopropyl, more preferably methyl, ethyl, and isopropyl.

The olefin compound represented by the aforementioned formula (3) that can be used in this step is not limited to BNDE as described above, and may also include a mixture of BNDE and BNDE-1. The content of BNDE in the mixture is preferably 50-99% by weight.

Alcohol compounds used in step 2 of the present invention, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, amyl alcohol, methoxyethanol, ethoxyethanol , ethylene glycol, triethylene glycol, etc., preferably methanol, ethanol, n-propanol, isopropanol, more preferably methanol, ethanol, isopropanol. In addition, these alcohols can be used individually or in mixture of 2 or more types.

The usage-amount of the aforementioned alcohol compound is preferably 0.1 to 200 g, and more preferably 1 to 100 g, relative to 1 g of the olefin compound of the aforementioned formula (3).

In step 2 of the present invention, organic solvents other than alcohols may or may not be used.

烷、1,2-亞甲基二氧基苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)等。較佳為脂肪族烴類、芳香族烴類、鹵化烴類、鹵化芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。The organic solvents other than alcohols to be used are not particularly limited as long as they do not interfere with the reaction, such as formic acid, aliphatic carboxylic acids (eg, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (eg, methanesulfonic acid, Trifluoromethanesulfonic acid, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (for example: N,N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone, etc.), urea (N,N'-dimethylimidazolidinone, etc.), ethers (for example: diethyl ether, diisopropyl ether, tetrahydrofuran, two

alkane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (eg: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (eg: chlorobenzene, 1,2-dichlorobenzene, etc.) , 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (for example: nitrobenzene, etc.), halogenated hydrocarbons (for example: dichloromethane, chloroform, tetrachloride carbon, 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Substances (eg: dimethyl sulfite, etc.), molybdenum (eg: cyclobutane, etc.) and the like. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The usage-amount of the organic solvent other than the said alcohol is normally preferably 0.1-200g with respect to 1g of the olefin compound of the said formula (3), More preferably, it is 1-100g.

The palladium compound used in this reaction is not particularly limited as long as it contains palladium, for example: palladium halides such as palladium chloride and palladium bromide; palladium organic acid salts such as palladium acetate and palladium oxalate; palladium inorganic acids such as palladium nitrate and palladium sulfate salts; palladium complexes such as bis(acetylacetone)palladium, bis(1,1,1-5,5,5-hexafluoroacetoneacetone)palladium, etc.; palladium supported on carbon, alumina As the palladium-carbon, palladium-alumina, etc. as the isosupport, preferably palladium chloride and palladium-carbon are used. Here, the "palladium compound" means a so-called compound, a palladium metal monomer, or a carrier-supported palladium obtained by supporting a palladium metal monomer on a carrier, and the like. Moreover, a palladium compound can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned palladium compound is preferably 0.0001-0.2 mol, more preferably 0.001-0.1 mol, relative to 1 mol of the olefin compound of the aforementioned formula (3).

In this reaction, the metal compound used together with the palladium compound is not particularly limited as long as it can oxidize Pd(0) to Pd(II) when Pd(II) in the palladium compound is reduced to Pd(0). Limitations, for example: copper compounds, iron compounds, etc., preferably copper compounds. Specific examples of the copper compound include copper, copper acetate, copper propionate, copper n-butyrate, copper 2-methylpropionate, copper trimethyl acetate, copper lactate, copper butyrate, copper benzoate, and copper trifluoroacetate. , bis(acetylacetone)copper, bis(1,1,1-5,5,5-hexafluoroacetylacetone)copper, copper chloride, copper bromide, copper iodide, copper nitrate, nitrous acid Copper, copper sulfate, copper phosphate, copper oxide, copper hydroxide, copper trifluoromethanesulfonate, copper p-toluenesulfonate, copper cyanide, etc. Moreover, as an iron compound, ferric chloride (III), nitric acid (III), sulfuric acid (III), acetic acid (III), etc. are mentioned. A divalent copper compound is preferable, and copper(II) chloride is more preferable. Here, in addition to the so-called compound, the term "copper compound" also includes the meaning of a copper monomer. In addition, "metal compound", such as "iron compound", is used in the meaning of including a metal monomer in addition to a compound. Moreover, these metal compounds can be used individually or in mixture of 2 or more types.

The usage amount of the aforementioned copper compound is preferably 4-50 mol, more preferably 5-20 mol, relative to 1 mol of the olefin compound of the aforementioned formula (3).

In step 2, the temperature (the temperature during the operation before the reaction and the reaction temperature) is usually -10~100°C, preferably -10~70°C, more preferably 0~50°C.

In step 2, at least one of the following operations (A) and (B) needs to be performed.

(A) After mixing a palladium compound, a copper compound, and an alcohol compound in a reaction vessel, the following (C-2) substitution operation and (C-1) stirring operation are carried out in order to mix with the aforementioned olefin compound. (B) After mixing a palladium compound, a copper compound, an alcohol compound, and an orthoester compound in a reaction vessel, the following substitution operation (C-2) is performed to mix it with the aforementioned olefin compound. (C-1) Stirring in a carbon monoxide gas atmosphere. (C-2) The operation of depressurizing the reaction vessel and then encapsulating carbon monoxide gas was carried out once or more.

In addition, in operation (A), operations (C-2) and (C-1) may be alternately repeated two or more times, or (C-2) may be performed after operation (C-1) is performed. After the operation, it is mixed with the olefin compound. In addition, in operation (B), the operation of (C-1) may be implemented after the operation of (C-2) is implemented.

(Operation (A)) Before adding the BNDE-containing olefin compound, carbon monoxide was added. In operation (A), after adding a palladium compound, a copper compound, an alcohol compound, and an optional other organic solvent to the reaction vessel, the reaction vessel is depressurized and then sealed with carbon monoxide (operation (C-2) above), Stirring is carried out in a gaseous atmosphere of carbon monoxide (operation of the aforementioned (C-1)). The operations of (C-2) and (C-1) before adding the olefin compound in this way are collectively referred to as pretreatment. If the pretreatment is carried out, the carbonylation reaction (that is, the reaction of forming the ester compound represented by the aforementioned formula (4)) proceeds rapidly, and the ester compound is obtained in high yield. When the pretreatment is not carried out or is carried out sufficiently, the yield of the ester compound decreases.

The above-mentioned pretreatment is performed by repeating the operation of depressurizing the reaction vessel and the operation of sealing carbon monoxide once or twice (the operation of the above-mentioned (C-2)), and then performing stirring for a certain period of time (the above-mentioned (C-2)). 1) operation) to implement.

The above-mentioned operation (C-2) is carried out in order to replace the gas in the reaction vessel with carbon monoxide, which can be appropriately adjusted by the degree of decompression and the encapsulation amount of carbon monoxide. It is performed once or more, preferably 2 to 5 times. In the operation of (C-2), the solution containing the palladium compound, the copper compound, the alcohol compound, and optionally other organic solvent may be stirred or not stirred during the depressurization and carbon monoxide sealing. This decompression degree can be adjusted appropriately, and is not particularly limited. For example, by setting it to 50 to 200 torr, preferably 70 to 150 torr, the gas in the reaction vessel can be efficiently replaced with carbon monoxide.

The above-mentioned operation (C-1) can be carried out while circulating carbon monoxide, or can be carried out by first pouring carbon monoxide into a sealed bag or container made of natural rubber or the like, or carried out after pressurizing the reaction container with carbon monoxide. The capacity of the carbon monoxide bag or container is, for example, 0.1 L or more, preferably 0.2 to 10 L, relative to 1 L of the reaction container. The time required for the operation (C-1) once, that is, the stirring time of the solution, is, for example, 1 hour or more, preferably 1 to 5 hours.

In addition, the number of times of pretreatment (the operation of (C-2) and the operation of (C-1)) can be appropriately adjusted according to the volume of the reaction vessel and carbon monoxide used, but it is preferably one or more times, preferably 2 ~5 times.

In addition, the operation of (C-1) and the operation of (C-2) do not have to be repeated the same number of times. For example, the operation of (C-1) may not be performed after the operation of (C-2), and the obtained solution mixed with olefinic compounds.

In this operation (A), the temperature during operation is usually -10 to 100°C, preferably -10 to 70°C, and more preferably 0 to 50°C.

(Operation (B)) In operation (B), a palladium compound, a copper compound, an alcohol compound, an orthoester compound, and an optional other organic solvent are mixed in a reaction vessel, and then the pressure of the reaction vessel is reduced. , and the operation of encapsulating carbon monoxide gas (the operation of the aforementioned (C-2)) is carried out by mixing it with the aforementioned olefin compound. The operation (B) is the same as the above-mentioned operation (A) except the point of mixing with the above-mentioned orthoester compound and the point that the operation of the above-mentioned (C-1) may not be performed. In operation (B), after the operation of the above-mentioned (C-2) and before the addition of the olefin compound, the operation of the above-mentioned (C-1) (solution in a carbon monoxide gas atmosphere) can be carried out similarly to the operation (A). However, in the case of the operation (B) using the orthoester compound, even if the operation (C-1) above is not carried out, the carbonylation reaction (that is, the formation of the ester compound represented by the above formula (4) reaction) still proceeds rapidly, yielding the ester compound in high yield. Moreover, in this operation (B), by using an orthoester compound, the number of repetitions of the decompression operation and the carbon monoxide gas sealing operation in operation (C-2) can be reduced.

In addition, the above-mentioned operation (C-2) is performed in order to replace the gas in the reaction vessel in operation (B) with carbon monoxide. The operation of encapsulating carbon monoxide gas after decompression should be performed more than once, preferably 2 to 5 times. In addition, in the operation of (C-2), in the middle of reducing pressure and sealing carbon monoxide, a solution containing a palladium compound, a copper compound, an alcohol compound, an orthoester compound, and other organic solvents as needed may be stirred or not. Stir. The degree of decompression can be adjusted appropriately and is not particularly limited. For example, by setting it to 50 to 200 torr, preferably 70 to 150 torr, the gas in the reaction vessel can be efficiently replaced with carbon monoxide.

In this operation (B), the temperature during operation is usually -10 to 100°C, preferably -10 to 70°C, and more preferably 0 to 50°C.

The orthoester compound used in this operation (B) includes compounds represented by the following formula (22), for example, methyl orthoformate, ethyl orthoformate, etc., preferably methyl orthoformate.

【Chemistry 28】

In the formula, R ^f represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In addition, ^Re represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group. The three ^Res may be the same or different, but are preferably the same.

The usage-amount of the aforementioned orthoester compound is preferably 0.5-5 mol, and more preferably 0.8-3 mol, relative to 1 mol of the olefin compound of the aforementioned formula (3). When the amount used is within this range, the carbonylation reaction proceeds efficiently, and the ester compound represented by the aforementioned formula (4) can be obtained in an industrially desirable yield.

