WO2015079957A1 - Method for producing cyclic olefin compound - Google Patents

Abstract

　Provided is a method for producing a cyclic olefin compound that makes it possible to suppress isomerization reactions and other such secondary reactions, and to efficiently obtain a high-purity cyclic olefin compound containing few impurities easily and at a high yield. In the method for producing a cyclic olefin compound of the present invention, a cyclic olefin compound having two or more cyclohexene rings in the molecule is produced by intramolecular dehydration of an alicyclic alcohol having two or more hydroxyl-group-bonded cyclohexane rings in the molecule in the presence of a dehydration catalyst, wherein the method is characterized in that a dehydration reaction is carried out while supplying the dehydration catalyst continuously or intermittently to a mixed solution containing the alicyclic alcohol and an organic solvent under reflux of an organic solvent that is azeotropic with water and separates from water at ordinary temperatures, or, when the dehydration catalyst is configured from multiple components, while supplying at least one of these components continuously or intermittently to a mixed solution containing the alicyclic alcohol and an organic solvent.

Description

Method for producing cyclic olefin compound

The present invention relates to a resin raw material excellent in heat resistance, hydrolysis resistance, weather resistance, transparency and the like and a method for producing an important cyclic olefin compound as an intermediate thereof. This application claims the priority of Japanese Patent Application No. 2013-246759 for which it applied to Japan on November 28, 2013, and uses the content here.

As a method for producing a cyclic olefin compound having a cyclohexene skeleton, a method for producing by a dehydration reaction of alcohol is widely known. For example, a technology for producing a cyclic olefin compound by dehydration reaction of alcohol using an alkali metal hydrogen sulfate, which is an acidic salt (see Patent Document 1, Patent Document 3, Non-Patent Document 2, and Non-Patent Document 3), concentrated sulfuric acid A technique for producing a cyclic olefin compound by dehydration of alcohol using an inorganic acid such as phosphoric acid as a catalyst (see Patent Document 2 and Non-Patent Document 1) is disclosed in the literature.

However, these known methods for producing a cyclic olefin compound are not always satisfactory in terms of yield and purity of the obtained cyclic olefin compound. That is, in the conventional method using concentrated sulfuric acid having a high acidity, side reactions are liable to occur, and there is a problem that a compound other than the desired cyclic olefin compound is by-produced to reduce the yield. In addition, in the conventional method using phosphoric acid or acidic salt with low acidity, it is necessary to lengthen the reaction time or increase the reaction temperature, and a side reaction occurs to reduce the yield, and the desired cyclic olefin. There has been a problem that isomeric components that are extremely difficult to separate from the compound are by-produced. In addition, since inorganic salts such as alkali metal hydrogen sulfate have extremely low solubility in the reaction raw materials and organic solvents, it is necessary to react at a higher temperature for a long time, resulting in significant side reactions.

In particular, when producing a cyclic olefin compound having two or more cyclohexene rings in the molecule by intramolecular dehydration of an alicyclic alcohol having two or more cyclohexane rings having hydroxyl groups in the molecule, isomerization may occur during the reaction. It occurs and various isomers with different double bond positions are by-produced. Since the above isomers are similar in physical properties to the target compound such as boiling point and solvent solubility, once formed, it is very difficult to separate from the target compound and it is mixed in the product, so that a high purity target compound is obtained. Is difficult.

In more detail, when a cyclohexyl alcohol derivative having a substituent at the 4-position is heated in the presence of a dehydration catalyst, in a system in which water coexists, a dehydration reaction is performed as shown in the following reaction formula (4). In addition to the reverse reaction (water addition reaction), not only the desired cyclic olefin but also two isomers with different double bond positions are by-produced. In the formula, R is a substituent.

で表される水添ビフェノールを原料とした場合を例にとると、下記式（３ａ）～（３ｆ）で表される６種の異性体（環状オレフィン化合物）が生成しうる。すなわち、式（３ａ）で表される化合物（ビシクロヘキシル－３，３′－ジエン；沸点２６０℃／７６０Ｔｏｒｒ、１４０℃／１０Ｔｏｒｒの無色透明の液体）を目的化合物とする場合には５種の副生物が生成しうる。

And when said R contains the cyclohexane ring which the hydroxyl group couple | bonded, the number of isomers will increase further. For example, the following formula (1a)

As an example, a hydrogenated biphenol represented by the following formula (3a) to (3f) can be produced as isomers (cyclic olefin compounds) represented by the following formulas (3a) to (3f). That is, when the compound represented by the formula (3a) (bicyclohexyl-3,3′-diene; colorless transparent liquid having boiling points of 260 ° C./760 Torr and 140 ° C./10 Torr) is used as the target compound, Living organisms can produce.

