JP6819961B2 - New diepoxy compound - Google Patents

Description

The present invention relates to novel diepoxy compounds. More specifically, the present invention relates to a diepoxy compound having three or four phenylene groups and having epoxy rings at both ends of the compound.

同文献に記載されているジエポキシ化合物（ａ）の示差走査熱量測定（ＤＳＣ）の分析結果では、融点１６６℃における１本の吸熱ピークのみが示され、その他の相転移を表す吸熱ピークは見られなかった。このことから、該文献記載のジエポキシ化合物は液晶性を持たず、絶縁構成材料に使用しても高い熱伝導性を示すことは期待できない。 With the miniaturization and high integration of electronic devices, heat generation of mounting parts (in-vehicle inverters, LED lighting, etc.) and high temperature of the usage environment have become problems. Epoxy resins are widely used as these insulating constituent materials. In such a field, an epoxy resin having high thermal conductivity is required. As one of the means for that, it is known that it is effective to make the epoxy compound liquid crystal (highly oriented).
Conventionally, as such a heat-resistant liquid crystal epoxy compound, some liquid crystal diepoxy compounds having a mesogen such as two phenyl groups of benzoate in the molecule are known (for example, Patent Documents 1 and 2). .. However, the liquid crystal diepoxy compound has a complicated molecular structure and is difficult to manufacture, and it is extremely difficult to handle.
On the other hand, as a heat-resistant epoxy compound that is easy to handle and synthesize, for example, a diepoxy compound having one biphenyl group in the molecule is known. Patent Document 3 describes the diepoxy compound (a) shown below, which has a phenoxybiphenyl structure, but does not describe thermal conductivity or liquid crystallinity.

The analysis result of differential scanning calorimetry (DSC) of the diepoxy compound (a) described in the same document shows only one endothermic peak at a melting point of 166 ° C., and other endothermic peaks representing a phase transition are observed. There wasn't. From this, the diepoxy compound described in the document does not have liquid crystallinity and cannot be expected to exhibit high thermal conductivity even when used as an insulating constituent material.

Patent Document 4 proposes an epoxy resin having a 4,4'-diphenoxybiphenyl skeleton, and it is described that the cured epoxy resin has excellent mechanical strength. However, regarding thermal conductivity and liquid crystallinity. Is not explained. Among them, for example, the following p, p'-bis (4-glycidoxyphenoxy) biphenyl only shows the melting point, and it is clear from this that it is not a liquid crystal compound. Such a compound is a biphenyl skeleton-containing epoxy resin having excellent heat resistance and mechanical strength, but since it does not exhibit liquid crystallinity, it is predicted that the thermal conductivity will not be sufficiently high even if it is used as an insulating component. To.

しかしながら、このようなエステル基を有する化合物もまた、液晶性を示さない。
さらに、エステル基を有するジエポキシ化合物は加水分解やアルカリ等により、特に高温環境下においては劣化が進行しやすいことが懸念される。 Further, Patent Document 5 describes the diepoxy compound (b) shown below, which contains a biphenyl skeleton and an ester group.

However, compounds having such ester groups also do not exhibit liquid crystallinity.
Further, there is a concern that the diepoxy compound having an ester group is likely to deteriorate due to hydrolysis, alkali, etc., particularly in a high temperature environment.

Japanese Unexamined Patent Publication No. 09-118673 Japanese Unexamined Patent Publication No. 2003-268070 Chinese Patent Application Publication No. 102211984 U.S. Pat. No. 3219670 Japanese Unexamined Patent Publication No. 2011-219737

An object of the present invention is to provide a novel diepoxy compound which has liquid crystal properties and is excellent in thermal conductivity and heat resistance.

（式中、Ｒ_１は酸素原子又はメチレン基を表し、Ｒ_２はＲ_１が酸素原子の場合はメチレン基を、Ｒ_１がメチレン基の場合は酸素原子を表し、Ｒ_３は水素原子又はメチル基を表し、ｎは０又は１を示す。） As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that a diepoxy compound having a specific structure having one biphenyl skeleton in the main chain and no ester group in the bonding group of the biphenyl skeleton is liquid crystal. The present invention has been completed by finding that such a diepoxy compound is a novel diepoxy compound having liquid crystallinity and excellent thermal conductivity and heat resistance.
That is, according to the present invention, a diepoxy compound represented by the following general formula (1) is provided.

(Wherein, R ₁ represents an oxygen atom or a methylene group, R ₂ represents a methylene group when R ₁ is an oxygen atom, if R ₁ is a methylene group represents an oxygen atom, R ₃ is a hydrogen atom or methyl Represents a group, where n represents 0 or 1)

The diepoxy compound of the present invention has liquid crystallinity and is excellent in thermal conductivity and heat resistance.
Further, since it has a biphenyl skeleton, it is excellent in heat resistance and mechanical strength, and since it does not have an ester group and has an ether bond of a methyleneoxy group, it is also excellent in hydrolysis resistance and alkali resistance.
Therefore, the diepoxy compound of the present invention and various curing agents, for example, an amine-based curing agent, an acid anhydride-based curing agent, an amide-based curing agent, a phenol-based curing agent, a cationic polymerization initiator, and the like are contained, and an optional curing accelerator. The epoxy resin composition which may contain a compounding agent such as an inorganic filler and a mold release agent is easy to handle, and when it is a cured resin, it has excellent thermal conductivity, heat resistance, mechanical strength, moisture resistance and alkali resistance. Since it is possible to form an excellent cured resin, it is suitably used as an insulating material for electronic parts, an adhesive, and the like.

で表されるジエポキシ化合物において、Ｒ_１は酸素原子又はメチレン基であり、Ｒ_２はＲ_１が酸素原子の場合はメチレン基を、Ｒ_１がメチレン基の場合は酸素原子であり、Ｒ_３は水素原子又はメチル基であり、ｎは０又は１の整数である。
したがって、前記一般式（１）で表される本発明のジエポキシ化合物として、具体的には、下記構造式で表されるジエポキシ化合物（２）〜（９）を例示することができる。 Hereinafter, the diepoxy compound of the present invention will be described in detail.
The following general formula (1) of the present invention

In the diepoxy compound represented by, R ₁ is an oxygen atom or a methylene group, R ₂ is a methylene group when R ₁ is an oxygen atom, R ₁ is an oxygen atom when R ₁ is a methylene group, and R ₃ is an oxygen atom. It is a hydrogen atom or a methyl group, and n is an integer of 0 or 1.
Therefore, as the diepoxy compound of the present invention represented by the general formula (1), specifically, the diepoxy compounds (2) to (9) represented by the following structural formulas can be exemplified.