(Operation common to operation (A) and operation (B)) (Mixing and dropwise addition of olefin compound) In operation (A) and (B) of step 2, the above-mentioned (C-1) or (C-2) is carried out After the operation, the aforementioned olefin compound is mixed with respect to the obtained solution. In this case, the olefin compound is preferably added dropwise to the obtained solution. In addition, when the olefin compound is liquid, it can also be added dropwise in this state, but it is preferable to add dropwise as a mixture with an organic solvent, preferably an organic solvent other than alcohols. The time required for the dropwise addition is not particularly limited. For example, the total amount to be dropped is added dropwise to the solution within 1 hour or more, preferably 2 hours or more, more preferably 2 hours or more and within 16 hours. The solvent for dissolving the olefin compound can be appropriately changed, but it is preferable to contain the solvent exemplified as the organic solvent other than the alcohols used in the above-mentioned step 2.

(Reaction) The reaction of step 2 of the present invention is performed after, for example, the above-mentioned operation (C-1) or (C-2), in the obtained solution (a solution containing a palladium compound, a copper compound, and an alcohol compound, or It is carried out by a method such as a solution containing a palladium compound, a copper compound, an alcohol compound, and an orthoester compound) mixed with an olefin compound (BNDE) and stirred. The reaction temperature at this time is usually -10 to 100°C, preferably -10 to 70°C, and more preferably 0 to 50°C.

Carbon monoxide is also used after the operation of the aforementioned (C-1) or (C-2). When an olefin compound (BNDE) is added, carbon monoxide is also absorbed as the reaction proceeds, so it is necessary to continuously supply carbon monoxide to the reactor. Therefore, even after the operation of (C-1) or (C-2) is completed, it is preferable to mix with the olefin compound while stirring in a carbon monoxide gas atmosphere.

In step 2 of the present invention, the reaction pressure of the reaction can be atmospheric pressure (under normal pressure) or pressurized. In addition, the reaction in step 2 of the present invention is carried out in a carbon monoxide gas environment, but it can also be carried out in a gas environment containing carbon monoxide and a passive gas by diluting with a passive gas (eg, nitrogen, argon, helium). In addition, the number of operations (C-1) and (C-2) and the reaction time can be appropriately adjusted according to the pressure and concentration of carbon monoxide.

(Purification) According to the step 2 of the present invention, the ester compound represented by the aforementioned formula (4) can be obtained, but in the present invention, for example, after the completion of the reaction, filtration, concentration, crystallization, recrystallization, distillation, column chromatography, etc. can be used In a general method, the ester compound is isolated and purified before proceeding to the next step. The isolation and purification may not be carried out.

Depending on the reaction conditions and purification conditions in Step 1, an olefin compound represented by the following formula may be contained.

【Chemical 29】

Therefore, in the reaction of step 2, an ester compound represented by the following formula may be produced.

【Chemical 30】

Specific examples of the ester compound include the following compounds.

【Chemical 31】

烷、1,2-亞甲基二氧基苯等)、芳香族烴類(例如：苯、甲苯、二甲苯等)、鹵化芳香族烴類(例如：氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯等)、硝基化芳香族烴類(例如：硝基苯等)、鹵化烴類(例如：二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷等)、羧酸酯類(例如：乙酸乙酯、乙酸丙酯、乙酸丁酯等)、腈類(例如：乙腈、丙腈、苯甲腈等)、亞碸類(例如：二甲基亞碸等)、碸類(例如：環丁碸等)、苯酚類(苯酚、甲基苯酚、對氯苯酚等)等。較佳為鹵化烴類、脂肪族烴類、及芳香族烴類。又，該等有機溶劑可單獨使用或混用二種以上。此再結晶操作在獲得前述式(4)表示之酯化合物時特別有效。In order to obtain only the target product from such a large number of ester compounds, the purification system by recrystallization is effective. The solvent to be used is not particularly limited as long as it can separate these compounds, and examples thereof include alcohols (for example, methanol, ethanol, isopropanol, tert-butanol, ethylene glycol, triethylene glycol, etc.), ketones, etc. (for example: acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (for example: n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (for example: N,N-di Methylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylbutanamide, etc.), urea (N,N'-dimethylimidazolidinone) etc.), ethers (for example: diethyl ether, diisopropyl ether, tetrahydrofuran, diethyl ether

alkane, 1,2-methylenedioxybenzene, etc.), aromatic hydrocarbons (eg: benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (eg: chlorobenzene, 1,2-dichlorobenzene, etc.) , 1,3-dichlorobenzene, 1,4-dichlorobenzene, etc.), nitroated aromatic hydrocarbons (for example: nitrobenzene, etc.), halogenated hydrocarbons (for example: dichloromethane, chloroform, tetrachloride carbon, 1,2-dichloroethane, etc.), carboxylic acid esters (for example: ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (for example: acetonitrile, propionitrile, benzonitrile, etc.), Sulfites (eg, dimethylsulfite, etc.), sulfites (eg, cyclobutane, etc.), phenols (phenol, methyl phenol, p-chlorophenol, etc.), and the like. Preferred are halogenated hydrocarbons, aliphatic hydrocarbons, and aromatic hydrocarbons. Moreover, these organic solvents can be used individually or in mixture of 2 or more types. This recrystallization operation is particularly effective in obtaining the ester compound represented by the aforementioned formula (4).

In addition, it is also desirable to perform activated carbon treatment in order to remove impurities generated during the reaction. This activated carbon treatment is carried out by adding activated carbon to the solution containing the ester compound after the reaction, stirring, and then filtering. The stirring temperature is usually 10 to 100°C, preferably 15 to 70°C. The amount of activated carbon used, when using BNDE (or a mixture containing BNDE and BNDE-1) as a raw material, is usually 30% by weight or less relative to BNDE, preferably 0.01 to 20% by weight. Other than activated carbon, as long as it can adsorb impurities, it can be used for purification instead of activated carbon, and is not particularly limited, and specific examples thereof include activated clay, silica gel, and the like. By this operation, an ideal ester compound as a raw material of polyimide can be obtained.

<Step 3> In step 3 of the present invention, the ester compound represented by the aforementioned formula (4) is reacted in an organic solvent in the presence of an acid to obtain the alicyclic tetracarboxylic dianhydride (DNDA) represented by the aforementioned formula (5). ) steps.

In step 3 of the present invention, an acid is used. There are no special restrictions as long as it is an acid, for example: inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, nitric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid; chloroacetic acid, Halogenated carboxylic acids such as trifluoroacetic acid, ion exchange resins, sulfuric acid silica gel, zeolite, acidic alumina, etc., are preferably inorganic acids, organic sulfonic acids, and more preferably organic sulfonic acids. Moreover, these acids can be used individually or in mixture of 2 or more types.

The usage-amount of the aforementioned acid is preferably 0.0001-0.1 mol, more preferably 0.001-0.05 mol, relative to 1 mol of the ester compound represented by the aforementioned formula (4).

The reaction of step 3 of the present invention is preferably carried out in an organic solvent. The solvent used is an organic solvent, especially organic acid solvents such as formic acid, acetic acid, and propionic acid are preferred. Moreover, these solvents can be used individually or in mixture of 2 or more types.

The amount of the solvent used can be appropriately adjusted by the uniformity and agitation of the reaction solution, and is preferably 0.1 to 100 ml, more preferably 1 to 10 ml, relative to 1 g of the ester compound represented by the aforementioned formula (4).

The reaction in Step 3 of the present invention can be carried out, for example, by mixing and stirring the ester compound represented by the aforementioned formula (4), an acid, and an organic solvent (preferably an organic acid solvent). The reaction temperature at this time is preferably 50 to 180°C, and more preferably 70 to 150°C.

The reaction pressure of the reaction in step 3 of the present invention is not particularly limited. In addition, the reaction environment is not particularly limited, and the reaction in step 3 of the present invention is preferably carried out under a flow of inert gas (eg, nitrogen, argon, helium), or in an inert gas environment.

In addition, the DNDA obtained here can be isolated and purified by general methods such as filtration, concentration, recrystallization, and sublimation after completion of the reaction.

In the present invention, in order to acquire DNDA, it is preferable to perform acquisition by filtering. However, when the solvent used in step 3 is an organic acid, especially formic acid, formic acid will dissolve DNDA, so if the formic acid solvent is directly filtered, the amount of DNDA obtained is low. Therefore, it is desirable to obtain DNDA by filtration after substituting formic acid with another solvent. The solvent used instead of the solvent is not particularly limited as long as it does not react with DNDA. Considering the low solubility of DNDA and the solubility of formic acid, hydrocarbon-based solvents such as toluene and heptane are preferred.

The DNDA obtained by filtration is preferably further purified by crystallization or the like.

In Non-Patent Document 1, after treating DNME with formic acid, p-toluenesulfonic acid, and acetic anhydride, a crystallization operation is performed with acetic anhydride to obtain DNDA. However, in DNDA obtained by the same crystallization method as in Non-Patent Document 1, acetic anhydride and acetic acid remained. Polyimide is produced by the reaction of acid dianhydride and diamine. Acetic anhydride and acetic acid will react with diamine, so DNDA with residual acetic anhydride and acetic acid is unfavorable as a raw material for synthesizing polyimide.

In the present invention, treatment (crystallization) with acetic anhydride can be carried out. In the DNDA obtained at this time, as in Non-Patent Document 1, acetic anhydride and acetic acid remained.

In the present invention, in order to remove acetic anhydride and acetic acid from DNDA containing acetic anhydride and acetic acid, a crystallization operation is performed in another solvent system. This crystallization operation is carried out by a general method. For example, the solid is dissolved in a solvent with high solubility (hereinafter also referred to as a good solvent) while heating, a solvent with low solubility (hereinafter also referred to as a poor solvent) is added, and the crystals are precipitated by cooling.

The good solvent used in the crystallization is not particularly limited as long as it has a high solubility for DNDA, and is preferably dimethyl sulfoxide and N,N-dimethylformamide used in the manufacture of polyimide , N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylbutylamide, γ-caprolactone, N,N-dimethylisobutylamide, 1, 3-dimethyl-2-imidazolidinone and the like are preferred. The poor solvent on the other hand is not particularly limited as long as it has a low solubility in DNDA, and from the viewpoint of remaining solid crystals, one with a lower boiling point is preferable. For example: hexane, cyclohexane, heptane, toluene, chlorobenzene, tetrahydrofuran, diethyl ether, diisopropyl ether, ethyl acetate, acetonitrile, acetone, cyclohexanone, etc.

In addition, even when the crystallization operation using acetic anhydride is not performed, it is preferable to perform the crystallization operation of the present invention.

After drying the DNDA obtained by carrying out the crystallization operation in the aforementioned manner, the DNDA will contain, for example, about 0.05 to 5% by weight of a good solvent. However, since the good solvent is used in the production of polyimide, there is no problem in the remaining of the good solvent. DNDA has low solubility in many organic solvents. Compared with DNDA obtained in the above-mentioned manner, DNDA with no residual solvent (eg, one whose solvent has been completely removed by sublimation refining) generally has poor solubility in solvents. Polyimide is usually produced by the reaction of acid dianhydride and diamine in a solvent. If the solubility of acid dianhydride is not good, the reaction with diamine is slow, which is very disadvantageous as an industrial production method of polyimide.

