JP5926130B2 - Method for producing diolefin compound and method for producing diepoxy compound containing the same - Google Patents

Description

  The present invention relates to a method for producing a diolefin compound as a raw material for a diepoxy compound capable of forming a cured product having excellent thermal characteristics, and a method for producing a diepoxy compound including the method for producing the diolefin compound.

  It is known that an epoxy compound is polymerized to form a cured product having excellent electrical characteristics, moisture resistance, heat resistance and the like. Among these, diepoxy compounds are coating agents, inks, adhesives, sealants, sealants, resists, composite materials, transparent substrates, transparent films or sheets, optical materials (for example, optical lenses), insulating materials, stereolithography. It is used in various fields including applications such as materials and electronic materials (for example, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, etc.).

  Various types of diepoxy compounds are currently commercially available, such as 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4,3 ′, 4′-diepoxy. Bicyclohexyl and the like can be mentioned. These epoxy compounds form a cured product by polymerization under various curing agents or curing catalysts.

  However, the 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate has a problem in that the cured product obtained has low strength and low heat resistance because the oxirane oxygen concentration is low and the number of crosslinking points is small. .

  On the other hand, since 3,4,3 ′, 4′-diepoxybicyclohexyl has a higher oxirane oxygen concentration than 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, the resulting cured product is more Although it has excellent heat resistance, it has not yet been sufficiently satisfactory in that mechanical properties (for example, elastic modulus, etc.) are greatly reduced and thermal stability is low as the temperature rises.

JP-A 63-264625 JP 63-012623 A JP 59-011317 A JP 2008-31424 A

  And 3,4,3 ′, 4′-diepoxybicyclohexyl is formed by connecting two alicyclic epoxy groups (= two carbon atoms and one oxygen atom constituting the alicyclic ring to each other). (A cyclic group) has a structure in which a single bond is rigidly bonded, and therefore, two alicyclic epoxy groups cannot necessarily exist in a position suitable for the crosslinking reaction and cannot participate in the crosslinking reaction. An alicyclic epoxy group was generated, and it was found that a cured product having sufficient heat resistance could not be obtained although the oxirane oxygen concentration of the monomer was high. A compound obtained by bonding two alicyclic epoxy groups with a hydrocarbon chain can always have an alicyclic epoxy group at a position suitable for the crosslinking reaction, and the alicyclic cannot participate in the crosslinking reaction. The epoxy group can be significantly reduced, thereby having extremely excellent thermal properties (specifically, heat that has extremely high heat resistance and can maintain excellent mechanical properties even when exposed to high temperature environments) It has been found that a cured product can be formed.

  As a method for producing a compound obtained by bonding the two alicyclic epoxy groups with a hydrocarbon chain, an expensive metal element such as ruthenium, rhodium, palladium, iridium, platinum, nickel, tungsten, molybdenum, titanium, vanadium, etc. Although a method of using a catalyst containing the catalyst has been found, the problem is that the cost increases.

Accordingly, an object of the present invention is to provide a diolefin compound that can be produced at low cost as a novel diolefin compound that can be used as a raw material for a diepoxy compound that can form a cured product having extremely excellent thermal properties when cured. It is in providing the manufacturing method of.
Another object of the present invention is to provide a novel diolefin compound.
Still another object of the present invention is to provide a method for producing a diepoxy compound, which can produce a diepoxy compound capable of forming a cured product having extremely excellent thermal properties by curing at low cost.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when a specific tetrahydrobenzyl compound and a Grignard reagent are reacted, expensive such as ruthenium, rhodium, palladium, iridium, platinum, nickel, tungsten, molybdenum, titanium, vanadium, etc. Even without using a catalyst containing various metal elements, a diolefin compound can be obtained efficiently and in an excellent yield using an inexpensive metal compound such as a copper compound or an iron compound as a catalyst. The diepoxy compound obtained by epoxidation has a structure in which two alicyclic epoxy groups are flexibly bonded via a hydrocarbon chain such as an ethylene group, so that the alicyclic epoxy group is always suitable for crosslinking reaction. Alicyclic epoxide that cannot be involved in the crosslinking reaction. It is possible to significantly reduce the group found that it is possible to form a cured product having excellent thermal properties. The present invention has been completed based on these findings.