４−［４−（オキシラン−２−イルメトキシ）フェニル］−１−｛［４−（オキシラン−２−イルメトキシ）フェニル］メトキシ｝ベンゼン

２−メチル−４−［４−（オキシラン−２−イルメトキシ）フェニル］−１−｛［４−（オキシラン−２−イルメトキシ）フェニル］メトキシ｝ベンゼン

４−｛［４−（オキシラン−２−イルメトキシ）フェニル］メトキシ｝−１−（４−｛［４−（オキシラン−２−イルメトキシ）フェニル］メトキシ｝フェニル）ベンゼン

３−メチル−４−｛［４−（オキシラン−２−イルメトキシ）フェニル］メトキシ｝−１−（４−｛［４−（オキシラン−２−イルメトキシ）フェニル］メトキシ｝フェニル）ベンゼン

４−（オキシラン−２−イルメトキシ）−１−（｛４−［４−（オキシラン−２−イルメトキシ）フェニル］フェニル｝メトキシ）ベンゼン

4- [4- (Oxylan-2-ylmethoxy) phenyl] -1-{[4- (Oxylan-2-ylmethoxy) phenyl] methoxy} benzene

2-Methyl-4- [4- (oxylan-2-ylmethoxy) phenyl] -1-{[4- (oxylan-2-ylmethoxy) phenyl] methoxy} benzene

4-{[4- (Oxylan-2-ylmethoxy) phenyl] methoxy} -1-(4-{[4- (Oxylan-2-ylmethoxy) phenyl] methoxy} phenyl) benzene

3-Methyl-4-{[4- (oxylan-2-ylmethoxy) phenyl] methoxy} -1-(4-{[4- (oxylan-2-ylmethoxy) phenyl] methoxy} phenyl) benzene

4- (Oxylan-2-ylmethoxy) -1-({4- [4- (Oxylan-2-ylmethoxy) phenyl] phenyl} methoxy) benzene

The method for producing the diepoxy compound represented by the general formula (1) according to the present invention is not particularly limited, and the selection of the starting material, the reaction step, and the reaction method are known methods according to the target diepoxy compound. Can be used as appropriate.
For example, the above-mentioned methods for producing the diepoxy compounds (2) and (3) can be synthesized by using p-cresol and epihalohydrin as starting materials and sequentially passing through the following steps STEP1-1 to STEP1-5.

（式中、Ｘはハロゲン原子を表す）
で表されるエピハロヒドリン（以下、化合物（１０）と記す）を反応させて、１−メチル−４−（オキシラン−２−イルメトキシ）ベンゼン（以下、化合物（Ａ）と称呼する）を得る工程。
（ＳＴＥＰ１−２）
化合物（Ａ）のメチル基を臭素化させて、１−（ブロモメチル）−４−（オキシラン−２−イルメトキシ）ベンゼン（以下、化合物（Ｂ）と称呼する）を得る工程。
（ＳＴＥＰ１−３）
化合物（Ｂ）と下記一般式（１１）

（式中、Ｒ_３は一般式（１）のそれと同じである）
で表される４−ブロモフェノール類（以下、化合物（１１）と称呼する）を反応させて、下記一般式（１２）

（式中、Ｒ_３は一般式（１）のそれと同じである）
で表される化合物（以下、化合物（１２）と称呼する）を得る工程。
（ＳＴＥＰ１−４）
化合物（１２）と４−ヒドロキシフェニルボロン酸を反応させて、下記一般式（１３）

（式中、Ｒ_３は一般式（１）のそれと同じである）
で表される化合物（以下、化合物（１３）と称呼する）を得る工程。
（ＳＴＥＰ１−５）
化合物（１３）と化合物（１０）を反応させて、ジエポキシ化合物（２）又は（３）を得る工程。 (STEP1-1)
p-cresol and the following general formula (10)

(In the formula, X represents a halogen atom)
A step of reacting epihalohydrin represented by (hereinafter referred to as compound (10)) to obtain 1-methyl-4- (oxylan-2-ylmethoxy) benzene (hereinafter referred to as compound (A)).
(STEP1-2)
A step of brominating the methyl group of compound (A) to obtain 1- (bromomethyl) -4- (oxylan-2-ylmethoxy) benzene (hereinafter referred to as compound (B)).
(STEP1-3)
Compound (B) and the following general formula (11)

(In the formula, R ₃ is the same as that of the general formula (1))
4-Bromophenols represented by (hereinafter referred to as compound (11)) are reacted to form the following general formula (12).

(In the formula, R ₃ is the same as that of the general formula (1))
A step of obtaining a compound represented by (hereinafter referred to as compound (12)).
(STEP1-4)
The compound (12) is reacted with 4-hydroxyphenylboronic acid to form the following general formula (13).

(In the formula, R ₃ is the same as that of the general formula (1))
A step of obtaining a compound represented by (hereinafter referred to as compound (13)).
(STEP1-5)
A step of reacting compound (13) with compound (10) to obtain a diepoxy compound (2) or (3).

（式中、Ｒ_３は一般式（１）に示すそれと同じであり、Ｘはハロゲン原子を表す。） The process scheme of STEP1-1 to STEP1-5 is shown by a reaction formula.

(In the formula, R ₃ is the same as that shown in the general formula (1), and X represents a halogen atom.)

Next, each of the above steps will be described in more detail.
(STEP1-1): Synthesis of compound (A) (glycidyl etherification)
Compound (A) can be easily synthesized by a known method (for example, Japanese Patent Application Laid-Open No. 62-148477) in which p-cresol and epihalohydrin are reacted (glycidyl etherification) in the presence of a basic compound.
In the reaction, epichlorohydrin or epibromohydrin can be preferably used as the epichlorohydrin (compound (10)). Epihalohydrin itself can also be used as a solvent. The amount of epihalohydrin used is usually 1 to 100 mol per 1 mol of p-cresol.
Specific examples of the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkaline earths such as magnesium hydroxide, calcium hydroxide and barium hydroxide. Metal hydroxides, inorganic salts such as alkali metal carbonates such as sodium carbonate and potassium carbonate, basic aromatic compounds such as pyridine, organic amines such as triethylamine, tetrabutylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, benzyl Examples thereof include ammonium salts such as trimethylammonium chloride. These basic compounds can be used in the form of a solution dissolved in the solvent used, or in the form of a solid. Further, it may be used alone or in combination of two or more. The amount of the basic compound used is usually 0.1 to 10 mol with respect to 1 mol of p-cresol.
In the reaction, the solvent may not be used if there is no problem in operability. When a solvent is used, there is no particular limitation as long as the solvent is inert to the reaction. Specific examples of the solvent used include water, aliphatic hydrocarbons such as n-pentane and n-hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and ethylbenzene. Ketones such as hydrogen, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, secondary butanol, tertiary butanol, ethylene glycol, trimethylene glycol Glycols such as glycols, methyl cellosolves, cellosolves such as ethyl cellosolves, ethers such as tetrahydrofuran, diethyl ether, dimethyl ether, 1,4-dioxane, 1,3-dioxane, diethoxyethane, and fats such as acetonitrile and propionitrile. Examples thereof include group nitriles, amides such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, and dimethylsulfoxide. Such a solvent may be used alone or in combination of two or more.
The reaction temperature varies depending on the solvent used, but is usually in the range of 40 ° C to 150 ° C. Under such reaction conditions, the reaction time varies depending on the reaction temperature, the type and amount of the basic compound and solvent used, and the like, but is usually in the range of 0.5 to 20 hours.
After completion of the reaction, it is preferable to purify and isolate the target compound from the reaction product mixture. For example, after completion of the reaction, post-treatment operations such as neutralization, washing with water, crystallization, filtration, drying and distillation are performed according to a conventional method. The compound (A) can be obtained by carrying out the above. The obtained compound (A) may be purified by distillation, recrystallization or column chromatography according to a conventional method in order to further increase the purity.