Therefore, DNDA with good solvent solvation is an ideal compound in the production of polymers such as polyimide. That is, the ideal compound (DNDA) obtained according to the present invention contains a good solvent, specifically, a compound selected from the group consisting of N,N-dimethylformamide, N,N-acetamide, N-methylpyrrolidone, and Alicyclic tetracarboxylic dianhydride represented by the following formula (5) in at least one solvent molecule in the group consisting of N,N-dimethylbutanamide. The content of the solvated solvent is relative to the total amount of the acid dianhydride described in the solvated formula (5), and is preferably 0.05 to 5% by weight.

【Chemical 32】

<<Applicability of the aforementioned step 2 (method for producing an ester compound)>> In the aforementioned step 2, in the reaction between the olefin compound, the alcohol compound, and carbon monoxide, the substrate is not limited to the olefin compound of the aforementioned formula (3), and the following may be used. An olefin compound represented by the general formula (7). The reaction conditions and operation methods can be appropriately changed according to the solubility and reactivity of the compound, and are the same as those of the olefin compound of the aforementioned formula (3).

【Chemical 33】

In the formula, R ¹ is an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms. The three R ¹ may be the same or different from each other, or two or more R ¹ may be bonded to each other and form one or more rings together with the carbon atoms to which they are bonded (for example, aryl groups with 6 to 15 carbon atoms, more preferably phenyl). The hydrogen atom on the alkyl group can also be substituted with an alkenyl group with 1 to 5 carbon atoms, an ester group represented by -COOR ^a , an aryl group with 6 to 15 carbon atoms, an alkoxy group represented by -OR ^b , a cyano group, or - In the group represented by OSO ₂ R ^c , the carbon atom in the alkyl group may also form a carbonyl group. The hydrogen atom on this aryl group can also be substituted with a phenyl group, an alkyl group with 1 to 10 carbon atoms, or an alkenyl group with 1 to 10 carbon atoms, preferably a phenyl group or a phenyl group with 1 to 10 carbon atoms. The alkenyl group is more preferably an alkenyl group having 1 to 10 carbon atoms. Moreover, each of R ^a , R ^b , and R ^c is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

The olefin compound represented by the aforementioned general formula (7) preferably includes a group derived from bicyclo[2.2.1]hept-2-ene, in other words, preferably includes a norbornene ring structure.

In addition, the ring structure formed by two or more of R ¹ being bonded to each other may include the structure represented by the aforementioned general formula (7). In other words, the olefin compound may include two or more structures represented by the aforementioned general formula (7).

The ester compound obtained by reacting the olefin compound represented by the aforementioned general formula (7) with carbon monoxide is a compound represented by the following general formula (7-1).

【Chemical 34】

In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl, or isopropyl. R ¹ is synonymous with the aforementioned.

Preferred examples of the olefin compound represented by the aforementioned general formula (7) and the ester compound represented by the aforementioned general formula (7-1) include the following formulae (8) and (8-1), and the following formulae (9) and (9-1) , the following formulae (10) and (10-1), the following formulae (11) and (11-1), the following formulae (11-2) and (11-3), the following formulae (12) and (12-1) , the following formulae (13) and (13-1), the following formulae (14) and (14-1), the following formulae (15) and (15-1), the following formulae (16) and (16-1), the following formulae A compound represented by any one of formulae (17) and (17-1).

【Chemical 35】

In the formula, R ² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an ester group represented by -COOR ^d , or a cyano group. The hydrogen atom on the alkyl group may be substituted with an ester group represented by -COOR ^a , or an aryl group having 6 to 10 carbon atoms. The two R ² may be the same or different from each other, or may be bonded to each other and form one or more rings together with the carbon atoms to which they are bonded. R ^d and R ^a in the ester group represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 36】

In the formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, or an ester group represented by -COOR ^d . The hydrogen atom on the alkyl group may be substituted with an ester group represented by -COOR ^a , or an aryl group having 6 to 10 carbon atoms. The two R ^3s may be the same or different from each other, or may be bonded to each other and form one or more rings together with the carbon atoms to which they are bonded. R ^d and R ^a in the ester group represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 37】

In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The two R ^4s may be the same or different from each other, or may be bonded to each other and form one or more rings together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 38】

In the formula, R ⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group represented by -OR ^b , or a group represented by -OSO ₂ R ^c . R ^b is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group. R ^c represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group. The two R ^5s may be the same or different from each other, or may be bonded to each other and form one or more rings together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 39】

In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 40】

In the formula, R ⁶ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms. The six R ⁶ may be the same or different from each other, or two or more R ⁶ may be bonded to each other and form one or more rings together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 41】

In the formula, R ⁷ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms. The three R ^7s may be the same or different from each other, or two or more R ^7s may be bonded to each other to form one or more rings together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 42】

In the formula, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The four R ^8s may be the same or different from each other, or two or more R ^8s may be bonded to each other and form one or more rings together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 43】

In the formula, R ⁹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms. The three R ^9s may be the same or different from each other, and two or more R ^9s may be bonded to each other to form one or more rings together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 44】

In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

【Chemical 45】

In the formula, R represents an alkyl group having 1 to 10 carbon atoms, preferably methyl, ethyl, n-propyl and isopropyl.

As in the case of the olefin compound represented by the aforementioned formula (3), if the olefin compound represented by the aforementioned formula (8) including isomers of different steric structures is reacted, the following formula (8-2 is preferable) may be obtained. ) represents the ester compound of the ester compound.

【Chemical 46】

In the formula, R ² and R are synonymous with the above.

Furthermore, for the aforementioned formulas (8), (9), (10), (11), (11-2), (12), (13), (14), (15), (16), (17) ), specifically, the following olefin compounds are mentioned. In addition, the scope of the present invention is not limited to these. The compounds contained in the aforementioned formula (8) are the following formulae (8a), (8b), (8c), and (8d). The same applies to other compounds.

【Chemical 47】

The aforementioned formulas (8-1), (9-1), (10-1), (11-1), (11-3), (12-1), (13-1), (14-1), Specific examples of the compounds represented by (15-1), (16-1) and (17-1) include the following ester compounds. The scope of the present invention is not limited to these.

【Chemical 48】

In the formula, R and Ms are synonymous with the above.

In addition, the same ester compound can be obtained depending on the olefin compound used. For example, the structure of the compound represented by the aforementioned formula (8b) and the compound represented by the aforementioned formula (17a) are different, but the structures of the compound represented by the aforementioned formula (8B) and the compound represented by the aforementioned formula (17A) are generated by them. same. However, depending on the raw materials used and reaction conditions, sometimes the stereochemistry is different.

From the viewpoint of a useful polyimide raw material, the ester compound represented by the aforementioned formula (9-1) is preferably an ester compound represented by the following formula (18).

【Chemical 49】

In the formula, R ¹⁰ may be the same or different, and represents any one of methyl, ethyl, n-propyl, and isopropyl, preferably methyl and ethyl.

In addition, from the viewpoint of a useful polyimide raw material, the olefin compound represented by the aforementioned formula (11) is preferably an olefin compound represented by the following formula (19).

【Chemical 50】

In the formula, Ms is a methylsulfonyl group represented by -SO ₂ CH ₃ .

Furthermore, from the viewpoint of a useful polyimide raw material, the ester compound represented by the aforementioned formula (11-1) is preferably an ester compound represented by the following formula (20).

【Chemical 51】

In the formula, Ms is synonymous with the above. R ¹¹ may be the same or different, and represents any of methyl, ethyl, n-propyl, and isopropyl, preferably methyl and ethyl. (Example)

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited to these.

In the following examples, the following abbreviations are used. The structural formula of the compound is also described together. BNDE and BNDE-1 correspond to the olefin compound represented by the formula (3), DNME corresponds to the ester compound represented by the formula (4), and DNDA corresponds to the alicyclic tetracarboxylic dianhydride represented by the formula (5). BNDE: (1R,4S,5S,8R)-1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethylnaphthalene

BNDE-1：(1R,4S,4as,5R,8S,8as)-1,4,4a,5,8,8a-六氫-1,4：5,8-二甲橋萘【Chemical 52】

BNDE-1: (1R,4S,4as,5R,8S,8as)-1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethylnaphthalene

DNME：(1R,2R,3S,4S,5S,6S,7R,8R)-十氫-1,4：5,8-二甲橋萘-2,3,6,7-四羧酸四甲酯【Chemical 53】

DNME: (1R,2R,3S,4S,5S,6S,7R,8R)-decahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylate tetramethyl ester

DNEE；(1R,2R,3S,4S,5S,6S,7R,8R)-十氫-1,4：5,8-二甲橋萘-2,3,6,7-四羧酸四乙酯【Chemical 54】

DNEE; (1R,2R,3S,4S,5S,6S,7R,8R)-decahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylate tetraethyl ester

DNDA：(3aR,4R,5R,5aR,8aS,9S,10S,10aS)-十氫-1H,3H-4,10：5,9-二甲橋萘并[2,3-c：6,7-c’]二呋喃-1,3,6,8-四酮【Chemical 55】

DNDA: (3aR,4R,5R,5aR,8aS,9S,10S,10aS)-decahydro-1H,3H-4,10:5,9-dimethylnaphtho[2,3-c:6,7 -c']difuran-1,3,6,8-tetraone

NOR：雙環[2.2.1]庚-2,5-二烯(2,5-降莰二烯)【Chemical 56】

NOR: Bicyclo[2.2.1]hept-2,5-diene (2,5-norbornadiene)

DCP：3a,4,7,7a-四氫-1H-4,7-甲橋茚【Chemical 57】

DCP: 3a,4,7,7a-tetrahydro-1H-4,7-methindene

CP：環庚-1,3-二烯【Chemical 58】

CP: cyclohept-1,3-diene

【Chemical 59】

<Step 1> Example 1 Synthesis of BNDE Under argon gas flow, NOR184g (2mol) and DCP132g (1mol) were added to a 1L autoclave so that NOR:CP=1:1 (mol ratio), and the pressure was 0.5MPa. After carrying out nitrogen sealing (gas substitution) 3 times, it stirred at 195 degreeC for 6 hours. Distillation was performed after completion|finish of reaction. The fractions obtained under the conditions of 59-62°C/2 Torr were collected to obtain 69.7 g of BNDE (a mixture of BNDE and BNDE-1; hereinafter referred to as "BNDE mixture"). Purity was 99% by weight, BNDE:BNDE-1=85:15 (mol ratio), and the yield based on cyclopentadiene was 18.7% by gas chromatography analysis (hereinafter also referred to as GC analysis).

The physical properties of the BNDE mixture are as follows.

