JP2017014163A - Manufacturing method of dicarboxylic acid ester having norbornane skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial manufacturing method of a dicarboxylic acid ester composition having a norbornane skeleton useful as a manufacturing raw material of various industrial chemical raw materials, optical functional materials or electron functional materials.SOLUTION: There is provided a method for manufacturing a dicarboxylic acid ester composition represented by the formula (1) having a norbornane skeleton by reacting unsaturated carboxylic acid ester represented by the formula (3) or the like derived from a material without problem to obtain such as dicyclopentadiene or methyl acrylate as a raw material with CO in presence of HF and reacting the resulting dicarboxylic acid fluoride represented by the formula (2) with alcohol.SELECTED DRAWING: None

Description

  The present invention relates to a dicarboxylic acid ester composition having a norbornane skeleton and a method for producing the same.

  Polyester resins synthesized from cycloaliphatic dicarboxylic acids having a norbornane skeleton and cycloaliphatic diols have excellent transparency, heat resistance, weather resistance, gas barrier properties, and optical properties, so optical materials, electronic information materials, and medical instruments It can be used for applications such as materials.

For example, a copolymer using dinorbornane dicarboxylic acid ester as the alicyclic dicarboxylic acid and 1,4-cyclohexanediol as the alicyclic diol is excellent in transparency and optical properties, has low water absorption, and is mechanical. Since physical properties and thermal characteristics are good, it is described that it is very useful as a molding material for various optical components (Patent Document 1, Patent Document 2).
However, in order to obtain a dinorbornane dicarboxylic acid ester, it is reacted using an equal amount or more of hydrogen cyanide which is difficult to recover at the stage of the precursor dicarbonitrile body, and subsequently hydrolyzed to obtain a carboxylic acid body, Further, a method is described in which thionyl chloride, which is difficult to recover, is converted to an acid chloride form by using two or more equivalents and then reacted with alcohol. However, the synthesis route involves many steps and is not economical because it consumes a large amount of reagents such as hydrogen cyanide and thionyl chloride, and it cannot be said to be a suitable method in terms of waste regulations.

The carbonylation method using an HF catalyst is a promising method for industrial implementation since the recovery of the HF catalyst is easy, and the method for carbonylation of a norbornene structure compound in the presence of HF is known. However, monocarboxylic acid ester was the main product (Patent Document 3 and Patent Document 4).
In addition, the inventors used 2,5-norbornadiene and methyl 5-norbornene-2-carboxylate as raw materials and studied carbonylation with carbon monoxide in the presence of HF, but dicarboxylic acid ester was obtained. In addition, a method for producing a dicarboxylic acid ester composition having a target norbornane skeleton with high yield has not been known.

JP 2003-286240 A JP 2003-292591 A Japanese Patent Laying-Open No. 2005-089398 WO2012-063433

  An object of the present invention is to provide a method for producing a dicarboxylic acid ester composition having a norbornane skeleton useful as a production raw material for various industrial chemical raw materials, optical functional materials and electronic functional materials at a low cost and in a high yield. There is.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following problems can be solved by the present invention.

That is, the present invention is a method for producing a dicarboxylic acid ester having a norbornane skeleton represented by the following general formula (1),
Dicarboxylic acid fluoride having a norbornane skeleton represented by the following general formula (2) obtained by reacting an unsaturated carboxylic acid ester represented by the following general formula (3) with carbon monoxide in the presence of hydrogen fluoride. Is produced by reacting with alcohol.

（式中Ｒ¹、Ｒ²、およびＲ³は炭素数１〜４のアルキル基である。nは０、１又は２である。）

(Wherein R ¹ , R ² , and R ³ are alkyl groups having 1 to 4 carbon atoms. N is 0, 1 or 2)

  According to the method of the present invention, an unsaturated carboxylic acid ester represented by the general formula (3) derived from a substance having no problem in availability such as dicyclopentadiene and methyl acrylate is used as a starting material, and optical characteristics are obtained. It is possible to produce a dicarboxylic acid ester composition having a norbornane skeleton represented by the general formula (1), which is excellent in the above, by an industrially advantageous method.

