JP3516699B2 - Method for producing fused ring-containing compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a dihydroxy compound having a norbornane skeleton, a perhydrodimethanonaphthalene skeleton or a perhydroanthracene skeleton. The fused ring-containing compound produced by the present invention is used as a raw material of a polymer compound useful as various structural materials and functional materials.

[0002]

2. Description of the Related Art Polyester obtained by using perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol as a raw material has a high glass transition temperature and excellent dimensional stability and is suitable for photographic use. It is known to be used as a base for films [US Defense Patent No. 896033 and Journal of Polymer Science: Polymer Chemistry Edition (Journal).
of Polymer Science: Polymer Chemistry Edition), 1
0, p. 3191 (1972)]. These references include perhydro-1,4: 5,8-dimethanonaphthalene-2,
As a method for producing 3-dimethanol, Diels-Alder (Diels-Alder) was prepared from diethyl fumarate and cyclopentadiene.
s-Alder) reaction of 1,2,3,4,4a, 5,8,
8a-Octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dicarboxylate diethyl was obtained, and then the double bond was hydrogenated in the presence of a palladium catalyst, and then the ester moiety was converted with a copper-chromite catalyst. A method of reducing is disclosed.

Further, in JP-A-3-31230, 1,2,3, obtained by a Diels-Alder reaction of cyclopentadiene or dicyclopentadiene with 2-butene-1,4-diol dicarboxylate. 4,
4a, 5,8,8a-octahydro-1,4: 5,8-
Dimethanonaphthalene-2,3-dimethanol dicarboxylate is converted into perhydro-1,4: 5,8-dimethanonaphthalene-2, by hydrogenation reaction and hydrolysis reaction.
It is disclosed to be converted to 3-dimethanol.
Further, Japanese Patent Laid-Open No. 3-56429 discloses 1, 2, 3,
4,4a, 5,8,8a-octahydro-1,4: 5,
Process for producing perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol by subjecting 8-dimethanonaphthalene-2,3-dimethanol dicarboxylate to hydrogenation reaction and hydrolysis reaction Is disclosed.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the methods described in JP-A-230 and JP-A-3-56429, 1,2,3,4,4a, 5,8,
8a-Octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol dicarboxylate (specifically diacetate) has been isolated from the reaction mixture by distillation under reduced pressure. However, according to the study by the present inventors, 1,2,3,4,4a, 5,8,8a-
Octahydro-1,4: 5,8-dimethanonaphthalene-
It was found that 2,3-dimethanol dicarboxylate is relatively unstable thermally and that the dicarboxylate is partially decomposed and the yield is reduced depending on the distillation operation conditions adopted. Furthermore, in the Diels-Alder reaction of cyclopentadiene or dicyclopentadiene and 2-butene-1,4-diol dicarboxylate, a high-boiling compound, which is thermally unstable, is by-produced and is a target product. 1,
2,3,4,4a, 5,8,8a-octahydro-1,
In order to improve the yield of 4: 5,8-dimethanonaphthalene-2,3-dimethanol dicarboxylate, it is necessary to heat the bottom of the distillation column to a high temperature during distillation. Is accompanied by a decomposition reaction and a polymerization reaction of the high boiling point compound. In order to suppress these reactions, it is necessary to carry out a distillation operation under high vacuum and low temperature,
It is an industrial disadvantage. That is, it seems that the distillation operation needs to be carried out at the stage where the compound is converted into the most thermally stable compound.

Also, in the method described in the above-mentioned JP-A-3-31230 and JP-A-3-56429, perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol is used. Dicarboxylate was converted to perhydro-1,4: 5,8-dimethanonaphthalene-
As a method of converting into 2,3-dimethanol, an operation called hydrolysis is performed, but in the hydrolysis reaction, perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol is simultaneously treated. Due to the formation of carboxylic acids, it is necessary to design the reactor with corrosion resistant materials. That is, from the viewpoint of reducing the cost of manufacturing equipment, it is desirable that the by-product has a lower chemical activity.