(STEP1-2): Synthesis of compound (B) (bromination)
Compound (B) can be synthesized by brominating the methyl group of compound (A) synthesized in STEP1-1. Bromination of compound (A) can be carried out by a known method. For example, it can be carried out by reacting with a brominating agent such as N-bromosuccinimide in a solvent such as carbon tetrachloride in the presence of a radical initiator such as benzoyl peroxide.
Specific examples of the brominating agent used in the reaction include N-bromosuccinimide, bromine, N-bromoglutarimide, and N-bromophthalimide. The amount of the brominating agent used is usually 1 to 10 mol per 1 mol of compound (A).
Specific examples of the radical initiator include benzoyl peroxide, azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile, diacyl peroxide, dialkylperoxydicarbonate, tert-alkylperoxyester, and monoperoxy. Examples thereof include carbonate, di (tert-alkylperoxy) ketal and ketone peroxide. The amount of the radical initiator used is usually 0.001 to 0.1 mol per 1 mol of compound (A).
The reaction is usually carried out in a solvent. Specific examples of the solvent used include hydrocarbons such as carbon tetrachloride, n-heptane, n-hexane, cyclohexane, n-pentane, toluene and xylene, diethyl ether, tetrahydrofuran and 1,4-dioxane. , Ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, ethers such as diisopropyl ether, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, fluorobenzene, difluorobenzene, trifluorobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, Halogenized hydrocarbons such as α, α, α-trifluorotoluene, α, α, α-trichlorotoluene, esters such as ethyl acetate and methyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetonitrile, Examples thereof include nitriles such as propionitrile. Such a solvent may be used alone or in combination of two or more.
The reaction temperature is usually in the range of -20 to 100 ° C. Under such reaction conditions, the reaction time varies depending on the reaction temperature, the type and amount of the solvent used, and the like, but is usually in the range of 0.5 to 24 hours.
After completion of the reaction, it is preferable to purify and isolate the target compound from the reaction product mixture, and after completion of the reaction, post-treatment operations such as neutralization, washing with water, crystallization, filtration, drying and distillation are performed according to a conventional method. As a result, compound (B) can be obtained. For example, when N-bromosuccinimide is used, a solid succinimide precipitates when the bromination reaction is carried out. Therefore, this is separated, and the obtained mother liquor is concentrated and fractionated by distillation, or a solvent is mixed with the mother liquor. The product can be crystallized or the concentrate of the mother liquor can be purified by column chromatography to obtain a purified product of compound (B).

(STEP1-3): Synthesis of compound (12) (etherification)
Compound (12) can be synthesized by reacting compound (B) synthesized in STEP 1-2 with compound (11) under basic conditions by a known method.
Here, specific examples of compound (11) include 4-bromophenol and 4-bromo-2-methylphenol.
In the reaction, the molar ratio of compound (B) to compound (11) is usually in the range of 1 to 20 mol with respect to 1 mol of compound (B).
Examples of the base used include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, inorganic salts such as sodium hydride, triethylamine and pyridine. Organic bases can be mentioned. The amount of the base used is 0.1 to 10 mol per 1 mol of compound (B).
The reaction is usually carried out in a solvent. The solvent used is not particularly limited as long as it is inert to the reaction, but specifically, for example, ketones such as acetone and methyl ethyl ketone, cellosolves such as methyl cellosolve and ethyl cellosolve, tetrahydrofuran and 1,4-dioxane. , Ethers such as 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. Each of these organic solvents may be used alone, or two or more of them may be used in combination as appropriate to adjust the polarity.
The reaction temperature is usually in the range of 0 ° C to 50 ° C. Under such reaction conditions, the reaction time is usually in the range of 1 to 48 hours, although it varies depending on the reaction temperature, the type and amount of the solvent used, and the like.
After completion of the reaction, it is preferable to purify and isolate the target compound from the reaction product mixture. For example, according to a conventional method, after completion of the reaction, neutralization, washing with water, crystallization, filtration, distillation, separation by column chromatography, etc. The compound (12) can be obtained by performing a post-treatment operation. The obtained compound (12) may be purified by distillation, recrystallization or column chromatography according to a conventional method in order to further increase the purity.

(STEP1-4): Synthesis of compound (13) (Suzuki cross-coupling reaction)
Compound (13) can be synthesized by subjecting compound (12) synthesized in STEP 1-3 and 4-hydroxyphenylboronic acid to a Suzuki cross-coupling reaction. In the cross-coupling reaction, a reaction catalyst and a base are used according to a known method.
In the reaction, the molar ratio of 4-hydroxyphenylboronic acid to compound (12) is usually in the range of 1 to 10 mol with respect to 1 mol of compound (12).
Examples of the coupling reaction catalyst used include a palladium-based catalyst and a nickel-based catalyst. Specific examples of the palladium-based catalyst include palladium-activated carbon, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), and tris (dibenzylideneacetone) dipalladium (0). Palladium acetate (II), palladium (II) chloride, bis (triphenylphosphine) palladium (II) dichloride, [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) ) Dichloride, [1,4-bis (diphenylphosphino) butane] palladium (II) dichloride, bis (acetritale) palladium (II) dichloride, bis (benzonitrile) palladium (II) dichloride, allylpalladium (II) chloride 2 Examples thereof include a metric, a divalent palladium compound such as cyclopentadienylallyl palladium (II) and palladium hydroxide. Further, the palladium compound may be dissolved or supported on some carrier during the reaction. Specific examples of the nickel-based catalyst include nickel compounds such as bis (triphenylphosphine) nickel chloride and tetrakis (triphenylphosphine) nickel. The palladium-based catalyst and the nickel-based catalyst may be used in combination of two or more, if necessary. The amount of the palladium-based catalyst and the nickel-based catalyst used is usually in the range of 0.001 to 0.1 mol with respect to 1 mol of the compound (12).
Specific examples of the base include alkali metal hydroxides such as lithium oxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, sodium carbonate and carbon dioxide. Alkali metal carbonates such as potassium and cesium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal acetates such as sodium acetate and potassium acetate, alkali metal phosphates such as sodium phosphate, and hydrogen. Metal hydrides such as sodium hydroxide and potassium hydride, alcohol metal salts such as sodium methoxydo, sodium ethoxydo and potassium tert-butoxide, triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylamino Examples thereof include organic bases such as pyridine and 1,8-diazabicyclo [5.4.0] -7-undecene. These can be used alone or in combination of two or more as required. Among them, alkali metal carbonate is preferable in terms of good yield. The amount of the base used is usually in the range of 0.5 to 5.0 mol per 1 mol of compound (12).
The reaction is usually carried out in a solvent. Specific examples of the solvent used include ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene or chlorobenzene; N, N-dimethylformamide (DMF). ), N, N-Dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane and other aprotic polar solvents; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate and ethyl propionate; Alibo hydrocarbons such as pentane, hexane, cyclohexane and heptane; alcohols such as methanol and ethanol; water. These can be used alone or in combination of two or more as required. The amount of the solvent used is in the range of 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, based on 1 part by weight of the compound (12).
The reaction temperature is usually in the range of 20-100 ° C. Under such reaction conditions, the reaction time is usually in the range of 0.5 to 10 hours, although it varies depending on the reaction temperature, the type and amount of the solvent used, and the like.
After completion of the reaction, it is preferable to purify and isolate the target compound from the reaction product mixture. For example, after completion of the reaction, neutralization, washing with water, crystallization, filtration, distillation, separation by column chromatography, etc. are performed according to a conventional method. The compound (13) can be obtained by performing a post-treatment operation.
When the color of the obtained product is strong, the color can be reduced by dissolving the product in a solvent and treating it with an adsorbent such as activated carbon, zeolite, silica gel, alumina gel, or activated clay.

(STEP1-5): Synthesis of diepoxy compound (2) or (3) (diglycidyl etherification)
The compound (13) obtained in STEP 1-4 can be obtained as a diepoxy compound (2) or (3) by subjecting the compound (10) to a glycidyl etherification reaction in the same manner as in STEP 1-1. Further, the obtained diepoxy compound (2) or (3) can be purified and isolated by performing the same post-treatment operation as in STEP1-1.

（式中、Ｒ_３は一般式（１）におけるそれと同じである。）
で表される４，４’−ジヒドロキシビフェニル類（以下、化合物（１４）と称呼する）を出発原料とし、公知の方法に従い、塩基性条件下に反応させる（ジエーテル化）ことにより得ることができる。
上記工程スキームを反応式で示す。

Next, regarding the methods for producing the diepoxy compounds (4) and (5) described above, for example, the compound (B) described above and the following general formula (14)

(In the formula, R ₃ is the same as that in the general formula (1).)
It can be obtained by using 4,4'-dihydroxybiphenyls represented by (hereinafter referred to as compound (14)) as a starting material and reacting them under basic conditions (dietheration) according to a known method. ..
The above process scheme is shown by a reaction formula.