On the other hand, an alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group in its molecule is completely neutralized with sulfonic acids, phosphoric acid, sulfuric acid, sulfonic acids and organic bases, phosphoric acid and organic bases in an organic solvent. Completely neutralized salt of sulfuric acid, fully neutralized salt of sulfuric acid and organic base, partially neutralized salt of sulfonic acid with organic base, partially neutralized salt of phosphoric acid with organic base, and partially neutralized salt of sulfuric acid with organic base Of a cyclic olefin compound that is heated to a temperature of 130 to 230 ° C. under a pressure exceeding 20 Torr (2.67 kPa) in the presence of at least one kind of dehydration catalyst and distilling off by-produced water. A method (Patent Document 4) has been proposed. By this method, the ratio of the target cyclic olefin to the isomer is improved from 80/20 to 81/19 in the comparative example to 86/14 to 92/8. However, even an improved isomer ratio of 86/14 to 92/8 is not satisfactory, and further improvement of the isomer ratio is desired.

JP 2000-169399 A JP 2004-346007 A JP 2005-97274 A WO2007 / 119743

Org. Synth. Coll. Vol. 2, 151 (1943) J. et al. Chem. Soc. , 1950, 2725 New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds I, 119 (1978), The Chemical Society of Japan

An object of the present invention is to provide a method for producing a cyclic olefin compound that can suppress side reactions such as isomerization reaction and can efficiently obtain a high-purity cyclic olefin compound having a small impurity content in a simple and high yield. There is.

In order to achieve the above object, the present inventor has studied in detail a side reaction such as isomerization in an intramolecular dehydration reaction of an alicyclic alcohol having two or more cyclohexane rings to which a hydroxyl group is bonded in the molecule. It was found that most of the side reactions such as crystallization occurred in the initial stage of the reaction, particularly in the temperature rising process. When heating is started after charging the alicyclic alcohol, the solvent, and the entire amount of the dehydration catalyst, the dehydration reaction proceeds even during the temperature rise, and the isomerization reaction of the formula (4) proceeds through the generated water. The isomer concentration increases. Therefore, by introducing a dehydration catalyst in a state where the reflux of the solvent is started and the generated water is sequentially removed, side reactions such as isomerization can be greatly suppressed, and a high-purity cyclic structure with a low impurity content. It has been found that an olefin compound can be produced easily and efficiently at a high yield. The present invention has been completed based on these findings.

That is, the present invention relates to a cyclic olefin compound having two or more cyclohexene rings in the molecule by intramolecular dehydration of an alicyclic alcohol having two or more cyclohexane rings bonded to a hydroxyl group in the molecule in the presence of a dehydration catalyst. The dehydration catalyst is continuously or intermittently mixed with the mixture containing the alicyclic alcohol and the organic solvent under reflux of an organic solvent that azeotropes with water and separates from water at room temperature. Or when the dehydration catalyst is composed of a plurality of components, dehydration is carried out while continuously or intermittently charging at least one of the components into the mixture containing the alicyclic alcohol and the organic solvent. Provided is a method for producing a cyclic olefin compound characterized by carrying out a reaction.

［式中、Ｙは、単結合、酸素原子、硫黄原子、－ＳＯ－、－ＳＯ₂－、及びハロゲン原子で置換されていてもよい炭素数１～１８の直鎖状、分岐鎖状又は環状骨格を有する２価の炭化水素基から選択された２価の基、又はこれらの基が複数個結合した２価の基を示す］
で表される脂環式アルコールを、分子内脱水して、下記式（２）

［式中、Ｙは前記に同じ］
で表される環状オレフィン化合物を製造してもよい。 In the production method, the following formula (1)

[Wherein Y is a single bond, an oxygen atom, a sulfur atom, —SO—, —SO ₂ — and a linear, branched or cyclic group having 1 to 18 carbon atoms which may be substituted with a halogen atom] A divalent group selected from divalent hydrocarbon groups having a skeleton, or a divalent group in which a plurality of these groups are bonded]
Intramolecular dehydration of the alicyclic alcohol represented by the formula (2)

[Wherein Y is the same as above]
You may manufacture the cyclic olefin compound represented by these.

