WO2019111853A1 - Method for producing dicarboxylic acid monoester, dicarboxylic acid monoester salt, and method for producing polymerizable liquid crystal compound - Google Patents

Abstract

The present invention addresses the problem of providing a method for producing a dicarboxylic acid monoester with excellent production efficiency, a method for producing a polymerizable liquid crystal compound, and a novel dicarboxylic acid monoester salt. This method for producing a dicarboxylic acid monoester has: a diesterification step for reacting a prescribed dicarboxylic acid compound represented by formula (1) with a prescribed hydroxyl group-containing vinyl compound represented by formula (2) to produce a prescribed dicarboxylic acid diester represented by formula (3); and a monoesterification step for hydrolyzing the dicarboxylic acid diester by means of a base in a solvent containing a secondary or tertiary alcohol to produce a prescribed dicarboxylic acid monoester represented by formula (4).

Description

Method for producing dicarboxylic acid monoester body, method for producing dicarboxylic acid monoester salt and polymerizable liquid crystal compound

The present invention relates to a method for producing a dicarboxylic acid monoester, a dicarboxylic acid monoester salt, and a method for producing a polymerizable liquid crystal compound.

Optical films such as an optical compensation sheet and a retardation film are used in various image display devices for the purpose of decoloring an image and enlarging a viewing angle.
A stretched birefringent film has been used as an optical film, but in recent years, it has been proposed to use an optical film having an optically anisotropic layer made of a liquid crystalline compound in place of the stretched birefringent film.

The liquid crystal compound used to form such an optically anisotropic layer is, for example, a hydroxy compound for forming a skeleton located at the molecular center of the liquid crystal compound (hereinafter also referred to as “core portion”), It is known that synthesis is performed utilizing an esterification reaction with a carboxylic acid compound to form a side chain portion of a liquid crystal compound (see, for example, Patent Documents 1 to 4).

Unexamined-Japanese-Patent No. 2010-031223 JP, 2012-097078, A International Publication No. 2014/010325 JP, 2016-081035, A

The present inventors examined the synthesis methods of the liquid crystal compounds described in Patent Documents 1 to 4. With regard to the carboxylic acid compound for forming the side chain, the productivity depending on the structure of the target side chain Revealed that there is room for improvement.

Then, this invention makes it a subject to provide the manufacturing method of the dicarboxylic acid monoester body excellent in production efficiency, the manufacturing method of a polymeric liquid crystal compound, and a novel dicarboxylic acid monoester salt.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors hydrolyze a dicarboxylic acid diester having a predetermined structure with a base in a solvent containing a secondary or tertiary alcohol to obtain a monoester. It turned out that it could produce dicarboxylic acid monoester body by a high yield, and completed the present invention.
That is, it discovered that the above-mentioned subject could be achieved by the following composition.

[1] A dicarboxylic acid compound represented by the formula (1) described later and a hydroxyl group-containing vinyl compound represented by the formula (2) described later are reacted, and a dicarboxylic acid diester represented by the formula (3) described later Diesterizing step to form a body,
A monoesterification step of hydrolyzing a dicarboxylic acid diester body using a base in a solvent containing a secondary or tertiary alcohol to form a dicarboxylic acid monoester salt represented by the formula (4) described later;
The manufacturing method of the dicarboxylic acid monoester body which has.

[2] The method according to [1], further comprising, after the monoesterification step, a deprotection step of adding an acid to the dicarboxylic acid monoester salt to form a devinylized compound represented by Formula (5) described later. Method of producing a dicarboxylic acid monoester body of

[3] The method for producing a dicarboxylic acid monoester according to [2], further comprising, after the deprotection step, a polymerizable group introducing step of forming a polymerizable compound represented by Formula (6) described later.

[4] [1] to [3], wherein the hydroxyl group-containing vinyl compound represented by the formula (2) described later is any one of compounds represented by the formulas (2-1) to (2-3) described later ] The manufacturing method of the dicarboxylic acid monoester body in any one of-.
[5] The method for producing a dicarboxylic acid monoester according to any one of [1] to [4], wherein the base is a Bronsted base.
[6] The process for producing a dicarboxylic acid monoester according to any one of [1] to [5], wherein the base is any of sodium hydroxide, potassium hydroxide and lithium hydroxide.
[7] The dicarboxylic acid mono described in any one of [1] to [6], wherein the dicarboxylic acid compound represented by the formula (1) described later is a compound represented by the formula (1-1) described later Method for producing an ester body.

