JP2003055283A - Method for producing condensed ring-containing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for industrially advantageously producing a condensed ring-containing compound having a dimethanonaphthalene skeleton, etc. SOLUTION: This method for producing the condensed ring-containing compound represented by general formula (3) (R<1> and R<2> denote each hydrogen or a 2-5C acyl group; and n is an integer of 0-2) comprises subjecting a compound represented by general formula (1) R<1> OCH2 CH=CHCH2 OR<2> (1) [R<1> and R<2> are each the same as in general formula (3)] and/or a norbornene compound represented by general formula (2) [R<1> are each the same as in general formula (3)] to the Diels-Alder reaction with cyclopentadiene and/or dicyclopentadiene to provide a reactional mixture. A purification step thereof includes an extraction step of separating and removing at least a part of a cyclopentadiene polymer such as a trimer or a tetramer of the cyclopentadiene by solvent extraction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a condensed ring-containing compound having a dimethanonaphthalene skeleton and the like, which is useful as a raw material for a polymer compound used as various structural materials and functional materials.

[0002]

2. Description of the Related Art Conventionally, a polyester obtained from a dimethanol compound having a perhydrodimethanonaphthalene skeleton and an aromatic dicarboxylic acid has a high glass transition temperature, as described in, for example, the literature Journal of Polymer Science: Po.
lymer Chemistry Edition, vol. 10, p. 3191, (1972)
Known by. In the document, as a method for producing the dimethanol compound, a compound having a norbornene skeleton or a skeleton in which norbornene is accumulated is obtained by a Diels-Alder reaction of diethyl ester of fumaric acid and cyclopentadiene, and then norbornane is obtained by a hydrogenation reaction. A method for producing the dimethanol compound by converting the compound into a compound having a skeleton or a skeleton in which norbornane is accumulated, and then reducing the ester moiety is disclosed. Further, in British Patent No. 796,135, 2
It is disclosed that norbornene-2,3-dimethanol is produced from butene-1,4-diol and dicyclopentadiene. On the other hand, JP-A-3-31230 and JP-A-3-56429 disclose cyclopentadiene or dicyclopentadiene and 2-butene-1,4.
-1,2,3,4,4a, 5,8,8a obtained by Diels-Alder reaction with diol dicarboxylate-
Octahydro-1,4: 5,8-dimethanonaphthalene-
2,3-dimethanol dicarboxylate is converted into perhydro-1,4: 5,8 by hydrogenation reaction and hydrolysis reaction.
-It is disclosed to be converted to dimethanonaphthalene-2,3-dimethanol. Furthermore, JP-A-5-132
No. 348 and JP-A-7-25797, cyclopentadiene or dicyclopentadiene, 2-butene-1,4-diol dicarboxylate and 5-norbornene-2,3-dimethanol dicarboxylate are treated with Diels. Alder reaction is performed, and the unreacted raw materials and the like are distilled off from the resulting reaction mixture, and the residue is subjected to a hydrogenation reaction to give perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol. A method of manufacturing is disclosed.

[0003]

According to the above-mentioned conventional method, perhydro-1,4: 5,8-dimethanonaphthalene-
2,3-dimethanol or its diacetate has been isolated by vacuum distillation and optionally further recrystallization. However, according to the study by the present inventors,
The reaction mixture always contains by-products, such as trimer and tetramer of cyclopentadiene, and those cyclopentadiene multimers or hydrogenated products of cyclopentadiene multimers produced by hydrogenation reaction. Has a boiling point close to that of perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol or its diacetate, making it difficult to separate efficiently by vacuum distillation or recrystallization. Became. An object of the present invention is to provide a method for industrially advantageously producing a condensed ring-containing compound having a dimethanonaphthalene skeleton and the like.

[0004]

Means for Solving the Problems That is, the first aspect of the present invention
Is a purification step of a reaction mixture obtained by a Diels-Alder reaction of a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2) with cyclopentadiene and / or dicyclopentadiene The method for producing a condensed ring-containing compound represented by the following general formula (3), which comprises an extraction step of separating and removing at least a part of a cyclopentadiene multimer such as a cyclopentadiene trimer or tetramer by solvent extraction. Is the way.

Embedded image R ¹ OCH ₂ CH═CHCH ₂ OR ² ... Formula (1) (In the formula, R ¹ and R ² each represent a hydrogen atom or an acyl group having 2 to 5 carbon atoms.)

[Chemical 6] (In the formula, R ¹ and R ² are the same as defined in the general formula (1).)

[Chemical 7] (In the formula, R ¹ and R ² are the same as defined in the above general formula (1). N is an integer of 0 to 2.)

A second aspect of the present invention is based on the general formula (1),
When R ¹ and / or R ^{2 in} (2) and (3) is an acyl group having 2 to 5 carbon atoms, a hydrolysis reaction or a transesterification reaction is performed in the purification step of the reaction mixture obtained by the Diels-Alder reaction. A method for producing a fused ring-containing compound according to the first invention, which comprises:

A third invention is represented by the following general formula (4), which includes a hydrogenation reaction by reacting with hydrogen gas in the presence of a catalyst in the purification step of the reaction mixture obtained by the Diels-Alder reaction. And a method for producing a condensed ring-containing compound.

[Chemical 8] (In the formula, R ¹ and R ² are the same as defined in the above general formula (1). N is an integer of 0 to 2.)

A fourth invention is that the above-mentioned extraction step is carried out by using two or more kinds of solvents to separate the reaction mixture into two or more layers, and at least one layer among them is cyclopentadiene trimer and cyclopentadiene. At least a part of the cyclopentadiene multimer such as a tetramer is dissolved, and at least a part of the compound represented by the general formula (3) or (4) is dissolved in the other layer, followed by a liquid separation operation. The method for producing a fused ring-containing compound according to any one of the first to third inventions, characterized in that

In a fifth aspect of the invention, the solvent used in the extraction step is an oxygen-containing compound having 10 or less carbon atoms and 5 carbon atoms.
The method for producing a condensed ring-containing compound according to any one of the first to fourth inventions, characterized in that it is one or more kinds in each of two compound groups consisting of the hydrocarbon compounds 10 to 10.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The manufacturing method of the present invention will be described in detail below. In the compound represented by the general formula (1) or (2) used in the present invention, R ¹ and R ² each represent a hydrogen atom or an acyl group having 2 to 5 carbon atoms. Examples include those represented by the following structural formulas.

[Chemical 9] Of these, an acetyl group is preferred for production.
The same applies to the compounds represented by the general formulas (3) and (4).

In the compound represented by the general formula (1), 2-butene-in which R ¹ and R ² are each a hydrogen atom
1,4-diol can be produced from acetylene and formalin by a known Reppe reaction, or can also be produced by hydrolyzing 2-butene-1,4-diol dicarboxylate. Further, in the compound represented by the general formula (1), 2-butene-1,4-diol in which R ¹ and R ² are each an acyl group having 2 to 5 carbon atoms.
Dicarboxylate can be synthesized, for example, by reacting butadiene, a lower carboxylic acid and oxygen in the presence of a palladium catalyst (see Japanese Examined Patent Publication No. 52-12172). From 2-butene-1,4-diol, 2
It is also possible to produce butene-1,4-diol dicarboxylate. The compound represented by the general formula (1) may be a cis isomer, a trans isomer, or a mixture thereof. Generally, 2-butene-1,4-diol produced from acetylene and formalin is cis. The main body is 2-butene-1,4-diol dicarboxylate produced from butadiene, a lower carboxylic acid and oxygen, and the trans body is main.