（式中、Ｒ¹〜Ｒ¹¹はそれぞれ独立した基であり、同一又は異なって、水素原子、メチル基、又はエチル基を示し、Ｘは塩素原子、臭素原子、ヨウ素原子、ベンゼンスルホニルオキシ基、ｐ−トルエンスルホニルオキシ基、メタンスルホニルオキシ基、又はトリフルオロメタンスルホニルオキシ基を示す）
で表される化合物と、下記式（２）

（式中、Ｒ¹²〜Ｒ²²はそれぞれ独立した基であり、同一又は異なって、水素原子、メチル基、又はエチル基を示し、Ｙは塩素原子、臭素原子、又はヨウ素原子を示す）
で表される化合物を反応させて、下記式（３）

（式中、Ｒ¹〜Ｒ²²は前記に同じ）
で表されるジオレフィン化合物を得るジオレフィン化合物の製造方法を提供する。 That is, the present invention provides the following formula (1):

(In the formula, R ^{1 to} R ¹¹ are each an independent group, and are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, and X represents a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group, or trifluoromethanesulfonyloxy group)
And a compound represented by the following formula (2)

(Wherein R ^{12 to} R ²² are each an independent group, the same or different, each representing a hydrogen atom, a methyl group, or an ethyl group, and Y represents a chlorine atom, a bromine atom, or an iodine atom)
And a compound represented by the following formula (3):

(Wherein R ^{1 to} R ²² are the same as above)
The manufacturing method of the diolefin compound which obtains the diolefin compound represented by these is provided.

（式中、Ｒ²³、Ｒ²⁴は同一又は異なって、鎖状脂肪族炭化水素基、環状脂肪族炭化水素基、又は芳香族炭化水素基を示す）
で表されるアルキンの存在下で行うことが好ましい。 The reaction is carried out in the presence of an iron catalyst or a copper catalyst and the following formula (4)

(Wherein R ²³ and R ²⁴ are the same or different and represent a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group)
It is preferable to carry out in presence of alkyne represented by these.

（式中、Ｒ¹〜Ｒ²²はそれぞれ独立した基であり、同一又は異なって、水素原子、メチル基、又はエチル基を示す）
で表されるジオレフィン化合物を提供する。 The present invention also provides the following formula (3):

(In the formula, R ^{1 to} R ²² are each an independent group, and are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group)
The diolefin compound represented by these is provided.

（式中、Ｒ¹〜Ｒ²²はそれぞれ独立した基であり、同一又は異なって、水素原子、メチル基、又はエチル基を示す）
で表されるジオレフィン化合物を得、得られた上記式（３）で表されるジオレフィン化合物を過酸と反応させることにより下記式（５）

（式中、Ｒ¹〜Ｒ²²は前記に同じ）
で表されるジエポキシ化合物を得るジエポキシ化合物の製造方法を提供する。 The present invention further includes the following formula (3) by the method for producing the diolefin compound.

(In the formula, R ^{1 to} R ²² are each an independent group, and are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group)
The diolefin compound represented by formula (5) is obtained, and the resulting diolefin compound represented by formula (3) is reacted with a peracid to give the following formula (5):

(Wherein R ^{1 to} R ²² are the same as above)
A process for producing a diepoxy compound is obtained.

According to the method for producing a diolefin compound of the present invention, a novel diolefin compound useful as a raw material of a diepoxy compound capable of forming a cured product having extremely excellent thermal properties by curing, at a low cost, and It can be manufactured efficiently.
And according to the manufacturing method of the diepoxy compound of this invention, the diepoxy compound which can form the hardened | cured material which has the very outstanding thermal characteristic by hardening can be manufactured cheaply and efficiently.
Therefore, the above production method of the present invention is extremely useful as a method for industrially producing the diolefin compound and diepoxy compound.