The object of the present invention is perhydro-1,4:
5,8-Dimethanonaphthalene-2,3-dimethanol and its by-product, a homologue of norbornane-
2,3-dimethanol and perhydro-1,4: 5,8:
An object of the present invention is to provide a method for industrially advantageously producing 9,10-trimethanoanthracene-2,3-dimethanol.

[0007]

According to the present invention, the above-mentioned object is achieved by the following general formula (I):

[0008]

Embedded image R ¹ COOCH ₂ CH═CHCH ₂ OCOR ² (I)

(Wherein R ¹ and R ² each represent a lower aliphatic group) and / or the following general formula (II)

[0010]

[Chemical 4]

[0011] (wherein, R ¹ and R ² above is far Ride definition.) Are reacted in a temperature range of 150 to 260 ° C. The compounds shown and the cyclopentadiene or dicyclopentadiene, the resulting General formula (I) from the reaction mixture
The part of the compound represented by in compound and / or the general formula shown (II) the residue after distillation, lower aliphatic alcohols in the presence of an acid or alkali catalyst - by Le transesterification reaction, subsequently the A hydrogenation reaction is carried out with hydrogen gas in the presence of a catalyst using a lower aliphatic alcohol as a solvent.
At least norbornane-2,3-dimethanol and
Luhydro-1,4: 5,8-dimethanonaphthalene-2,
To obtain a reaction mixture containing 3-dimethanol, after recovering the catalyst by filtration from the reaction mixture, Noruboruna
Get the down-2,3-methanol by evaporation Tomemisao operation child
And norbornane-2,3-dimethanol
And perhydro-1,4: 5,8-dimethanonaphthale
To provide a method for simultaneously producing benzene-2,3-dimethanol.
Achieved by. Norbornane-2,3 mentioned above
-Dimethanol and perhydro-1,4: 5,8-di
Methanonaphthalene-2,3-dimethanol and Perch
Doro-1,4: 5,8: 9,10-Trimethanoanthra
Sen-2,3-dimethanol has the following general formula (III):

[0012]

[Chemical 5]

An alicyclic dihydroxy compound having a norbornene skeleton represented by the formula (wherein n is 0, 1 or 2) , and in the present specification, norbornane-2,3-
Dimethanol, perhydro-1,4: 5,8-dimethano
Naphthalene-2,3-dimethanol and perhydro-
1,4: 5,8: 9,10-trimethanoanthracene-
2,3-dimethanol is sometimes abbreviated as " alicyclic dihydroxy compound represented by the general formula (III) ".

The lower aliphatic group represented by R ¹ and R ² in the above general formula is preferably an aliphatic group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and an n-pentyl group. Bicyclo [2.2.1] hept-5-ene-2,3-dimethano-represented by the general formula (II)
Among the rudicarboxylates, the compound having the lowest boiling point is a compound in which both R ¹ and R ² are methyl groups,
Bicyclo [2.2.1] hept-5-ene-2,3-dimethanol diacetate is particularly preferred.

The compound represented by the general formula (I) and the compound represented by the general formula (II) may be in a trans isomer, a cis isomer or a mixture thereof, and a general compound corresponding to these geometric isomers. Geometric isomers of alicyclic dihydroxy compounds of formula (III) are obtained. General formula (I)
The yield of the alicyclic dihydroxy compound represented by the general formula (III) obtained when the trans isomer is used as the compound represented by the formula and the compound represented by the general formula (II) is higher than that when the cis isomer is used. Therefore, it is preferable.

The reaction of the compound represented by the general formula (I) and / or the compound represented by the general formula (II) with cyclopentadiene or dicyclopentadiene is 150 to 26.
It is carried out within the temperature range of 0 ° C. The reaction temperature is 180
It is preferably within the range of to 240 ° C. When the temperature is lower than 150 ° C, the reaction rate is low, and when the temperature is higher than 260 ° C, a high boiling point compound is generated due to an undesired side reaction, and the yield is lowered. The reaction time is in the range of about 10 minutes to 30 hours, preferably about 30 minutes to 15 hours. The reaction can be carried out in air, but it can be carried out in an atmosphere of an inert gas such as nitrogen, argon or carbon dioxide represented by the general formula (II
It is preferable from the viewpoint of the yield of the alicyclic dihydroxy compound represented by I).