The norbornene compound represented by the general formula (2) can be synthesized by a Diels-Alder reaction of the compound represented by the general formula (1) with cyclopentadiene and / or dicyclopentadiene. The two substituents on the norbornene ring of the compound represented by the general formula (2) may independently be in the exo position or the endo position, and the compound represented by the general formula (3) corresponding to these isomers The isomer is obtained. The dimethanonaphthalene ring of the compound represented by the general formula (3) or (4) may be an exo isomer, an endo isomer, or a mixture thereof, and the three-dimensional structure is not limited.

In the production method of the present invention, first, the compound represented by the general formula (1) and / or the general formula (2)
A Diels-Alder reaction between the compound represented by and cyclopentadiene or dicyclopentadiene is carried out.At this time, it is preferable to use dicyclopentadiene, and industrially large quantities of those recovered from pyrolysis oil such as naphtha are used. It is preferable because it can be obtained and is inexpensive. As dicyclopentadiene, a commercially available product can be used, and if it is industrially available, a product having a purity of 70% or more can be used, but normally, a product having a purity of 95% is preferably used. it can. Furthermore, dicyclopentadiene having a purity of more than 95% can be used. Further, the content of the endo form in the dicyclopentadiene component in the raw material dicyclopentadiene is preferably 80% or more. In addition, dicyclopentadiene including cyclopentadiene can be used.

The Diels-Alder reaction is 150-
It is performed within a temperature range of 300 ° C., more preferably 160 to
The temperature is 280 ° C, more preferably 180 to 240 ° C. By heating within the above temperature range, the cyclopentadiene produced by the thermal decomposition of dicyclopentadiene causes the Diels-Alder reaction to produce the target compound. If the temperature is lower than 150 ° C., the reaction becomes slow, which is not preferable, and if the temperature is higher than 300 ° C., it is represented by a cyclopentadiene trimer or tetramer (hereinafter referred to as cyclopentadiene multimer) or the general formula (3). This is not preferable because the amount of a product (hereinafter referred to as a cyclopentadiene-added heavy product) obtained by further addition-reacting cyclopentadiene with the resulting compound increases. Reaction time is 0.1
~ 30 hours, preferably 0.5 to 20 hours.

Dicyclopentadiene is used in an amount of 0.1 to 10 moles, preferably 0.2 to 5 moles, more preferably 0.5 to 3 moles, relative to 1 mole of the compound represented by the general formula (1). It is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, and more preferably 0.6 to 2 mol, per 1 mol of the compound represented by the general formula (2). Further, the amount of dicyclopentadiene with respect to the compounds represented by the general formulas (1) and (2) is preferably 0.1 to 5 mol times. When the amount of dicyclopentadiene is less than the above range, the yield of the compound represented by the general formula (3), which is one of the intended products, is low, which is not preferable. And the amount of cyclopentadiene-added heavy product is increased, which is not preferable. The amount of cyclopentadiene used is preferably such that the amount of cyclopentadiene converted to dicyclopentadiene falls within the above range. Further, cyclopentadiene or an amount of dicyclopentadiene within the above range can be continuously or continuously supplied to the reaction system, and as a result, formation of cyclopentadiene multimer or cyclopentadiene-added heavy product can be suppressed. It is preferable because it is possible. Further, it is preferable to carry out the reaction under pressure because the reaction rate is high, and in that case, 10 MPa
It is preferably 5 MPa or less, more preferably 3 MPa or less.

Furthermore, the Diels-Alder reaction in the present invention can be carried out in the absence of a solvent, but it can also be carried out in the presence of a suitable solvent. For example, hydrocarbon solvents such as benzene, toluene, xylene, hexanes, cyclohexane and methylcyclohexane, alcohols such as methanol, ethanol, isopropanol and butanol, ethers such as tetrahydrofuran, ethyl ether, propyl ether and 1,4-dioxane. ,
Esters such as ethyl acetate and propyl acetate, halogen-containing solvents such as methylene chloride and chloroform, nitrogen-containing solvents such as N-methylpyrrolidone and the like can be used.

The Diels-Alder reaction is carried out under the above conditions, but the reaction may be carried out in any of batch system, semi-batch system and continuous system. When the reaction is carried out in a continuous manner, any of a perfect mixing type and a piston flow type can be used. As a commercial product of the piston flow type reactor, "Static Mixer" manufactured by Noritake Company, Inc.,
Sumitomo Heavy Industries, Ltd. "Sul-the-mixer", Sakura Seisakusho "Sukeya mixer" and the like. The reactor may have a single-stage or multi-stage structure of two or more stages. The complete mixing type reactor and the piston flow type reactor can be used in combination in series or in parallel.

The reaction can be carried out in the presence of an antioxidant and a polymerization inhibitor. For example, hydroquinone, 2,
6-di-t-butylphenol, phenolic compounds such as 2,6-di-t-butyl-p-cresol and 4-methoxyphenol, hydroxyl such as N, N-dimethylhydroxylamine and N, N-diethylhydroxylamine An amine compound or the like is preferably added. The addition amount thereof is usually 10 to 10000 ppm, preferably 50 to 5000 p based on the total amount of the reaction raw materials supplied to the reactor.
It is in the range of pm. Further, it can be preferably added to the product represented by the general formula (3) in the range of 50 to 5000 ppm.

The compound represented by the above general formula (3), which is one of the intended products, is a fused ring-containing compound having an unsaturated bond in which n in the formula is an integer of 0 to 2,
Typical examples are 1, 2, 3, 4, 4a, where n is 1,
5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol or 1,2,3,4,
4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol diacetate and the like can be mentioned. The compound represented by the general formula (4), which is a desired product, is produced by a hydrogenation reaction of the compound represented by the general formula (3) in the modification step of the purification step described below. Similar to the compound represented by the formula (3), it is a condensed ring-containing compound in which n in the formula is an integer of 0 to 2. Typical examples are 1,2,3,4,4a, 5,6,7,8,8a-decahydro-1,4: 5,8-dimethanonaphthalene-2,3-di in which n is 1. Methanol or 1,2,3,4,4a, 5,6,7,8,8a-
Decahydro-1,4: 5,8-dimethanonaphthalene-2,
3-dimethanol diacetate etc. are mentioned. In addition,
As the compounds represented by the general formulas (3) and (4), n is a composition containing compounds of 0 and 1, n is a composition containing compounds of 1 and 2, or n is 0, 1 and 2. It may be a composition containing the compound.

In the reaction mixture obtained as a result of carrying out the Diels-Alder reaction under the reaction conditions as described above, in addition to the compound of the general formula (3) which is the desired product, the unreacted general formula (1 ) And a compound represented by the general formula (2)
In addition to the compounds represented by the formula 1, unreacted cyclopentadiene and dicyclopentadiene, and the solvent when a solvent is used in the reaction, cyclopentadiene multimers and cyclopentadiene adducts are also included. Of these, especially cyclopentadiene multimers are compounds that are by-produced in a considerable amount in the reaction solution regardless of which of the above-mentioned reaction conditions is selected, and chemical and physical properties such as boiling point are represented by the general formula. Since they are similar to the compound represented by (3), it is necessary to efficiently separate them.

The above reaction mixture is subjected to the purification step described below. The purification step includes at least (A) extraction step, and is appropriately constituted by (B) distillation step and (C) denaturation step. The extraction step (A) is essential for efficiently separating and removing the cyclopentadiene multimer from the compound represented by the general formula (3) or (4) to obtain high purity. (C) The modification step is specifically a step of carrying out (c-1) hydrogenation reaction carried out with hydrogen gas in the presence of a catalyst and / or a compound represented by the general formula (1) to (4) (C-2) is a step of carrying out a hydrolysis reaction or a transesterification reaction, which is carried out when R ¹ and / or R ² is an acyl group having 2 to 5 carbon atoms. The combination of the above steps, the number of times of execution, and the order are not particularly limited. The purification step may be carried out by any of batch method, semi-batch method and continuous method.

