JP2015000866A - Novel ethyladamantane dicarboxylate compound and production method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel ethyladamantane dicarboxylate compound that is useful as various industrial chemical raw materials and production raw materials of optical functional materials or electronic functional materials, and to provide an industrial production method for the compound.SOLUTION: A novel ethyladamantane dicarboxylate compound is produced by allowing 1-ethyladamantane as a raw material to react with carbon monoxide in the presence of hydrogen fluoride and boron trifluoride, and then allowing the obtained ethyladamantane dicarboxylic acid fluoride to react with alcohol.

Description

  The present invention relates to a novel ethyladamantane dicarboxylic acid ester compound and a method for producing the same.

  Polyester resins synthesized from alicyclic dicarboxylic acids and alicyclic diols are excellent in transparency, heat resistance, weather resistance, gas barrier properties, and optical properties, so they can be used for optical materials, electronic information materials, medical device materials, etc. Can be used.

For example, 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) as alicyclic dicarboxylic acid and 1,4-cyclohexanedimethanol (1,4-CHDM) as alicyclic diol are excellent in biodegradability. Polyester resin (Patent Document 1), conductive polyester (Patent Document 2) with a small amount of released gas, and polyester suitable for medical use are synthesized (Patent Document 3). Further, tricyclo alicyclic dicarboxylic acid [3.3.1.1 ^{3, 7]} decane dicarboxylic acid, optically using a tricyclo [3.3.1.1 ^{3, 7]} decane diol alicyclic diols different A polyester resin having a small isotropic property and excellent moldability is synthesized (Patent Document 4).

JP 2000-290356 A JP 2004-124022 A JP 2005-298555 A Japanese Patent No. 3862538

  An object of the present invention is to provide a novel ethyladamantane dicarboxylic acid ester compound useful as a raw material for producing various industrial chemical raw materials, optical functional materials and electronic functional materials, and a method for producing the same.

As a result of studying a method for producing a novel ethyladamantane dicarboxylic acid ester compound represented by formula (1) from 1-ethyladamantane represented by formula (3), the present inventors have found that hydrogen fluoride (hereinafter referred to as hydrogen fluoride) HF) and boron trifluoride (hereinafter also referred to as BF ₃ ) in the presence of 1-ethyladamantane represented by the formula (3) and carbon monoxide, and then represented by the formula (2) obtained. It was proved that ethyl adamantane dicarboxylic acid fluoride represented by the formula (1) can be produced by reacting ethyl adamantane dicarboxylic acid fluoride with alcohol.
The present invention has been completed based on such findings.

（式中Ｒは炭素数1〜４のアルキル基、m、nは0又は1の数値である。）

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, and m and n are values of 0 or 1.)

That is, the present invention is as follows.
[1] An ethyladamantane dicarboxylic acid ester compound represented by the formula (1).

（式中Ｒは炭素数1〜４のアルキル基、m、nは0又は1の数値である。）

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, and m and n are values of 0 or 1.)

[2] In the presence of hydrogen fluoride and boron trifluoride, 1-ethyladamantane represented by the formula (3) is reacted with carbon monoxide, and then the obtained ethyladamantane dicarboxylic acid represented by the formula (2) A method for producing an ethyladamantane dicarboxylic acid ester compound comprising reacting an acid fluoride with an alcohol to produce an ethyladamantane dicarboxylic acid ester compound represented by the formula (1).

（式中Ｒは炭素数1〜４のアルキル基、m、nは0又は1の数値である。）

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, and m and n are values of 0 or 1.)

  When the novel ethyladamantane dicarboxylic acid ester compound represented by the formula (1) of the present invention is used as a raw material for a polyester resin, the material exhibits excellent optical properties and heat resistance.