In the reaction, the molar ratio of compound (B) to compound (14) is usually in the range of 2 to 50 mol with respect to 1 mol of compound (14).
The base used is the same as the base used in STEP 1-3 described above. The amount of the base used is usually in the range of 0.1 to 10 mol per 1 mol of compound (14).
The reaction is usually carried out in a solvent. The solvent used is the same as the solvent used in STEP 1-3 described above. The amount of the solvent used is usually in the range of 10 to 500 parts by weight with respect to 1 part by weight of the compound (14).
The reaction temperature is usually in the range of 10 to 50 ° C. Under such reaction conditions, the reaction time is usually in the range of 5 to 48 hours, although it varies depending on the reaction temperature, the type and amount of the solvent used, and the like.
After completion of the reaction, it is preferable to purify and isolate the target compound from the reaction product mixture. For example, when the product precipitates as a solid after completion of the reaction, a solvent is mixed as necessary, and the mixture is collected by filtration. .. If it does not precipitate, the product can be crystallized and recovered by mixing or concentrating a poor solvent to obtain the diepoxy compound (4) or (5).
The obtained diepoxy compound (4) or (5) may be purified by distillation, recrystallization or column chromatography according to a conventional method in order to further increase the purity.

（式中、Ｒ_３は一般式（１）のそれと同じであり、Ｘはハロゲン原子である。）
で表される４−ブロモベンジルハライド類（以下、化合物（１５）と称呼する）とハイドロキノンを反応させて、下記一般式（１６）

（式中、Ｒ_３は一般式（１）のそれと同じである。）
で表される化合物（以下、化合物（１６）と称呼する）を得る工程。
（ＳＴＥＰ３−２）
化合物（１６）と４−ヒドロキシフェニルボロン酸を反応させて、下記一般式（１７）

（式中、Ｒ_３は一般式（１）のそれと同じである。）
で表される化合物（以下、化合物（１７）と称呼する）を得る工程。
（ＳＴＥＰ３−３）
化合物（１７）と化合物（１０）を反応させて、ジエポキシ化合物（６）又は（７）を得る工程。 Next, regarding the method for producing the diepoxy compounds (6) and (7) described above, for example, 4-bromobenzyl halides represented by the following general formula (15) and hydroquinone are used as starting materials, and the following STEP3-1 It can be synthesized through the steps of ~ 3-3 in sequence.
(STEP3-1)
The following general formula (15)

(In the formula, R ₃ is the same as that of the general formula (1), and X is a halogen atom.)
Hydroquinone is reacted with 4-bromobenzyl halides (hereinafter referred to as compound (15)) represented by the following general formula (16).

(In the formula, R ₃ is the same as that of the general formula (1).)
A step of obtaining a compound represented by (hereinafter referred to as compound (16)).
(STEP3-2)
The compound (16) is reacted with 4-hydroxyphenylboronic acid to the following general formula (17).

(In the formula, R ₃ is the same as that of the general formula (1).)
A step of obtaining a compound represented by (hereinafter referred to as compound (17)).
(STEP3-3)
A step of reacting compound (17) with compound (10) to obtain a diepoxy compound (6) or (7).

（式中、Ｒ_３は一般式（１）のそれと同じであり、Ｘはハロゲン原子である。） The process scheme of STEP3-1 to STEP3-3 is shown by a reaction formula.

(In the formula, R ₃ is the same as that of the general formula (1), and X is a halogen atom.)

Next, each of the above steps will be described in more detail.
(STEP3-1): Synthesis of compound (16) (etherification)
Compound (16) can be easily obtained by reacting compound (15) with hydroquinone in the presence of a basic compound according to a known method.
Specific examples of the raw material compound (15) include 4-bromobenzyl bromide, 4-bromo-2-methylbenzyl bromide, 4-bromobenzyl chloride, 4-bromo-2-methylbenzyl chloride, and 4-bromobenzyliode. , 4-Bromo-2-methylbenzyl iodo and the like.
In the reaction, the molar ratio of compound (16) to hydroquinone is usually in the range of 1 to 10 mol with respect to 1 mol of compound (16).
The base used is the same as the base used in STEP 1-3 described above. The amount of the base used is usually in the range of 0.1 to 10 mol per 1 mol of compound (15).
The reaction is usually carried out in a solvent. The solvent used is the same as the solvent used in STEP 1-3 described above. The amount of the solvent used is in the range of 5 to 100 parts by weight with respect to 1 part by weight of the compound (15).
The reaction temperature is usually in the range of 20-100 ° C.
Under such reaction conditions, the reaction time is usually in the range of 1 to 10 hours, although it varies depending on the reaction temperature, the type and amount of the solvent used, and the like.
After completion of the reaction, it is preferable to purify and isolate the target compound from the reaction product mixture. For example, after completion of the reaction, post-treatment operations such as neutralization, washing with water, crystallization, filtration, drying and distillation are performed according to a conventional method. By doing so, compound (16) can be obtained.
The obtained compound (16) may be purified by distillation, recrystallization or column chromatography according to a conventional method in order to further increase the purity.

(STEP3-2): Synthesis of compound (17) (Suzuki cross-coupling reaction)
The compound (16) obtained in STEP3-1 can be obtained by subjecting 4-hydroxyphenylboronic acid to a Suzuki cross-coupling reaction in the same manner as in STEP1-4 described above.
In addition, compound (17) can be purified and isolated from the obtained reaction product by performing the same post-treatment operation as in STEP1-4.

(STEP3-3): Synthesis of diepoxy compound (6) or (7) (diglycidyl etherification)
The compound (17) obtained in STEP 3-2 can be reacted with the compound (10) in the same manner as in STEP 1-5 to obtain a diepoxy compound (6) or (7).
Further, the obtained reaction product can be purified and isolated from the diepoxy compound (6) or (7) by performing the same post-treatment operation as in STEP1-5.

（式中、Ｒ_３は一般式（１）のそれと同じである）
で表される化合物（以下、化合物（１８）と称呼する）を合成する工程。
（ＳＴＥＰ４−２）
化合物（１８）と４−ヒドロキシフェニルボロン酸を反応させて、下記一般式（１９）

（式中、Ｒ_３は一般式（１）のそれと同じである）
で表される化合物（以下、化合物（１９）と称呼する）を合成する工程。
（ＳＴＥＰ４−３）
化合物（１９）と化合物（Ｂ）を反応させて化合物（８）又は（９）を合成する工程。 Next, regarding the method for producing the diepoxy compounds (8) and (9) described above, for example, the following steps STEP4-1 to 4-3 are sequentially performed using the compound (16) and the compound (10) as starting materials. Can be synthesized via.
(STEP4-1)
The compound (16) and the compound (10) are reacted to form the following general formula (18).

(In the formula, R ₃ is the same as that of the general formula (1))
A step of synthesizing a compound represented by (hereinafter referred to as compound (18)).
(STEP4-2)
The compound (18) is reacted with 4-hydroxyphenylboronic acid to the following general formula (19).

(In the formula, R ₃ is the same as that of the general formula (1))
A step of synthesizing a compound represented by (hereinafter referred to as compound (19)).
(STEP4-3)
A step of reacting compound (19) with compound (B) to synthesize compound (8) or (9).

（式中、Ｒ_３は一般式（１）のそれと同じであり、Ｘはハロゲン原子である。） The process scheme of STEP4-1 to STEP4-3 is shown by a reaction formula.

(In the formula, R ₃ is the same as that of the general formula (1), and X is a halogen atom.)