The result of DEPT135 degree-NMR measurement of the component 3 obtained in Example 1 is shown. The result of the HSQC-NMR measurement of the component 3 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the H2BC-NMR measurement of the component 3 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the HMBC-NMR measurement of the component 3 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the INADEQUAT-NMR measurement of the component 3 obtained in Example 1 is shown. It is an enlarged view of the measurement result of 31-56 ppm part in FIG. The result of NOESY-NMR measurement of the component 3 obtained in Example 1 is shown. It is an enlarged view of the measurement result of the 1.0-2.6 ppm part in FIG. The result of the NOE difference spectrum-NMR measurement of the component 3 obtained in Example 1 is shown. The result of DEPT135 degree-NMR measurement of the component 4 obtained in Example 1 is shown. The result of the HSQC-NMR measurement of the component 4 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the H2BC-NMR measurement of the component 4 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the HMBC-NMR measurement of the component 4 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the INADEQUAT-NMR measurement of the component 4 obtained in Example 1 is shown. It is an enlarged view of the measurement result of 31-56 ppm part in FIG. The result of NOESY-NMR measurement of the component 4 obtained in Example 1 is shown. It is an enlarged view of the measurement result of the 1.0-2.6 ppm part in FIG. The result of the NOE difference spectrum-NMR measurement of the component 4 obtained in Example 1 is shown. The result of DEPT135 degree-NMR measurement of the component 1 obtained in Example 1 is shown. The result of the HSQC-NMR measurement of the component 1 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the H2BC-NMR measurement of the component 1 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the HMBC-NMR measurement of the component 1 obtained in Example 1 is shown. It is an enlarged view of the measurement result of 0.9-3.8 ppm part in FIG. The result of NOESY-NMR measurement of the component 1 obtained in Example 1 is shown. It is an enlarged view of the measurement result of the 1.0-2.6 ppm part in FIG. The result of NOE difference spectrum-NMR measurement of component 1 obtained in Example 1 (irradiating a magnetic field to # 9 hydrogen atom) is shown. The result of NOE difference spectrum-NMR measurement of component 1 obtained in Example 1 (irradiating a magnetic field to # 12 hydrogen atom) is shown. The result of DEPT135 degree-NMR measurement of the component 2 obtained in Example 1 is shown. The result of the HSQC-NMR measurement of the component 2 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the H2BC-NMR measurement of the component 2 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of the HMBC-NMR measurement of the component 2 obtained in Example 1 is shown. It is an enlarged view of the measurement result of FIG. The result of NOESY-NMR measurement of the component 2 obtained in Example 1 is shown. It is an enlarged view of the measurement result of the 1.0-2.6 ppm part in FIG. The result of NOE difference spectrum-NMR measurement of component 2 obtained in Example 1 (irradiating a magnetic field to # 9 hydrogen atom) is shown. The result of NOE difference spectrum-NMR measurement of component 2 obtained in Example 1 (irradiating a magnetic field to # 12 hydrogen atom) is shown.

  The dicarboxylic acid ester compound having a norbornane skeleton produced by the method of the present invention is represented by the following general formula (1).

式中Ｒ¹、Ｒ²、およびＲ³は、炭素数1〜４のアルキル基である。ｎは、０、１又は２である。Ｒ¹、Ｒ²、およびＲ³は、好ましくはメチル基であり、ｎは、好ましくは０又は１である。

In the formula, R ¹ , R ² , and R ³ are each an alkyl group having 1 to 4 carbon atoms. n is 0, 1 or 2. R ¹ , R ² , and R ³ are preferably methyl groups, and n is preferably 0 or 1.

The method for producing a dicarboxylic acid ester compound having a norbornane skeleton of the present invention,
(A) An unsaturated carboxylic acid ester represented by the following general formula (3) is reacted with carbon monoxide in the presence of a hydrogen fluoride (hereinafter sometimes referred to as HF) catalyst to obtain a formula (2) A step of obtaining a dicarboxylic acid fluoride having a norbornane skeleton represented (hereinafter sometimes abbreviated as “carbonylation step”),
(B) Next, the reaction solution obtained is reacted with an alcohol to obtain a dicarboxylic acid ester compound having a norbornane skeleton represented by the formula (1) (hereinafter sometimes abbreviated as “esterification step”),
Consists of.

式中Ｒ¹、Ｒ²、およびＲ³は、炭素数1〜４のアルキル基である。ｎは、０、１又は２である。Ｒ¹、Ｒ²、およびＲ³は、好ましくはメチル基であり、ｎは、好ましくは０又は１である。

In the formula, R ¹ , R ² , and R ³ are each an alkyl group having 1 to 4 carbon atoms. n is 0, 1 or 2. R ¹ , R ² , and R ³ are preferably methyl groups, and n is preferably 0 or 1.

<(A) Carbonylation step>
In the present invention, the carbonylation reaction of the unsaturated carboxylic acid ester represented by the following general formula (3) is carried out under pressure of carbon monoxide in the presence of an HF catalyst. Thereby, dicarboxylic acid fluoride having a norbornane skeleton represented by the formula (2) is obtained together with various by-products (including other isomers).

式中Ｒ¹およびＲ²は、炭素数１〜４のアルキル基である。ｎは、０、１又は２である。Ｒ¹およびＲ²は、好ましくはメチル基であり、ｎは、好ましくは０又は１である。

In the formula, R ¹ and R ² are each an alkyl group having 1 to 4 carbon atoms. n is 0, 1 or 2. R ¹ and R ² are preferably methyl groups, and n is preferably 0 or 1.