Boiling point; 59-62°C/2Torr ¹ H-NMR (CDCl _{3 ,} σ (ppm)); BNDE: 0.95 (d, J=8.8 Hz, 1H), 1.47-1.53 (m, 1H), 1.70 (dt, J =7.6Hz, J=1.6Hz, 1H), 2.15-2.25(m, 2H), 2.45-2.50(m, 2H), 2.56(d, J=8.8Hz, 1H), 6.00-6.05(m, 2H) , 6.15-6.25(m, 2H); BNDE-1: 1.48-1.50(m, 4H), 2.58-2.62(m, 4H), 2.73-2.76(m, 2H), 5.30(s, 4H) CI-MS (m/z); 159 (M+1)

Example 2 Synthesis of BNDE Under argon gas flow, in the manner of NOR:CP=4:1 (mol ratio), NOR125g (1.36mol) and DCP22.4g (0.169mol) were fed into a 200mL autoclave, After 3 times of nitrogen sealing at 0.5 MPa, the mixture was stirred at 180° C. for 8 hours. The reaction liquid was analyzed by GC and contained 32.6 g of BNDE. The reaction yield based on cyclopentadiene was 61%.

Example 3 Synthesis of BNDE In a 200mL autoclave, NOR127.9g (1.39mol) and DCP18.4g (0.139mol) were fed into a 200mL autoclave in the manner of NOR:CP=5:1 (mol ratio) under argon gas flow , and after 3 times of nitrogen sealing at 0.5 MPa, the mixture was stirred at 180° C. for 8 hours. As a result of GC analysis, the reaction solution contained 27.7 g of BNDE. The reaction yield was 63% based on cyclopentadiene.

Example 4 Synthesis of BNDE Under the flow of argon, NOR1769g (19.2mol) and DCP335g (2.53mol) were fed into a 3L autoclave in a manner of NOR:CP=3.8:1 (mol ratio), and carried out at 0.5MPa After the nitrogen gas was sealed three times, the mixture was stirred at 180° C. for 8 hours (the quantitative value determined by GC analysis was the reaction yield of 58.7%). Similarly, 1923 g (20.9 mol) of NOR and 276 g (2.09 mol) of DCP were charged so that NOR:CP=5:1 (mol ratio), and stirred at 180° C. for 8 hours (the quantitative value obtained by GC analysis is the reaction yield 61.5%). Similarly, NOR1961g (21.3mol) and DCP235g (1.78mol) were charged so that NOR:CP=6:1 (mol ratio), and stirred at 180°C for 8 hours (the quantitative value obtained by GC analysis was the reaction yield 66.1%). These 3 batches of reaction solutions were combined. Distillation was performed, and 1273 g of BNDE mixtures were obtained. The purity obtained by GC analysis was 99% by weight, BNDE:BNDE-1=86:14 (mol ratio), and the yield based on cyclopentadiene was 54.1%.

Example 5 Synthesis of BNDE Under argon gas flow, NOR127.9g (1.39mol) and DCP18.4g (0.139mol) were fed into a 200mL autoclave in a manner of NOR:CP=5:1 (mol ratio). , after 3 times of nitrogen sealing at 0.5 MPa, the mixture was stirred at 155° C. for 10 hours. Then, it stirred at 165 degreeC for 10 hours. Distillation was performed after completion|finish of reaction. The fractions obtained at a liquid temperature of 98-116°C/13 Torr were collected to obtain 48.9 g of a BNDE mixture. The purity measured by GC analysis was 97% by weight, BNDE:BNDE-1=85:15 (molar ratio), and the yield obtained based on cyclopentadiene was 45.8%.

<Step 2> Example 6 Synthesis of DNME Under an argon gas stream, 27 g of a BNDE mixture (purity 99%, BNDE:BNDE-1=86:14 (mol ratio), 145 mmol) was added at room temperature (25°C). To 578 mL of MeOH (methanol), 188 g (1.4 mol) of CuCl ₂ and 5.4 g of 10 wt % Pd/C (2.5 mmol in terms of Pd; manufactured by NE Chemcat; 50 wt % aqueous product) were added. The pressure reduction in the reaction vessel and the encapsulation of carbon monoxide (replaced with carbon monoxide gas) were repeated three times to make the system a carbon monoxide gas atmosphere, and the mixture was stirred at 23-26° C. for 6 hours. In this operation, the decompression degree was 100 torr. Subsequent examples were also carried out in the same manner.

After carbon monoxide was removed, insoluble matter was filtered off with diatomaceous earth to obtain a filtrate. The filtrate was washed with 190 mL of chloroform and combined with the above-mentioned filtrate. The filtrate was concentrated under reduced pressure, 190 mL of chloroform was added to the obtained concentrated residue, and after stirring for 0.5 hours, the insoluble matter (cupric chloride) was filtered off and washed with 100 mL of chloroform 6 times. The filtrate was washed with 190 mL of water, 190 mL of saturated sodium bicarbonate x 2, and 190 mL of saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After filtration, the mixture was concentrated under reduced pressure to obtain 37.2 g of a brown foam. Attempts were made to crystallize the brown foam, but no crystals were obtained.

The obtained foam was purified by silica gel column chromatography (n-heptane/ethyl acetate=5/1→2/1→1/1 (volume ratio)). The obtained fraction was concentrated to obtain 13.8 g of DNME as a pale yellow solid. GC analysis revealed a purity of 97.0% by weight and a yield of 23.4%.

The physical properties of DNME are as follows.

Melting point; 169-170°C ¹ H-NMR (CDCl ₃ , σ (ppm)); 1.34 (d, J=8.4 Hz, 1H), 1.56 (d, J=10 Hz, 1H), 1.84 (s, 2H), 1.96(d,J=10Hz,1H), 2.14(d,J=8.4Hz,1H), 2.55-2.65(m,6H), 3.06(d,J=1.6Hz,2H), 3.61(s,6H) , 3.62(s,6H) CI-MS(m/z); 395(M+1)

Example 7 Synthesis of DNME 13.9 L of methanol was charged into a 20 L flask, and 4.50 kg (33.5 mol) of CuCl ₂ and 65 g of 10 wt % Pd/C (30.5 mmol in Pd conversion; manufactured by NEChemcat; 50 wt % aqueous product) were added.

After adding 650 g of BNDE mixture (purity 99%, BNDE:BNDE-1=86:14 (mol ratio), 3.50 mol), it was cooled in a cold water bath, and the pressure was reduced until the liquid surface was slightly foamed, and returned to normal with argon. pressure. After the pressure was reduced again, carbon monoxide was sealed and returned to normal pressure, and the mixture was stirred at 11 to 26° C. for 4 hours while introducing carbon monoxide intermittently. In high-speed liquid chromatography analysis (hereinafter also referred to as HPLC analysis), the BNDE mixture (BNDE and BNDE-1) disappeared. Carbon monoxide was removed, and the insoluble matter was removed by filtration through celite, followed by concentration under reduced pressure. To the obtained concentrated residue, 10.8 L of chloroform was added, and after stirring for 1 hour, the insoluble matter was filtered off with Celite. The same operation was performed twice using chloroform 4.8 to obtain 23.3 kg of a chloroform solution. As a result of GC analysis, the solution contained DNME482g. The yield was 29.8%.

Example 8 Synthesis of DNME 4.2 L of methanol was added to a 10 L flask, 1.37 kg (10.2 mol) of CuCl ₂ , 19.8 g of 10 wt % Pd/C (9.3 mmol in Pd conversion; manufactured by NEChemcat; 50 wt % aqueous product) and toluene were added 706g.

198.0 g of a BNDE mixture (purity 99%, BNDE:BNDE-1=86:14 (mol ratio), 1.07 mol) was added, washed with 96 g of toluene, cooled in a cold water bath, and depressurized until the liquid surface was slightly foamed So far, return to normal pressure with argon. After the pressure was reduced again, the pressure was returned to normal pressure with carbon monoxide, and the mixture was stirred at 11 to 26° C. for 4 hours while introducing carbon monoxide intermittently. In HPLC analysis, the BNDE mixture (BNDE and BNDE-1) disappeared. Carbon monoxide was removed, and insoluble matter was removed by filtration through celite, and the mixture was concentrated under reduced pressure. To the obtained concentrated residue, 2.4 L of chloroform was added, and after stirring for 1 hour, the insoluble matter was filtered off with celite. The same operation was performed twice using 1.5 L of chloroform to obtain 7.08 kg of a chloroform solution. Washed with 1.4 L of water, washed twice with 1.4 L of saturated aqueous sodium bicarbonate solution, washed with 1.4 L of saturated brine in this order, and dried with anhydrous magnesium sulfate. Magnesium sulfate was filtered off to obtain 9.2 kg of a chloroform solution. As a result of GC analysis, the solution contained 249 g of DNME. The yield was 50.4%.

Example 9 Synthesis of DNME In a 0.3 L 4-neck flask, 0.69 g of 10 wt % Pd/C (0.32 mmol in Pd conversion; manufactured by NEChemcat; 50 wt % water-containing product) and 44.2 g (329 mmol) of CuCl ₂ were added. To this, 135 mL of MeOH and 31 mL of toluene were added, followed by bubbling with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Then, 6.35 g of BNDE mixture (purity 99%, BNDE:BNDE-1=89:11 (mol ratio), 35.4 mmol) was diluted in 12.0 mL of toluene, pumped with a syringe, and it took 2 hours at 20°C to 30°C hourly addition. It was stirred at the same temperature for 6 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 78.9%.

Example 10 Synthesis of DNME Into a 0.3 L 4-neck flask were added 0.70 g of 10 wt % Pd/C (0.33 mmol in Pd conversion; manufactured by NEChemcat; 50 wt % aqueous product) and 44.4 g (330 mmol) of CuCl ₂ . To this, 70 mL of MeOH and 18.5 mL of CHCl ₃ were added, followed by bubbling with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Then 6.35 g of BNDE mixture (purity 99%, BNDE:BNDE-1=89:11 (molar ratio), 35.4 mmol) was diluted in 12 mL of toluene, and added dropwise at 20°C to 30°C using a syringe pump over a period of 2 hours . It was stirred at the same temperature for 6 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 89.7%.

Example 11 Synthesis of DNME 10wt% Pd/C2.87g (Pd conversion 1.35mmol; manufactured by NEChemcat; 50wt% aqueous product) and 182.5g (1.36mol) of CuCl2 _were added to a 1.0L 4-neck flask. To this were added 434 mL of MeOH and 76 mL of CHCl ₃ , and bubbled under N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Then 27.4 g of BNDE mixture (purity 99%, BNDE:BNDE-1=82:18 (mol ratio), 141 mmol) was diluted in 30 mL of CHCl ₃ and added dropwise at 20°C to 30°C using a syringe pump over a period of 2 hours . It was stirred at the same temperature for 6 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 65.7%.