Next, each of the above steps will be described in more detail.
(STEP4-1): Synthesis of compound (18) (glycidyl etherification)
Compound (18) can be obtained by reacting compound (16) and compound (10), which may be obtained in STEP3-1, in the same manner as in STEP1-5. ..
In addition, compound (18) can be purified and isolated from the obtained reaction product by performing the same post-treatment operation as in STEP1-5.
(STEP4-2): Synthesis of compound (19) (Suzuki cross-coupling reaction)
The compound (18) obtained in STEP 4-1 can be obtained by subjecting 4-hydroxyphenylboronic acid to a Suzuki cross-coupling reaction in the same manner as in STEP 1-4 described above.
Further, the obtained reaction product can be purified and isolated of compound (19) by performing the same post-treatment operation as in STEP1-4.
(STEP4-3): Synthesis of diepoxy compound (8) or (9) (etherification)
The compound (19) obtained in STEP 4-2 can be reacted with the compound (B) in the same manner as in STEP 1-3 to obtain a diepoxy compound (8) or (9).
Further, the obtained reaction product can be purified and isolated from the diepoxy compound (8) or (9) according to the same post-treatment method as in STEP1-3.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The presence or absence of liquid crystallinity of the diepoxy compound was determined by the following confirmation method and measurement method.
(1) Confirmation method using a polarizing microscope Whether or not the obtained epoxy compound exhibits liquid crystallinity can be determined by observing a change of state of a substance in the process of raising the temperature from room temperature using a polarizing microscope.
In the observation in the cross Nicol state, an interference pattern due to depolarization is observed in the crystal phase and the liquid crystal phase, and the isotropic phase appears in the dark field. In addition, the phase transition from the crystalline phase to the liquid crystal phase can be confirmed by the presence or absence of fluidity.
That is, in the observation with a polarizing microscope, if it has fluidity and the temperature range in which the interference pattern due to depolarization is observed is confirmed, it is judged to have a liquid crystal phase.
(2) Confirmation method by differential scanning calorimetry (DSC) The temperature at which the obtained diepoxy compound transitions from the crystal phase to the liquid crystal phase and the temperature at which the liquid crystal phase transitions to the isotropic phase are determined by the differential scanning calorimetry device (DSC). Can be measured using. The energy change associated with the phase transition appears as an endothermic peak in DSC measurement.
Therefore, it is preferable to confirm the temperature at which the diepoxy compound changes from the crystal phase to the liquid crystal phase and the temperature at which the diepoxy compound changes from the liquid crystal phase to the isotropic phase by both DSC measurement and polarization microscope observation.
(3) Measurement of liquid crystal property (a) Measurement of melting point and phase transition temperature Using a differential scanning calorimetry device (DSC6100 manufactured by Seiko Instruments), the temperature rise rate is 10 ° C / min (however, compound (6) is 1 ° C. The differential scanning calorimetry of a sample of about 3 mg sealed in an aluminum pan was performed under the conditions of a measurement temperature range of 25 to 350 ° C. and a flow rate of 20 mL / min in an argon atmosphere.
(B) Observation with a polarizing microscope While heating the obtained diepoxy compound sample or cooling the heated sample, the state change was observed in a cross-nicol state using a polarizing microscope (ECLIPSE 50iPOL manufactured by Nikon). .. If the diepoxy compound has fluidity in the heating process or the cooling process and an interference pattern due to depolarization is observed, it is judged that the diepoxy compound has liquid crystallinity.

<Example 1> The synthetic process scheme of the diepoxy compound (2) is shown by a reaction formula.

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：CDCl₃）：2.29(s,3H:c), 2.75(dd,1H:E), 2.90(dd,1H:D), 3.32-3.37(m,1H:C), 3.95(dd,1H:B), 4.18(dd,1H:A), 6.83(d,2H:b), 7.09(d,2H:a). (Synthesis 1) Synthesis of compound (A) In a 200 mL flask equipped with a reflux device, 21.6 g (0.2 mol) of p-cresol, 46.3 g (0.5 mol) of epichlorohydrin, and sodium hydroxide water (water). 12 g (0.3 mol) of sodium oxide was dissolved in 30 mL of water), and the mixture was reacted at a bath temperature of 80 ° C. for 1 hour. Then, it cooled to room temperature and separated the aqueous layer. Ethyl acetate and water were added to the obtained oil layer, and the mixture was stirred at room temperature, and then the aqueous layer was separated. Next, saturated brine was added, and the mixture was stirred at room temperature, and then the aqueous layer was separated. Sodium sulfate was added to the obtained oil layer, dehydrated, and filtered. The obtained oil layer was concentrated, and 19.5 g of a colorless transparent liquid having a purity of 100% (based on the peak area at 254 nm by high performance liquid chromatography) was obtained by simple distillation under reduced pressure. In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: CDCl ₃ ): 2.29 (s, 3H: c), 2.75 (dd, 1H: E), 2.90 (dd, 1H: D), 3.32-3.37 (m, 1H:: C), 3.95 (dd, 1H: B), 4.18 (dd, 1H: A), 6.83 (d, 2H: b), 7.09 (d, 2H: a).

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：CDCl₃）：2.76(dd,1H:E), 2.90(dd,1H:D), 3.33-3.37(m,1H:C), 3.95(dd,1H:B), 4.23(dd,1H:A), 4.49(s,2H:c), 6.88(d,2H:b), 7.32(d,2H:a). (Synthesis 2) Synthesis of compound (B) 2.96 g (18 mmol) of compound (A) obtained in Synthesis 1 and 3.36 g (18.9 mmol) of N-bromosuccinimide in a 100 mL flask equipped with a reflux device. 174 mg (0.7 mmol) of benzoyl and 20 mL of carbon tetrachloride were charged and reacted at a bath temperature of 91 ° C. for 2 hours. Then, the mixture was cooled to room temperature, and the succinimide produced by the reaction was filtered off. The obtained filtrate was concentrated to obtain 4.78 g of a pale yellowish white solid. In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: CDCl ₃ ): 2.76 (dd, 1H: E), 2.90 (dd, 1H: D), 3.33-3.37 (m, 1H: C), 3.95 (dd, 1H:: B), 4.23 (dd, 1H: A), 4.49 (s, 2H: c), 6.88 (d, 2H: b), 7.32 (d, 2H: a).

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：CDCl₃）：2.76(dd,1H:E), 2.91(dd,1H:D), 3.34-3.38(m,1H:C), 3.97(dd, 1H:B), 4.24(dd,1H:A), 4.95(s,2H:e), 6.84, 6.93, 7.34, 7.37(each d,2H×4:a,b,c,d). (Synthesis 3) Synthesis of 1-[(4-bromophenoxy) methyl] -4- (oxylan-2-ylmethoxy) benzene 1.95 g (8.0 mmol) of compound (B) obtained in Synthesis 2 in a 50 mL flask. 0.69 g (4.0 mmol) of 4-bromophenol, 2.21 g (16 mmol) of potassium carbonate, and 25 mL of acetone were charged and reacted at room temperature for 16 hours. Then, the reaction solution was filtered off, and the obtained filtrate was concentrated. Silica gel column separation of this concentrate was carried out to obtain 0.6 g of a white solid having a purity of 100% (based on the peak area at 254 nm by high performance liquid chromatography). In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: CDCl ₃ ): 2.76 (dd, 1H: E), 2.91 (dd, 1H: D), 3.34-3.38 (m, 1H: C), 3.97 (dd, 1H:: B), 4.24 (dd, 1H: A), 4.95 (s, 2H: e), 6.84, 6.93, 7.34, 7.37 (each d, 2H × 4: a, b, c, d).