（式中、Ｒ¹〜Ｒ¹¹はそれぞれ独立した基であり、同一又は異なって、水素原子、メチル基、又はエチル基を示し、Ｘは塩素原子、臭素原子、ヨウ素原子、ベンゼンスルホニルオキシ基、ｐ−トルエンスルホニルオキシ基、メタンスルホニルオキシ基、又はトリフルオロメタンスルホニルオキシ基を示す）
で表される化合物と、下記式（２）

（式中、Ｒ¹²〜Ｒ²²はそれぞれ独立した基であり、同一又は異なって、水素原子、メチル基、又はエチル基を示し、Ｙは塩素原子、臭素原子、又はヨウ素原子を示す）
で表される化合物を反応させて、下記式（３）

（式中、Ｒ¹〜Ｒ²²は前記に同じ）
で表されるジオレフィン化合物を得ることを特徴とする。 [Method for producing diolefin compound]
The method for producing a diolefin compound of the present invention comprises the following formula (1):

(In the formula, R ^{1 to} R ¹¹ are each an independent group, and are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, and X represents a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group, or trifluoromethanesulfonyloxy group)
And a compound represented by the following formula (2)

(Wherein R ^{12 to} R ²² are each an independent group, the same or different, each representing a hydrogen atom, a methyl group, or an ethyl group, and Y represents a chlorine atom, a bromine atom, or an iodine atom)
And a compound represented by the following formula (3):

(Wherein R ^{1 to} R ²² are the same as above)
It is characterized by obtaining the diolefin compound represented by these.

  The reaction is preferably performed in the presence of a catalyst. Examples of the catalyst include an iron catalyst, a copper catalyst, and a nickel catalyst. In the present invention, it is particularly preferable to use an iron catalyst or a copper catalyst.

Examples of the iron catalyst include organic chelate compounds of iron (III) and acetylacetone (= acac), dibenzoylmethane (= DBM), etc. [specifically, Fe (acac) ₃ , Fe (DBM) _3, etc. And iron halides such as FeCl ₃ . These can be used alone or in combination of two or more.

  The amount of the iron catalyst used is, for example, about 0.001 to 0.3 mol, preferably 0.005 to 0.2 mol, particularly preferably 0, relative to 1 mol of the compound represented by the above formula (1). 0.01 to 0.1 mol. If an iron catalyst is used in the said range, a diolefin compound can be obtained with the outstanding yield.

  When the above reaction is carried out in the presence of an iron catalyst, a tertiary carboxylic acid amide such as N-methylpyrrolidinone (NMP) and a tertiary phosphoric acid amide such as hexamethylphosphoric triamide (HMPA) are used together with the iron catalyst. The use of tertiary amides is preferable in that the yield can be remarkably improved. The amount of the tertiary amide used is, for example, about 0.1 to 5 mol, preferably 0.5 to 3 mol, particularly preferably 0, relative to 1 mol of the compound represented by the formula (1). .5 to 2 moles.

Examples of the copper catalyst include copper halides such as CuCl _{2 and} copper sulfonates such as copper (I) trifluoromethanesulfonate (Cu (OTf)). These can be used alone or in combination of two or more.

  As the usage-amount of a copper catalyst, it is about 0.005-0.2 mol with respect to 1 mol of compounds represented by the said Formula (1), Preferably it is 0.005-0.15 mol, Most preferably, it is 0. 0.01 to 0.1 mol. If a copper catalyst is used in the said range, a diolefin compound can be obtained with the outstanding yield.