Example 12 Synthesis of DNME Into a 1.0L separable flask, 10wt% Pd/C2.86g (1.34 mmol in Pd conversion; manufactured by NEChemcat; 50wt% aqueous product) and 183.2g (1.36mol) of CuCl ₂ were added. Thereto were added 443 mL of MeOH and 77 mL of CHCl ₃ , and bubbled in Ar for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature (25°C) for 2 hours (pretreatment). The inside of the flask was depressurized (degassed), and CO was sealed again. Then 27.5 g of BNDE mixture (purity 99%, BNDE:BNDE-1=82:18 (molar ratio), 141 mmol) was diluted in 29 mL of CHCl ₃ , and added dropwise over 2 hours at 20°C to 30°C using a syringe pump . It was stirred at the same temperature for 6 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 90.5%.

Example 13 Synthesis of DNME In a 1.0L separable flask, 0.126 g (0.71 mmol) of PdCl ₂ and 182.9 g (1.36 mol) of CuCl ₂ were added. To this were added 452 mL of MeOH and 77 mL of CHCl ₃ , and bubbled with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). The inside of the flask was depressurized, and carbon monoxide was sealed again. Then 27.2 g of BNDE mixture (purity 99%, BNDE:BNDE-1=82:18 (mol ratio), 140 mmol) was diluted in 28 mL of CHCl ₃ and added dropwise over 2 hours at 20°C to 30°C using a syringe pump . It was stirred at the same temperature for 6 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 85.0%.

Example 14 Synthesis of DNME 0.023 g (0.13 mmol) of PdCl ₂ and 187.0 g (1.39 mol) of CuCl ₂ were added to a 1.0 L separable flask. To this were added 451.3 mL of MeOH and 77.2 mL of CHCl ₃ , and bubbled with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). After that, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The flask was depressurized, carbon monoxide was sealed again, 27.7 g of a BNDE mixture (purity 99%, BNDE:BNDE-1=82:18 (mol ratio), 141 mmol) was diluted in 26.3 mL of CHCl ₃ , and a syringe pump was used. Pu was added dropwise at 20°C to 30°C over a period of 8 hours. Stir at the same temperature for 3 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 85.6%.

Example 15 Synthesis of DNME In a 1.0 L separable flask, 0.062 g (0.35 mmol) of PdCl ₂ and 233.8 g (1.74 mol) of CuCl ₂ were added. To this were added 454 mL of MeOH and 81.4 mL of CHCl ₃ , and bubbled with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). Then, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The flask was depressurized, carbon monoxide was sealed again, 27.3 g of a BNDE mixture (purity 99%, BNDE:BNDE-1=82:18 (mol ratio), 139 mmol) was diluted in 20.0 mL of CHCl ₃ , and a syringe pump was used. Pu was added dropwise at 20°C to 30°C over a period of 8 hours. Stir at the same temperature for 3 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 94.3%.

Example 16 Synthesis of DNME 0.067 g (0.38 mmol) of PdCl ₂ and 139.6 g (1.04 mol) of CuCl ₂ were added to a 1.0 L separable flask. To this were added 465 mL of MeOH and 102 mL of CHCl ₃ , and bubbled with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). Then, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The flask was depressurized, carbon monoxide was sealed again, 27.1 g of a BNDE mixture (purity 93%, BNDE:BNDE-1=79:21 (mol ratio), 126 mmol) was diluted in 26 mL of CHCl ₃ , and a syringe pump was used It was added dropwise over 8 hours at 20°C to 30°C. Stir at the same temperature for 3 hours. HPLC analysis of the reaction solution was carried out. The yield of DNME was 94.3%.

Example 17 Synthesis of DNME In a 1.0 L separable flask, 0.067 g (0.38 mmol) of PdCl ₂ and 139.6 g (1.04 mol) of CuCl ₂ were added. Thereto were added 465 mL of MeOH, 102 mL of CHCl ₃ , and 18 g (171 mmol) of trimethyl orthoformate, followed by bubbling under N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. 27.0 g of a BNDE mixture (purity 93%, BNDE:BNDE-1=79:21 (molar ratio), 125 mmol) was diluted in 25 mL of CHCl ₃ , and added dropwise at 20°C to 30°C over 8 hours using a syringe pump. Stir at the same temperature for 3 hours. HPLC analysis of the reaction solution was carried out. DNME yield 91.5%.

Example 18 Synthesis of DNME In a 1.0L separable flask, 0.061 g (0.35 mmol) of PdCl ₂ and 233.5 g (1.74 mol) of CuCl ₂ were added. To this were added 440 mL of MeOH and 77 mL of CHCl ₃ , and bubbled with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). Then, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The inside of the flask was depressurized, carbon monoxide was sealed again, and 27.5 g of a BNDE mixture (purity 83.0%, BNDE:BNDE-1=78:22 (molar ratio), 112.5 mmol) was diluted in 25.5 mL of CHCl ₃ , and a syringe was used. The pump was added dropwise over 8 hours at 20°C to 30°C. Stir at the same temperature for 3 hours.

After the reaction, carbon monoxide was removed, and after concentration under reduced pressure, 655 g of CHCl ₃ was added, followed by concentration under reduced pressure, and solvent substitution with MeOH and CHCl ₃ was carried out under reduced pressure. The insoluble matter was filtered off, the filtrate was washed with 655 g of CHCl ₃ , and the filtrate and the washing solution were combined. The DNME in the organic layer was analyzed and it was found to contain 38.2 g of DNME. The yield was 86.1%. It was concentrated under reduced pressure until the liquid volume became about half, and it was added dropwise to 330 g of a 7% by weight aqueous sodium bicarbonate solution. 55 g of diatomaceous earth was added to the suspension, followed by stirring. After filtering off insoluble matter, the filtrate was washed with CHCl ₃ , and the filtrate and the washing solution were combined. After the liquid separation, the CHCl ₃ layers were washed twice with 330 g of a 7 wt % aqueous sodium bicarbonate solution, and the CHCl ₃ layers were washed 3 times with 330 g of water. After adding 2.7 g of MgSO ₄ to the obtained organic layer, the mixture was stirred and filtered. 2.7 g of activated carbon was added, stirred and filtered.

The solvent was completely removed by concentration under reduced pressure, 68.8 g of toluene was added, and the temperature was raised to 100°C. Then, after adding 82.5 g of heptane, it stirred at 20 degreeC, and matured a crystal. Filtration and drying were carried out to obtain 36.3 g of DNME as a white solid (purity 97.5% by weight determined by NMR; yield 79.8% based on BNDE). In addition, this product does not contain stereoisomers other than DNME.

Example 19 Synthesis of DNME 0.064 g (0.36 mmol) of PdCl ₂ and 233.4 g (1.74 mol) of CuCl ₂ were added to a 1.0 L separable flask. To this were added 441 mL of MeOH and 77 mL of CHCl ₃ , and bubbled with N ₂ for 0.5 hours. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). Then, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The inside of the flask was depressurized, carbon monoxide was sealed again, 27.2 g of a BNDE mixture (purity 98.4%, BNDE:BNDE-1=52:48 (mol ratio), 88.0 mmol) was diluted in 25.8 mL of CHCl ₃ , and a syringe was used. The pump was added dropwise over 8 hours at 20°C to 30°C. Stir at the same temperature for 3 hours.

After the reaction, carbon monoxide was removed, and after concentration under reduced pressure, 641 g of CHCl ₃ was added, and further concentration under reduced pressure was performed, and solvent substitution with MeOH and CHCl ₃ was carried out under reduced pressure. The insoluble matter was filtered off, the filtrate was washed with CHCl ₃ 641 g, and the filtrate and the washing solution were combined. The DNME in the organic layer was analyzed and it was found to contain 27.9 g of DNME. The yield was 80.4%. It was concentrated under reduced pressure until the liquid volume became about half, and it was added dropwise to 334 g of a 7% by weight aqueous sodium bicarbonate solution. To the suspension, 55 g of celite was added and stirred, and the insoluble matter was filtered off, and the filtrate was washed with CHCl ₃ , and the filtrate and the washing solution were combined. After the liquid separation, the CHCl ₃ layers were washed twice with 334 g of a 7 wt % sodium bicarbonate aqueous solution, and the CHCl ₃ layers were washed with 334 g of water three times. To the obtained organic layer, 2.7 g of MgSO ₄ was added, followed by stirring and filtration. 2.7 g of activated carbon was added, stirred and filtered.

The solvent was completely removed by concentration under reduced pressure, 67.0 g of toluene was added, and the temperature was raised to 100°C. Then, after adding 79.5 g of heptane, the mixture was stirred at 20°C to mature the crystals. Filtration and drying were carried out to obtain 27.7 g of DNME as a white solid (purity 99.1% by weight determined by NMR; yield 79.1% based on BNDE). In addition, this product hardly contains stereoisomers other than DNME.

Example 20 Synthesis of DNEE In a 2L glass flask, 51.7 mg (0.29 mmol) of PdCl ₂ and 195.1 g (1451 mmol) of CuCl ₂ were added. To this, 455 mL of EtOH (ethanol) and 21.5 g (145.1 mmol) of triethyl orthoformate were added. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. 23.0 g of a BNDE mixture (purity 98.7%, BNDE:BNDE-1=83:17 (mol ratio), 118.9 mmol) was diluted in 24.7 mL of EtOH, and added dropwise over 8 hours using a syringe pump. Stir at 25°C for 15 hours.

After the reaction, carbon monoxide was removed, and after concentration under reduced pressure, 546 g of toluene was added, and the mixture was further concentrated under reduced pressure, and the solvent was substituted with EtOH and toluene under reduced pressure. The insoluble matter was filtered off, the filtrate was washed with 546 g of toluene, and the filtrate and the washing solution were combined. The DNEE in the organic layer was analyzed, and it was found that it contained 49.2 g of DNEE. The yield was 91.9%. It was concentrated under reduced pressure until the liquid volume was about half, and it was added dropwise to 276 g of a 7% by weight aqueous sodium bicarbonate solution. To the suspension, 46 g of diatomaceous earth was added and stirred. After filtering off insoluble matter, the filtrate was washed with toluene, and the filtrate and the washing solution were combined. After the liquid separation, the toluene layer was washed twice with 276 g of a 7 wt % sodium bicarbonate aqueous solution, and the toluene layer was washed three times with 276 g of water. To the obtained organic layer, 2.3 g of MgSO ₄ was added and stirred. 2.3 g of activated carbon was added, stirred and filtered.

The solvent was completely removed by concentration under reduced pressure, 39.4 g of toluene was added, and the temperature was raised to 90°C. Then, after adding 477 g of heptanes, the mixture was stirred at 0°C to mature the crystals. Filtration and drying were carried out to obtain 46.7 g of DNEE as a white solid (purity 99.4% by weight determined by NMR; yield 86.7% based on BNDE). In addition, this product does not contain stereoisomers other than DNEE.