[Unsaturated carboxylic acid ester]
The unsaturated carboxylic acid ester represented by the general formula (3) can be synthesized, for example, by a Diels-Alder reaction in which a corresponding olefin and a diene compound are heated and reacted.
Examples of olefins used in the synthesis of unsaturated carboxylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and crotonic acid. Methyl, ethyl crotonate, propyl crotonate, butyl crotonate, and the like, and more preferable olefins include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl crotonate, ethyl crotonate, 3 -Methyl methyl crotonate, ethyl 3-methyl crotonate, methyl tiglate and the like.

  The diene compound used for the synthesis of the unsaturated carboxylic acid ester represented by the general formula (3) is dicyclopentadiene, preferably having a high purity, and content of butadiene, isoprene, etc. is avoided as much as possible. It is desirable. The purity of dicyclopentadiene is more preferably 90% or more, and still more preferably 95% or more. Further, since it is known that dicyclopentadiene is depolymerized to be cyclopentadiene under heating conditions, it is also possible to use cyclopentadiene instead of dicyclopentadiene.

  In order for the Diels-Alder reaction to proceed efficiently, it is important that cyclopentadiene is present in the reaction system, so the reaction temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. preferable. On the other hand, the reaction is preferably performed at a temperature of 250 ° C. or lower in order to suppress the by-product of the high boiling substance. In addition, hydrocarbons, alcohols, esters and the like can be used as reaction solvents, such as aliphatic hydrocarbons having 6 or more carbon atoms, cyclohexane, toluene, xylene, ethylbenzene, mesitylene, propanol, butanol and the like. Is preferred.

  As a reaction system of Diels-Alder reaction of this embodiment, a batch type using a tank reactor, a semi-batch type for supplying a substrate or a substrate solution to a tank reactor under reaction conditions, a reaction condition for a tube reactor It is possible to adopt various reaction methods such as a continuous flow method in which substrates are distributed below.

  The reaction product obtained by the Diels-Alder reaction of this embodiment can be used as a raw material for the next carbonylation reaction as it is, but after being purified by a method such as distillation, extraction or crystallization, it is used for the next step. May be.

[Carbon monoxide]
Carbon monoxide used in the carbonylation step of the present invention may contain an inert gas such as nitrogen or methane, but the carbon monoxide partial pressure is in the range of 0.5 to 5 MPa, preferably in the range of 1 to 3 MPa. To implement. If the carbon monoxide partial pressure is higher than 0.5 MPa, the carbonylation reaction proceeds sufficiently, side reactions such as disproportionation and polymerization do not occur at the same time, and the alicyclic carbonyl compound, which is the target product, is produced in high yield. Can be obtained. The carbon monoxide partial pressure is preferably 5 MPa or less from the viewpoint of equipment load.

[Hydrogen fluoride]
Since HF used in the carbonylation step is a solvent for the reaction, a catalyst, and a secondary material, a substantially anhydrous one is used. The amount of HF used is 10 to 100 mol times, preferably 15 to 50 mol times, based on the unsaturated carboxylic acid ester of the raw material. If the molar ratio of HF is 10 mol times or more, the carbonylation reaction proceeds efficiently, side reactions such as disproportionation and polymerization can be suppressed, and the target dicarboxylic acid fluoride can be obtained in high yield. . Further, from the viewpoint of raw material cost and productivity, it is preferable to use 50 mol times or less of HF.

[Reaction conditions]
The type of the carbonylation reaction is not particularly limited, and any method such as a batch system, a semi-continuous system, or a continuous system may be used.

  The reaction temperature of the carbonylation reaction is -30 ° C to 80 ° C, preferably -10 ° C to 50 ° C. The carbonylation reaction proceeds at a reaction temperature of −30 ° C. or higher. However, since polymerization occurs at 80 ° C. or higher, it is preferably performed at around 0 ° C. from the viewpoint of selectivity and reaction rate.

<(B) Esterification step>
The dicarboxylic acid fluoride reaction liquid produced by the carbonylation reaction is reacted with an alcohol having 1 to 4 carbon atoms to form a dicarboxylic acid ester compound. At this time, a method of adding a predetermined amount of alcohol to the acid fluoride reaction liquid is preferable from the viewpoint of the corrosiveness of the reaction apparatus.

  Moreover, the acid fluoride reaction liquid produced | generated by carbonylation reaction is refine | purified by conventional methods, such as distillation, after distilling off excess HF instead of this esterification process, and it is an acid fluoride with a next process. It can also be used as a raw material for the esterification step of a certain carbonyl group, or (II) after distilling off excess HF, it is hydrolyzed to obtain the corresponding carboxylic acid, and the carboxylic acid is obtained by a conventional method such as distillation. It can also be used as a raw material for the carbonyl group esterification step which is the next step after purification.