The result of the ¹³ C-NMR measurement by the inverse gate decoupling method of one component (di-isomer [A]) of the ethyladamantane dicarboxylic acid ester compound obtained in Example 1 is shown. The result of DEPT135 degree-NMR measurement of di-body [A] obtained in Example 1 is shown. The result of DEPT90 degree-NMR measurement of di-body [A] obtained in Example 1 is shown. The result of the HSQC-NMR measurement of the dibody [A] obtained in Example 1 is shown. It is an enlarged view of the measurement result of the 0.6-2.8 ppm part in FIG. The result of the HMBC-NMR measurement of the dibody [A] obtained in Example 1 is shown. It is an enlarged view of the measurement result of -0.2-2.7 ppm part in FIG. The result of the COSY-NMR measurement of the di-form [A] obtained in Example 1 is shown. The result of the ¹³ C-NMR measurement by the inverse gate decoupling method of one component (di-form [B]) of the ethyladamantane dicarboxylic acid ester compound obtained in Example 1 is shown. The result of DEPT135 degree-NMR measurement of di-body [B] obtained in Example 1 is shown. The result of DEPT90 degree-NMR measurement of di-body [B] obtained in Example 1 is shown. The result of the HSQC-NMR measurement of di-body [B] obtained in Example 1 is shown. It is an enlarged view of the measurement result of the 0.6 to 2.7 ppm portion in FIG. The result of the HMBC-NMR measurement of di-body [B] obtained in Example 1 is shown. FIG. 15 is an enlarged view of a measurement result of a portion of 0.5 to 2.4 ppm in FIG. The result of the COSY-NMR measurement of di-body [B] obtained in Example 1 is shown. The result of the ¹³ C-NMR measurement by the inverse gate decoupling method of one component (di-isomer [C]) of the ethyladamantane dicarboxylic acid ester compound obtained in Example 1 is shown. The result of DEPT135 degree-NMR measurement of di-body [C] obtained in Example 1 is shown. The result of DEPT90 degree-NMR measurement of di-body [C] obtained in Example 1 is shown. The result of the HSQC-NMR measurement of di-body [C] obtained in Example 1 is shown. FIG. 21 is an enlarged view of a measurement result of a portion of 0.5 to 2.4 ppm in FIG. The result of the HMBC-NMR measurement of di-body [C] obtained in Example 1 is shown. FIG. 23 is an enlarged view of a measurement result of a portion of −0.2 to 2.5 ppm in FIG. The result of the COSY-NMR measurement of di-body [C] obtained in Example 1 is shown.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  The novel ethyladamantane dicarboxylic acid ester compound of the present embodiment is represented by the above formula (1). In formula (1), examples of the alkyl group having 1 to 4 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, and a t-butyl group. Is mentioned.

Moreover, the novel ethyladamantane dicarboxylic acid ester compound production method of the present embodiment is obtained by reacting (a) 1-ethyladamantane represented by the above formula (3) with carbon monoxide in the presence of HF and BF _3. A step of obtaining ethyladamantane dicarboxylic acid fluoride represented by (2) (hereinafter sometimes abbreviated as “carbonylation step”),
(B) Next, a step of reacting with alcohol to obtain an ethyladamantane dicarboxylic acid ester compound represented by the formula (1) (hereinafter sometimes abbreviated as “esterification step”) is included.

<(A) Carbonylation step>
The carbonylation reaction of 1-ethyladamantane is carried out under pressure of carbon monoxide in the presence of HF and BF ₃ . Thereby, the ethyladamantane dicarboxylic acid fluoride represented by the formula (2) is obtained together with various by-products (including isomers).

（式中m、nは0又は1の数値である。）

(In the formula, m and n are numerical values of 0 or 1.)

[Carbon monoxide]
Carbon monoxide used in the carbonylation step of the present embodiment may contain an inert gas such as nitrogen or methane, but the carbon monoxide partial pressure is 0.5 to 5 MPa, preferably 1 to 4 MPa. Implement in scope. 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 target product, ethyladamantane dicarboxylic dicarboxylic acid fluoride, is obtained 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 to be used is 10 to 60 mol times, preferably 15 to 50 mol times with respect to 1-ethyladamantane as a 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 product, ethyladamantane dicarboxylic dicarboxylic acid fluoride, is obtained in high yield. be able to. In addition, from the viewpoint of raw material cost and productivity, it is preferable to use 60 mol times or less of HF.

[Boron trifluoride]
The amount of BF ₃ used is in the range of 0.3 to 2.0 mol times, preferably 0.5 to 1.5 mol times relative to the raw material 1-ethyladamantane. If the molar ratio of BF ₃ is 0.3 mol times or more, the carbonylation reaction proceeds efficiently. In addition, when the molar ratio of BF ₃ is 2.0 mol times or less, the BF 3 partial pressure becomes excessive and the carbon monoxide partial pressure is not suppressed, so that a good yield can be obtained.