In addition, a mixture of an acid component and a base component is used as the dehydration catalyst, and at least the acid component of the acid component and the base component, which are constituent components of the dehydration catalyst, is added to the alicyclic alcohol and the organic solvent under reflux of the organic solvent. The dehydration reaction may be carried out while continuously or intermittently charged into the mixed solution containing.

According to the present invention, side reactions such as an isomerization reaction can be suppressed, and a high-purity cyclic olefin compound having a small impurity content can be easily and efficiently produced at a high yield.

It is the schematic of the reaction apparatus used in the Example.

In the present invention, an alicyclic alcohol (hereinafter sometimes referred to as “substrate”) having two or more cyclohexane rings to which hydroxyl groups are bonded is dehydrated in the molecule in the presence of a dehydration catalyst. To produce a cyclic olefin compound having two or more cyclohexene rings.

The alicyclic alcohol having two or more cyclohexane rings having hydroxyl groups bonded thereto is not particularly limited as long as the compound has two or more cyclohexane rings having hydroxyl groups bonded thereto. For example, a compound in which two hydroxycyclohexyl groups (2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group or 4-hydroxycyclohexyl group) are bonded via a single bond or a divalent group (for example, Y described later), 3 A compound in which two hydroxycyclohexyl groups are bonded via a trivalent group, a compound in which four hydroxycyclohexyl groups are bonded via a tetravalent group, and a polycyclic compound containing at least two cyclohexane rings to which hydroxyl groups are bonded Etc.

A typical example of the alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group bonded thereto in the molecule is the alicyclic alcohol represented by the formula (1). In the formula (1), Y represents a straight or branched chain having 1 to 18 carbon atoms which may be substituted with a single bond, an oxygen atom, a sulfur atom, —SO—, —SO ₂ —, or a halogen atom. Alternatively, it represents a divalent group selected from divalent hydrocarbon groups having a cyclic skeleton, or a divalent group in which a plurality of these groups are bonded.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the divalent hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 18 carbon atoms include methylene, ethylene, methylmethylene, trimethylene, propylene, dimethylmethylene, tetramethylene, pentamethylene, hexa C1-C18 linear or branched alkylene groups such as methylene, heptamethylene, octamethylene, decamethylene, etc .; 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexene C3-C18 divalent alicyclic hydrocarbon group such as silene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclopentylidene, cyclohexylidene group; 1,2-phenylene, 1, C6-C18 divalent aromatic hydrocarbon groups such as 3-phenylene and 1,4-phenylene groups; phenylmethylene, cyclohexyl Aromatic hydrocarbon groups such as Rumechiren group, such as an alkylene group having a cyclic skeleton such as an alicyclic hydrocarbon group. Examples of the divalent hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 18 carbon atoms substituted with a halogen atom include, for example, —C (Br) ₂ —, —C (CBr _3). ) _2- , -C (CF ₃ ) _2- and the like.

As Y, in particular, a single bond, an oxygen atom, a sulfur atom, —SO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, — (CH ₂ ) ₂ —, —C (Br ₂ ), —C (CBr ₃ ) ₂ —, —C (CF ₃ ) ₂ —, a divalent hydrocarbon group having a linear, branched or cyclic skeleton having 3 to 18 carbon atoms is preferred.

Specific examples of the alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group bonded thereto are, for example, hydrogenated biphenol, bis (cyclohexanol) methane, bis (dimethylcyclohexanol) methane, 1,2-bis ( Cyclohexanol) ethane, 1,3-bis (cyclohexanol) propane, 2,2-bis (cyclohexanol) propane, 1,4-bis (cyclohexanol) butane, 1,5-bis (cyclohexanol) pentane, , 6-bis (cyclohexanol) hexane, 2,2-bis (cyclohexanol) propane, bis (cyclohexanol) phenylmethane, 3,3-bis (cyclohexanol) pentane, 5,5-bis (cyclohexanol) heptane , 2,2-bis [4,4'-bis (sic Hexanol) cyclohexyl] an alicyclic alcohol having two cyclohexane rings to which hydroxyl groups are bonded, such as propane and dodecahydrofluoreneol; α, α-bis (4-hydroxycyclohexyl) -4- (4- Hydroxyl-α, α-dimethylcyclohexyl) -ethylbenzene, tris (cyclohexanol) methane, tris (cyclohexanol) ethane, 1,3,3-tris (cyclohexanol) butane, etc. An alicyclic alcohol having three cyclohexane rings having a hydroxyl group bonded thereto, such as tetrakis (cyclohexanol) ethane, and the like may be mentioned.