[8] A dicarboxylic acid monoester salt represented by the formula (4-1) described later.
[9] A dicarboxylic acid monoester salt according to [8], wherein Ma in formula (4-1) described later represents any of sodium, potassium and lithium.

[10] A polymerizable compound represented by the formula (6) described later prepared by the method for producing a dicarboxylic acid monoester according to [3] and a compound having a hydroxyl group are reacted to obtain a polymerizable liquid crystal compound And a method of producing a polymerizable liquid crystal compound.

According to the present invention, it is possible to provide a method for producing a dicarboxylic acid monoester body excellent in production efficiency, a method for producing a polymerizable liquid crystal compound, and a novel dicarboxylic acid monoester salt.

Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.

　ここで、式（１）～（４）中、
　ｎは、０～２の整数を表す。
　Ｒ^１およびＲ^２は、それぞれ独立に、環構造を表し、Ｌ^１は、単結合または２価の連結基を表し、ｎが２である場合、複数のＬ^１は、それぞれ同一であっても異なっていてもよく、複数のＲ^２は、それぞれ同一であっても異なっていてもよい。
　ＳＰ^１は、炭素数１～１２の直鎖状もしくは分岐状のアルキレン基、または、炭素数１～１２の直鎖状もしくは分岐状のアルキレン基を構成する－ＣＨ_２－の１個以上が－Ｏ－、－Ｓ－、－ＮＨ－、－Ｎ（Ｑ）－、もしくは、－ＣＯ－に置換された２価の連結基を表し、Ｑは、置換基を表す。
　Ｍは、アルカリ金属原子またはアルカリ土類金属原子を表し、ｍは、Ｍの価数を表す。 [Method for producing dicarboxylic acid monoester body]
The method for producing a dicarboxylic acid monoester of the present invention (hereinafter simply referred to as “the production method of the present invention”) is represented by a dicarboxylic acid compound represented by the following formula (1), and the following formula (2) And a hydroxyl group-containing vinyl compound to produce a dicarboxylic acid diester represented by the following formula (3).
In the production method of the present invention, the dicarboxylic acid diester body represented by the following formula (3) is hydrolyzed using a base in a solvent containing a secondary or tertiary alcohol, and the following formula (4) It has a monoesterification step to produce the dicarboxylic acid monoester salt represented.

Here, in the formulas (1) to (4),
n represents an integer of 0 to 2;
R ¹ and R ² each independently represent a ring structure, L ¹ represents a single bond or a divalent linking group, and when n is 2, plural L ^{1 s} may be identical to each other It may be different, and multiple R ^{2 s} may be the same or different.
In SP ¹ , one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms is — It represents a divalent linking group substituted by O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent.
M represents an alkali metal atom or an alkaline earth metal atom, and m represents a valence of M.

As described above, according to the production method of the present invention, the dicarboxylic acid diester represented by the above formula (3) is hydrolyzed using a base in a solvent containing a secondary or tertiary alcohol, and the above formula (4) By having the mono-esterification process which produces | generates the dicarboxylic acid monoester salt represented by these, the dicarboxylic acid monoester body can be produced | generated by high yield.
Although this is not clear in detail, the present inventors speculate as follows.
First, unexpectedly, in the monoesterification step, the dicarboxylic acid diester represented by the above formula (3) is hydrolyzed using a base in a solvent containing a secondary or tertiary alcohol. By depositing the dicarboxylic acid monoester salt represented by the above formula (4) in the reaction solution, the reaction selectivity is improved, and it becomes possible to isolate it only by the filtration operation.
Therefore, in the present invention, when monoesterification to generate a dicarboxylic acid monoester salt from a dicarboxylic acid diester body, a monoester salt having high purity could be recovered by a simple method, and thus the dicarboxylic acid monoester is produced. It is believed that the body could be produced in high yield.