The steps (A), (B), and (C) will be described in detail below. (A) Extraction step In this step, the reaction mixture is separated into two or more layers by using a solvent, the cyclopentadiene multimer and the like are mainly dissolved in at least one layer, and the other layer is formed by the above-mentioned general formula (3). Alternatively, the compound or the like shown in (4) is mainly dissolved to perform liquid separation. In the extraction step, unreacted cyclopentadiene and / or dicyclopentadiene can be simultaneously dissolved in the layer in which the cyclopentadiene polymer is dissolved, and the layer is represented by the general formula (3) or (4). In the layer in which the compound is dissolved, the general formula (1)
And / or the compound represented by (2) can be simultaneously dissolved.

[0022] The present step can be carried out for the case of the general formula (3) or R ¹ and R ² are each a hydrogen atom or an acyl group having 2 to 5 carbon atoms of the compound represented by (4), R ¹ When R ² and R ² are each a hydrogen atom, the separation efficiency is good and the separation is preferably carried out. Specifically 2
-Butene-1,4-diol and / or 5-norbornene-2,3-dimethanol with cyclopentadiene and / or dicyclopentadiene for a Diels-Alder reaction mixture, or 2
-Butene-1,4-diol dicarboxylate and / or 5-norbornene-2,3-dimethanol dicarboxylate and cyclopentadiene and / or dicyclopentadiene are subjected to Diels-Alder reaction and a reaction mixture is described in detail in the latter stage. (C-2) which is carried out after hydrolysis or transesterification.

In this step, it is possible to use two or more kinds of solvents in total, one or more kinds each selected from two compound groups consisting of an oxygen-containing compound having 10 or less carbon atoms and a hydrocarbon compound having 5 to 10 carbon atoms. it can. As the oxygen-containing compound having 10 or less carbon atoms, methanol, ethanol, n-
Propyl alcohol, isopropyl alcohol, 1-butanol, sec-butanol, tert-butanol, 1-
Pentanol, 2-pentanol, 3-pentanol,
3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, tert-amyl alcohol, neopentyl alcohol, 1-hexanol,
2-hexanol, 3-hexanol, 2-methyl-1
-Pentanol, 3-methyl-3-pentanol, 4-
Methyl-2-pentanol, 3,3-dimethyl-2-butanol, 1-heptanol, 2-heptanol, 3-
Heptanol, 2-methyl-3-hexanol, 2,4
-Dimethyl-3-pentanol, 1-octanol, 2
-Octanol, 3-octanol, 2-ethyl-1-
Hexanol, 2,4,4-trimethyl-1-pentanol, 1-nonanol, 2-nonanol, 2,6-dimethyl-4-heptanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 2 Aliphatic monoalcohols such as decanol, 4-decanol and 3,7-dimethyl-1-octanol; alicyclic monoalcohols such as cyclopentanol, cyclohexanol; ethylene glycol, propylene glycol, 1,4-butanediol, Polyhydric alcohols such as 1,4-dihydroxy-2-butene, 1,2-dihydroxy-3-butene and glycerin; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and methyl isopropyl ketone; dimethyl ether, diethyl ether , Dipropyl ete , Butyl ethyl ether, methyl tert-butyl ether, dibutyl ether, dipentyl ether, tetrahydrofuran and ethers such as tetrahydropyran; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; and water. , Methanol, ethanol, isopropyl alcohol, ethylene glycol, diethyl ether and ethyl acetate can be preferably used.

As the hydrocarbon having 5 to 10 carbon atoms, n-
Linear or branched aliphatic carbonization such as pentane, n-hexane, methylpentane, n-heptane, methylhexane, dimethylpentane, n-octane, methylheptane, dimethylhexane, trimethylpentane, dimethylheptane, n-decane Hydrogen; linear or branched aliphatic terminal or internal olefin such as 1-pentene, 1-hexene, 1-heptene; aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene, propylbenzene; cyclopentane, methyl Examples thereof include alicyclic compounds such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and propylcyclohexane, and n-hexane, toluene, cyclohexane, and methylcyclohexane are preferred in production. Ku can be used.

Extraction is carried out using at least one of each of these oxygen-containing compounds and hydrocarbon compounds, the reaction mixture is separated into two or more layers, and cyclopentadiene multimers and the like are mainly dissolved in at least one layer, and other than that. The combination is optional as long as the compound represented by the general formula (3) or (4) or the like can be mainly dissolved in the layer to separate the layers. As a preferred combination of solvents, one type of each of the above oxygen-containing compound and hydrocarbon compound is used, and when the extraction operation is performed, the reaction mixture often separates into two layers, and one layer contains cyclopentadiene. The polymer can be dissolved and the compound represented by the general formula (3) or (4) can be dissolved in the other layer. Specifically, methanol and n-hexane, methanol and cyclohexane, methanol and toluene, ethylene glycol and n-hexane, ethylene glycol and octane, ethylene glycol and toluene, diethyl ether and n-hexane, ethyl acetate and n-hexane, etc. Can also be mentioned, and a combination in which water is further added to these examples can also be mentioned. Further, it is also possible to add at least one kind of the extraction solvent used to each of the layers that have been subjected to the main extraction step once and perform re-extraction.

The weight ratio of the oxygen-containing compound to the hydrocarbon compound is the former / the latter = 1/99 to 99/1, preferably 10 /.
90-90 / 10, more preferably 20 / 80-80 /
20 and the mixing weight ratio of the Diels-Alder reaction liquid and the total value of the oxygen-containing compound and the hydrocarbon compound is 1 /
99-99 / 1, preferably 20 / 80-80 / 20,
More preferably, it is in the range of 30/70 to 70/30.
The temperature condition in this extraction step is, for example, 10 to 150.
℃, preferably 10 to 100 ℃, more preferably 10
It is 80 ° C.

When these solvents are used as the reaction solvent in the Diels-Alder reaction, the cyclopentadiene polymer is separated only by cooling and standing after the reaction to separate the reaction mixture into layers. You can also Further, when the Diels-Alder reaction is carried out using 2-butene-1,4-diol, 2-butene-
It is also possible to use an excess amount of 1,4-diol to serve as a reaction raw material and extraction solvent. In addition, the raw material components recovered in the extraction step can be recycled as a raw material for the Diels-Alder reaction, if necessary, and the cyclopentadiene multimer or cyclopentadiene adduct separated in the extraction step can also be recycled into cyclopentadiene and It can also be reused as a reaction raw material equivalent to / or dicyclopentadiene.

(B) Distillation Step In this distillation step, R ¹ and R ² in the general formula (3) or (4) are each a hydrogen atom or a carbon number of 2 to 5, respectively.
Can be performed for the acyl group of
The order is not particularly limited. The distillation step can be carried out under either normal pressure conditions or reduced pressure conditions, but it is preferably carried out under reduced pressure, and the temperature at which the bottom temperature of the distillation column does not exceed 300 ° C, preferably does not exceed 250 ° C. More preferably, it is desirable to set the depressurization condition at a temperature not exceeding 220 ° C.

(C) Modification step (c-1) Hydrogenation reaction The compound represented by the general formula (3) in the present invention is relatively unstable thermally, and when a distillation step is incorporated in the purification step, Depending on the distillation conditions used, some may be thermally decomposed and the yield may decrease. Further, depending on the distillation conditions adopted, the decomposition reaction and polymerization reaction of cyclopentadiene multimers and cyclopentadiene-added heavy substances proceed. By appropriately performing the hydrogenation reaction in the purification step, the general formula (3)
The compound represented by can be converted into a thermally stable compound represented by the general formula (4), and the cyclopentadiene multimer can be converted into its hydrogenated product. The polymerization reaction can be suppressed.
This step can be performed when R ¹ and R ² in the above general formula (3) are each a hydrogen atom or an acyl group having 2 to 5 carbon atoms.