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：DMSO-d₆）：2.71(dd,1H:E), 2.83(dd,1H:D), 3.28-3.33(m,1H:C), 3.92(dd,1H:B), 4.31(dd,1H:A), 5.06(s,2H:g), 6.82, 6.98, 7.03, 7.37, 7.40, 7.47(each d,2H×6:a,b,c,d,e,f), 9.15(s,1H:h). (Synthesis 4) Synthesis of 4- (4-{[4- (oxylan-2-ylmethoxy) phenyl] methoxy} phenyl) phenol 0.50 g (1.) of the compound obtained in Synthesis 3 in a 50 mL flask equipped with a reflux device. 5 mmol), 4-hydroxyphenyl boronic acid 0.23 g (1.7 mmol), sodium carbonate _{0.32g (3.0mmol), PdCl 2 (} dppf) · CH 2 Cl 2 0.03g (0.03mmol), 1, 7.5 mL of 4-dioxane and 5.0 mL of water were charged and reacted at a bath temperature of 50 ° C. for 1 hour under an argon atmosphere. Then, the mixture was cooled to room temperature, water was added, and the mixture was filtered to obtain a solid substance. This solid was dissolved in acetone and separated, and 0.5 g of activated carbon was added to the obtained filtrate and stirred at room temperature for 1 hour. Then, the activated carbon was removed by filtration, and 0.26 g of an off-white solid having a purity of 97.3% (based on the peak area at 254 nm by high performance liquid chromatography) was obtained from the obtained filtrate. In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: DMSO-d ₆ ): 2.71 (dd, 1H: E), 2.83 (dd, 1H: D), 3.28-3.33 (m, 1H: C), 3.92 (dd, dd, 1H: B), 4.31 (dd, 1H: A), 5.06 (s, 2H: g), 6.82, 6.98, 7.03, 7.37, 7.40, 7.47 (each d, 2H × 6: a, b, c, d, e, f), 9.15 (s, 1H: h).

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：DMSO-d₆）：2.70-2.73(m,2H:E,E'), 2.82-2.86(m,2H:D,D'), 3.28-3.35(m,2H:C,C'), 3.89-3.97(m,2H:B,B'), 4.29-4.36(m,2H:A,A'), 5.07(s,2H:g), 6.96-7.08, 7.37-7.40, 7.45-7.54(each m,2H×6:a,b,c,d,e,f).
示差走査熱量測定法による熱分析の結果、３つの相転移（１６１、１８６、２０１℃、このうち融点は１６１℃）が確認できた。さらに、偏光顕微鏡観察にて１６１〜１８６℃及び１８６〜２０１℃の間で、流動性及びそれぞれで異なる干渉模様が観察され、目的物が液晶化合物であることが明らかとなった。 (Synthesis 5) Synthesis of diepoxy compound (2) 0.14 g (0.4 mmol) of the compound obtained in Synthesis 4, 0.03 g (0.1 mmol) of tetrabutylammonium bromide, epichloro in a 30 mL flask equipped with a reflux device. 1.48 g (16 mmol) of hydrin was charged and reacted at a bath temperature of 55 ° C. for 8 hours. Then, water was added and the precipitate was obtained by filtration. The obtained precipitate was dissolved in DMAc (15 mL), 0.05 g of sodium hydroxide was added, and the mixture was stirred at room temperature for 30 minutes. Water was added to this solution, and the precipitate was filtered off and dried to obtain 0.08 g of a white solid having a purity of 93.8% (based on the peak area at 254 nm by high performance liquid chromatography). Mass spectrometry by DART-MS was performed, and a molecular ion peak suggesting the target product (Exact Mass: 404.2) was confirmed, and it was confirmed from the ¹ H-NMR analysis result that the compound was the target compound.

^{1 1} H-NMR (300MHz) measurement (solvent: DMSO-d ₆ ): 2.70-2.73 (m, 2H: E, E'), 2.82-2.86 (m, 2H: D, D'), 3.28-3.35 (m) , 2H: C, C'), 3.89-3.97 (m, 2H: B, B'), 4.29-4.36 (m, 2H: A, A'), 5.07 (s, 2H: g), 6.96-7.08, 7.37-7.40, 7.45-7.54 (each m, 2H × 6: a, b, c, d, e, f).
As a result of thermal analysis by the differential scanning calorimetry method, three phase transitions (161, 186, 201 ° C., of which the melting point was 161 ° C.) were confirmed. Further, by observing with a polarizing microscope, fluidity and different interference patterns were observed between 161 to 186 ° C. and 186 to 201 ° C., and it was clarified that the target product was a liquid crystal compound.

<Example 2> Synthesis of diepoxy compound (3) The process scheme is shown by a reaction formula.

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：CDCl₃）：2.22(s,3H:g), 2.76(dd,1H:E), 2.91(dd,1H:D), 3.34-3.39(m,1H:C), 3.97(dd,1H:B), 4.24(dd,1H:A), 4.97(s,2H:f), 6.74(d,1H:c), 6.93(d,2H:e), 7.22(d,1H:b), 7.26(s,1H:a), 7.33(d,2H:d). (Synthesis 1) Synthesis of 4-bromo-2-methyl-1-{[4- (oxylan-2-ylmethoxy) phenyl] methoxy} benzene Compound (B) 1 obtained in Synthesis 2 of Example 1 in a 100 mL flask. .46 g (6.0 mmol), 0.75 g (4.0 mmol) of 4-bromo-2-methylphenol, 1.11 g (8.0 mmol) of potassium carbonate, and 25 mL of acetone were charged and reacted at room temperature for 16 hours. Then, the reaction solution was filtered off, and the obtained filtrate was concentrated. Silica gel column separation of this concentrate was carried out to obtain 1.07 g of a white solid having a purity of 96.2% (based on the peak area at 254 nm by high performance liquid chromatography). In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: CDCl ₃ ): 2.22 (s, 3H: g), 2.76 (dd, 1H: E), 2.91 (dd, 1H: D), 3.34-3.39 (m, 1H:: C), 3.97 (dd, 1H: B), 4.24 (dd, 1H: A), 4.97 (s, 2H: f), 6.74 (d, 1H: c), 6.93 (d, 2H: e), 7.22 ( d, 1H: b), 7.26 (s, 1H: a), 7.33 (d, 2H: d).

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：DMSO-d₆）：2.23(s,3H:i), 2.70(dd,1H:E), 2.82(dd,1H:D), 3.27-3.33(m,1H:C), 3.91(dd,1H:B), 4.30(dd,1H:A), 5.05(s,2H:h), 6.80(d,2H:a), 6.98(d,2H:g), 7.02(d,1H:e), 7.28-7.39(m,6H:b,c,d,f), 9.11(s,1H:j). (Synthesis 2) Synthesis of 4- (3-methyl-4-{[4- (oxylan-2-ylmethoxy) phenyl] methoxy} phenyl) phenol Compound 0 obtained in Synthesis 1 in a 100 mL flask equipped with a recirculator. 52 g (1.5 mmol), 0.23 g (1.7 mmol) of 4-hydroxyphenylboronic acid, 0.32 g (3.0 mmol) of sodium carbonate, 0.03 g (0.03 mmol) of PdCl ₂ (dppf) and CH ₂ Cl _2. ), 1,4-Dioxane (12 mL) and water (12 mL) were charged and reacted at a bath temperature of 50 ° C. for 2.5 hours under an argon atmosphere. Then, the mixture was cooled to room temperature, water was added, and the mixture was filtered to obtain a solid substance. This solid was dissolved in acetone and separated, and 0.5 g of activated carbon was added to the obtained filtrate and stirred at room temperature for 30 minutes. Then, the activated carbon was removed by filtration, the obtained filtrate was concentrated, and silica gel column separation was performed to obtain 0.31 g of a pale yellowish white solid having a purity of 93.1% (based on the peak area at 254 nm by high performance liquid chromatography). It was. In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: DMSO-d ₆ ): 2.23 (s, 3H: i), 2.70 (dd, 1H: E), 2.82 (dd, 1H: D), 3.27-3.33 (m, 1H: C), 3.91 (dd, 1H: B), 4.30 (dd, 1H: A), 5.05 (s, 2H: h), 6.80 (d, 2H: a), 6.98 (d, 2H: g), 7.02 (d, 1H: e), 7.28-7.39 (m, 6H: b, c, d, f), 9.11 (s, 1H: j).