[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 45 ° C to 90 ° C, preferably 60 ° C to 80 ° C. The carbonylation reaction proceeds at a reaction temperature of 45 ° C. or higher. However, since polymerization occurs at 80 ° C. or higher, it is preferably performed at around 70 ° C. from the viewpoint of selectivity and reaction rate.

<(B) Esterification step>
The ethyladamantane dicarboxylic acid fluoride reaction solution produced by the carbonylation reaction is reacted with an alcohol having 1 to 4 carbon atoms to obtain an ethyladamantane dicarboxylic acid ester compound. In this case, a method of adding a predetermined amount of alcohol to the ethyladamantane dicarboxylic acid fluoride reaction liquid is preferable from the viewpoint of the corrosiveness of the reaction apparatus.
In addition, the ethyl adamantane dicarboxylic acid fluoride reaction solution produced by the carbonylation reaction can be directly used as a raw material for the esterification reaction. (I) After the excess HF is distilled off, purification is performed by a conventional method such as distillation. And (II) after distilling off excess HF, hydrolysis is performed to obtain the corresponding carboxylic acid, and the carboxylic acid is purified by a conventional method such as distillation. It can also be used as a raw material for the esterification step.

（式中Ｒは炭素数1〜４のアルキル基、m、nは0又は1の数値である。）

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, and m and n are values of 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 1-ethyladamantane of a carbonylation process, Preferably it is 1.5-2.2 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 ethyladamantane 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.

  After distilling off HF from the obtained reaction solution containing the ethyladamantane dicarboxylic acid ester compound represented by the formula (1), it is purified by a conventional method such as distillation.

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 ethyl adamantane]
By gas chromatography analysis, the weight ratio (wt%) of the starting ethyl adamantane 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}
[Ethyl adamantane dicarboxylic acid ester compound yield, ester compound composition ratio]
By gas chromatography analysis, the weight ratio (wt%) of several kinds of ethyladamantane dicarboxylic acid ester compounds (hereinafter, sometimes abbreviated as “di-form”) as products is obtained by an internal standard method, and the di-form total yield, The production ratio of each dimer was calculated by the following formula. As will be described later, the di-form has three kinds of components with a relatively large production amount, which are referred to as di-form [A], di-form [B] and di-form [C], respectively. Ingredients other than seeds shall be other di forms.
{Di-isomer total yield (mol%)} = {Di-isomer [A] acquisition amount / 280.4 + Di-isomer [B] acquisition amount / 294.4 + Di-isomer [C] acquisition amount / 308.4 + Other di-isomers Acquired amount / 294.4} / {raw material charge / 164.3} × 100
{Di-body composition ratio (%)} = {each di-body composition (di-body [A], di-body [B], di-body [C], other di-body) (%)} / {di-body total composition ( %)} × 100

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

[NMR]
Apparatus: Bruker Avance 600II (600 MHz-NMR)
Mode: Proton, Carbon, Carbon (Inverse gate decoupling method), DEPT 90 °, 135 °, HSQC, HMBC, COSY
Solvent: CDCl3 (deuterated chloroform)
Internal standard: Tetramethylsilane

<Example 1>
Preparation of ethyl adamantanedicarboxylic acid dimethyl ester compound

（式中m、nは0又は1の数値である。）

(In the formula, m and n are numerical values of 0 or 1.)

[Carbonylation step]
A stainless-steel autoclave with an internal volume of 500 ml, equipped with a Nack drive agitator, three inlet nozzles at the top, and one extraction nozzle at the bottom, and the internal temperature can be suppressed by the jacket, is cooled with 1-ethyladamantane Co., Ltd.) 66.0 g (0.40 mol), anhydrous HF 241.2 g (12.05 mol), BF ₃ 20.4 g (0.30 mol) were charged, the contents were stirred, and the liquid temperature was raised to 78 ° C. Thereafter, the pressure was increased to 3 MPa with carbon monoxide. Thereafter, the carbonylation reaction was carried out while maintaining the pressure at 3 MPa and the liquid temperature at 78 ° C. for 3 hours.

[Esterification process]
Subsequently, after the reaction temperature was cooled to 5 ° C., 25.7 g (0.80 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. .
As a result of internal standard analysis of the obtained reaction liquid by gas chromatography, the conversion rate was 99.1 mol%, the di-isomer total yield was 48.2 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of the di-form [B], di-form [C], and other di-forms were 14.7%, 57.2%, 12.5%, and 15.6%, respectively.