式中Ｒ¹、Ｒ²、およびＲ³は、炭素数１〜４のアルキル基である。ｎは、０、１又は２である。Ｒ¹、Ｒ²、およびＲ³は、好ましくはメチル基であり、ｎは、好ましくは０又は１である。

In the formula, R ¹ , R ² , and R ³ are each an alkyl group having 1 to 4 carbon atoms. n is 0, 1 or 2. R ¹ , R ² , and R ³ are preferably methyl groups, and n is preferably 0 or 1.

  Specific alcohols used in the esterification step include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, i-butyl alcohol, and t-butyl alcohol. Of these, methanol or ethanol is preferred from the viewpoint of reactivity.

  The usage-amount of alcohol is 1.0-2.5 mol times with respect to the raw material unsaturated carboxylic acid ester of a carbonylation process, Preferably it is 1.5-2.0 mol times. If the molar ratio of alcohol is 1.0 mol times or more, it is preferable because the remaining amount of unreacted fluoride is small and the device corrosion in the subsequent process is small. From the viewpoint of suppression, 2.5 mole times or less is preferable.

  The reaction temperature in the esterification step is −40 ° C. or higher and 20 ° C. or lower from the viewpoint of inhibiting decomposition of the dicarboxylic acid ester compound represented by the chemical formula (1). By setting the reaction temperature to −40 ° C. or higher, the esterification rate can be increased and the yield can be improved. Moreover, by making it 20 degrees C or less, while suppressing decomposition | disassembly of ester, the byproduct of water by the dehydration reaction of alcohol can be suppressed.

The obtained reaction liquid contains a complex of HF and a dicarboxylic acid ester compound represented by the formula (1). For example, the esterification reaction product liquid is heated to obtain a dicarboxylic acid represented by the formula (1). By decomposing the bond between the acid ester and HF, HF can be vaporized and separated, recovered and reused. In addition, it is preferable to perform decomposition | disassembly operation | movement of this complex as rapidly as possible from a viewpoint of suppressing the heat alteration of a product, isomerization, etc. In order to rapidly proceed with the thermal decomposition of the complex, for example, it is preferable to heat under reflux of a solvent inert to HF (for example, a saturated aliphatic hydrocarbon such as heptane or an aromatic hydrocarbon such as benzene). .
In addition, isolation of the dicarboxylic acid ester compound represented by Formula (1) can be performed according to a conventional method, and the method is not particularly limited. For example, after the esterification reaction product liquid is extracted into ice water and the oil phase and the aqueous phase are separated, the oil phase is washed alternately with an aqueous sodium hydroxide solution and distilled water, dehydrated with anhydrous sodium sulfate, After distilling off the low boilers, etc., the dicarboxylic acid ester compound represented by the formula (1) is obtained with relatively high purity by performing rectification using, for example, a rectification column having about 5 theoretical plates. be able to.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. In the following, “%” means mass% unless otherwise specified.

<Analysis methods and conditions>
[Gas chromatography]
For gas chromatography, GC-17A manufactured by Shimadzu Corporation and HR-1 manufactured by ULBON (0.32 mmφ × 25 m × 0.50 μm) were used as capillary columns. The temperature was raised from 100 ° C. to 300 ° C. at a rate of 5 ° C./min.

[Conversion rate of unsaturated carboxylic acid ester]
By gas chromatography analysis, the weight ratio (wt%) of the raw material unsaturated carboxylic acid ester was determined by the internal standard method, and the conversion rate was calculated by the following formula.
Conversion (mol%) = 100− {Remaining amount of raw material / Amount of raw material charged × 100}

[Carboxylic acid ester compound yield, isomer ratio]
By gas chromatography analysis, the weight ratio (wt%) of several kinds of isomer dicarboxylic acid ester compounds as products was obtained by an internal standard method, and the dicarboxylic acid ester compound yield and isomer ratio were calculated by the following formulas.
{Yield of dicarboxylic acid ester compound (mol%)} = {Component 1 acquisition amount + Component 2 acquisition amount + Component 3 acquisition amount + Component 4 acquisition amount + Other isomer acquisition amount} /278.3/ {Preparation of raw materials Amount / 218.3} × 100
{Isomer ratio (%)} = {Each dicarboxylic acid ester compound (component 1, component 2, component 3, component 4, other isomers) (%)} / {total of dicarboxylic acid ester compounds (%)} × 100

[GC-TOF-MS]
Waters GC-MS equipment GCT Premier

[Preparative HPLC]
Equipment: LC system (LC-20AP) manufactured by Shimadzu Corporation
Column: Tosoh TSKgel ODS-80Ts
Mobile phase: CH3CN / H2O = 80 / 20-60 / 40