The hydrogenation reaction is not particularly limited in the number and order of execution, but since it proceeds to the carbon-carbon double bond, in addition to the compound represented by the general formula (3), unreacted general formula ( When the compound represented by 1) and the compound represented by the general formula (2), unreacted cyclopentadiene, dicyclopentadiene, and the like coexist, these are also subjected to hydrogenation at the same time, and the raw materials are recovered to react. In consideration of recycling and recycling, it is preferable to carry out on the mixture after separating the unreacted raw materials.

This hydrogenation reaction is carried out with hydrogen gas in the presence of a catalyst. As the catalyst, a catalyst generally used for hydrogenation reaction of carbon-carbon double bond can be used,
For example, heterogeneous catalysts such as palladium-supported activated carbon, Raney nickel, Raney cobalt, platinum oxide, platinum-supported activated carbon, nickel diatomaceous earth, and copper chromite; or chlorotris (triphenylphosphine) rhodium, platinum-tin complex, tertiary phosphine-cobalt. Mention may be made of homogeneous catalysts such as carbonyl complexes. The amount of catalyst used is
Usually, the amount within the range of 0.001 to 10% by weight is suitable for the reaction mixture.

The hydrogenation reaction can be carried out in the absence of a solvent, but if it is carried out in the presence of a suitable solvent, the viscosity of the mixed solution will be lowered, and in particular, in the case of using a heterogeneous catalyst, It is preferable because it facilitates separation. As the solvent that can be used, various solvents that can be generally used in the hydrogenation reaction can be exemplified, but it is preferable to appropriately select and use a solvent equivalent to the solvent used in the extraction step (A) in production. You can

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 often high. When it is carried out under pressure, it is 30 MPa or less, preferably 20 MPa or less, more preferably 10 M.
Pa of less than or equal to Pa is industrially advantageous in terms of reactor, operability and the like. Other inert gases that do not affect the hydrogenation reaction, such as nitrogen, carbon dioxide, helium, and argon, may coexist. The hydrogenation reaction is
It is in the range of 30 to 250 ° C, more preferably 60 to 220 ° C, and more preferably 80 to 200 ° C. The reaction time is 1 minute to 50 hours, preferably 10 minutes to 20 hours.

(C-2) Hydrolysis or Transesterification Reaction The hydrolysis or transesterification reaction is carried out according to the general formula (3) above.
Alternatively, R ¹ and / or R ² in (4) may be an acyl group having 2 to 5 carbon atoms, and the dicarboxylate compound represented by the general formula (3) or (4) and water or lower fat A dimethanol compound is obtained by reacting with a group alcohol in the presence of a catalyst. The number of times and the order of carrying out this step are not particularly limited, and they can be carried out in combination with (c-1) hydrogenation reaction. When a compound represented by the general formula (1) or (2) in which unreacted R ¹ and / or R ² is an acyl group having 2 to 5 carbon atoms is present in the mixture for carrying out hydrolysis or transesterification reaction However, since these also undergo hydrolysis or transesterification at the same time, considering that the reaction can be performed efficiently and the raw materials can be collected and recycled for the reaction, it can be performed on the mixture after separating the unreacted raw materials. preferable.

As the lower aliphatic alcohol used in the transesterification reaction, for example, methanol, ethanol,
Examples include n-propanol, isopropanol, allyl alcohol, n-butanol, tert-butanol and the like. Of these, methanol is particularly preferable.

Used in hydrolysis reaction or transesterification reaction
Examples of the catalyst used include sulfuric acid, nitric acid and hydrochloric acid.
Mineral acids such as benzene sulfonic acid, p-toluene sulfone
Acid, p-chlorobenzene sulfonic acid, methane sulfone
Acid, ethanesulfonic acid, trifluoromethanesulfone
Acid, trichloromethanesulfonic acid, trifluoroacetic acid,
Organic acids such as trichloroacetic acid and acetic acid; H_ThreePW₁₂O
₄₀, H_FourSiW₁₂O_{Four 0}, H_FourTiW₁₂O₄₀,
H₅CoW₁₂O₄₀, H₅FeW₁₂O₄₀, H ₆P
_TwoW₁₈O₆₂, H₇PW₁₁O₃₃, H_FourTiMo
₁₂O₄₀, H_ThreePMo₁₂O₄₀, H₇PMo₁₁O
₃₉, H₆P_TwoMo₁₈O₆₂, H_FourPMoW ₁₁O
₄₀, H_FourPVMo₁₁O₄₀, H_FourSiMo₁₂O
₄₀, H₅PV_TwoMo₁₀O₄₀, H_ThreePMo₆W₆O
₄₀, H_0.5Cs_2.5PW₁₂O₄₀And these
Hydrates such as tungstic acid, molybdic acid or this
Heteropolyacid; Amberlyst IR120 and other positive dyes
On-exchange resin; H-type zeolite such as H-ZSM-5, etc.
In addition to the acid catalyst, in the transesterification reaction, for example, water
Sodium oxide, potassium hydroxide, lithium hydroxide, sodium
Base catalysts such as thorium methoxide can also be mentioned.
It The amount of catalyst used is 0.001-
A range of 15 mol% is preferable, and 0.01 to 10 mol% is preferable.
Ranges are preferred.

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

By removing the ester of a carboxylic acid having 2 to 5 carbon atoms or a lower aliphatic alcohol resulting from the hydrolysis reaction or transesterification reaction from the outside of the system, the equilibrium of the reaction can be shifted and the reaction can proceed. In this case, since the lower aliphatic alcohol used for the transesterification reaction with the carboxylic acid and water or ester may form an azeotropic mixture and can be distilled out of the reaction system,
The amount of water or lower aliphatic alcohol used is preferably set in consideration of the amount required for the reaction as well as the amount distilled by azeotropic distillation.

Further, the general formula (1) and / or (2)
The compound represented by and cyclopentadiene and / or dicyclopentadiene are used as the solvent for the water or the lower alcohol, and the Diels-Alder reaction is carried out in the presence of the catalyst to cause the Diels-Alder reaction and hydrolysis or transesterification. It is also possible to directly proceed the reaction to directly produce the dimethanol compound represented by the general formula (3). Here, the hydrolysis or transesterification reaction can be promoted by adding a small amount of an acid or base catalyst. Further, depending on the catalyst used in the hydrolysis reaction or the transesterification reaction, coloring may be observed after the reaction, but the coloring component and the compound represented by the general formula (3) can be separated by the extraction step (A), and coloring It is one of the advantages of this production method that the compound represented by the general formula (3) having a small amount of or no coloration can be isolated.

As a method for converting the carboxylate compound represented by the general formula (3) or (4) into a dimethanol compound, other than the transesterification reaction, a conventionally known reduction reaction in the presence of, for example, a copper-chromite catalyst is carried out. Although it is possible to carry out the above, it is not an industrially advantageous method due to the problem that high temperature and high pressure hydrogen conditions are required, and it is preferable to select the hydrolysis reaction or transesterification reaction. Although the purification step has been described in detail above, there is no particular limitation on the combination and execution order of each step as long as the purification step always includes at least (A) extraction step. Can be carried out preferably.