Among these, in particular, a compound having two or more 4-hydroxycyclohexyl groups (for example, 2 to 4, particularly 2), such as hydrogenated biphenol (for example, 4,4′-bicyclohexanol), bis (cyclohexanol). ) Methane [eg, bis (4-hydroxycyclohexyl) methane), etc.], 1,2-bis (cyclohexanol) ethane [eg, 1,2-bis (4′-hydroxycyclohexyl) ethane), etc.], 2,2 -Bis (cyclohexanol) propane [for example, 2,2-bis (4'-hydroxycyclohexyl) propane, etc.] and the like are suitable as a raw material in the production method of the present invention. The alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group bonded thereto can be used alone or in combination of two or more.

As the dehydration catalyst, an acid component alone or a mixture of an acid component and a base component is used. The acid component of the dehydration catalyst can be selected from, for example, phosphoric acid; sulfuric acid; sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid.

Examples of the base component of the dehydration catalyst include alkali metal hydroxides such as LiOH, NaOH, KOH, inorganic base compounds such as NH ₃ , or 1,8-diazabicyclo [5.4.0] undecene-7 ( DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), piperidine, N-methylpiperidine, pyrrolidine, N-methylpyrrolidine, triethylamine, tributylamine, benzyldimethylamine, 4-dimethylaminopyridine Amines such as N, N-dimethylaniline (particularly tertiary amines); nitrogen-containing aromatic heterocyclic compounds such as pyridine, collidine, quinoline and imidazole; guanidines; organic base compounds such as hydrazines be able to.

Among these, as the base component, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), triethylenediamine, Tertiary amines such as triethylamine (particularly cyclic amines), guanidines and hydrazines are preferable, and DBU, DBN, triethylenediamine and triethylamine are particularly preferable.

The acid component and the base component may be used alone or in combination of two or more.

When a mixture of an acid component and a base component is used as the dehydration catalyst, the ratio of the acid component to the base component is preferably 0.01 to 1 mol, more preferably 0.1 to 1 mol, with respect to 1 mol of the acid component. 1 mole. Alternatively, the base component is preferably 0.01 to 1 gram equivalent, more preferably 0.1 to 1 gram equivalent, relative to 1 gram equivalent of the acid component. In addition, when using the mixture of an acid component and a base component as a dehydration catalyst, according to the quantity ratio, a corresponding salt is normally formed.

The amount of the acid component used in the dehydration catalyst is, for example, about 0.001 to 0.5 mol with respect to 1 mol of the alicyclic alcohol as a substrate.

In the present invention, whether the dehydration catalyst is continuously or intermittently charged into the mixed solution containing the alicyclic alcohol and the organic solvent under reflux of the organic solvent that azeotropes with water and separates from water at room temperature. Or when the dehydration catalyst is composed of a plurality of components (for example, a mixture of an acid component and a base component), at least one of the components (for example, at least the acid component) is The dehydration reaction is carried out while continuously or intermittently charged into the mixed solution containing the formula alcohol and the organic solvent.

The organic solvent is not particularly limited as long as it is an organic solvent that azeotropes with water and separates from water at room temperature (for example, 23 ° C.) and is inert under the reaction conditions.

Representative examples of preferred organic solvents include, for example, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, tetramethylcyclohexane, ethylcyclohexane, diethylcyclohexane, propylcyclohexane, Aliphatic hydrocarbons having 6 to 18 carbon atoms such as isopropylcyclohexane; benzene, toluene, xylene, trimethylbenzene (for example, pseudocumene), tetramethylbenzene, styrene, ethylbenzene, diethylbenzene, propylbenzene, cumene, indene, tetrahydronaphthalene, Aromatic hydrocarbons having 6 to 18 carbon atoms such as phenylcyclohexane, methylnaphthalene and diphenyl; diethyl 4 carbon atoms such as ether, diisopropyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, dicyclohexyl ether, dibutyl ether, anisole, phenetole, phenylpropyl ether, benzyl methyl ether, benzyl ethyl ether, benzyl propyl ether, benzyl butyl ether And ethers containing no more than 18 hydroxyl groups. Solvents that react in the presence of an acid, such as ketones and esters, are not preferred. Alcohol is not preferred because it may cause a dehydration reaction.