When performing the said reaction in presence of a copper catalyst, it is preferable to use the alkyne represented by following formula (4) with a copper catalyst at the point which can improve a yield remarkably. In formula (4), R ²³ and R ²⁴ are the same or different and each represents a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group.

Examples of the chain aliphatic hydrocarbon group for R ²³ and R ²⁴ include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. An alkyl group having about 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 3 carbon atoms); 2 to 20 carbon atoms (preferably 2 to 10 and more preferably 2) such as vinyl, allyl and 1-butenyl groups. ˜3) alkenyl group; alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 3) such as ethynyl and propynyl groups.

Examples of the cyclic aliphatic hydrocarbon group for R ²³ and R ²⁴ include 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. ) About cycloalkyl group; about 3-20 membered (preferably 3-15 membered, more preferably 5-8 membered) cycloalkenyl group such as cyclopentenyl, cyclohexenyl group; perhydronaphthalen-1-yl, Norbornyl, adamantyl, tetracyclo [4.4.0.1 ^2,5 . And a bridged cyclic hydrocarbon group such as 1 ^7,10 ] dodecan-3-yl group.

Examples of the aromatic hydrocarbon group in R ²³ and R ²⁴ include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl, p-methylphenyl, and naphthyl groups. Can do.

As the alkyne represented by the formula (4) of the present invention, one of R ²³ and R ²⁴ is preferably an aromatic hydrocarbon group, and in particular, 1-phenylpropyne, 1-phenylbutyne, 1- (P-methylphenyl) propyne, 1- (p-methylphenyl) butyne and the like are preferable.

  As usage-amount of the alkyne represented by Formula (4), it is about 0.01-0.4 mol with respect to 1 mol of compounds represented by the said Formula (1), Preferably it is 0.01-0. 3 mol, particularly preferably 0.02 to 0.2 mol. When the usage-amount of the alkyne represented by Formula (4) is less than the said range, reaction will stop and there exists a tendency for a yield to fall. On the other hand, if the amount of the alkyne represented by formula (4) exceeds the above range, the purity tends to decrease during purification.

  The above reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not inhibit the progress of the reaction. For example, hydrocarbons (for example, hexane, cyclohexane, heptane, toluene, etc.), ethers (for example, diethyl) Ether, tetrahydrofuran (THF) and the like. The amount of the solvent used is, for example, about 1 to 10 times the weight of the compound represented by the formula (1).

  The above reaction may be performed under normal pressure, or may be performed under reduced pressure or under pressure. Further, the reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature is, for example, about 20 to 100 ° C. The reaction time is, for example, about 2 to 10 hours. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  After completion of the reaction, the reaction product can be separated and purified by separation / purification means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination of these.

  The compound represented by the above formula (1) can be obtained, for example, by reacting 1,2,5,6-tetrahydrobenzyl alcohol and HX (X is the same as above).

  The reaction between 1,2,5,6-tetrahydrobenzyl alcohol and HX is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the progress of the reaction. For example, hydrocarbons (for example, hexane, cyclohexane, heptane, toluene, etc.), ethers (for example, diethyl) Ether, tetrahydrofuran (THF) and the like. The amount of the solvent used is, for example, about 1 to 10 times the weight of 1,2,5,6-tetrahydrobenzyl alcohol.

  The reaction between the 1,2,5,6-tetrahydrobenzyl alcohol and HX may be performed under normal pressure, or may be performed under reduced pressure or under pressure. Further, the reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature is, for example, about 20 to 130 ° C. The reaction time is, for example, about 1 to 50 hours. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

The compound represented by the above formula (2) (= Grignard reagent) is, for example, 1,2,5,6-tetrahydrobenzyl alcohol and HX (X represents a chlorine atom, a bromine atom or an iodine atom, preferably chlorine or It is obtained by further reacting magnesium and iodine (I ₂ ) with the compound represented by the formula (1) obtained by reacting with (a bromine atom).