[Isolation and purification of product]
When the obtained liquid was subjected to rectification using a rectification column having 20 theoretical plates (distillation temperature: 165 ° C., vacuum degree: 5 torr), di-form [A] 13.0% as distillate, di-form [B] 53.2 g (distillation yield 90.4 mol%, based on esterification reaction solution) of 53.2%, di-form [C] 11.6%, other di-form 15.4% It was. There was no significant change in composition ratio due to distillation.

<Identification of product>
The main product was further rectified using a rectification column having 50 theoretical plates, and di-form [A], di-form [B], and di-form [C] were fractionated. The three components were GC-MS and the molecular weights were 280, 294, and 308, respectively.
For each component, using the NMR apparatus, 1H-NMR measurement, 13C-NMR measurement, 13C-NMR measurement (Inverse gate decoupling method), dept90-NMR measurement, dept135-NMR measurement, HSQC-NMR measurement, HMBC -NMR measurement and COSY-NMR measurement were performed.
The results of 1H-NMR measurement and 13C-NMR measurement are shown below, and NMR measurement by inverse gate decoupling method, depth 135 °, 90 ° -NMR measurement, HSQC-NMR measurement, HMBC-NMR measurement, COSY-NMR measurement and results are shown. Shown in FIGS.

[NMR measurement result of di-isomer [A] obtained in Example 1]
1H-NMR (600 MHz, CDCl3, TMS, ppm) δ: 0.821 (t, 3H), 1.212 (m, 2H), 1.417 (d, 2H), 1.583 (m, 4H), 1.792 (d, 4H), 1.986 (m, 2H), 2.215 (m, 1H), 3.667 (s, 6H)
13C-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 6.90, 28.33, 33.95, 36.73, 37.66, 39.57, 39.95, 40.77, 41.81, 51.77, 177.36

FIG. 1 shows the result of ¹³ C-NMR measurement by the inverse gate decoupling method. From FIG. 1 it can be seen that the two carbonyl carbons are equivalent. FIG. 2 shows the results of DEPT135 ° -NMR measurement. It can be seen that secondary carbon atoms # 3, # 5, # 6, # 7, and # 8 are detected downward, and that peaks 4 and # 9 that are quaternary carbon atoms disappear. FIG. 3 shows the results of DEPT 90 ° -NMR measurement. It can be seen that the peak No. 10 which is a tertiary carbon atom is strongly detected. 4 and 5 show the results of HSQC-NMR measurement (FIG. 5 is an enlarged view of the measurement results of the 0.6 to 2.8 ppm portion in FIG. 4). From FIG. 4 and FIG. 5, it is grasped about the hydrogen atom bonded to each carbon atom. 6 and 7 show the results of HMBC-NMR measurement (FIG. 7 is an enlarged view of the measurement results of the −0.2 to 2.7 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. FIG. 8 shows the results of COSY-NMR measurement. The hydrogen atoms of adjacent carbon atoms are grasped.
Judging comprehensively from these measurement results, the di-isomer [A] was identified as dimethyl-5-ethyladamantane-1,3-dicarboxylate.

[NMR measurement result of di-form [B] obtained in Example 1]
1H-NMR (600 MHz, CDCl3, TMS, ppm) δ: 0.801 (t, 3H), 1.191 (m, 2H), 1.302 (m, 2H), 1.384 (m, 2H), 1.1.512 (m, 4H), 1.777 (m, 2H), 1.757 (d, 2H), 2.157 (m, 3H), 3.653 (s, 6H)
13C-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 6.96, 28.70, 33.36, 33.56, 35.75, 37.79, 39.97, 40.85, 442.23, 42.46, 43.10, 45.82, 47.90, 51.22, 51.68, 171.89, 177.69