Cyclopentadiene is used in an amount of 0.5 mol times or more, preferably 1.0 mol times or more, more preferably 1.25 mol times or more, relative to 1 mol of the compound represented by the general formula (I). , 0.25 mol times or more, preferably 0.5 mol, per mol of the compound represented by the general formula (II).
It is used in an amount of mole times or more, more preferably 0.625 mole times or more. The amount of dicyclopentadiene used is preferably such that the amount of dicyclopentadiene converted into cyclopentadiene falls within the above range. Since cyclopentadiene is a compound which itself is easily polymerized, the ratio to the compound represented by the general formula (I) and the compound represented by the general formula (II) is finally within the above range. Thus, it is preferable to supply continuously or intermittently into the reaction system and control so that the concentration of cyclopentadiene in the reaction system does not become too high. There is no particular upper limit to the amount of cyclopentadiene or dicyclopentadiene used, but it is usually 5 in the amount converted to cyclopentadiene for the compound represented by the general formula (I) and the compound represented by the general formula (II).
It is mole times.

The reaction of the compound represented by the general formula (I) and / or the compound represented by the general formula (II) with cyclopentadiene or dicyclopentadiene can be carried out in the absence of a solvent, but is suitable. It can also be carried out in the presence of an organic solvent. Examples of the organic solvent include benzene, toluene, xylene, tetrahydrofuran, methanol, ethanol, propanol, butanol, ethyl acetate, 1,4-dioxane, methylene chloride, chloroform and N-methylpyrrolidone. Is preferably used.

After the reaction of the compound represented by the general formula (I) and / or the compound represented by the general formula (II) with cyclopentadiene or dicyclopentadiene is completed, the unreacted cyclopentadiene and < br /> distillation using part of dicyclopentyldimethoxysilane and some or all of the cyclopentadiene compound represented by a compound represented by the general formula (I) and / or formula (II). In the distillation operation, it is desirable to adjust the degree of reduced pressure so that the above compound is distilled at a temperature at which the bottom temperature of the distillation column does not exceed 230 ° C.

After the completion of distillation, there are roughly the following two operations that can be performed on the obtained residue. One is a method of first performing a hydrogenation reaction, converting to a thermally stable compound, and then performing distillation purification or transesterification,
The other is a method in which transesterification is first carried out in a thermally stable temperature region, followed by hydrogenation reaction, and finally by distillation purification. In the present invention , the latter method is adopted.
It A series of alicyclic dihydroxy compounds are lower aliphatic alcohols than diacetate compounds of the dihydroxy compounds.
Le, in particular solubility high Ikoto of methanol, better to adopt the latter method, that the transesterification and the hydrogenation reaction may be carried out with the same solvent and moreover a high concentration, yet after the hydrogenation reaction catalyst It is excellent in that the filtration operation in the recovery stage is easy.

The distillation residue thus obtained is transesterified with a lower aliphatic alcohol in the presence of a catalyst to give a compound of the general formula (I) and / or the general formula (II).
The diacetate compound, which is a Diels-Alder reaction adduct of the compound represented by and cyclopentadiene, is converted into a dihydroxy compound having the same carbon skeleton.

As the lower aliphatic alcohol, for example,
Methanol, ethanol, n-propanol, isopropanol, allyl alcohol, n-butanol, tert-butanol and the like are used. Among these, use of methanol is more preferable in terms of the production process because the boiling point of the carboxylic acid ester (particularly, acetic acid ester) formed as a result of the transesterification reaction is lower than the boiling point of the alcohol.

The lower aliphatic alcohol is the remaining amount of the acyl group in the compound represented by the general formula (I) and / or the general formula (II) used as a raw material, excluding the amount recovered by distillation. It is preferably used in an equimolar amount or more.

As the catalyst, any acid catalyst and base catalyst used in a usual transesterification reaction can be used, but the base catalyst is preferred in terms of yield and no coloring of the product. . As the base catalyst, for example,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
It is preferable to use sodium methoxide or the like. The amount of the catalyst used is preferably in the range of 0.001 to 10 mol% with respect to the acyl group contained in the raw material compound, and is preferably 0.
The range of 01 to 5 mol% is more preferable.