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：DMSO-d₆）：2.24(s,3H:i), 2.69-2.72(m,2H:E,E'), 2.81-2.85(m,2H:D,D'), 3.27-3.34(m,2H:C,C'), 3.88-3.96(m,2H:B,B'), 4.28-4.34(m,2H:A,A'), 5.07(s,2H:h), 6.96-7.06, 7.33-7.53(each m,11H:a,b,c,d,e,f,g).
示差走査熱量測定法による熱分析の結果、２つの相転移（１０６、１４４℃、このうち融点は１０６℃）が確認できた。さらに、偏光顕微鏡観察にて、１０６〜１４４℃の間で流動性と干渉模様が観察され、目的物が液晶化合物であることが明らかとなった。 (Synthesis 3) Synthesis of diepoxy compound (3) 0.18 g (0.5 mmol) of the compound obtained in Synthesis 2, 0.04 g (0.1 mmol) of tetrabutylammonium bromide, epichloro in a 50 mL flask equipped with a reflux device. 1.85 g (20 mmol) of hydrin was charged and reacted at a bath temperature of 55 ° C. for 4 hours. Then, 30 mL of ethyl acetate and 15 mL of water were added, and an oil layer was obtained by liquid separation. The obtained oil layer was concentrated and dissolved in 15 mL of THF, 0.08 g of sodium hydroxide was added, and the mixture was stirred at room temperature for 1 hour. Water was added to this solution, and the precipitate was filtered off and dried to obtain 0.15 g of a pale yellowish white solid having a purity of 97.5% (based on the peak area at 254 nm by high performance liquid chromatography). Mass spectrometry by DART-MS confirmed a molecular ion peak suggesting the target substance (Exact Mass: 418.2), and ¹ H-NMR analysis result confirmed that the compound was the target compound.

^{1 1} H-NMR (300MHz) measurement (solvent: DMSO-d ₆ ): 2.24 (s, 3H: i), 2.69-2.72 (m, 2H: E, E'), 2.81-2.85 (m, 2H: D,, D'), 3.27-3.34 (m, 2H: C, C'), 3.88-3.96 (m, 2H: B, B'), 4.28-4.34 (m, 2H: A, A'), 5.07 (s, 2H: h), 6.96-7.06, 7.33-7.53 (each m, 11H: a, b, c, d, e, f, g).
As a result of thermal analysis by the differential scanning calorimetry method, two phase transitions (106, 144 ° C., of which the melting point was 106 ° C.) were confirmed. Further, by observing with a polarizing microscope, fluidity and an interference pattern were observed between 106 and 144 ° C., and it was clarified that the target product was a liquid crystal compound.

１００ｍＬのフラスコに実施例１の合成２で得た化合物（Ｂ）０．９７ｇ（４．０ｍｍｏｌ）、４，４’−ジヒドロキシビフェニル０．１９ｇ（１．０ｍｍｏｌ）、炭酸カリウム０．４２ｇ（３．０ｍｍｏｌ）、アセトン２０ｍＬを仕込み、室温にて２０時間反応させた。その後、反応液をろ別し、白色固体を得た。ＤＭＳＯを用いてこの白色固体の再結晶を行い、純度９１．２％（高速液体クロマトグラフィー法２５４ｎｍにおけるピーク面積基準）の白色固体０．２５ｇを得た。また、^１Ｈ−ＮＭＲ分析結果から目的化合物であることを確認した。

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：DMSO-d₆）：2.70(dd,2H:E), 2.82(dd,2H:D), 3.27-3.32(m,2H:C), 3.93(dd,2H:B), 4.29(dd,2H:A), 5.06(s,4H:e), 6.98, 7.04, 7.37, 7.50(each d,16H:a,b,c,d).
示差走査熱量測定法による熱分析の結果、２つの相転移（２２９、２５４℃、このうち融点は２２９℃）が確認できた。さらに、偏光顕微鏡観察にて２２９〜２５４℃の間で流動性と干渉模様が観察され、目的物が液晶化合物であることが明らかとなった。 <Example 3> Synthesis of diepoxy compound (4) The process scheme is shown by a reaction formula.

In a 100 mL flask, 0.97 g (4.0 mmol) of the compound (B) obtained in Synthesis 2 of Example 1, 0.19 g (1.0 mmol) of 4,4′-dihydroxybiphenyl, and 0.42 g (3.) Potassium carbonate. (0 mmol) and 20 mL of acetone were charged and reacted at room temperature for 20 hours. Then, the reaction solution was filtered off to obtain a white solid. This white solid was recrystallized using DMSO to obtain 0.25 g of a white solid having a purity of 91.2% (based on the peak area at 254 nm by high performance liquid chromatography). In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: DMSO-d ₆ ): 2.70 (dd, 2H: E), 2.82 (dd, 2H: D), 3.27-3.32 (m, 2H: C), 3.93 (dd, dd, 2H: B), 4.29 (dd, 2H: A), 5.06 (s, 4H: e), 6.98, 7.04, 7.37, 7.50 (each d, 16H: a, b, c, d).
As a result of thermal analysis by the differential scanning calorimetry method, two phase transitions (229, 254 ° C., of which the melting point was 229 ° C.) were confirmed. Furthermore, fluidity and interference patterns were observed between 229 and 254 ° C. by polarizing microscope observation, and it was clarified that the target product was a liquid crystal compound.

<Example 4> Synthesis of diepoxy compound (6) The process scheme is shown by a reaction formula.

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：CDCl₃）：4.48(s,1H:f), 4.95(s,2H:e), 6.75, 6.83, 7.29, 7.50(each d,8H:a,b,c,d). (Synthesis 1) Synthesis of 4-[(4-bromophenyl) methoxy] phenol In a 200 mL flask equipped with a reflux device, 5.0 g (20 mmol) of 4-bromobenzyl bromide, 11.0 g (100 mmol) of hydroquinone, and potassium carbonate 4 .1 g (30 mmol) and 70 mL of acetone were charged and reacted at a bath temperature of 70 ° C. for 3 hours. Then, the mixture was cooled to room temperature and the inorganic salt was filtered off. The obtained filtrate was concentrated and washed several times with chloroform. This washing solution was concentrated, dissolved in ethyl acetate, and then hexane was added to obtain pale yellowish white crystals. Further, it was dissolved in toluene, washed with water, and hexane was added to obtain 1.9 g of pale yellowish white crystals having a purity of 97.7% (based on the peak area at 280 nm by high performance liquid chromatography). In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (300MHz) measurement (solvent: CDCl ₃ ): 4.48 (s, 1H: f), 4.95 (s, 2H: e), 6.75, 6.83, 7.29, 7.50 (each d, 8H: a, b, c, d).