FIG. 9 shows the result of ¹³ C-NMR measurement by the inverse gate decoupling method. From FIG. 9, it can be seen that the two carbonyl carbons are not equivalent. FIG. 10 shows the results of DEPT135 ° -NMR measurement. Secondary carbon atoms # 5, # 6, # 6, # 7, # 8, # 10, # 11, # 12 and # 13 are detected downward, and # 9 is a quaternary carbon atom. And the disappearance of the 14th and 15th peaks. FIG. 11 shows the results of DEPT 90 ° -NMR measurement. It can be seen that the peak No. 16 which is a tertiary carbon atom is strongly detected. FIGS. 12 and 13 show the results of HSQC-NMR measurement (FIG. 13 is an enlarged view of the measurement results at 0.6 to 2.7 ppm in FIG. 12). From FIG. 12 and FIG. 13, it is grasped about the hydrogen atom bonded to each carbon atom. 14 and 15 show the results of HMBC-NMR measurement (FIG. 15 is an enlarged view of the measurement results at 0.5 to 2.4 ppm in FIG. 14). From FIG. 14 and FIG. 15, it is understood about hydrogen atoms that are two bonds away from each carbon atom. FIG. 16 shows the results of COSY-NMR measurement. The hydrogen atoms of adjacent carbon atoms are grasped.
Judging comprehensively from these measurement results, the di-form [B] was identified as methyl-3-ethyl-5- (2-methoxy-2-oxoethyl) adamantane-1-dicarboxylate.

[NMR measurement result of di-form [C] obtained in Example 1]
1H-NMR (600 MHz, CDCl3, TMS, ppm) δ: 0.785 (t, 3H), 1.159 (m, 2H), 1.275 (m, 4H), 1.321 (m, 2H), 1.376 (m, 2H), 1.479 (m, 4H), 2.127 (m, 5H), 3.647 (s, 6H)
13C-NMR (600 MHz, CDCl 3, TMS, ppm) δ: 7.03, 29.15, 33.75, 33.99, 35.77, 40.11, 42.01, 45.92, 46.86, 47.90, 51.12, 172.06

FIG. 17 shows the result of ¹³ C-NMR measurement by the inverse gate decoupling method. From FIG. 17, it can be seen that the two carbonyl carbons are equivalent. FIG. 18 shows the results of DEPT135 ° -NMR measurement. You can see that the secondary carbon atoms # 3, # 4, # 5, # 6, # 7, and # 8 are detected downward, and the peak disappearance of the # 9 and # 10 carbon atoms. . FIG. 19 shows the results of DEPT 90 ° -NMR measurement. It turns out that the 11th peak which is a tertiary carbon atom is detected strongly. 20 and 21 show the results of HSQC-NMR measurement (FIG. 21 is an enlarged view of the measurement result of the 0.5 to 2.4 ppm portion in FIG. 20). From FIG. 20 and FIG. 21, the hydrogen atom bonded to each carbon atom is grasped. 22 and FIG. 23 show the results of HMBC-NMR measurement (FIG. 23 is an enlarged view of the measurement results at −0.2 to 2.5 ppm in FIG. 22). From FIG. 22 and FIG. 23, it is grasped about hydrogen atoms that are two bonds away from each carbon atom. FIG. 24 shows the results of COSY-NMR measurement. The hydrogen atoms of adjacent carbon atoms are grasped.
Judging comprehensively from these measurement results, the di-isomer [C] was identified as dimethyl-2,2- (5-ethyladamantane-1,3-diyl) diacetate.

<Example 2>
Carbonylation, esterification, and treatment of the reaction product liquid were performed in the same manner as in Example 1 except that the carbonylation reaction pressure was 2 MPa. As a result of internal standard analysis of the obtained reaction solution by gas chromatography, the conversion rate was 99.1 mol%, the di-isomer total yield was 39.5 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of the di-form [B], di-form [C], and other di-forms were 7.2%, 61.0%, 13.6%, and 18.2%, respectively.

<Example 3>
Carbonylation, esterification, and treatment of the reaction product solution were performed in the same manner as in Example 2 except that the carbonylation reaction time was 6 hours. As a result of internal standard analysis of the obtained reaction liquid by gas chromatography, the conversion was 99.1 mol%, the di-isomer total yield was 45.0 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of the di-form [B], di-form [C], and other di-forms were 16.5%, 54.3%, 11.6%, and 17.5%, respectively.

<Example 4>
Carbonylation, esterification, and treatment of the reaction product liquid were performed in the same manner as in Example 2 except that the amount of BF ₃ charged in the carbonylation reaction was 13.6 g (0.20 mol). As a result of internal standard analysis of the obtained reaction liquid by gas chromatography, the conversion rate was 99.0 mol%, the di-isomer total yield was 36.3 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of the di-form [B], di-form [C], and other di-forms were 18.6%, 58.1%, 7.6%, and 15.8%, respectively.