The transesterification reaction is preferably carried out within a temperature range of 50 to 200 ° C., and can be carried out under either normal pressure or increased pressure. Usually, it is carried out at normal pressure, but it is possible to raise the reaction temperature if carried out under pressure,
It is preferable because the reaction time is shortened. The time required for the transesterification reaction varies depending on the reaction temperature, the type and amount of the catalyst used, the amount of lower aliphatic alcohol, etc.
It is usually within the range of 10 minutes to 10 hours.

By removing the ester of the lower aliphatic alcohol resulting from the transesterification reaction out of the system, the equilibrium of the transesterification reaction can be shifted and the reaction can proceed. In such a case, the ester and the lower aliphatic alcohol used for transesterification are usually azeotropic,
In order to distill out of the reaction system, it is desirable to set the amount of the lower aliphatic alcohol used in consideration of the amount required for the transesterification reaction as well as the amount azeotropically distilled.

After completion of the transesterification reaction, the residual lower aliphatic alcohol solution is used as it is, or the concentration is adjusted,
If necessary, the transesterification catalyst is neutralized, and then hydrogenation reaction is carried out with hydrogen gas in the presence of the catalyst. As the catalyst, a catalyst generally used for hydrogenation reaction of double bond can be used, for example, activated carbon with palladium,
Heterogeneous catalysts such as Raney nickel, Raney cobalt, platinum oxide, activated carbon with platinum, nickel diatom degree, copper chromite; and chlorotris (triphenylphosphine)
Examples include homogeneous catalysts such as rhodium, platinum-tin complex, and tertiary phosphine-cobalt carbonyl complex. The amount of the catalyst used is usually 0.00 with respect to the reaction mixture.
A range of 1 to 10% by weight is suitable.

The hydrogenation reaction may be carried out in the presence of hydrogen gas at normal pressure depending on the type of catalyst used, but it is desirable to carry out the hydrogenation reaction under pressure because the reaction rate is high in many cases. When it is carried out under pressure, the pressure is 300 atm or less, preferably 200 atm or less, and more preferably 100 atm or less, which is industrially advantageous in terms of reaction apparatus, operability and the like. It should be noted that another inert gas that does not affect the hydrogenation reaction, such as nitrogen, carbon dioxide, or argon, may coexist.

The hydrogenation reaction is preferably carried out in the temperature range of 40 to 210 ° C. for 1 minute to 50 hours. The reaction temperature is more preferably within the range of 60 to 200 ° C., and 60
It is more preferably in the range of 180 ° C. The reaction time is more preferably within the range of 10 minutes to 10 hours.

The hydrogenation reaction can be carried out by a usual apparatus such as a stirring system or a bubble column system by a continuous system or a batch system.

[0031] After the hydrogenation reaction completion, after the catalyst was filtered off from the reaction mixture, norbornane and purpose-2,3
-Dimethanol, perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol and perhydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dimethanol are Each can be separately obtained by a distillation operation . Since the dihydroxy compound is thermally stable, no decomposition reaction or the like occurs during the distillation even if the distillation operation is performed at a high temperature, and the boiling points are sufficiently separated. It can be easily separated by equipment. In addition, since the high boiling point compound generated by the side reaction during the Diels-Alder reaction is also converted into a thermally stable compound by the hydrogenation reaction, the decomposition reaction is induced even if the bottom temperature of the distillation column is increased. The high-purity dihydroxy compound is obtained in high yield.

The compound represented by the general formula (I) can be produced, for example, by reacting butadiene, lower carboxylic acid and oxygen in the presence of a palladium catalyst (see Japanese Patent Publication No. 52-12172).