The amount of the organic solvent used can be appropriately selected in consideration of operability, reaction rate, etc., but is preferably about 0.1 to 10 parts by weight with respect to 1 part by weight of the alicyclic alcohol as a substrate. More preferably 0.5 to 5 parts by weight.

The reaction temperature can be selected from the range of 100 to 250 ° C., for example. When the activity of the dehydration catalyst is high or when the concentration of the dehydration catalyst is high, a low reaction temperature is selected. When the activity of the dehydration catalyst is low or when the concentration of the dehydration catalyst is low, a high reaction temperature is selected.

As a method for preparing the dehydration catalyst, for example, when the dehydration catalyst is composed only of an acid component, the mixed liquid containing the alicyclic alcohol and the organic solvent is heated to a temperature at which the organic solvent is refluxed. The dehydration catalyst is preferably charged continuously or intermittently. The ratio of the dehydration catalyst charged continuously or intermittently after reflux of the mixed solution is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight, based on the total amount of the dehydration catalyst used. Above, particularly preferably 100% by weight. It is preferable that a dehydration catalyst is not present as much as possible before the mixture is refluxed.

Further, when the dehydration catalyst is composed of a mixture of an acid component and a base component, a mixed liquid containing the alicyclic alcohol and an organic solvent (or a component constituting the dehydration catalyst and the alicyclic alcohol and the organic solvent). A mixture containing a part or all of the base component) is heated to a temperature at which the organic solvent is refluxed, and at least the acid component among the components constituting the dehydration catalyst is charged continuously or intermittently. Is preferred. The ratio of the acid component charged continuously or intermittently after reflux of the mixed solution is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight with respect to the total amount of the acid component used. % Or more, particularly preferably 100% by weight. It is preferable that the acid component is not present as much as possible before the mixture is refluxed.

When the mixture of the alicyclic alcohol, the organic solvent and the total amount of the dehydration catalyst is heated to a temperature at which the organic solvent is refluxed in advance, the dehydration reaction proceeds even during the temperature rise, and the above formula (4) is mediated by the generated water. ) Isomerization reaction proceeds, and the isomer concentration increases.

When the dehydration catalyst is a mixture of an acid component and a base component, the acid component accelerates the dehydration reaction, and the base component adjusts the acidity of the dehydration catalyst and suppresses side reactions such as isomerization. Therefore, at least the acid component in the dehydration catalyst is charged with the organic solvent refluxed as described above, and is prepared in a state in which the generated water is ready to be sequentially removed. Can be suppressed.

The reaction pressure may be normal pressure, reduced pressure, or increased pressure, and the pressure is selected so that the organic solvent is refluxed at the selected reaction temperature. The reflux rate of the organic solvent is, for example, about 0.05 to 1 kg / hr with respect to 1 mol of the alicyclic alcohol.

After completion of the reaction, the reaction mixture is subjected to separation / purification means such as concentration, distillation, crystallization, extraction, column chromatography, etc. to thereby obtain a cyclic olefin compound having two or more cyclohexene rings in the molecule [for example, the above formula (2) Can be isolated.

Representative examples of the cyclic olefin compound represented by the formula (2) include bicyclohexyl-3,3′-diene, bis (3-cyclohexenyl) methane, 1,2-bis (3′-cyclohexenyl). Examples include ethane and 2,2-bis (3′-cyclohexenyl) propane.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, the analysis of the product was performed by GC analysis (gas chromatography) and GC / MS analysis (gas chromatography / mass spectrometry) (refer to WO2007 / 119743).