<Step 3> Example 21 Synthesis of DNDA A 10L GL reactor was substituted with argon, and 255 g of DNME (purity 99.9%, 646.5 mmol was found by HPLC analysis), 3.9 kg of formic acid, and 2.45 g of p-toluenesulfonic acid monohydrate ( 12.9 mmol), heated and stirred at an internal temperature of 89°C to 92°C. During this period, methyl formate by-produced with the progress of the reaction was removed. It took 15 hours to complete the reaction. Then, the formic acid was distilled off under reduced pressure, and the solid was dried under reduced pressure to obtain 199 g of DNDA crude product (I) as a pale brown solid.

The 5L GL reactor was substituted with argon, 3.0 kg of acetic anhydride and 199 g of crude DNDA (I) were added, and the mixture was heated and stirred at an internal temperature of 121°C to completely dissolve crude DNDA (I). Then, it cooled to 20 degreeC, and it stirred at 20 degreeC for 19 hours. Filtration was carried out, the solid was washed with 0.8 kg of toluene, and the obtained solid was dried under reduced pressure. 59 g of DNDA crude product (II) was obtained as a pale off-white solid (purity 89.6% by weight, DNME-based yield 27.3% by NMR quantification). The DNDA crude product (II) contained 3.5% by weight of acetic anhydride and 1.0% by weight of acetic acid.

Example 22 Synthesis of DNDA A 500 mL glass flask was substituted with argon, and 29.93 g of DNME obtained in Example 18 (purity 97.5%; 74.0 mmol), 150 g of formic acid, and 0.28 g of p-toluenesulfonic acid monohydrate were added. Heating and stirring were performed at 95°C to 99°C for 10 hours. After the completion of the reaction, it was concentrated under reduced pressure to distill off the formic acid, and the azeotropic operation with 90.0 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered, and the solid was washed with toluene and dried under reduced pressure. 22.6 g of crude DNDA (I) was obtained as a pale gray solid.

A 500 mL glass flask was replaced with argon, 400 g of acetic anhydride and 20.0 g of DNDA crude product (I) were added, and the mixture was heated and stirred at an internal temperature of 125 to 129° C. to completely dissolve the solid. After that, it was concentrated under reduced pressure, and 340 g of the solvent was distilled off. Toluene 360g was added, heating and stirring at 100 degreeC, and it stirred at 25 degreeC. Filtration was carried out, the solid was washed with toluene, and the filtrate was dried under reduced pressure to obtain 18.7 g of DNDA crude product (II) as an off-white solid.

A glass flask was substituted with argon, charged with 300 g of N,N-dimethylacetamide, and added with 17.1 g of the crude DNDA (II) obtained earlier, and heated and stirred at an internal temperature of 50-60° C. to complete the solid. dissolve. Then, 0.8 g of activated carbon (egret A) was added, and the mixture was stirred at the same temperature. The filtrate was filtered and washed with 17.1 g of N,N-dimethylacetamide, the filtrate and the washing liquid were combined, concentrated under reduced pressure, and 222 g of the solvent was distilled off. A solution containing 257 g of toluene and 86 g of heptane was added to the obtained suspension while heating and stirring at 100°C, followed by stirring at 25°C. Filtration was carried out, the solid was washed with toluene, and the filtrate was dried under reduced pressure. 15.5 g of DNDA was obtained as a white solid (purity 99.7% by weight as determined by NMR; step yield 85.4%). The obtained DNDA contained 0.3% by weight of N,N-dimethylacetamide.

The physical properties of DNDA are as follows.

Melting point; 313°C ¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 0.87 (d, J=13Hz, 1H), 1.15 (d, J=11Hz, 1H), 1.38 (d, J=11Hz, 1H), 1.49(d, J=13Hz, 1H), 2.02(s, 2H), 2.67(s, 2H), 2.73(s, 2H), 2.96(d, J=1.4Hz, 2H), 3.24(d , J=1.4Hz, 2H) CI-MS(m/z); 303(M+1)

Example 23 Synthesis of DNDA A 500 mL glass flask was substituted with argon, DNME 24.8 g (purity 99.1 wt %; 62.3 mmol), formic acid 74 g, p-toluenesulfonic acid monohydrate 0.23 g were added, and the temperature was 95° C. to 99° C. The mixture was heated and stirred at °C for 10 hours. After the completion of the reaction, the mixture was concentrated under reduced pressure, the formic acid was distilled off, and the azeotropic operation with 74.4 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered, and the solid was washed with toluene and dried under reduced pressure. 18.8 g of crude DNDA (I) was obtained as a light gray solid.

A 500 mL glass flask was replaced with argon, 353 g of acetic anhydride and 17.7 g of DNDA crude product (I) were added, and the mixture was heated and stirred at an internal temperature of 125 to 129° C. to completely dissolve the solid. After that, it was concentrated under reduced pressure, and 283 g of the solvent was distilled off. Toluene 317g was added, heating and stirring at 100 degreeC. Stir at 25°C. Filtration was carried out, the solid was washed with toluene, and the filtrate was dried under reduced pressure to obtain 17.6 g of DNDA crude product (II) as an off-white solid.

A glass flask was substituted with argon, charged with 240 g of N,N-dimethylacetamide, and added with 16.0 g of the DNDA crude product (II) obtained earlier, and heated and stirred at an internal temperature of 50 to 60° C. to complete the solid. dissolve. After that, 0.8 g of activated carbon was added, and the mixture was stirred at the same temperature. Filtration was performed, the filtrate was washed with 17.1 g of N,N-dimethylacetamide, the filtrate and the washing solution were combined, concentrated under reduced pressure, and 216.4 g of the solvent was distilled off. A solution containing 239 g of toluene and 80.6 g of heptane was added to the obtained suspension while heating and stirring at 100°C, followed by stirring at 25°C. Filtration was carried out, the solid was washed with toluene, and the filtrate was dried under reduced pressure. DNDA 14.4 g was obtained as a white solid (purity 99.3% by weight determined by NMR; yield 88.7% based on DNME). The obtained DNDA contained 0.3% by weight of N,N-dimethylacetamide.

Example 24 Synthesis of DNDA A 500 mL glass flask was substituted with argon, 72 g of DNME (purity 99.1%; 180.9 mmol), 360 g of formic acid, and 0.69 g (3.6 mmol) of p-toluenesulfonic acid monohydrate were added, and the mixture was heated at an internal temperature of 95°C to Heating and stirring were performed at 100°C for 8 hours. After the completion of the reaction, it was concentrated under reduced pressure to distill off the formic acid, and the azeotropic operation with 144 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered, and the solid was washed with 72 g of toluene and dried under reduced pressure. 53.4 g of crude DNDA (I) was obtained as a pale gray solid.

A glass flask was substituted with argon, charged with 375 g of N,N-dimethylacetamide, and added with 25 g of the DNDA crude product (I) obtained earlier, and heated and stirred at an internal temperature of 50 to 60° C. to completely dissolve the solid. . After that, 1.3 g of activated carbon was added, and the mixture was stirred at the same temperature. Filtration was carried out, the filtrate was washed with 17.1 g of N,N-dimethylacetamide, the filtrate and the washing solution were combined and concentrated under reduced pressure, and 216.4 g of the solvent was distilled off. While heating and stirring the obtained suspension at 100°C, a solution containing 239 g of toluene and 80.6 g of heptane was added, and the mixture was stirred at 25°C. Filtration was carried out, the solid was washed with toluene, and the filtrate was dried under reduced pressure. 19.2 g of DNDA was obtained as a white solid (purity 99.3% by weight determined by NMR; yield 74.6% based on DNME). The obtained DNDA contained 0.6% by weight of N,N-dimethylacetamide.

Example 25 Synthesis of DNDA A 500 mL glass flask was substituted with argon gas, DNME 39.7 g (purity 98.5%; 99.2 mmol), formic acid 200 g, p-toluenesulfonic acid monohydrate 0.39 g (2.05 mmol) were added, and the internal temperature was 95 ℃ to 99 ℃ for 11 hours with heating and stirring. After completion of the reaction, it was concentrated under reduced pressure to distill off the formic acid, and the azeotropic operation with 84 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered, and the solid was washed with toluene and dried under reduced pressure. 29.3 g of crude DNDA (I) was obtained as a light gray solid.

A 500 mL glass flask was substituted with argon, 320 g of acetic anhydride and 16.02 g of DNDA crude product (I) were added, and the mixture was heated and stirred at an internal temperature of 125 to 129° C. to completely dissolve the solid. After that, it was concentrated under reduced pressure, and 272 g of the solvent was distilled off. Toluene 289g was added, heating and stirring at 100 degreeC, and it stirred at 25 degreeC. Filtration was carried out, the solid was washed with toluene, and the filtrate was dried under reduced pressure to obtain 13.82 g of DNDA crude product (II) as an off-white solid.

A glass flask was substituted with argon, 150 g of N-methylpyrrolidone was charged, 10.0 g of the DNDA crude product (II) obtained earlier was added, and the solid was completely dissolved by heating and stirring at an internal temperature of 50 to 60°C. Then, 0.5 g of activated carbon was added, and the mixture was stirred at the same temperature. Filtration was carried out, the filtrate was washed with 10 g of N-methylpyrrolidone, the filtrate and the washing solution were combined and concentrated under reduced pressure, and 131 g of the solvent was distilled off. A solution containing 100 g of toluene and 50 g of heptane was added to the obtained suspension while heating and stirring at 100°C, followed by stirring at 25°C. Filtration was carried out, the solid was washed with toluene, and the filtrate was dried under reduced pressure. 9.36 g of DNDA was obtained as a white solid (purity 98.3% by weight determined by NMR; yield 88.7% based on DNME). The obtained DNDA contained 0.9% of N-methylpyrrolidone.

Example 26 Synthesis of DNDA A 200 mL glass flask was substituted with argon, 19.0 g of DNEE (purity 99.4% by weight; 41.9 mmol), 95 g of formic acid, and 82.5 mg of methanesulfonic acid were added, and the reaction was carried out at an internal temperature of 95°C to 99°C for 16 hours. Heat and stir. After completion of the reaction, it was concentrated under reduced pressure to distill off the formic acid, and azeotropic operation with 38 g of toluene was performed three times to completely remove the formic acid. The toluene suspension was filtered, and the solid was washed with toluene and dried under reduced pressure. 12.3 g of crude DNDA (I) was obtained as a pale gray solid.

A 200 mL glass flask was replaced with argon, 165 g of N-methylpyrrolidone was charged, 11.0 g of the crude DNDA (I) obtained earlier was added, and the solid was completely dissolved by heating and stirring at an internal temperature of 50°C to 60°C. Then, 0.5 g of activated carbon was added, and the mixture was stirred at the same temperature. Filtration was carried out, the filtrate was washed with N-methylpyrrolidone, the filtrate and the washing solution were combined and concentrated under reduced pressure, and 132.5 g of the solvent was distilled off. While heating and stirring the obtained suspension at 60°C, a solution containing 110 g of diisopropyl ether and 50 g of heptane was added, and the mixture was stirred at 20°C. Filtration was carried out, the solid was washed with heptane, and the filtrate was dried under reduced pressure. 10.7 g of DNDA was obtained as a white solid (purity 98.5% by weight determined by NMR; yield 93.0% based on DNEE). The obtained DNDA contained 1.4% by weight of N-methylpyrrolidone.