^１Ｈ−ＮＭＲ（６００ＭＨｚ）測定（溶媒：DMSO-d₆）：4.99 (s,2H:g), 6.66, 6.82, 6.84, 7.43, 7.48, 7.56(each d,12H:a,b,c,d,e,f), 8.93, 9.54(each s,2H:h,i). (Synthesis 2) Synthesis of 4- (4-{[4- (oxylan-2-ylmethoxy) phenyl] methoxy} phenyl) phenol 0.56 g (2.) The compound obtained in Synthesis 1 in a 50 mL flask equipped with a reflux device. 0 mmol), 4-hydroxyphenyl boronic acid 0.30 g (2.2 mmol), sodium carbonate _{0.42g (4.0mmol), PdCl 2 (} dppf) · CH 2 Cl 2 0.03g (0.04mmol), 1, 4.0 mL of 4-dioxane and 4.0 mL of water were charged and reacted at a bath temperature of 70 ° C. for 2 hours under an argon atmosphere. Then, the mixture was cooled to room temperature, water was added, and the mixture was filtered to obtain a solid substance. This solid substance was dissolved in acetone, activated carbon was added, and the mixture was stirred at a bath temperature of 40 ° C. for 30 minutes. Then, the activated carbon was removed by filtration to obtain 0.51 g of an off-white solid from the obtained filtrate. Further, recrystallization was performed using methanol to obtain 0.25 g of an off-white solid having a purity of 83.9% (based on the peak area at 280 nm by high performance liquid chromatography). In addition, it was confirmed that it was the target compound from the ¹ H-NMR analysis result.

^{1 1} H-NMR (600MHz) measurement (solvent: DMSO-d ₆ ): 4.99 (s, 2H: g), 6.66, 6.82, 6.84, 7.43, 7.48, 7.56 (each d, 12H: a, b, c, d , e, f), 8.93, 9.54 (each s, 2H: h, i).

^１Ｈ−ＮＭＲ（３００ＭＨｚ）測定（溶媒：THF-d₈）：2.61, 2.65(each dd,2H:E,E'), 2.73-2.80(m,2H:D,D'), 3.18-3.29(m,2H:C,C'), 3.81, 3.93(each dd,2H:B,B'), 4.13, 4.25(each dd,2H:A,A'), 5.04(s, 2H:g), 6.83-7.03, 7.44-7.59(each m,12H:a,b,c,d,e,f).
示差走査熱量測定法による熱分析の結果、４つの相転移（１５１、１７５、１７７、１８１℃、このうち融点は１５１℃）が確認できた。さらに、偏光顕微鏡観察にて、１５１〜１８１℃の間で流動性と干渉模様が観察され、目的物が液晶化合物であることが明らかとなった。 (Synthesis 3) Synthesis of diepoxy compound (6) 0.19 g (0.65 mmol) of the compound obtained in Synthesis 2, 0.05 g (0.16 mmol) of tetrabutylammonium bromide, epichloro in a 30 mL flask equipped with a reflux device. 2.10 g (22.8 mmol) of hydrin was charged and reacted at a bath temperature of 55 ° C. for 15 hours. Then, water was added and the precipitate was obtained by filtration. The obtained precipitate was dissolved in DMAc (10 mL), 0.05 g of sodium hydroxide was added, and the mixture was stirred at a bath temperature of 20 ° C. for 1 hour. Water was added to this solution and the precipitate was filtered off. The obtained filtrate was slurry-washed with methanol to obtain 0.16 g of a white solid having a purity of 94.4% (based on the peak area at 254 nm by high performance liquid chromatography). Mass spectrometry by DART-MS confirmed a molecular ion peak suggesting the target substance (Exact Mass: 404.2), and ¹ H-NMR analysis result confirmed that the compound was the target compound.

^{1 1} H-NMR (300MHz) measurement (solvent: THF-d ₈ ): 2.61, 2.65 (each dd, 2H: E, E'), 2.73-2.80 (m, 2H: D, D'), 3.18-3.29 ( m, 2H: C, C'), 3.81, 3.93 (each dd, 2H: B, B'), 4.13, 4.25 (each dd, 2H: A, A'), 5.04 (s, 2H: g), 6.83 -7.03, 7.44-7.59 (each m, 12H: a, b, c, d, e, f).
As a result of thermal analysis by the differential scanning calorimetry method, four phase transitions (151, 175, 177, 181 ° C., of which the melting point was 151 ° C.) were confirmed. Further, by observing with a polarizing microscope, fluidity and an interference pattern were observed between 151 and 181 ° C., and it was clarified that the target product was a liquid crystal compound.

４，４’−ジヒドロキシ−３，３’−ジメチルビフェニルと化合物（Ｂ）を原料に用いて、実施例３と同様な方法で化合物（２０）を合成し、その得られた化合物（２０）とエピクロロヒドリンを原料に用いて、実施例１の合成５と同様な方法で化合物（２１）を合成した。
示差走査熱量測定法による熱分析の結果、１つの相転移（１５１℃）しか確認されず、化合物（２１）に液晶性は確認できなかった。 <Comparative Example 1> Synthesis of a compound represented by the following formula (21)

Using 4,4'-dihydroxy-3,3'-dimethylbiphenyl and compound (B) as raw materials, compound (20) was synthesized in the same manner as in Example 3, and the obtained compound (20) and the compound (20) were synthesized. Using epichlorohydrin as a raw material, compound (21) was synthesized in the same manner as in Synthesis 5 of Example 1.
As a result of thermal analysis by the differential scanning calorimetry method, only one phase transition (151 ° C.) was confirmed, and the liquid crystal property of compound (21) could not be confirmed.

実施例１の合成１におけるｐ−クレゾールに代えてｍ−クレゾールを用いて、実施例１と同様な方法により化合物（２２）を合成した。
示差走査熱量測定法による熱分析の結果、１つの相転移（１２８℃）しか確認されず、化合物（２２）に液晶性は確認できなかった。 <Comparative Example 2> Synthesis of a compound represented by the following formula (22)

Compound (22) was synthesized by the same method as in Example 1 using m-cresol instead of p-cresol in Synthesis 1 of Example 1.
As a result of thermal analysis by the differential scanning calorimetry method, only one phase transition (128 ° C.) was confirmed, and the liquid crystal property of compound (22) could not be confirmed.

パラヒドロキシフェネチルアルコールを出発原料として用いて、臭素化、４，４’−ジヒドロキシビフェニルとのエーテル化、エピクロロヒドリンとの反応によるグリシジルエーテル化を行って、化合物（２３）を合成した。
示差走査熱量測定法による熱分析の結果、１つの相転移（１２１℃）しか確認されず、化合物（２３）に液晶性は確認できなかった。 <Comparative Example 3> Synthesis of a compound represented by the following formula (23)

Using parahydroxyphenethyl alcohol as a starting material, bromide, etherification with 4,4'-dihydroxybiphenyl, and glycidyl etherification by reaction with epichlorohydrin were carried out to synthesize compound (23).
As a result of thermal analysis by the differential scanning calorimetry method, only one phase transition (121 ° C.) was confirmed, and the liquid crystal property of compound (23) could not be confirmed.

実施例３における４，４’−ジヒドロキシビフェニルに代えて、３，３’−ジメチル−４，４’−ジヒドロキシビフェニルを用いて、実施例３と同様な方法で、化合物（２４）を合成した。
示差走査熱量測定法による熱分析の結果、１つの相転移（２１４℃）しか確認されず、化合物（２４）に液晶性は確認できなかった。 <Comparative Example 4> Synthesis of a compound represented by the following formula (24)

Compound (24) was synthesized in the same manner as in Example 3 using 3,3'-dimethyl-4,4'-dihydroxybiphenyl instead of 4,4'-dihydroxybiphenyl in Example 3.
As a result of thermal analysis by the differential scanning calorimetry method, only one phase transition (214 ° C.) was confirmed, and the liquid crystal property of compound (24) could not be confirmed.

Claims (1)

A diepoxy compound represented by the general formula (1).

(Wherein, R ₁ represents an oxygen atom or a methylene group, R ₂ represents a methylene group when R ₁ is an oxygen atom, if R ₁ is a methylene group represents an oxygen atom, R ₃ is a hydrogen atom or methyl Represents a group, where n represents 0 or 1)