[NMR]
Apparatus: Bruker Avance 600II (600 MHz-NMR)
Mode: Proton, Carbon, DEPT135 °,
NOE difference spectrum (1D), H2SC, HSQC, HMBC,
INADEQUATE, NOESY
Solvent: CDCl3 (deuterated chloroform)
Internal standard: Tetramethylsilane

[Glass transition temperature (Tg)]
Apparatus: Differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC / TA-60WS)

<Example 1>
Production of dinorbornane dicarboxylic acid ester composition

[Preparation of dinorbornene carboxylic acid ester]
A 500 ml stainless steel reactor was charged with 195 g (2.27 mol) of methyl acrylate and 188 g (1.42 mol) of dicyclopentadiene and reacted at 195 ° C. for 2 hours. This operation was performed 5 times to obtain a reaction liquid containing 574 g of dinorbornene carboxylic acid ester. After distillation and purification, a part of the reaction liquid was subjected to the subsequent reaction.

[Carbonylation step]
After replacing the inside of a stainless steel autoclave with an internal volume of 500 ml that can be controlled by the jacket with carbon monoxide, equipped with a Nack drive stirrer, three inlet nozzles at the top and one extraction nozzle at the bottom, and then fluorinated After introducing 201 g (5.0 mol) of hydrogen to a liquid temperature of 0 ° C., the pressure was increased to 2 MPa with carbon monoxide.
While maintaining the reaction temperature at 0 ° C. and maintaining the reaction pressure at 2 MPa, a mixture of 109.5 g (0.50 mol) of the prepared dinorbornenecarboxylic acid ester and 54.7 g of heptane was supplied from the top of the autoclave. A carbonylation reaction was performed. After completion of the supply, stirring was continued for about 60 minutes until absorption of carbon monoxide was not observed.

[Esterification process]
Subsequently, while maintaining the reaction temperature at 0 ° C., 24.1 g (0.75 mol) of methanol was supplied from the top of the autoclave, and esterification was performed for 1 hour with stirring.
The reaction solution was extracted from the bottom of the autoclave into ice water, and the oil phase and the aqueous phase were separated. The oil phase was then washed twice with 100 ml of 2% aqueous sodium hydroxide solution and twice with 100 ml of distilled water, and dehydrated with 10 g of anhydrous sodium sulfate. . The obtained liquid was analyzed by gas chromatography. As a result, the conversion was 100 mol%, the dicarboxylic acid ester compound yield was 85.4 mol% (based on dinorbornene carboxylic acid ester), and it was an isomer of the dicarboxylic acid ester compound. The isomer ratios of Component 1, Component 2, Component 3, Component 4, and other isomers were 7.2%, 22.1%, 47.3%, 20.6%, and 2.8%, respectively. .

[Isolation and purification of product]
When the obtained liquid was subjected to rectification using a rectification column having 5 theoretical plates (distillation temperature of 160 ° C., vacuum degree of 1 torr), component 1 was 6.6% and component 2 was 20 as the main fraction. 0.45%, Component 3 44.9%, Component 4 19.5%, and other isomers total 2.7% 101.5 g (distillation yield 80.1 mol%, based on esterification reaction solution) Was obtained.

<Identification of product>
The main product was further subjected to column purification using the HPLC apparatus, and fractions 1, 2, 3, and 4 were collected. The four components were all compounds having a molecular weight of 278, a composition formula of C ₁₆ H ₂₂ O ₄ and an unsaturated number of 6 in the GC-TOF-MS analysis.
Moreover, about each component, using the said NMR apparatus, 1H-NMR measurement, 13C-NMR measurement, DEPT135-NMR measurement, NOE difference spectrum (1D) measurement, H2SC-NMR measurement, HSQC-NMR measurement, HMBC-NMR measurement , INADEQUAT-NMR measurement and NOESY-NMR measurement were performed.
The results of 1H-NMR measurement and 13C-NMR measurement are shown below. DEPT135-NMR measurement, HSQC-NMR measurement, H2SC-NMR measurement, HMBC-NMR measurement, INADEQUATATE-NMR measurement, NOE difference spectrum (1D) measurement, NOESY -NMR measurement and results are shown in FIGS.

[Results of NMR measurement of component 3 as the main product obtained in Example 1]
1H-NMR (600 MHz, CDCl3, TMS, ppm) δ: 1.10 (d, 2H), 1.40 (t, 2H), 1.49 (s, 2H), 1.76 (m, 4H), 2.20 (m, 2H), 2.24 (m, 2H), 2.43 (s, 2H), 3.65 (s, 6H)
13C-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 33.44, 35.26, 39.75, 44.57, 47.05, 51.62, 52.71, 175.95
From the above-mentioned GC-TOF-MS measurement results and NMR measurement results, it was found that component 3 has a symmetrical structure, with 2 mol of carbon overlapping each other.