Example 27 Synthesis of DNCMS and DNMTE

【Chemical 60】

Referring to the method described in J.Chin.Chem.Soc.1998,45,799, using (1R,4S,5S,8R)-1,4,4a,5,8,8a,9a,10a-octahydro-1,4: Synthesis of (1R,4S,5S,8R,9S,10R)-1,4,4a,5,8,8a,9, 9a,10,10a-Decahydro-1,4:5,8-Dimethyl anthracene-9,10-diol (DNHQ).

(Synthesis of DNCMS) 87.0 g (356 mmol) of DNHQ, 4.3 g (35.2 mmol) of N,N-dimethylaminopyridine, and 1740 g of pyridine were added to a reaction vessel with a capacity of 5 L, and the mixture was cooled to a temperature of 5°C. Then, 87.0 g (760 mmol) of methanesulfonic acid chloride was added dropwise over 20 minutes, the temperature was raised to 25°C, and the reaction was carried out at the same temperature for 9 hours. Then, 2500 g of ion-exchanged water was added dropwise, and the precipitated white solid was filtered. The obtained white solid was washed 5 times with 200 mL of 10 wt % hydrochloric acid, 200 mL of a 10 wt % aqueous sodium bicarbonate solution, and further with 200 mL of ion-exchanged water, and vacuum-dried. 128.9 g of the obtained white solid was dissolved in 2800 g of ethyl acetate, and dried (dehydrated) with 35 g of anhydrous magnesium sulfate. Then, this ethyl acetate solution was passed through a silica gel column, and the solvent was distilled off with an evaporator to obtain (1R,4S,5S,8R,9S,10R)-1,4,4a,5, 8,8a,9,9a,10,10a-decahydro-1,4:5,8-dimethylanthracene-9,10-diyldimethanesulfonate (DNCMS) 124.5g ( ¹ H-NMR analysis It was found that the purity was 99% by weight and the yield was 87.4%).

The physical properties of DNCMS are as follows.

¹ H-NMR (DMSO-d _{6 ,} σ (ppm)); 1.18 (d, J=8.3 Hz, 1H), 1.32 (d, J=8.2 Hz, 1H), 1.39-1.42 (m, 2H), 2.00 -2.15(m,2H), 2.81(s,2H), 2.85-2.90(m,2H), 2.97(s,2H), 3.22(s,6H), 4.10-4.20(m,2H), 6.23(s , 2H), 6.27(s, 2H) CI-MS(m/z); 401(M+1)

(Synthesis of DNMTE) 364 g of methanol, 62 g of chloroform, 136 g (1011 mmol) of copper (II) chloride, and 6 g (33.7 mmol) of palladium chloride were placed in a reaction vessel with a capacity of 1 L and stirred. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). Then, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The inside of the flask was depressurized, carbon monoxide was sealed again, and a solution of 27 g (67.3 mmol) of DNCMS dissolved in 178 g of chloroform was added dropwise over 3 hours, and the reaction was carried out for 4 hours. Next, after replacing the gas atmosphere in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 621 g of chloroform was added. The same operation is repeated 2 more times. Then, insoluble matter was filtered off from the obtained brown-green suspension. The obtained solution was washed 3 times with 324 g of saturated sodium bicarbonate aqueous solution and 3 times with 324 g of purified water, 2.7 g of anhydrous magnesium sulfate was added to the organic layer, 2.7 g of activated carbon was added after stirring, and the mixture was stirred and filtered. Then, the obtained solution was concentrated under reduced pressure to obtain 51 g of a white solid. Next, purification by silica gel chromatography (developing solvent; hexane:ethyl acetate=10:1 (volume ratio)) was performed to obtain (1R, 2R, 3S, 4S, 5S, 6S, 7R, 8R,9S,10R)-9,10-bis((methylsulfonyl)oxy)tetrahydro-1,4:5,8-dimethyl anthracene-2,3,6,7-tetracarboxyl 27 g of acid ester (DNMTE) (purity 97.1% by weight, yield 64.4% by HPLC analysis).

The physical properties of DNMTE are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.49 (d, J=10 Hz, 2H), 2.31 (d, J=10 Hz, 2H), 2.62-2.67 (m, 2H), 2.69 (s, 2H) ), 2.87(s, 4H), 3.06(s, 6H), 3.19(s, 2H), 3.32(s, 2H), 3.64(s, 6H), 3.66(s, 6H), 4.98-5.12(m, 2H) CI-MS (m/z); 637 (M+1)

Example 28 Synthesis of TNME

【Chemistry 61】

Into an autoclave with a capacity of 200 mL, 120 g (755.75 mmol) of BNDE and 10 g (75.86 mmol) of dicyclopentadiene were charged. After replacing the inside of the system with nitrogen, the reaction was carried out at a temperature of 180 to 185° C. for 8 hours. After completion of the reaction, 127.5 g of light brown liquid was obtained. Under the conditions of a temperature of 87°C, a column top temperature of 73°C, and a vacuum degree of 1.5kPa~0.5kPa, vacuum distillation was performed to remove the fraction containing BNDE. 41.2 g of toluene was added to 29.3 g of the residue, and the temperature was raised to 56°C to completely dissolve. Next, after adding 297 g of methanol at the same temperature, and cooling to 50°C, a two-layer system having a white suspension in the upper layer and a yellow oil component in the lower layer was obtained. The white suspension in the upper layer was taken out and concentrated under reduced pressure to obtain 1,4,4a,5,8,8a,9,9a,10,10a-decahydro-1,4:5,8:9,10 as a white solid - 24.03 g of trimethyl anthracene (TNDE) (purity 94.8 wt % (isomer ratio 31:68:1), yield 14.2%, obtained by GC analysis).

299 g of methanol, 50 g of chloroform, 200 g (1.48 mol) of copper (II) chloride, and 351 mg (1.98 mmol) of palladium chloride were placed in a reaction vessel with a capacity of 1 L and stirred. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). Then, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The inside of the flask was depressurized, carbon monoxide was sealed again, a solution of TNDE 22 g (93.9 mmol) dissolved in 92 g of chloroform was added dropwise over 6.5 hours, and the reaction was carried out for 20 hours. After replacing the gas atmosphere in the system with argon gas from carbon monoxide, the solvent was distilled off from the reaction mixture, and 506 g of chloroform was added. The same operation was further repeated 2 times. Then, the insoluble matter was removed by filtration from the brown-green suspension. The obtained solution was washed 3 times with 269 g of saturated sodium bicarbonate aqueous solution and 3 times with 269 g of purified water, then 2.2 g of anhydrous magnesium sulfate was placed in the organic layer and stirred, and then 2.2 g of activated carbon was placed and stirred. filter. Then, the solution was filtered and concentrated under reduced pressure to obtain 46.63 g of a brown solid. Next, purification by recrystallization (solvent ratio; toluene:heptane=1:1.6 (weight ratio)) and silica gel chromatography (developing solvent; hexane:ethyl acetate:chloroform=10:1:1 ( capacity ratio)), and obtained as a white solid tetradecanehydro-1,4:5,8:9,10-trimethylanthracene-2,3,6,7-tetracarboxylic acid tetramethyl ester (TNME) 18.39 g (purity 97% by weight, yield 41.3% by HPLC analysis).

Example 29 Synthesis of BNME

【Chemistry 62】

Referring to the method described in Can. J. Chem. 1975, 53, 256, using 1,4,5,8-tetrahydro-1,4-naphthalene-6,7-dicarboxylate dimethyl ester Dichloro-5,6-dicyano-p-benzoquinone was used to synthesize 1,4-dihydro-1,4-naphthalene-6,7-dicarboxylate dimethyl ester (CYPDM).

Into a reaction vessel with a capacity of 500 mL, 135 g of methanol, 41 g of chloroform, 52 g (387 mmol) of copper(II) chloride, and 14 mg (0.08 mmol) of palladium chloride were placed. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). Then, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The inside of the flask was depressurized, carbon monoxide was sealed again, a solution of 20 g (76.7 mmol) of CYPDM dissolved in 66 g of chloroform was added dropwise over 6 hours, and the reaction was carried out at room temperature for 3 hours. Next, after replacing the gas atmosphere in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 300 g of chloroform was added. It was concentrated under reduced pressure, the solvent was distilled off, and 300 g of chloroform was added. The insolubles were removed by filtration from the brown-green suspension obtained. The obtained solution was washed three times with 240 g of a saturated sodium bicarbonate aqueous solution and three times with 240 g of purified water, and then 4 g of anhydrous magnesium sulfate was charged into the organic layer and stirred, and then 2 g of activated carbon was charged, stirred and filtered. Then, the solution was filtered and concentrated under reduced pressure to obtain 26.7 g of a light brown solid. Next, purification by silica gel chromatography (developing solvent; hexane:ethyl acetate=15:1 (weight ratio)) was carried out, followed by recrystallization (solvent ratio; toluene/heptane=2.5:1 (volume ratio) )) was purified to obtain (1R,2S,3R,4S)-1,2,3,4-tetrahydro-1,4-naphthalene-2,3,6,7-tetracarboxylate as a white solid 22.4 g of acid tetramethyl ester (BNME) (purity 94.8% by weight, yield 67.5% by HPLC analysis).

The physical properties of BNME are as follows.