As an example of the purification step when R ¹ and R ² of the compounds represented by the above general formulas (1) and (2) are hydrogen atoms, i) immediately after the Diels-Alder reaction, After separation into a mixture of compounds represented by the general formulas (1), (2) and (3) and a mixture of cyclopentadiene, dicyclopentadiene and a cyclopentadiene multimer, the former is subjected to a distillation step (B). When the compounds of the general formulas (1) and (2) are separated to obtain the compound of the general formula (3) to be produced, i
i) The Diels-Alder reaction solution is subjected to the distillation step (B), and the unreacted compound represented by the general formula (1) and the compound represented by the general formula (2), unreacted cyclopentadiene and di When a solvent is used in the reaction, cyclopentadiene, a cyclopentadiene multimer obtained by separating low boiling point components such as the solvent, and a distillation residue containing the compound represented by the general formula (3) (c-1 ) After being subjected to a hydrogenation reaction and converted into a reaction mixture containing a compound represented by the general formula (4) and a hydrogenated product of a cyclopentadiene multimer, the mixture is subjected to (A) an extraction step to obtain a water of the cyclopentadiene multimer. When the additive is separated to obtain the compound represented by the general formula (4), iii) the distillation residue containing the cyclopentadiene multimer obtained through the distillation step and the compound represented by the general formula (3) And (c-1) hydrogenation reaction is not carried out and (A) is subjected to the extraction step to obtain the compound represented by the general formula (3).

In the case where R ¹ and R ² of the compounds represented by the general formulas (1) and (2) are acyl groups having 2 to 5 carbon atoms, i) immediately after the Diels-Alder reaction (B) is subjected to the distillation step, and the unreacted compound represented by the general formula (1) and the compound represented by the general formula (2), the unreacted cyclopentadiene and dicyclopentadiene, and the solvent for the reaction are contained in the mixture. When used, the cyclopentadiene multimer obtained by separating low-boiling components such as the solvent and the distillation residue containing the compound represented by the general formula (3) are subjected to (c-1) hydrogenation reaction. And then converted into a reaction mixture containing a compound represented by the general formula (4) and a hydrogenated product of a cyclopentadiene multimer, and then subjected to (c-2) hydrolysis or transesterification reaction to give the general formula When a dimethanol compound represented by the general formula (4) is obtained by converting it into a reaction mixture containing a dimethanol compound represented by 4) and a hydrogenated product of a cyclopentadiene multimer, and then subjecting the mixture to an extraction step (A), ii) Immediately after the Diels-Alder reaction, (B) is subjected to a distillation step to distill off low-boiling components such as unreacted raw materials contained in the mixture, and then the obtained distillation residue is (c-2) hydrolyzed or transesterified. When the dimethanol compound represented by the general formula (3) is obtained by subjecting it to the reaction and then subjecting it to the extraction step (A), the following can be mentioned.

Further, the dimethanol compound represented by the general formula (3) or (4) obtained through the above-described purification step can be further purified by a usual method such as recrystallization. Further, depending on the distillation conditions of the (B) distillation step, the dimethanol compound represented by the general formula (3) or (4) obtained may contain a dimethanol compound represented by the general formula (2) or a hydrogenated product thereof. It is also possible to obtain such compositions.

General formula (3) produced by the above method
Alternatively, the content of the cyclopentadiene multimer or the hydrogenated product of the dimethanol compound represented by (4) can be easily adjusted to 5% by weight or less, and can be adjusted to 1% by weight or less by repeating extraction. And can be of high purity.

The fused ring-containing compound represented by the general formula (3) or (4) obtained by the above-mentioned production method is
Since it has a cyclic structure and is similar in properties to aliphatic compounds, its use in various applications utilizing these structures and properties has been investigated, either directly or by epoxy derivative, acrylic acid derivative. , Methacrylic acid derivatives,
Various (co) polymers can be produced by converting to carbonates, polyol derivatives and the like for use. Specific examples of various (co) polymers will be shown below, but the present invention is not limited thereto.

"Polyester" The condensed ring-containing diol compound produced by the production method of the present invention can be used as a diol component in a saturated polyester such as polyethylene terephthalate or polybutylene terephthalate. For example, as a substitute for or in combination with a diol component such as ethylene glycol or butylene glycol, a mixture of high purity terephthalic acid and L
A low polycondensate is obtained by heating to 200 to 250 ° C. in the presence of i, Ca, Zn, Mn, and Co acetate, etc., and further Sb ₂ O ₃ , Sb (OCH ₃ ) ₃ , Pb (CH
270-3 under high vacuum conditions using a catalyst such as ₃ COO) _3.
A polyester can be obtained by a polycondensation reaction at 00 ° C.

"Unsaturated Polyester" An unsaturated polyester resin is an unsaturated polyester obtained by condensing an unsaturated dibasic acid or an acid component in which a part of the unsaturated dibasic acid is replaced with various saturated dibasic acids, and a dihydric alcohol. It consists of dissolved in a vinyl monomer that copolymerizes with unsaturated polyester. As the dihydric alcohol, for example, propylene glycol and the like are often used, and the dihydric alcohol in which at least a part of them is replaced with the condensed ring-containing diol compound of the present invention is used, and the temperature is 200 ° C. while passing an inert gas such as nitrogen.
The unsaturated polyester resin can be obtained by heating to about a degree to cause an esterification reaction to obtain an unsaturated polyester, and mixing with this a vinyl monomer such as styrene and a polymerization stabilizer. This resin can be obtained by mixing it with a promoter such as cobalt or a curing agent such as methyl ethyl ketone peroxide and reacting it with heat, or by directly irradiating with an electron beam or ultraviolet ray to obtain a cured resin.

"Polycarbonate" The fused ring-containing diol compounds of the present invention can be converted into, for example, carbonates or biscarbonates, which are, for example, Na,
Simple substance of alkali or alkaline earth metal such as K, Mg, Ca, oxide or hydroxide, ZnO, PbO, Sb ₂
Its own condensation reaction in the presence of a catalyst such as a basic metal oxide such as O ₃ or a borane such as trimethylenebis (triphenylphosphonium) bistriphenylboranate;
Alternatively, for example, a polycarbonate can be obtained by carrying out a transesterification reaction with bisphenol A under conditions of high temperature of about 250 to 300 ° C. and reduced pressure.

"Polyurethane" Polyurethane includes, for example, diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, p, p'-diphenylmethane diisocyanate and 1,4-butylene glycol, hexamethylene glycol, glycerin, trimethylolpropane, penta It can be produced by reacting a polyol such as erythritol with or without a catalyst, or in some cases, a catalyst such as a tertiary amine or a tin salt of an organic acid, a foaming agent, or the like. The contained diol compound can be reacted as the diol compound itself or as a mixture with the above-mentioned polyol. Polyurethane has a wide variety of applications including fibers, foams, elastomers, casting resins, paints, and sealants, and can be applied to any of these.

"Epoxy Resin" For example, the fused ring-containing diol compound of the present invention contains 2 equivalents of epichlorohydrin and B.
When it is reacted at 50-70 ° C in the presence of Lewis acid such as F ₃ · OEt ₂ complex or SnCl ₄ , it is converted into bischlorohydrin ether, which is cyclized in the presence of a base such as sodium hydroxide or sodium aluminate. When reacted, it can be converted to diglycidyl ether and can be used as an epoxy resin. As the widely used diepoxy compound, there is a diglycidyl ether of bisphenol A, etc., but the above-mentioned diglycidyl ether of a condensed ring-containing diol is used alone or in a mixture with a diglycidyl ether of bisphenol A. Ingredients include diethylenetriamine, diaminodiphenylmethane, phthalic anhydride, hexahydrophthalic anhydride, tris (dimethylaminomethyl) phenol, 2
- ethyl-4-methylimidazole and _BF 3 · _{C 2}
Hardeners such as H ₅ NH ₂ complex and other plasticizers, liquid rubber,
Mix fillers, diluents, pigments and solvents, and
An epoxy resin can be obtained by heating and curing at 00 to 200 ° C. Further, when the condensed ring-containing diol compound of the present invention is reacted with epichlorohydrin in the vicinity of an equivalent amount, it is converted into monochlorohydrin ether, and when this is subjected to a ring closure reaction in the presence of a base, it can be converted into monoglycidyl ether. Further, for example, among the condensed ring-containing diol compounds of the present invention, octahydrodimethanonaphthalene dimethanol compounds having a carbon-carbon double bond in the dimethanonaphthalene skeleton are peracetic acid, perbenzoic acid and m-chloroperbenzoic acid. It can be converted into a compound in which the carbon-carbon double bond is epoxidized by reacting with a peroxide such as, and can be added as a reactive diluent (also referred to as a reactive flow regulator).