FIG. 1 shows the results of DEPT135 ° -NMR measurement. It can be seen that the secondary carbon atoms No. 1 and No. 2 are detected downward and the peak disappearance of the No. 8 quaternary carbon atom. 2 and 3 show the results of HSQC-NMR measurement (FIG. 3 is an enlarged view of the measurement result of the 0.9 to 3.8 ppm portion in FIG. 2). From FIG. 2 and FIG. 3, the hydrogen atoms bonded to each carbon atom are grasped. 4 and 5 show the results of the H2BC-NMR measurement (FIG. 5 is an enlarged view of the measurement results of the 0.9 to 3.8 ppm portion in FIG. 4). From FIG. 4 and FIG. 5, it is grasped about a hydrogen atom one bond away from each carbon atom. 6 and 7 show the results of HMBC-NMR measurement (FIG. 7 is an enlarged view of the measurement results in the 0.9 to 3.8 ppm portion in FIG. 6). From FIG. 6 and FIG. 7, it is understood about hydrogen atoms that are two bonds away from each carbon atom. 8 and 9 show the results of the INADEQUAT-NMR measurement (FIG. 9 is an enlarged view of the measurement results at 31 to 56 ppm in FIG. 8). From FIG. 8 and FIG. 9, the carbon atoms that are bonded to each carbon atom are grasped. FIGS. 10 and 11 show the results of NOESY-NMR measurement (FIG. 11 is an enlarged view of the measurement results of the 1.0 to 2.6 ppm portion in FIG. 10). 10 and 11, the correlation between the hydrogen atom at the carbonyl group bonding position and each hydrogen atom can be grasped. FIG. 12 shows the results of NOE difference spectrum-NMR measurement. When the 5th hydrogen atom at the carbonyl group bonding position is irradiated with a magnetic field, the spatially adjacent 3rd hydrogen atom is excited, so that the exo-exo isomer is recognized.
Judging comprehensively from these measurement results, Component 3 was identified as an exo-exo form of methyl dinorbornane-2,6-dicarboxylate.

[Results of NMR measurement of component 4 obtained in Example 1]
1 H-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 1.10 (d, 2H), 1.40 (t, 2H), 1.49 (s, 2H), 1.77 (m, 4H), 2.20 (m, 2H), 2.24 (m, 2H), 2.44 (s, 2H), 3.65 (s, 6H)
13C-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 33.44, 35.02, 39.76, 44.52, 47.27, 51.66, 52.33, 53.18, 175.97

FIG. 13 shows the results of DEPT135 ° -NMR measurement. It can be seen that the secondary carbon atoms No. 1 and No. 2 are detected downward and the peak No. 9 of the quaternary carbon atom is lost. 14 and 15 show the results of HSQC-NMR measurement (FIG. 15 is an enlarged view of the measurement result of 0.9 to 3.8 ppm in FIG. 14). From FIG. 14 and FIG. 15, it is grasped about the hydrogen atom bonded to each carbon atom. 16 and 17 show the results of the H2BC-NMR measurement (FIG. 17 is an enlarged view of the measurement results in the 0.9 to 3.8 ppm portion in FIG. 16). From FIG. 16 and FIG. 17, it is grasped about a hydrogen atom one bond away from each carbon atom. 18 and 19 show the results of HMBC-NMR measurement (FIG. 19 is an enlarged view of the measurement results of the 0.9 to 3.8 ppm portion in FIG. 18). From FIG. 18 and FIG. 19, it is understood about hydrogen atoms that are two bonds away from each carbon atom. 20 and 21 show the results of INADEQUAT-NMR measurement (FIG. 21 is an enlarged view of the measurement results of the 31-56 ppm portion in FIG. 20). From FIG. 20 and FIG. 21, the carbon atoms that are bonded to each carbon atom are grasped. 22 and FIG. 23 show the results of NOESY-NMR measurement (FIG. 23 is an enlarged view of the measurement results of the 1.0 to 2.6 ppm portion in FIG. 22). The correlation between the hydrogen atom at the carbonyl group bonding position and each hydrogen atom can be understood from FIGS. FIG. 24 shows the results of NOE difference spectrum-NMR measurement. When the 5th hydrogen atom at the carbonyl group bonding position is irradiated with a magnetic field, the spatially adjacent 3rd hydrogen atom is excited, so that the exo-exo isomer is recognized.
Judging comprehensively from these measurement results, Component 4 was identified as an exo-exo form of methyl dinorbornane-2,7-dicarboxylate.