Norbornane produced according to the present invention
2,3-dimethanol, perhydro-1,4: 5,8-
Dimethanonaphthalene-2,3-dimethanol and perhydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dimethanol are polymer compounds useful as various structural materials and functional materials. It can be used as a raw material.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 An autoclave having a content of 1 liter equipped with an electromagnetic stirrer was charged with 240 g of 2-butene-1,4-diol diacetate (mixture of 95% trans isomer and 5% cis isomer) and 300 g paraxylene. The system was replaced with nitrogen gas. Then, the internal temperature of the autoclave was raised to 200 ° C., and the dicyclopentadiene 9 was stirred with a metering pump under stirring.
0 g was continuously fed into the autoclave over 8 hours, reacted for 2 hours at the same temperature, and then the stirring was stopped. After cooling, remove the reaction mixture from the autoclave,
After the para-xylene was distilled off from this, it was subjected to vacuum distillation to give a boiling point of 89 to 9 in addition to the unreacted raw material compounds.
162 g was obtained as a fraction at 3 ° C./0.1 mmHg. In this distillation operation, the kettle bath temperature of the distillation apparatus was kept at 170 ° C. or lower.

As a result of analysis by gas chromatography, mass spectrum and ¹ H-NMR, the above-mentioned fraction was found to be bicyclo [2.2.1] hept-5-ene-2,3-dimethanol diacetate. I was confirmed. The fraction of bicyclo [2.2.1] hept-5-ene-trans-2,3-dimethanol diacetate in the fraction was 92%, and a small amount of bicyclo [2.2]. .1] Hept-5-ene-cis-2,3-dimethanol diacetate and cyclopentadiene trimer were included.

This bicyclo [2.2.1] hept-5-
150 g of a fraction mainly containing en-trans-2,3-dimethanol diacetate and 300 parts of paraxylene.
g was charged into the same autoclave as above, and the inside of the system was replaced with nitrogen gas. Then, the internal temperature of the autoclave is set to 210.
The temperature was raised to 0 ° C., and 60 g of dicyclopentadiene was continuously fed into the autoclave over a period of 6 hours under stirring at the same temperature using a metering pump, and after stirring for 2 hours, stirring was stopped. .

After cooling, the reaction mixture was taken out of the autoclave and distilled. Also in this case, the temperature of the kettle bath was maintained at 170 ° C. or lower, and the distillation operation was stopped when 52.3 g of a fraction having a boiling point of 89 to 93 ° C./0.1 mmHg was obtained.

Content 300 with rectifier and stirrer
In a ml flask, add the above 1,2,3,4,4
a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol diacetate (bicyclo [2.2.1] hept-5 as a by-product)
-Ene-2,3-dimethanol diacetate and 1,
2, 3, 4, 4a, 10, 10a, 5, 8, 8a, 9,
9a-dodecahydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dimethanol diacetate (containing a small amount) and 100 g of a residue are charged, and 80 g of methanol and 0.1 g of sodium hydroxide are added. The mixture was charged and stirred at a bath temperature of 90 ° C. for 3 hours. Methyl acetate produced by the transesterification reaction was azeotropically distilled with methanol to promote the reaction. By analyzing the reaction mixture with a gas chromatograph over time, 1,2,3,4,4a, 5,8,8a was obtained 1 hour after the start of the reaction.
Most of the octaoctahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol diacetate disappeared, and no peaks of diacetate and monoacetate were observed after 3 hours. It was confirmed that it was changed to methanol. In addition, by-products 1, 2,
3, 4, 4a, 10, 10a, 5, 8, 8a, 9, 9a
-Dodecahydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dimethanol diacetate and bicyclo [2.2.1] hept-5-ene-2,3-
It was confirmed that each of the dimethanol diacetate was also converted into the corresponding dimethanol.

After 3 hours, a methanol solution of the residue after the transesterification reaction was charged into the above autoclave,
After adding 3 g of activated carbon with 5% palladium and replacing the inside of the system with hydrogen gas, pressurizing to 80 kg / cm ² with the same gas, 8
The mixture was stirred at 0 ° C for 2 hours. During the reaction, hydrogen gas was continuously supplied from a pressure control valve installed in the autoclave so that the pressure in the system was maintained at 80 kg / cm ² .