[Alkyd Resin] The condensed ring-containing diol compound of the present invention can be used as a polyhydric alcohol component of an alkyd resin, and is used as phthalic anhydride, isophthalic acid, trimellitic anhydride, maleic anhydride and adipic acid. Modifiers represented by fatty acids such as polybasic acid, soybean oil fatty acid, linseed oil fatty acid, coconut oil fatty acid and castor oil fatty acid, oxides and hydroxides of Ca, Pb, Zn, Li and the like as catalysts, if necessary Finally, an alkyd resin can be obtained by finally reacting with a solvent such as xylene at 230 to 260 ° C. As the polyhydric alcohol component, glycerin, pentaerythritol, trimethylolpropane, ethylene glycol, propylene glycol and neopentyl glycol are generally used, but at least a part of them is used as the condensed ring-containing diol compound of the present invention. Substitutions can also be used.

"Acrylic Resin" The condensed ring-containing dimethanol di (meth) acrylate compound in the present invention is a condensed ring-containing dimethanol or a condensed ring-containing dimethanol.
It is also produced by subjecting a dicarboxylate such as diacetate to an esterification reaction or a transesterification reaction with a (meth) acrylic acid compound such as (meth) acrylic acid, methyl (meth) acrylate and ethyl (meth) acrylate. be able to. The reaction is carried out using mineral acids such as sulfuric acid, nitric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid and trifluoroacetic acid, heteropolyacids, cation exchange resins and H-type zeolites as acid catalysts, and in transesterification reactions. In addition to these acid catalysts, 3ZnO-2B
₂ O ₃ , Cadmium acetate, Zinc acetate and Calcium acetate are used as a basic catalyst such as a fatty acid salt of a Group II compound represented by periodic table or sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium methoxide. Correspondingly in the presence of a solvent at a temperature of 70-150 ° C. Further, this di (meth) acrylate can also be produced by reacting a condensed ring-containing dimethanol and a (meth) acrylic acid halide compound in the presence of a base. Specific (meth) acrylic acid halide compounds include (meth) acryloyl chloride and the like, and bases include chain alkylamines such as trimethylamine, triethylamine and tripropylamine; pyridine, aniline and N-methylaniline. Aromatic amines of 1,
5-diazabicyclo [4,3,0] no-5-nene (DB
N) 1,4-diazabicyclo [2,2,2] octane (DBO) and 1,8-diazabicyclo [5,4,0]
Cyclic alkylamines such as undec-7-ene (DBU); metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, and the like. Triethylamine and tripropylamine are preferably used, and if necessary, Temperature in the presence of solvent
React with. Furthermore, a condensed ring-containing mono (meth) acrylate compound can also be produced by reacting a (meth) acrylic acid compound with respect to a condensed ring-containing dimethanol or dimethanol acetate in an equivalent amount and reacting under the same conditions as above. . The condensed ring-containing mono- or di (meth) acrylate compound produced by the above may be used alone or as (meth) acrylic acid, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylamide, vinyl acetate. A monomer having a polymerizable double bond such as styrene and acrylonitrile and / or an epoxy type, urethane type and ester type (meth) acrylate oligomer having a radical polymerizable double bond, and tert-butyl hydroperoxide, Methods such as cumene hydroperoxide, organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide, heating by using an azobis compound such as azobisisobutyronitrile as a catalyst, benzophenone, benzoin, and benzoinmethyl Ether or diet A resin is produced by a method in which a photopolymerization initiator such as cyacetophenone and optionally amines such as triethanolamine and ethyl 4-dimethylaminobenzoate are irradiated with ultraviolet rays or electron beams in the presence of a photosensitizer. be able to.

Since the (co) polymers exemplified above have a structure such as a dimethanonaphthalene skeleton introduced thereinto, they have heat resistance, transparency, low birefringence, weather resistance as compared with conventional polymers.
It can enhance light resistance, low water absorption, moisture resistance, low dielectric constant, low dielectric properties, insulation, adhesiveness, mechanical properties such as impact resistance and hardness, and dimensional stability and chemical resistance. ,
It can be applied to a wide range of applications as various structural materials and functional materials. For example, printed wiring boards, electrical / electronic materials such as electronic device sealants, optical fibers,
Optical elements, optical lenses, optical materials such as optical disks,
Various paints and adhesives, curable resins that cure with electron beams and ultraviolet rays, films such as photographic films and transparent films, dental fillings, medicines and dental materials such as medicine packaging materials,
It can be applied to transparent resin coatings, tableware and packaging materials, automobile parts, etc.

[0054]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. <Example 1> 2-butene-1,4-diol 128 was added to an autoclave having an internal volume of 5 L equipped with an electromagnetic induction stirring device.
6 g (14.43 mol) and 500 g of toluene were charged and the system was replaced with nitrogen gas. Then, the mixture was heated with a mantle heater to an internal temperature of 200 ° C. under stirring, and 966 g (6.92 mol) of dicyclopentadiene having a purity of 95% was continuously added into the autoclave over 4 hours using a metering pump, and further for 1 hour. Diels-Alder reaction was carried out while maintaining the same temperature. After completion of the reaction, the reaction mixture was cooled and the contents were taken out, and the reaction mixture was analyzed by gas chromatography. As a result, 384.2 g of 2-butene-1,4-diol (4.3
6 mol), 134.4 g of dicyclopentadiene (1.0
2 mol), 5-norbornene-2,3-dimethanol 1268.6 g (8.23 mol), cyclopentadiene trimer 89.0 g (0.45 mol), 1,2,3,4,4
a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 199.7 g (0.
91 mol), and cyclopentadiene tetramer 9.5
A composition containing g (0.04 mol) was obtained at 2740 g. Then, toluene was distilled off from this reaction solution with a rotary evaporator, and 760 g of methanol and 760 g of cyclohexane were added to 2230 g of the obtained mixture, and the mixture was heated at 60 ° C.
After vigorously stirring with, the mixture was allowed to stand and cooled, and the mixture was separated into two layers, so the layers were separated. 2-butene on the upper layer
1,4-diol 4.1 g (0.05 mol), dicyclopentadiene 89.5 g (0.68 mol), 5-norbornene-2,3-dimethanol 47.3 g (0.31 mo)
l), 59.8 g (0.30 m) of cyclopentadiene trimer
ol), 1,2,3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 8.1 g (0.04 mol), and cyclo 793 g of a composition containing 8.4 g (0.03 mol) of a pentadiene tetramer was obtained, and in the lower layer, 380.0 g (4.31 mol) of 2-butene-1,4-diol and 44.2 g (0) of dicyclopentadiene were obtained. .33 mol), 5-norbornene-
1,2-dimethanol 1220.9 g (7.92 mo)
l), 28.9 g (0.15 m) of cyclopentadiene trimer
ol), 1,2,3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 190.9 g (0.87 mol), and cyclo 2950 g of a composition containing 0.8 g (3.0 mmol) of pentadiene tetramer was obtained. This lower layer was further extracted twice with 500 g of cyclohexane at 60 ° C., and 359.4 g (4.0%) of 2-butene-1,4-diol was added to the lower layer.
8 mol), 4.2 g of dicyclopentadiene (0.03 m)
ol), 5-norbornene-2,3-dimethanol 12
14.2 g (7.87 mol), cyclopentadiene trimer 2.1 g (0.01 mol), 1,2,3,4,4a, 5,
17,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 178.6 g (0.81 m)
ol), and 0.1 g (0.1%) of the cyclopentadiene tetramer.
2787 g of a composition containing 4 mmol) was obtained. After the composition was concentrated by a rotary evaporator, vacuum distillation was performed at a pressure of 0.13 KPa and a distillation column tower bottom temperature of 220 ° C. to give 2-butene-1,4-diol, dicyclopentadiene, 5-norbornene-2,3. Distilling out dimethanol to obtain 150 g of bottom residue, which is then pressured to 1
When subjected to thin film distillation at 3.3 Pa and a temperature of 230 ° C., 1,2,3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2 having a purity of 99.1% was obtained. , 3-dimethanol was obtained.