The reaction of the compound represented by the above formula (1), magnesium and iodine (I ₂ ) is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the progress of the reaction. For example, hydrocarbons (eg, hexane, heptane, toluene, etc.), ethers (eg, diethyl ether, Tetrahydrofuran (THF) and the like. The amount of the solvent used is, for example, about 2 to 10 times the weight of the compound represented by the formula (1).

The reaction of the compound represented by the formula (1), magnesium and iodine (I ₂ ) may be performed under normal pressure, or may be performed under reduced pressure or under pressure. In addition, the reaction atmosphere of the above reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature is, for example, about 10 to 100 ° C. The reaction time is, for example, about 1 to 3 hours. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  Since the method for producing a diolefin compound of the present invention has the above-described structure, an excellent yield (for example, 20% or more, preferably 50% or more, more preferably, by using an inexpensive catalyst (iron catalyst, copper catalyst). Is 55% or more, particularly preferably 70% or more), and the desired diolefin compound can be obtained efficiently. In the present invention, it is not necessary to use a catalyst containing an expensive metal element such as ruthenium, rhodium, palladium, iridium, platinum, nickel, tungsten, molybdenum, titanium, vanadium, and the amount of the catalyst containing the expensive metal element is The amount of the compound represented by the formula (1) is 1 mol or less, for example, 0.1 mol or less, preferably 0.05 mol or less, and it is particularly preferable not to use it substantially. Moreover, the diolefin compound obtained by the manufacturing method of the diolefin compound of this invention is especially useful as a raw material of the diepoxy compound which can form the hardened | cured material which is excellent in a thermal characteristic.

[Method for producing diepoxy compound]
The method for producing a diepoxy compound of the present invention comprises the following formula (5) by reacting a diolefin compound represented by the formula (3) obtained by the method for producing a diolefin compound with a peracid to epoxidize. It is characterized by obtaining the diepoxy compound represented. In formula (5), R < ¹ > -R < ²² > is respectively independent group, and is the same or different and shows a hydrogen atom, a methyl group, or an ethyl group. R ^{1 to} R ²² in the formula (5) respectively correspond to R ^{1 to} R ²² in the formula (3).

  As the peracid, formic acid, peracetic acid, perbenzoic acid, metachloroperbenzoic acid, trifluoroperacetic acid and the like can be used, for example. In the present invention, it is preferable to use metachloroperbenzoic acid because it is easily available.

  The usage-amount of a peracid is 3.0 mol or less with respect to 1 mol of diolefin compounds represented by Formula (3), Preferably it is 2.2-2.6 mol.

  The epoxidation reaction can be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the progress of the reaction, and examples thereof include aromatic compounds such as toluene and benzene, aliphatic hydrocarbons such as hexane and cyclohexane, esters such as ethyl acetate, and the like. Can be mentioned. As a usage-amount of a solvent, it is about 3-10 weight times of the diolefin compound represented by Formula (3), for example.

  The reaction temperature in the epoxidation reaction is, for example, about 0 to 60 ° C., preferably 10 to 50 ° C., particularly preferably 20 to 40 ° C. If the reaction temperature is below 0 ° C, the reaction may be slow. On the other hand, when the reaction temperature exceeds 60 ° C., the epoxidizing agent may be decomposed. The reaction can be carried out, for example, by stirring the above mixture for about 1 to 5 hours.

  In the epoxidation reaction, for example, a reducing agent such as sodium sulfite, potassium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, sodium thiosulfate, potassium thiosulfate is added to the reaction system, and the epoxidizing agent is added. Can be terminated by quenching. After completion of the reaction, the reaction product can be separated and purified by separation / purification means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination of these.

  Since the diepoxy compound represented by the formula (5) obtained by the above method has a structure in which two alicyclic epoxy groups are bonded via a hydrocarbon chain such as an ethylene group, the alicyclic epoxy group is It can be appropriately moved to a position suitable for the crosslinking reaction, and the alicyclic epoxy groups not involved in the crosslinking reaction can be reduced to a very low level. Therefore, a crosslinked structure can be formed densely, has excellent heat resistance, can maintain excellent mechanical properties even when exposed to high temperature environments, and forms a cured product with excellent thermal stability. be able to.