¹ H-NMR (CDCl _{3 ,} σ (ppm)); 1.89 (d, J=10 Hz, 1H), 2.54 (d, J=10 Hz, 1H), 2.74 (d, J=2.0 Hz, 2H), 3.67 ( t, J=2.0Hz, 2H), 3.70(s, 6H), 3.89(s, 6H), 7.57(s, 2H) CI-MS(m/z); 377(M+1)

Example 30 Synthesis of NMTE

於容量2L之反應容器中裝入甲醇730g、氯仿221g、氯化銅(II)190.3g(1.42mol)、氯化鈀12.5g(70.5mmol)、原甲酸甲酯37.5g(624.5mmol)。然後以隔膜泵減壓到液面輕微起泡為止，封入一氧化碳並將系內以一氧化碳氣體取代。於室溫攪拌2小時(前處理)。之後，實施同樣的操作(系內的減壓、一氧化碳之封入、反應液之攪拌)2次，共計實施3次前處理。將燒瓶內減壓，再度實施一氧化碳之封入，費時4小時滴加溶於氯仿76g之雙環[2.2.1]庚-5-烯-2-羧酸甲酯(NME)54g(354.8mmol)之溶液，於室溫使其反應1小時。其次，將系內的氣體環境從一氧化碳取代為氬氣後，從反應混合物將溶劑餾去，添加氯仿1140g。再減壓濃縮而餾去溶劑，並添加氯仿1140g。並且從獲得之褐綠色之懸浮液將不溶物以過濾除去。將獲得之溶液以飽和碳酸氫鈉水溶液648g洗淨3次，再以精製水240g洗淨3次後，於有機層加入無水硫酸鎂11g並攪拌後，加入活性碳5.4g並攪拌、過濾。然後將溶液過濾後減壓濃縮，獲得黃色液體98g。其次，於178.6℃/1mmHg之條件實施蒸餾精製，獲得為淡黃色油的雙環[2.2.1]庚烷-2,3,5-三羧酸三甲酯(NMTE)80.5g(利用GC分析得知純度95.8重量%、產率80.3%)。 [產業利用性]【Chemistry 63】

730 g of methanol, 221 g of chloroform, 190.3 g (1.42 mol) of copper(II) chloride, 12.5 g (70.5 mmol) of palladium chloride, and 37.5 g (624.5 mmol) of methyl orthoformate were placed in a reaction vessel with a capacity of 2 L. Then, the pressure is reduced with a diaphragm pump until the liquid level is slightly foamed, carbon monoxide is sealed, and the system is replaced with carbon monoxide gas. Stir at room temperature for 2 hours (pretreatment). After that, the same operation (pressure reduction in the system, sealing of carbon monoxide, and stirring of the reaction liquid) was performed twice, and the pretreatment was performed three times in total. The flask was depressurized, carbon monoxide was sealed again, and a solution of 54 g (354.8 mmol) of methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (NME) dissolved in 76 g of chloroform was added dropwise over 4 hours. , and allowed to react for 1 hour at room temperature. Next, after replacing the gas atmosphere in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 1140 g of chloroform was added. Further, it was concentrated under reduced pressure to distill off the solvent, and 1140 g of chloroform was added. And the insolubles were removed by filtration from the obtained brown-green suspension. The obtained solution was washed three times with 648 g of saturated sodium bicarbonate aqueous solution and three times with 240 g of purified water. After adding 11 g of anhydrous magnesium sulfate to the organic layer and stirring, 5.4 g of activated carbon was added, stirred and filtered. Then, the solution was filtered and concentrated under reduced pressure to obtain 98 g of a yellow liquid. Next, distillation and purification were carried out at 178.6°C/1 mmHg to obtain 80.5 g of trimethyl bicyclo[2.2.1]heptane-2,3,5-tricarboxylate (NMTE) as pale yellow oil (according to GC analysis Known purity 95.8% by weight, yield 80.3%). [industrial availability]

The present invention relates to a method for producing a cyclic tetracarboxylic dianhydride and an ester compound. Among them, alicyclic tetracarboxylic dianhydrides are useful compounds as monomers for the production of polyimide. In the present invention, it is possible to provide a method for producing an industrially desirable alicyclic tetracarboxylic dianhydride or ester compound, which can produce alicyclic tetracarboxylic dianhydride or ester compound such as DNDA in high yield by a simple method under mild conditions. . Furthermore, ideal alicyclic tetracarboxylic dianhydrides and ester compounds can be provided as monomers for polymer production such as polyimide. Furthermore, in step 1 of obtaining an olefin compound from norbornadiene and cyclopentadiene, and step 2 of obtaining an ester compound by reacting an olefin compound, an alcohol compound, and carbon monoxide, the stereoisomers may not be completely separated. On the other hand, alicyclic tetracarboxylic dianhydride is obtained with industrially ideal operation and purity by crystallization.

Claims (10)

A method for producing an alicyclic tetracarboxylic dianhydride, comprising the following steps: Step 1, reacting norbornadiene represented by the following formula (1) with cyclopentadiene represented by the following formula (2) to obtain the following formula ( 3) an olefin compound represented by; step 2, then in the presence of a palladium compound and a copper compound, the olefin compound represented by the formula (3), an alcohol compound, and carbon monoxide are reacted to obtain an ester compound represented by the following formula (4); and In step 3, the ester compound represented by the formula (4) is reacted in an organic solvent in the presence of an acid to obtain an alicyclic tetracarboxylic dianhydride represented by the following formula (5); in step 2, the following two operations are performed (A) at least one of (B); (A) After mixing the palladium compound, the copper compound and the alcohol compound in the reaction vessel, the following (C-2) substitution operation and the following (C- 1) The stirring operation is to mix with the olefin compound represented by the formula (3); (B) After mixing the palladium compound, the copper compound, the alcohol compound, and the orthoester compound in the reaction vessel, the following (C-2) is carried out. ), mix it with the olefin compound represented by the formula (3); (C-1) stir in a carbon monoxide gas atmosphere; (C-2) carry out an operation of depressurizing the reaction vessel and then encapsulating carbon monoxide gas more than 1 time;

In the formula, R represents an alkyl group with 1 to 10 carbon atoms;

The method for producing an acid dianhydride according to claim 1, wherein in the step 2, in the olefin compound represented by the formula (3) used, the content of the compound represented by the following formula (6) is 50-99% by weight;

The method for producing an acid dianhydride according to claim 1 or 2, wherein in the operations (A) and (B) of the step 2, when mixing with the olefin compound, it is for the compound containing a palladium compound, a copper compound, and an alcohol compound. The olefin compound represented by the formula (3) is added dropwise to the mixture, or to a mixture containing a palladium compound, a copper compound, an alcohol compound, and an orthoester compound. A method for producing an ester compound, comprising reacting an olefin compound, an alcohol compound, and carbon monoxide represented by the following general formula (7) in the presence of a palladium compound and a copper compound to obtain an ester compound represented by the following general formula (7-1). In this step, at least one of the following 2 operations (A) and (B) is carried out: (A) after mixing the palladium compound, the copper compound and the alcohol compound in the reaction vessel, the following (C- 2) The substitution operation and the following (C-1) stirring operation are carried out to mix with the olefin compound; (B) The palladium compound, the copper compound, the alcohol compound, and the orthoester compound are mixed in the reaction vessel, and then carried out The following (C-2) substitution operation is performed to mix the olefin compound with the olefin compound; (C-1) stirring is carried out in a carbon monoxide gas atmosphere; (C-2) operation 1 of depressurizing the reaction vessel and encapsulating carbon monoxide gas is carried out times or more;

In the formula, R ¹ is an alkyl group with 1 to 15 carbon atoms, or an alkenyl group with a carbon number of 1 to 15; 3 R ¹ can be the same or different from each other, or two or more R ¹ can be bonded to each other and combined with them. The bonded carbon atoms together form one or more rings; R ¹ enclosed by the circle represented by the following general formula (7') in the general formula (7) can be represented as a hydrogen atom;

The hydrogen atom on the alkyl group can also be substituted with an alkenyl group with 1 to 5 carbon atoms, an ester group represented by -COOR ^a , an aryl group with 6 to 15 carbon atoms, an alkoxy group represented by -OR ^b , a cyano group, or - For the group represented by OSO ₂ R ^c , the carbon atom in the alkyl group can also form a carbonyl group; the hydrogen atom on the aryl group can also be substituted with a phenyl group, an alkyl group with 1 to 10 carbon atoms, or an alkene with 1 to 10 carbon atoms. and R ^a , R ^b , and R ^c are each an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms;

In the formula, R ¹ has the same meaning as above, and R represents an alkyl group having 1 to 10 carbon atoms. The method for producing an ester compound according to claim 4, wherein, in the operations (A) and (B), when mixing with an olefin compound, a mixture containing a palladium compound, a copper compound, and an alcohol compound, or a mixture containing a palladium compound, a copper compound, and an alcohol compound A mixture of the compound, the copper compound, the alcohol compound, and the orthoester compound, and the olefin compound is added dropwise. The method for producing an ester compound according to claim 4 or 5, wherein the olefin compound and the ester compound are each of the following formulae (8) and (8-1), the following formulae (9) and (9-1), and the following formula ( 10) and (10-1), the following formulae (11) and (11-1), the following formulae (11-2) and (11-3), the following formulae (12) and (12-1), the following formulae ( 13) and (13-1), the following formulae (14) and (14-1), the following formulae (15) and (15-1), the following formulae (16) and (16-1), or the following formulae (17) ) and a compound represented by any one of (17-1);

In the formula, R ² is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an ester group represented by -COOR ^d , or a cyano group; the hydrogen atom on the alkyl group can also be substituted with an ester group represented by -COOR ^a , or a carbon group. Aryl groups of 6 to 10; 2 R ² can be the same or different from each other, or can be bonded to each other and form 1 or more rings together with the carbon atoms to which they are bonded; R ^d and R in the ester group ^a represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R ³ represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cyano group, or an ester group represented by -COOR ^d ; the hydrogen atom on the alkyl group can also be substituted with an ester group represented by -COOR ^a , or a carbon Aryl groups of 6 to 10; 2 R ³ can be the same or different from each other, or can be bonded to each other and form 1 or more rings together with the carbon atoms to which they are bonded; R ^d and R in the ester group ^a represents an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R ⁴ represents a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms; two R ⁴ can be the same or different from each other, and can also be bonded to each other and form one or more carbon atoms together with the carbon atoms to which they are bonded. In the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group represented by -OR ^b , or a group represented by -OSO ₂ R ^c ; R ^b represents an alkyl group having 1 to 10 carbon atoms, or Aryl with carbon number 6~10, R ^c represents alkyl group with carbon number 1~10, or aryl group with carbon number 6~10; 2 R ⁵ can be the same or different from each other, or can be bonded to each other and combined with them The bonded carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R ⁶ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; 6 R ⁶ may be the same or different from each other, or two or more R ⁶ may be bonded to each other and to which they are bonded. The carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R ⁷ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; 3 R ⁷ may be the same or different from each other, or two or more R ⁷ may be bonded to each other and to which they are bonded. The carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R ⁸ represents a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms; 4 R ⁸ may be the same or different from each other, or two or more R ⁸ may be bonded to each other and to the carbon atom to which they are bonded. form one or more rings together; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R ⁹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms; 3 R ⁹ may be the same or different from each other, or two or more R ⁹ may be bonded to each other and to which they are bonded. The carbon atoms together form one or more rings; in the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R represents an alkyl group with 1 to 10 carbon atoms;

In the formula, R represents an alkyl group having 1 to 10 carbon atoms. The method for producing an ester compound according to claim 4, wherein in the operation (A), after the substitution operation of (C-2) and the stirring operation of (C-1) are performed in this order, and before mixing with the olefin compound , and the operation of depressurizing the reaction vessel and then encapsulating carbon monoxide gas again. An ester compound represented by the following formula (18);

In the formula, R ¹⁰ may be the same or different, and represents any one of methyl, ethyl, n-propyl, or isopropyl. An olefin compound represented by the following formula (19);

In the formula, Ms represents a methanesulfonyl group represented by -SO ₂ CH ₃ . An ester compound represented by the following formula (20);

In the formula, Ms represents a methylsulfonyl group represented by -SO ₂ CH ₃ ; R ¹¹ may be the same or different, and represents any one of methyl, ethyl, n-propyl, or isopropyl.