After cooling, the reaction mixture was taken out of the autoclave, and the catalyst was separated by filtration with a pressure filtration device. As a result of analysis by gas chromatography, 1, 2, 3, 4, 4
The peak corresponding to a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol disappeared completely and perhydro-1,4: 5,8-dimethano A peak corresponding to naphthalene-2,3-dimethanol was observed. In addition, by-products 1, 2, 3,
4,4a, 10,10a, 5,8,8a, 9,9a-dodecahydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dimethanol and bicyclo [2.
2.1] Hept-5-ene-trans-2,3-dimethanol was also converted to the corresponding saturated form.

Methanol was distilled off from the above reaction mixture, and the mixture was subjected to vacuum distillation. Kettle bath temperature 160 ℃, boiling point 1
8.6 g as the first fraction up to 30 ° C / 1 mmHg, 210 ° C kettle bath temperature, 41.5 g as the second fraction up to 180 ° C / 1 mmHg boiling point, 260 ° C kettle bath temperature, 230 ° C boiling point /
9.2 g was obtained as the third fraction up to 1 mmHg. As a result of analysis by gas chromatography, mass spectrum and ¹ H-NMR, the main components of the first, second and third fractions were norbornane-2,3-dimethanol and (trans-) perhydro-1,4: 5,8-Dimethanonaphthalene-2,3-dimethanol, perhydro-1,4: 5
It was confirmed to be 8: 9,10-trimethanoanthracene-2,3-dimethanol. The second fraction also contains about 1% of cis-perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol and a small amount of the tetrameric hydrogenation product of cyclopentadiene. It was About 10 g of solid was obtained as the final bottom residue.

Example 2 To the same autoclave used in Example 1, 400 g of 2-butene-1,4-diol diacetate (mixture of 95% trans isomer and 5% cis isomer) was charged, and the system was filled with nitrogen gas. The inside was replaced. Then, the internal temperature of the autoclave is set to 22.
The temperature was raised to 0 ° C., and 300 g of cyclopentadiene was continuously fed into the autoclave for 4 hours with stirring by a metering pump, and the reaction was continued for 2 hours at the same temperature. Then, stirring was stopped and the mixture was cooled. The reaction mixture was taken out of the autoclave and analyzed by gas chromatography to confirm that unreacted 2-butene-1,4-diol diacetate and cyclopentadiene were scarcely left.

In the same manner as in Example 1, the temperature of the kettle bath of the distillation apparatus was controlled to be 170 ° C. or lower, and distillation was carried out under reduced pressure to obtain mainly bicyclo [2.2.1] hept-5-ene-. 343 g of a mixture consisting of trans-2,3-dimethanol diacetate and bicyclo [2.2.1] hept-5-en-cis-2,3-dimethanol diacetate were obtained. In addition, about 7% in this mixture
It was confirmed by gas chromatographic analysis that the cyclopentadiene trimer was contained.

340 g of the above distillation residue and 30 parts of ethanol
Using 0 g and 0.2 g of sodium hydroxide, a transesterification reaction was carried out at a bath temperature of 110 ° C. in the same manner as in Example 1 to give 1,2,3,4,4a, 5,8,8a-octahydro-1. , 4: 5,8-Dimethanonaphthalene-2,3-
Diacetate based on dimethanol diacetate was converted to a dimethanol compound based on perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol.

The ethanol solution of the residue after completion of the transesterification reaction was transferred to the above autoclave, charged with 3 g of activated carbon with 5% palladium, and the system was replaced with hydrogen gas in the same manner as in Example 1, and then 80 kg with the same gas. The pressure was increased to / cm ² and the mixture was stirred at 80 ° C. for 2 hours.

After cooling, the reaction mixture was taken out of the autoclave, the catalyst was filtered off, ethanol was distilled off, and vacuum distillation was performed. First, second and third fractions were obtained in the same manner as in Example 1. Each fraction is composed mainly of norbornane-2,3-dimethanol (25 g), (trans-) perhydro-1,4: 5,8-dimethanonaphthalene-2,
The one containing 3-dimethanol as the main component (158 g) and the one containing perhydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dimethanol as the main component (28 g). .