Example 1
1,4 g of 4,4′-bicyclohexanol, 1,500 g of pseudocumene as an organic solvent, 69.1 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) as a base component of the dehydration catalyst, Were charged into a 5 L glass four-necked flask equipped with a condenser, decanter, stirrer, and catalyst dropping funnel, and heated at a pressure of 328 mmHg (absolute pressure), pseudocumene distilled at a can temperature of 150 ° C. The decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant. The heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr.
As an acid component of the dehydration catalyst, 55.6 g of sulfuric acid was charged in a catalyst dropping funnel, and sulfuric acid was continuously dropped at a constant rate over 1 hour. When the dropping of sulfuric acid was started, water accumulated in the lower phase of the decanter, and therefore the lower phase water was appropriately extracted into the lower phase liquid receiver.
Three hours after the completion of the dropwise addition of sulfuric acid, the pressure was changed from 328 mmHg (absolute pressure) to 428 mmHg (absolute pressure), and the reaction was continued at a can temperature of 160 ° C. for 6 hours. Furthermore, when the pressure was changed from 428 mmHg (absolute pressure) to 518 mmHg (absolute pressure) and the reaction was continued at a can temperature of 170 ° C. for 12 hours, the reaction was stopped because decanter lower phase water did not increase.
When the reaction solution was analyzed, the 4,4′-bicyclohexanol concentration was 0.05% by weight, the 4,4′-bicyclohexanol change rate was 99.87%, and the bicyclohexyldiene concentration was 28.85% by weight. The bicyclohexyldiene yield was 92.52%. Further, among the bicyclohexyldienes, bicyclohexyl-2,3′-diene (isomer) was 5.84%, and the remainder was bicyclohexyl-3,3′-diene.

Example 2
1,000 g of 4,4′-bicyclohexanol and 1,500 g of pseudocumene as an organic solvent were charged into a 5 L glass four-necked flask equipped with a condenser, decanter, stirrer, and catalyst dropping funnel shown in FIG. 1, and a pressure of 328 mmHg. When heated at (absolute pressure), pseudocumene distilled at a can temperature of 150 ° C. The decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant. The heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr.
55.6 g of sulfuric acid as an acid component of a dehydration catalyst and 69.1 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) as a base component were mixed in advance and charged into a catalyst dropping funnel over 2 hours. The dehydration catalyst was dripped continuously at a constant rate. When dripping of the dehydration catalyst was started, water accumulated in the lower phase of the decanter, and thus the lower phase water was appropriately extracted into the lower phase liquid receiver.
Three hours after the completion of the dropping of the dehydration catalyst, the pressure was changed from 328 mmHg (absolute pressure) to 428 mmHg (absolute pressure), and the reaction was continued at a can temperature of 160 ° C. for 6 hours. Furthermore, when the pressure was changed from 428 mmHg (absolute pressure) to 518 mmHg (absolute pressure) and the reaction was continued at a can temperature of 170 ° C. for 12 hours, the reaction was stopped because decanter lower phase water did not increase.
When the reaction solution was analyzed, the 4,4′-bicyclohexanol concentration was 0.04% by weight, the 4,4′-bicyclohexanol change rate was 99.90%, and the bicyclohexyldiene concentration was 28.50% by weight. The bicyclohexyldiene yield was 91.41%. Further, among the bicyclohexyldienes, bicyclohexyl-2,3′-diene (isomer) was 7.99%, and the remainder was bicyclohexyl-3,3′-diene.

Example 3
1,2-bis (4′-hydroxycyclohexyl) propane 1,000 g, pseudocumene 1,500 g as an organic solvent, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) 69 as a base component of a dehydration catalyst .1 g was charged into a 5 L glass four-necked flask equipped with a condenser, decanter, stirrer, and catalyst dropping funnel shown in FIG. 1 and heated at a pressure of 328 mmHg (absolute pressure). Distilled. The decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant. The heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr.
As an acid component of the dehydration catalyst, 55.6 g of sulfuric acid was charged in a catalyst dropping funnel, and sulfuric acid was continuously dropped at a constant rate over 1 hour. When the dropping of sulfuric acid was started, water accumulated in the lower phase of the decanter, and therefore the lower phase water was appropriately extracted into the lower phase liquid receiver.
Three hours after the completion of the dropwise addition of sulfuric acid, the pressure was changed from 328 mmHg (absolute pressure) to 428 mmHg (absolute pressure), and the reaction was continued at a can temperature of 160 ° C. for 6 hours. Furthermore, when the pressure was changed from 428 mmHg (absolute pressure) to 518 mmHg (absolute pressure) and the reaction was continued at a can temperature of 170 ° C. for 12 hours, the reaction was stopped because decanter lower phase water did not increase.
When the reaction solution was analyzed, the 2,2-bis (4′-hydroxycyclohexyl) propane concentration was 0.08% by weight and the 2,2-bis (4′-hydroxycyclohexyl) propane conversion was 99.79%. The 2,2-bis (cyclohexenyl) propane concentration was 29.86% by weight and the yield of 2,2-bis (cyclohexenyl) propane was 92.19%. Furthermore, out of 2,2-bis (cyclohexenyl) propane, 2- (2′-cyclohexenyl) -2- (3 ″ -cyclohexenyl) propane (isomer) is 4.79% and the rest is 2,2. 2-bis (3′-cyclohexenyl) propane.