  Since the diepoxy compound represented by the formula (5) can form a cured product having excellent thermal characteristics as described above, the coating agent, ink, adhesive, sealant, sealant, resist, composite material , Transparent substrate, transparent film or sheet, optical material (eg, optical lens), insulating material, stereolithography material, electronic material (eg, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory) It is used in various fields including applications such as.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Preparation Example 1 (Preparation of Grignard reagent)
Magnesium (0.414 g, 0.0171 mol) and iodine (0.043 g, 0.17 mmol) were added to tetrahydrofuran (8.5 mL), and the mixture was stirred at 40 ° C. for 30 minutes in a nitrogen atmosphere. Tetrahydrobenzyl chloride (2.23 g, 0.171 mol) represented by the following formula (1-1) is added dropwise at 40 ° C. over 1 hour, then refluxed for 2 hours, and represented by the following formula (2-1). Grignard reagent was prepared.

Example 1 (Synthesis of 1,2-bis (cyclohex-3-enyl) ethane)
Tetrahydrobenzyl bromide (2.00 g, 0.0114 mol) represented by the following formula (1-2), 1-phenylpropyne (0.066 g, 0.571 mmol, 0.05 mol times tetrahydrobenzyl bromide), copper chloride ( II) Grignard reagent represented by the following formula (2-1) obtained in Preparation Example 1 in a mixed solution of (0.031 g, 0.224 mmol, 0.02 mol times tetrahydrobenzyl bromide) under ice-cooling. It was added dropwise over a period of minutes. The reaction solution was warmed to 30 ° C. and stirred for 3 hours, and then 10% hydrochloric acid was added to stop the reaction, followed by liquid separation.
The organic layer was washed twice with water and then concentrated to obtain a crude product containing 1,2-bis (cyclohex-3-enyl) ethane represented by the following formula (3-1). As a result of quantifying the crude product by gas chromatography, the yield based on tetrahydrobenzyl bromide was 87%.
¹ H-NMR (CDCl ₃ ): 5.66 (s, 4H), 2.12-2.03 (m, 6H), 1.76-1.72 (m, 2H), 1.67-1.61 (m, 2H), 1.52-1.47 (m, 2H ), 1.31-1.17 (m, 6H)

Example 2 (Synthesis of 1,2-bis (cyclohex-3-enyl) ethane)
Example 1 except that tetrahydrobenzyl chloride represented by the following formula (1-1) was used instead of tetrahydrobenzyl bromide represented by the formula (1-2), and the reaction solution was refluxed at 68 ° C. for 10 hours. In the same manner, 1,2-bis (cyclohex-3-enyl) ethane represented by the following formula (3-1) was obtained. The yield based on tetrahydrobenzyl chloride was 51%, and the amount of unreacted tetrahydrobenzyl chloride was 21%.

Example 3 (Synthesis of 1,2-bis (cyclohex-3-enyl) ethane)
Implemented except that tetrahydrobenzyl methanesulfonate represented by the following formula (1-3) was used instead of tetrahydrobenzyl bromide represented by the formula (1-2) and the reaction solution was refluxed at 68 ° C. for 5 hours. In the same manner as in Example 1, 1,2-bis (cyclohex-3-enyl) ethane represented by the following formula (3-1) was obtained. The yield based on tetrahydrobenzyl methanesulfonate was 65%.