Example 2 Diels-Alder reaction and solvent extraction were carried out in the same manner as in Example 1, and the obtained composition was then concentrated by a rotary evaporator, followed by a pressure of 0.13 KPa and a distillation column bottom temperature of 220. Distilled under reduced pressure at ℃, distilling 2-butene-1,4-diol, dicyclopentadiene, and 5-norbornene-2,3-dimethanol, 142 g of the residue obtained with 500 g of methylcyclohexane was added to 1 L autoclave. And loaded nickel catalyst (N-113 catalyst manufactured by JGC Chemical Co., Ltd.) in an amount of 7% by weight.
In the presence of, temperature 110 ℃, hydrogen gas pressure 5.0 MPa
The hydrogenation reaction was carried out for 5 hours under the above conditions. After completion of the reaction, the contents were cooled and the contents were taken out, the catalyst was filtered off, and the reaction mixture was analyzed by gas chromatography to find that the hydrogenated cyclopentadiene trimer was 2.0 g (0.01 mo).
l) 1,2,3,4,4a, 5,6,7,8,8a-decahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 179.4 g (0.81 mol) ), And 0.11 g (0.4 mmol) of a hydrogenated cyclopentadiene tetramer were obtained. After concentrating the hydrogenation reaction product with a rotary evaporator, the pressure condition was 0.13K.
When vacuum distillation was carried out at a distillation column bottom temperature of 270 ° C. with Pa, 1,2,3,4,4a, 5,6,7,8,8a having a purity of 99.0%.
-Decahydro-1,4: 5,8-dimethanonaphthalene-
2,3-dimethanol was obtained.

Example 3 The reaction and purification were carried out in the same manner as in Example 1 except that diethyl ether was used instead of methanol and n-hexane was used instead of cyclohexane, and the extraction operation was carried out at a temperature of 30 ° C. Purity 99.2%
1,2,3,4,4a, 5,8,8a-octahydro-1,
4: 5,8-Dimethanonaphthalene-2,3-dimethanol was obtained.

Example 4 The reaction and purification were carried out in the same manner as in Example 1 except that ethyl acetate was used instead of methanol and n-hexane was used instead of cyclohexane. As a result, 1,2 having a purity of 99.0% was obtained. , 3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,
3-dimethanol was obtained.

<Comparative Example 1> A reaction mixture obtained by carrying out the Diels-Alder reaction in the same manner as in Example 1 was charged into a 5 L autoclave, and a supported nickel catalyst (manufactured by JGC Chemical Co., N
(-113 catalyst) was added at 7% by weight, and a hydrogenation reaction was carried out for 5 hours under the conditions of a temperature of 110 ° C. and a hydrogen gas pressure of 5.0 MPa. After the completion of the reaction, the contents were cooled, the contents were taken out, the catalyst was filtered off, and the reaction mixture was analyzed by gas chromatography. As a result, 1,4-butanediol 387.
0 g (4.30 mol), hydrogenated dicyclopentadiene 137.5 g (1.01 mol), norbornane-2,3
-Dimethanol 1280.8g (8.20mol), hydrogenated cyclopentadiene trimer 91.0g (0.45mo)
l) 1,2,3,4,4a, 5,6,7,8,8a-decahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 202.3 g (0.91 mol) ), And hydrogenated cyclopentadiene tetramer 10.5 g (0.04 mol)
2710 g of a composition containing was obtained. After concentrating the hydrogenation reaction product, the pressure was 0.13 KPa and the distillation column tower bottom temperature was raised to a maximum of 270 ° C. to perform batch-type vacuum distillation. Distilled purpose 1,2,3,4,4a, 5,6,7,8,8
a-decahydro-1,4: 5,8-dimethanonaphthalene-
The purity of 2,3-dimethanol reached a maximum of 94.7%, and the hydrogenated cyclopentadiene trimer and tetramer of the fraction was 5.0%.

<Embodiment 5> In a autoclave having an internal volume of 200 ml, 2-butene-1,4-diol (18.8 g, 0.1).
21 mol), 5-norbornene-2,3-dimethanol 32.9 g (0.21 mol) and methanol 63.
2 g was charged and the system was replaced with nitrogen gas. Then, the mixture was heated with a mantle heater to an internal temperature of 200 ° C. with stirring to obtain a purity of 95
% Dicyclopentadiene 28.2 g (0.20 mol)
Was continuously added to the autoclave over 4 hours using a metering pump, and the Diels-Alder reaction was carried out while maintaining the same temperature for 1 hour. After completion of the reaction, the reaction mixture was cooled, the contents were taken out, and the reaction mixture was analyzed by gas chromatography. As a result, 5.1 g of 2-butene-1,4-diol was obtained.
(0.06 mol), dicyclopentadiene 9.5 g
(0.07 mol), 5-norbornene-2,3-dimethanol 40.9 g (0.27 mol), cyclopentadiene trimer 5.7 g (0.03 mol), 1,2,3,4,4
a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 11.6 g (0.0
5 mol), and cyclopentadiene tetramer 0.8 g
127 g of a composition containing (3.0 mmol) was obtained.
Then, toluene was distilled off from this reaction solution with a rotary evaporator, and 50 g of methanol and 50 g of cyclohexane were added to 83 g of the obtained mixture, and solvent extraction was carried out in the same manner as in Example 1. 2-butene-1,4- 4.4 g (0.05 mol) of diol, 0.2 g (1.5 mmol) of dicyclopentadiene, 5-norbornene-2,
3-dimethanol 38.2 g (0.25 mol), cyclopentadiene trimer 0.3 g (1.5 mmol), 1,2,
3,4,4a, 5,8,8a-octahydro-1,4: 5,8
-Dimethanonaphthalene-2,3-dimethanol 10.2 g
A composition containing (0.05 mol) and 0.1 g (0.4 mmol) of the cyclopentadiene tetramer was obtained. After the composition was concentrated by a rotary evaporator, vacuum distillation was performed at a pressure of 0.13 KPa and a distillation column tower bottom temperature of 220 ° C. to give 2-butene-1,4-diol, dicyclopentadiene, 5-norbornene-2,3. Distilling out dimethanol to give 12.1 g of bottom residue, which is then pressured to 1
When subjected to thin film distillation at 3.3 Pa and a temperature of 230 ° C., 1,2,3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2 having a purity of 99.0% was obtained. , 3-dimethanol was obtained.