Comparative Example 1
1,000 g of 4,4′-bicyclohexanol, 1,500 g of pseudocumene as the organic solvent, 55.6 g of sulfuric acid as the acid component of the dehydration catalyst, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU as the base component) ) When 69.1 g was charged into a 5 L glass four-necked flask equipped with a condenser, decanter, stirrer, and catalyst dropping funnel shown in FIG. 1 and heated at normal pressure, pseudocumene and water were heated at a can temperature of 115 ° C. Distillation started. The decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant. Since water accumulated in the lower phase of the decanter, the lower phase water was appropriately removed from the lower phase liquid receiver.
The can temperature gradually increased and finally increased to 180 ° C. The heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr.
Six hours after the start of distillation, the decanter lower phase water stopped increasing, and the reaction was stopped.
When the reaction solution was analyzed, the 4,4′-bicyclohexanol concentration was 0.06% by weight, the 4,4′-bicyclohexanol conversion was 99.84%, and the bicyclohexyldiene concentration was 27.55% by weight. The bicyclohexyldiene yield was 88.37%. Furthermore, among the bicyclohexyldienes, bicyclohexyl-2,3′-diene (isomer) was 10.37% and the remainder was bicyclohexyl-3,3′-diene.
Compared to Examples 1 to 3, the bicyclohexyldiene yield is low and the production of isomers is increased.

According to the method for producing a cyclic olefin compound of the present invention, side reactions such as an isomerization reaction can be suppressed, and a high-purity cyclic olefin compound having a small impurity content can be produced easily and efficiently at a high yield. The high-purity cyclic olefin compound obtained by the production method of the present invention is useful as a resin raw material excellent in heat resistance, hydrolysis resistance, weather resistance, transparency and the like, and an intermediate thereof.

1 Flask (Reactor)
2 Heater 3 Thermometer 4 Catalyst dropping funnel 5 Stirrer 6 Condenser 7 Decanter 8 Upper phase liquid receiver 9 Lower phase liquid receiver 10 Reflux pump

Claims (3)

This is a method for producing a cyclic olefin compound having two or more cyclohexene rings in a molecule by intramolecular dehydration of an alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group in the molecule in the presence of a dehydration catalyst. The dehydration catalyst is continuously or intermittently charged into the mixture containing the alicyclic alcohol and the organic solvent under reflux of an organic solvent that azeotropes with water and separates from water at room temperature, or When the dehydration catalyst is composed of a plurality of components, the dehydration reaction is performed while continuously or intermittently charging at least one of the components into the mixed solution containing the alicyclic alcohol and the organic solvent. A method for producing a cyclic olefin compound. Following formula (1)

[Wherein Y is a single bond, an oxygen atom, a sulfur atom, —SO—, —SO ₂ — and a linear, branched or cyclic group having 1 to 18 carbon atoms which may be substituted with a halogen atom] A divalent group selected from divalent hydrocarbon groups having a skeleton, or a divalent group in which a plurality of these groups are bonded]
Intramolecular dehydration of the alicyclic alcohol represented by the formula (2)

[Wherein Y is the same as above]
The manufacturing method of the cyclic olefin compound of Claim 1 which manufactures the cyclic olefin compound represented by these. A mixture of an acid component and a base component is used as the dehydration catalyst, and at least the acid component of the acid component and the base component that are components of the dehydration catalyst includes the alicyclic alcohol and the organic solvent under reflux of the organic solvent. The method for producing a cyclic olefin compound according to claim 1 or 2, wherein a dehydration reaction is carried out while continuously or intermittently charging the mixture.

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