Comparative Example 2-butene-1,4-dio-under the same conditions as in Example 2.
Diels of diacetate and cyclopentadiene
The Alder reaction is carried out, and bicyclo [2.2.1] hept-
The 5-ene-2,3-dimethanol diacetate was distilled under reduced pressure. After a while, the distillation residue after distillation and methanol 30
Example 1 using 0 g and 5 g of Raney nickel catalyst under the conditions of hydrogen gas pressure of 80 kg / cm ² , 80 ° C., and 3 hours.
The hydrogenation reaction was carried out in the same manner as in. After completion of the reaction, the reaction mixture was taken out from the autoclave and filtered. At this time, a gel-like insoluble matter was present in addition to the catalyst. The catalyst and the insoluble matter were 5 kg /
I tried to separate it with a pressure of cm ² , but the gel-like substance became an obstacle, and filtration took a very long time.
g was added to dissolve the gel-like substance, and filtration was performed. The reaction mixture obtained as a filtrate was placed in a flask having a content of 1 liter equipped with a rectifier and a stirrer, 1 g of sodium hydroxide was added as a catalyst, and a transesterification reaction was carried out for 3 hours. When the reaction solution was analyzed by gas chromatography, the transesterification reaction was not completed, and a peak corresponding to perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol monoacetate was produced. Compound Perhydro-1,4: 5,8-dimethanonaphthalene-
About 10% of the peak area of 2,3-dimethanol remained.

[0049]

EFFECTS OF THE INVENTION According to the present invention, perhydro-1,
4: 5,8 dimethanol naphthalene-2,3-dimethanol, Roh Ruborunan 2,3-dimethanol and perhydro-1,4: 5,8: 2,3 9,10 tri methanolate anthracenedicarboxylic Methanol can be produced simultaneously .

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C07C 29/76 C07C 29/76 29/78 29/78 29/80 29/80 35/37 35/37 35/44 35/44 // C07B 61/00 300 C07B 61/00 300 (56) Reference JP 5-132438 (JP, A) JP 5-70386 (JP, A) JP 4-221329 (JP, A) JP-A-4-208249 (JP, A) JP-A-4-208240 (JP, A) JP-A-3-188035 (JP, A) JP-A-3-99040 (JP, A) JP-A-3-99039 (JP, A) JP-A-3-68538 (JP, A) JP-A-3-66646 (JP, A) JP-A-3-56429 (JP, A) JP-A-3-31230 (JP, A) open Akira 56-140940 (JP, a) (58 ) investigated the field (Int.Cl. ^7, DB name) C07C 35/00 C07C 27/00 C07C 29/00 CA (STN) REGI TRY (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (I): embedded image R ¹ COOCH ₂ CH═CHCH ₂ OCOR ² (I) (wherein R ¹ and R ² each represent a lower aliphatic group). Compound and / or the following general formula (II): (In the formula, R ¹ and R ² are far Ride is. As defined above) is reacted with the compound and the temperature range of a cyclopentadiene or dicyclopentadiene 150 to 260 ° C. represented by, from the reaction mixture obtained formula the residue after distillation separation of the part of the compound and / or a compound represented by the general formula (II) represented by (I), acid or lower aliphatic alcohol in the presence of an alkali catalyst - Le transesterification After the reaction, the lower aliphatic alcohol is used as a solvent to carry out a hydrogenation reaction with hydrogen gas in the presence of a catalyst to reduce the amount.
Norbornene-2,3-dimethanol and perhydro-
1,4: 5,8-dimethanonaphthalene-2,3-dimeta
A reaction mixture containing a norl was obtained, and the catalyst was recovered from the reaction mixture by filtration, and then the norbornane-2,3
- and acquiring the dimethanol by evaporation Tomemisao operation, norbornane-2,3-dimethanol and pel
Hydro-1,4: 5,8-dimethanonaphthalene-2,3
-Simultaneous production method of dimethanol . 2. Norbornane-2,3-dimethanol is used
From the reaction mixture after it was obtained, perhydro-1,4: 5,
Distillation of 8-dimethanonaphthalene-2,3-dimethanol
And optionally, perhydro-1,
4: 5,8: 9,10-trimethanoanthracene-2,
Characterized in that 3-dimethanol is obtained by distillation
The method of claim 1, wherein