<Example 6> 2-butene-1,4-diol diacetate 2601 was placed in an autoclave having an internal volume of 5 L.
g (12.38 mol) and 400 g of toluene were charged, and the system was replaced with nitrogen gas. Then, the internal temperature was raised to 200 ° C. with a mantle heater while stirring, and 999 g (7.16 mol) of dicyclopentadiene having a purity of 95% was continuously added into the autoclave over 4 hours using a metering pump, and further 1 The same temperature was maintained for the time and Diels-Alder reaction was performed. After completion of the reaction, the reaction mixture was cooled, the contents were taken out, and the reaction mixture was analyzed by gas chromatography. As a result, 2-butene-1,4-diol diacetate 68
3.7 g (3.97 mol), dicyclopentadiene 6
1.1 g (0.46 mol), 5-norbornene-2,3
1536.6 g of dimethanol diacetate (6.45
mol), cyclopentadiene trimer 278.6 g (1.
40 mol), 1,2,3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-
Dimethanol diacetate 323.1g (1.06mo
1), and 34.7 g (0.4) of cyclopentadiene tetramer.
3950 g of a composition containing 13 mol) was obtained. Then, toluene was distilled off from this reaction solution with a rotary evaporator, and 3634 g of the obtained mixture was added under a pressure of 0.13 KP.
a. Distillation under reduced pressure at a distillation column tower bottom maximum temperature of 204 ° C.
-Butene-1,4-diol diacetate, dicyclopentadiene, 5-norbornene-2,3-dimethanol
The diacetate and cyclopentadiene trimer were distilled off to obtain 588 g of a bottom residue. 20.7 g of 5-norbornene-2,3-dimethanol diacetate (0.
09 mol), and cyclopentadiene trimer 0.7 g (3.
5 mmol), 1,2,3,4,4a, 5,8,8a-octahydro-1,4: 5,8-dimethanonaphthalene-2,3-
Dimethanol diacetate 320.1g (1.05mo
l), and 34.1 g (0.1%) of a cyclopentadiene tetramer.
13 mol). Next, 10 g of this residue, 150 ml of methanol and 60 ml of 5% aqueous sodium hydroxide solution were charged into a 300 ml three-necked flask and refluxed in an oil bath for 3 hours to carry out a transesterification reaction. After completion of the reaction, the mixture was cooled, neutralized with 18% hydrochloric acid, methanol was distilled off with a rotary evaporator, and then extracted and concentrated with ether to obtain 8.0 g of a reaction liquid. As a result of analyzing the reaction solution by gas chromatography, the yield was 99.2.
mol% (3.9 g) 1,2,3,4,4a, 5,8,8a-
Octahydro-1,4: 5,8-dimethanonaphthalene-
Since 2,3-dimethanol was produced and contained 12 mg (0.1 mmol) of cyclopentadiene trimer and 0.6 g (2.3 mmol) of cyclopentadiene tetramer, 5 g of methanol and 5 of cyclohexane were added.
When g was added and solvent extraction was performed in the same manner as in Example 1, 5-norbornene-2,3-dimethanol was added to the lower layer in an amount of 0.1.
3 g (1.9 mmol), 1,2,3,4,4a, 5,8,8a
-Octahydro-1,4: 5,8-dimethanonaphthalene-
3.5 g (0.02 mol) of 2,3-dimethanol, and 55 mg of cyclopentadiene tetramer (0.2 mmo)
14 g of a composition containing 1) was obtained. After concentrating this composition on a rotary evaporator, the pressure was 13.3 Pa,
As a result of purification by distillation at a maximum temperature of 230 ° C, purity is 99.1%
1,2,3,4,4a, 5,8,8a-octahydro-1,
4: 5,8-Dimethanonaphthalene-2,3-dimethanol was obtained.

Example 7 120 g of the mixture produced by carrying out the Diels-Alder reaction and the transesterification reaction in the same manner as in Example 6 was charged into a 1 L autoclave together with 500 g of methanol, and a supported nickel catalyst (manufactured by JGC Chemical Co., N -113 catalyst) in the presence of 7% by weight, the hydrogenation reaction was carried out for 5 hours under the conditions of a temperature of 110 ° C. and a hydrogen gas pressure of 5.0 MPa. After the reaction was completed, the contents were cooled, the contents were taken out, the catalyst was filtered off, and the reaction mixture was analyzed by gas chromatography.
3.5 g (0.02 mol) of 2,3-dimethanol and 0.2 g (0.9 mmo) of hydrogenated cyclopentadiene trimer.
l) 1,2,3,4,4a, 5,6,7,8,8a-decahydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol 57.3 g (0.26 mol) ) And hydrogenated cyclopentadiene tetramer (8.9 g, 0.03 mol) were obtained. The hydrogenation reaction was concentrated on a rotary evaporator and then methanol 40
g and 40 g of n-hexane were added, and solvent extraction was performed in the same manner as in Example 1. As a result, norbornane-2,
3-dimethanol 3.0 g (0.02 mol), 1,2,
3,4,4a, 5,8,8a-octahydro-1,4: 5,8
-Dimethanonaphthalene-2,3-dimethanol 51.6 g
147 g of a composition containing (0.23 mol) and a cyclopentadiene tetramer (0.6 g, 2.2 mmol) was obtained. After the composition was concentrated by a rotary evaporator, the pressure was 0.13 KPa and the distillation column bottom temperature was 270 at maximum.
As a result of distillation purification by heating up to ℃ 1, the purity of 99.3%
2,3,4,4a, 5,8,8a-octahydro-1,4: 5,
8-Dimethanonaphthalene-2,3-dimethanol was obtained.

[0062]

According to the production method of the present invention, the condensed ring-containing compound having a dimethanonaphthalene skeleton and the like and the cyclopentadiene trimer and tetramer are used because the extraction step using a specific solvent is combined in the purification step. And cyclopentadiene multimers or hydrogenated products of cyclopentadiene multimers can be efficiently separated, and a highly pure fused ring-containing compound can be industrially advantageously produced.

Claims (5)

[Claims] 1. A reaction mixture obtained by a Diels-Alder reaction of a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2) with cyclopentadiene and / or dicyclopentadiene. In the purification step, the method includes an extraction step of separating / removing at least a part of cyclopentadiene multimers such as trimer or tetramer of cyclopentadiene by solvent extraction.
A method for producing a fused ring-containing compound represented by the following general formula (3). Embedded image R ¹ OCH ₂ CH═CHCH ₂ OR ² ... Formula (1) (In the formula, R ¹ and R ² each represent a hydrogen atom or an acyl group having 2 to 5 carbon atoms.) ] (In the formula, R ¹ and R ² are the same as defined in the above general formula (1).) (In the formula, R ¹ and R ² are the same as defined in the above general formula (1). N is an integer of 0 to 2.) 2. The above general formulas (1), (2) and (3).
In the case where R ¹ and / or R ² is an acyl group having 2 to 5 carbon atoms, the step of purifying the reaction mixture obtained by the Diels-Alder reaction includes a hydrolysis reaction or a transesterification reaction. A method for producing a condensed ring-containing compound according to claim 1. 3. A condensed ring-containing compound represented by the following general formula (4), which comprises a hydrogenation reaction by reacting with hydrogen gas in the presence of a catalyst in the step of purifying the reaction mixture obtained by the Diels-Alder reaction. Manufacturing method. [Chemical 4] (In the formula, R ¹ and R ² are the same as defined in the above general formula (1). N is an integer of 0 to 2.) 4. The reaction step is carried out using two or more kinds of solvents to separate the reaction mixture into two or more layers, and at least one of the layers is a cyclopentadiene trimer,
At least a part of the cyclopentadiene multimer such as a cyclopentadiene tetramer is dissolved, and at least a part of the compound represented by the general formula (3) or (4) is dissolved in the other layer, followed by a liquid separation operation. 4. The method for producing a fused ring-containing compound according to claim 1, which is a step of 5. The solvent used in the extraction step is one or more kinds in each of two compound groups consisting of an oxygen-containing compound having 10 or less carbon atoms and a hydrocarbon compound having 5 to 10 carbon atoms. The method for producing a fused ring-containing compound according to any one of claims 1 to 4, wherein