Example 4 (Synthesis of 1,2-bis (cyclohex-3-enyl) ethane)
Tetrahydrobenzyl chloride (0.50 g, 0.0038 mol) represented by the following formula (1-1), Fe (acac) ₃ (0.135 g, 0.00038 mmol, 0.1 mol times tetrahydrobenzyl chloride), N- It is represented by the following formula (2-1) obtained in Preparation Example 1 in a tetrahydrofuran solution (2.5 g) of methylpyrrolidinone (NMP) (0.45 g, 0.0049 mmol, 1.2 mol times tetrahydrobenzyl chloride). The Grignard reagent was added dropwise over 30 minutes under ice cooling. The reaction solution was refluxed at 68 ° C. for 10 hours, 10% hydrochloric acid was added to stop the reaction, and the solution was separated. The organic layer was washed twice with water and then concentrated to obtain a crude product containing 1,2-bis (cyclohex-3-enyl) ethane represented by the following formula (3-1). As a result of quantifying the crude product by gas chromatography, the yield based on tetrahydrobenzyl chloride was 24%.

Example 5 (Synthesis of 1,2-bis (3,4-epoxycyclohexanyl) ethane)
To a toluene (5.0 g) solution of 1.00 g (5.24 mmol) of 1,2-bis (cyclohex-3-enyl) ethane represented by the following formula (3-1) at 30 ° C., 3.16 g of benzoic acid (purity: 70%, 12.6 mmol, 2.4 mol times of 1,2-bis (cyclohex-3-enyl) ethane) was added in three portions and stirred at 30 ° C. for 2 hours. Thereafter, the mixture was diluted with ethyl acetate, an aqueous sodium thiosulfate solution was further added, and the mixture was stirred for 30 minutes.
The aqueous layer was extracted with ethyl acetate, and the obtained organic layer was washed twice with an aqueous sodium bicarbonate solution and once with water, and then concentrated. The concentrated residue was purified by silica gel column chromatography to obtain 0.689 g of 1,2-bis (3,4-epoxycyclohexanyl) ethane represented by the following formula (5-1) as a transparent liquid. The yield based on 1,2-bis (cyclohex-3-enyl) ethane was 59%. The oxirane oxygen concentration (HBr method) was 14.4% (calculated value) and 13.9% (actual value).
¹ H-NMR (CDCl ₃ ): 3.15-3.11 (m, 4H), 2.15-2.11 (m, 2H), 2.03-1.98 (m, 2H), 1.85-1.78 (m, 1H), 1.73-1.67 (m , 1H), 1.45-1.28 (m, 5H), 1.13-1.07 (m, 6H), 0.91-0.88 (m, 1H)

Claims (5)

Following formula (1)

(In the formula, R ^{1 to} R ¹¹ are each an independent group, and are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, and X represents a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group, or trifluoromethanesulfonyloxy group)
And a compound represented by the following formula (2)

(Wherein R ^{12 to} R ²² are each an independent group, the same or different, each representing a hydrogen atom, a methyl group, or an ethyl group, and Y represents a chlorine atom, a bromine atom, or an iodine atom)
And a compound represented by the following formula (3):

(Wherein R ^{1 to} R ²² are the same as above)
The manufacturing method of the diolefin compound which obtains the diolefin compound represented by these.   The method for producing a diolefin compound according to claim 1, wherein the reaction is carried out in the presence of an iron catalyst. Copper catalyst and the following formula (4)

(Wherein R ²³ and R ²⁴ are the same or different and represent a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group)
The manufacturing method of the diolefin compound of Claim 1 which reacts in presence of alkyne represented by these. Following formula (3)

(In the formula, R ^{1 to} R ²² are each an independent group, and are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group)
The diolefin compound represented by these. By the manufacturing method of the diolefin compound as described in any one of Claims 1-3, following formula (3)

(In the formula, R ^{1 to} R ²² are each an independent group, and are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group)
The diolefin compound represented by formula (5) is obtained, and the resulting diolefin compound represented by formula (3) is reacted with a peracid to give the following formula (5):

(Wherein R ^{1 to} R ²² are the same as above)
The manufacturing method of the diepoxy compound which obtains the diepoxy compound represented by these.