<Example 5>
Carbonylation, esterification, and treatment of the reaction product solution were performed in the same manner as in Example 2 except that the amount of BF ₃ charged in the carbonylation reaction was 34.1 g (0.50 mol). As a result of internal standard analysis of the resulting reaction liquid by gas chromatography, the conversion rate was 98.9 mol%, the di-isomer total yield was 26.6 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of di-body [B], di-body [C], and other di-forms were 15.6%, 47.1%, 14.3%, and 23.0%, respectively.

<Example 6>
Example 2 except that the amount of each carbonylation reaction was changed to 33.0 g (0.20 mol) of 1-ethyladamantane, 160.8 g (8.03 mol) of anhydrous HF, and 10.2 g (0.15 mol) of BF _3. Similarly, carbonylation, esterification, and the reaction product solution were processed. As a result of internal standard analysis of the obtained reaction liquid by gas chromatography, the conversion rate was 98.9 mol%, the di-isomer total yield was 45.4 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of di-body [B], di-body [C], and other di-forms were 10.5%, 56.7%, 13.7%, and 19.0%, respectively.

<Example 7>
Carbonylation, esterification, and treatment of the reaction product solution were performed in the same manner as in Example 2 except that the amount of HF charged in the carbonylation reaction was 160.8 g (8.03 mol). As a result of internal standard analysis of the obtained reaction solution by gas chromatography, the conversion rate was 99.3 mol%, the di-isomer total yield was 27.9 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of di-body [B], di-body [C], and other di-forms were 11.4%, 57.6%, 9.3%, and 21.7%, respectively.

<Example 8>
Carbonylation, esterification, and treatment of the reaction product solution were performed in the same manner as in Example 2 except that the carbonylation reaction temperature was 86 ° C. As a result of internal standard analysis of the obtained reaction solution by gas chromatography, the conversion rate was 99.0 mol%, the di-isomer total yield was 37.2 mol% (based on 1-ethyladamantane), and the diisomer [A], The di-body composition ratio of di-body [B], di-body [C], and other di-bodies was 10.5%, 54.5%, 14.3%, and 20.7%, respectively.

<Example 9>
Carbonylation, esterification, and treatment of the reaction product solution were performed in the same manner as in Example 2 except that the carbonylation reaction temperature was 70 ° C. As a result of internal standard analysis of the obtained reaction liquid by gas chromatography, the conversion rate was 99.1 mol%, the di-isomer total yield was 42.2 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratios of di-body [B], di-body [C], and other di-forms were 18.5%, 56.1%, 10.9%, and 14.5%, respectively.

<Example 10>
Carbonylation, esterification, and treatment of the reaction product solution were performed in the same manner as in Example 2 except that the carbonylation reaction temperature was 50 ° C. As a result of internal standard analysis of the obtained reaction solution by gas chromatography, the conversion rate was 98.8 mol%, the di-isomer total yield was 24.0 mol% (based on 1-ethyladamantane), and the di-isomer [A], The di-body composition ratio of di-body [B], di-body [C], and other di-body was 8.2%, 75.0%, 10.6%, and 6.2%, respectively.

<Example 11>
The amount of each carbonylation reaction was 33.0 g (0.20 mol) of 1-ethyladamantane, 201.0 g (10.04 mol) of anhydrous HF, 10.2 g (0.15 mol) of BF ₃ , carbon monoxide pressure of 3 MPa, reaction time. Carbonylation, esterification, and treatment of the reaction product solution were performed in the same manner as in Example 9 except that the reaction was performed in 6 hours. The obtained reaction liquid was subjected to internal standard analysis by gas chromatography. As a result, the conversion rate was 100 mol%, the di-isomer total yield was 55.1 mol% (based on 1-ethyladamantane), and di-form [A], di-form. The composition ratios of [B], di-form [C], and other di-forms were 13.2%, 60.9%, 12.5%, and 13.4%, respectively.

Table 1 summarizes the reaction conditions and reaction results of each example.

  The novel ethyladamantane dicarboxylic acid ester compound 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 (2)

An ethyladamantane dicarboxylic acid ester compound represented by the chemical structural formula (1).

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, and m and n are values of 0 or 1.) In the presence of hydrogen fluoride and boron trifluoride, 1-ethyladamantane represented by the formula (3) is reacted with carbon monoxide, and the resulting ethyladamantane dicarboxylic acid fluoride represented by the formula (2) is converted into alcohol. And a method for producing an ethyladamantane dicarboxylic acid ester compound represented by the formula (1).

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, and m and n are values of 0 or 1.)

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