[NMR measurement result of component 1 obtained in Example 1]
1H-NMR (600 MHz, CDCl3, TMS, ppm) δ: 1.03 (d, 1H), 1.10 (d, 1H), 1.40 (m, 1H), 1.43 (m, 1H), 1.55 (d, 1H), 1.60 (m, 2H), 1.73 (m, 1H), 1.80 (d, 1H), 1.96 (d, 1H), 2.18 (m , 1H), 2.24 (m, 1H), 2.42 (s, 1H), 2.49 (s, 1H), 2.62 (m, 1H), 3.64 (s, 3H), 3 .69 (s, 3H)
13C-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 33.02, 33.90, 34.97, 37.12, 39.92, 40.79, 43.94, 44.50, 46.94, 47.24, 47.92, 51.69, 52.54, 77.02, 175.04, 176.15

FIG. 25 shows the results of DEPT135 ° -NMR measurement. It can be seen that the secondary carbon atoms No. 1, No. 2, No. 3, and No. 4 are detected downward, and the peak disappearance of the No. 15 and No. 16 carbon atoms. FIG. 26 and FIG. 27 show the results of HSQC-NMR measurement (FIG. 27 is an enlarged view of the measurement results of 0.9 to 3.8 ppm in FIG. 26). From FIG. 26 and FIG. 27, it is grasped about the hydrogen atom bonded to each carbon atom. 28 and FIG. 29 show the results of H2BC-NMR measurement (FIG. 29 is an enlarged view of the measurement results of 0.9 to 3.8 ppm in FIG. 28). From FIG. 28 and FIG. 29, it is grasped about a hydrogen atom that is one bond away from each carbon atom. 30 and 31 show the results of HMBC-NMR measurement (FIG. 31 is an enlarged view of the measurement results of the 0.9 to 3.8 ppm portion in FIG. 30). From FIG. 30 and FIG. 31, it is understood about hydrogen atoms that are two bonds away from each carbon atom. 32 and 33 show the results of NOESY-NMR measurement (FIG. 33 is an enlarged view of the measurement results in the 0.9 to 2.8 ppm portion in FIG. 32). 32 and 33, the correlation between the hydrogen atoms of the 9th and 12th carbonyl groups and each hydrogen atom can be grasped. 34 and 35 show the results of NOE difference spectrum-NMR measurement. Irradiating a magnetic field to the 9th hydrogen atom at the carbonyl bond position excites the spatially adjacent 4th hydrogen atom, and irradiating the 12th hydrogen atom to the magnetic field results in the 1st spatially adjacent hydrogen atom. Is excited to be an exo-endo body.
Judging comprehensively from these measurement results, Component 1 was identified as an exo-endo form of methyl dinorbornane-2,7-dicarboxylate.

[Results of NMR measurement of component 2 obtained in Example 1]
1H-NMR (600 MHz, CDCl3, TMS, ppm) δ: 1.03 (d, 1H), 1.10 (d, 1H), 1.38 (m, 1H), 1.40 (m, 1H), 1.55 (d, 1H), 1.60 (m, 2H), 1.73 (m, 1H), 1.80 (d, 1H), 1.96 (d, 1H), 2.18 (m , 1H), 2.24 (m, 1H), 2.42 (s, 1H), 2.49 (s, 1H), 2.62 (m, 1H), 3.64 (s, 3H), 3 .69 (s, 3H)
13C-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 33.26, 33.91, 35.18, 37.10, 39.74, 40.80, 43.94, 44.75, 46.79, 46.98, 47.57, 51.63, 51.67, 52.86, 175.09, 176.21

FIG. 36 shows the results of DEPT135 ° -NMR measurement. It can be seen that the secondary carbon atoms No. 1, No. 2, No. 3, and No. 4 are detected downward, and the peak disappearance of the No. 15 and No. 16 carbon atoms. 37 and 38 show the results of HSQC-NMR measurement (FIG. 38 is an enlarged view of the measurement result of 0.9 to 3.8 ppm portion in FIG. 37). From FIG. 37 and FIG. 38, the hydrogen atom bonded to each carbon atom is grasped. 39 and 40 show the results of the H2BC-NMR measurement (FIG. 40 is an enlarged view of the measurement results of the 0.9 to 3.8 ppm portion in FIG. 39). From FIG. 39 and FIG. 40, it is grasped about the hydrogen atom that is one bond away from each carbon atom. 41 and 42 show the results of HMBC-NMR measurement (FIG. 42 is an enlarged view of the measurement results of the 0.9 to 3.8 ppm portion in FIG. 41). 41 and 42, the hydrogen atoms separated from each carbon atom by two bonds are grasped. 43 and 44 show the results of NOESY-NMR measurement (FIG. 44 is an enlarged view of the measurement results of 0.9 to 2.8 ppm in FIG. 43). 43 and 44, the correlation between the hydrogen atoms at the 9th and 12th carbonyl groups and each hydrogen atom can be understood. 45 and 46 show the results of NOE difference spectrum-NMR measurement. Irradiating a magnetic field to the 9th hydrogen atom at the carbonyl group bonding position excites a spatially adjacent 5th hydrogen atom, and irradiating the 12th hydrogen atom to a magnetic field results in a spatially adjacent 1st hydrogen atom. Is excited to be an exo-endo body.
Judging comprehensively from these measurement results, Component 2 was identified as an exo-endo form of methyl dinorbornane-2,6-dicarboxylate.

<Example 2>
(Carbonylation / esterification reaction)
A stainless steel autoclave with an internal volume of 10 liters equipped with a Nack drive type stirrer, three inlet nozzles at the top and one extraction nozzle at the bottom and whose internal temperature can be controlled by a jacket is replaced with carbon monoxide, and then hydrogen fluoride. 1220 g (61.0 mol) was introduced, the contents were stirred, and the pressure was increased to 2 MPa with carbon monoxide while maintaining the liquid temperature at 0 ° C. Thereafter, while maintaining the pressure at 2 MPa and the liquid temperature at 0 ° C., a mixture of 266.2 g (1.22 mol) of dinorbornenecarboxylic acid ester prepared in Example 1 and 133.1 g of heptane was added from the top of the autoclave to 1. The carbonylation reaction was carried out by feeding over 5 hours. After the supply of the raw material was completed, stirring was continued for about 60 minutes until carbon monoxide absorption was not observed.
Next, while maintaining the reaction temperature at 0 ° C., 58.6 g (1.83 mol) of methanol was supplied from the top of the autoclave, and esterification was performed for 1 hour with stirring.
A part of the obtained reaction solution was sampled in ice water, and the oil layer obtained by neutralization treatment was analyzed by gas chromatography to obtain the reaction results. The isomer ratios of Component 2, Component 3, Component 4, and other isomers were 8.1%, 21.2%, 45.1%, 23.0%, and 2.6%, respectively.

(Complex thermal decomposition)
A distillation tower having an inner diameter of 76 cm and a length of 176 cm was filled with a Teflon Raschig ring to decompose the HF / dicarboxylic acid ester compound complex. The supply flow rate of the complex solution supplied to the middle column of the distillation column was 300 g / H, and heptane was supplied to the lower column of the distillation column as a decomposition aid at 500 g / H. The pressure inside the tower was 0.2 MPa, the tower bottom temperature was 140 ° C., and the bottom liquid drainage was 550 g / H. HF as a catalyst was recovered from the top of the column, and the dicarboxylic acid ester compound was extracted along with a large amount of heptane from the bottom of the column. The inorganic fluorine content / dicarboxylic acid ester compound at the bottom of the column was 3 ppm, and the complex decomposition rate was 99.9%. The purity of the dicarboxylic acid ester compound was 75.7%.

(Distillation purification)
The obtained complex tower bottom liquid was neutralized and washed with 2% by weight NaOH aqueous solution and distilled water, and after removing low-boiling substances by an evaporator, rectification was performed using a rectification tower having five theoretical plates ( (Distillation temperature 160 ° C, degree of vacuum 1 torr), component 1 is 7.2%, component 2 is 20.0%, component 3 is 47.5%, component 4 is 24.3%, other isomers A total of 1.0% was obtained at 178.5 g (distillation yield 64.5 mol%, based on esterification reaction solution).

<Example 3>
(Synthesis of polymer of dicarboxylic acid ester compound and measurement of physical properties)
In a 0.2 L polyester production apparatus equipped with a partial condenser, total condenser, cold trap, stirrer, heating apparatus, and nitrogen introduction tube, 40.0 g of the dicarboxylic acid ester compound synthesized in Example 2 and cyclohexanedimethanol 41 0.5 g (molar ratio 1/2) was charged, and the temperature was raised to 245 ° C. to carry out the esterification reaction. After setting the reaction conversion rate of the dicarboxylic acid component to 90% or more, add 51 ppm of tetra-i-propoxytitanium and 52 ppm of triethyl phosphate to the dicarboxylic acid component, gradually increase and decrease the pressure, and finally Polycondensation was performed at 260 ° C. The reaction was terminated when an appropriate melt viscosity was reached (4.5 hours), and a polyester resin was produced.
When the physical properties of the obtained polyester resin were measured, the average molecular weight was 18800 and Tg was 112.2 ° C., which was higher than that of the general-purpose polyester resin.

  The alicyclic dicarboxylic acid ester compound having a norbornane skeleton obtained in the present invention is useful as a raw material for producing various industrial chemical raw materials, optical functional materials and electronic functional materials.

Claims (1)

A method for producing a dicarboxylic acid ester having a norbornane skeleton represented by the following general formula (1),
Dicarboxylic acid fluoride having a norbornane skeleton represented by the following general formula (2) obtained by reacting an unsaturated carboxylic acid ester represented by the following general formula (3) with carbon monoxide in the presence of hydrogen fluoride. Reacting with an alcohol.

(Wherein R ¹ , R ² , and R ³ are alkyl groups having 1 to 4 carbon atoms. N is 0, 1 or 2)

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