Below, the diesterification process and mono-esterification process which the manufacturing method of this invention has, and any other process are explained in full detail.
In the production method of the present invention, water or an organic solvent can be used in each step as necessary. As the solvent, for example, ethers such as tetrahydrofuran (THF), 1,4-dioxane; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene; chlorinated solvents such as methylene chloride, chloroform, trichloroethylene Ketones such as acetone and 2-butanone; aprotic polar solvents such as N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and hexamethylphosphoric triamide; acetonitrile And nitriles such as propionitrile; esters such as ethyl acetate and n-butyl acetate; alcohols such as methanol, ethanol and t-butyl alcohol; and the like, and these may be used alone. Two or more may be used in combination.

[Diesterification process]
In the di-esterification process of the production method of the present invention, the dicarboxylic acid compound represented by the above formula (1) and the hydroxyl group-containing vinyl compound represented by the above formula (2) are reacted with each other by the above formula (3) It is a process of producing the dicarboxylic acid diester body to be represented.

<Dicarboxylic acid compound>
The dicarboxylic acid compound used for the said diesterization process is a compound represented by following formula (1).

In the above formula (1), n represents an integer of 0 to 2, preferably 0 or 1.
Also, R ¹ and R ² each independently represent a ring structure.
L ¹ represents a single bond or a divalent linking group, and is preferably a single bond.
Here, when n is 2, plural L ^{1 s} may be the same or different, and plural R ^{2 s} may be the same or different.

As a ring structure which R ¹ and R ² of the said Formula (1) show, the C3-C20 bivalent alicyclic hydrocarbon group which may have a substituent, and a substituent are mentioned, for example Examples thereof include C6-20 divalent aromatic hydrocarbon groups which may be possessed.

As a C3-C20 bivalent alicyclic hydrocarbon group, a C3-C20 cycloalkylene group etc. are mentioned, for example, Specifically, a cyclohexylene group, a cyclo pentylene group, norbornylene group And an adamantylene group.
Further, examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an arylene group having 6 to 12 carbon atoms, and specific examples include a phenylene group and a naphthylene group.

On the other hand, as a substituent which these hydrocarbon groups may have, an alkyl group, an alkoxy group, a halogen atom etc. are mentioned, for example.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group) N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group and the like are more preferable, an alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group or an ethyl group is more preferable Is particularly preferred.
The alkoxy group is, for example, preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) More preferably, it is an alkoxy group of the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that it is a fluorine atom and a chlorine atom.

Further, among the single bond or divalent linking group represented by L ¹ in the above formula (1), examples of the divalent linking group include a linear or branched alkylene group having 1 to 12 carbon atoms, And one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms is —O—, —S—, —NH—, —N (Q) — or — Examples thereof include a divalent linking group substituted by CO- and the like. In addition, Q represents a substituent, and examples thereof include the same substituents as the above-mentioned alicyclic hydrocarbon group and the like may have.

As the linear or branched alkylene group having 1 to 12 carbon atoms, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylhexylene group, heptylene group and the like are preferable. It can be mentioned.

In the present invention, the dicarboxylic acid compound represented by the above formula (1) has the following formula from the viewpoint of the ease of precipitation of the dicarboxylic acid monoester salt, and the usefulness of the polymerizable liquid crystal compound to be derived: The compound is preferably a compound represented by (1-1a), and more preferably a compound represented by the following formula (1-1).

In the above formula (1-1), s represents an integer of 1 to 3 and is preferably an integer of 1 to 2. When s is 2 or 3, plural cyclohexylene groups are linked to each other by a single bond.
P represents an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.

Specifically as a compound represented by the said Formula (1-1), the compound represented by a following formula is mentioned suitably, for example.

<Hydroxyl group-containing vinyl compound>
The hydroxyl group-containing vinyl compound used in the above-described diesterization step is a compound represented by the following formula (2).

In the above formula (2), SP ¹ is —CH ₂ constituting a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms One or more of-represents a divalent linking group substituted by -O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent.

Examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ¹ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group and a heptylene group. Etc. are mentioned suitably.
As the substituents represented Q is, in the description of R ¹ and R ² of formula (1) described above, similarly to the illustrated alicyclic hydrocarbon substituent which may be have such groups as the ring structure The ones of

In the present invention, any of the compounds represented by the following formulas (2-1) to (2-3) is preferably mentioned from the viewpoint of the ease of obtaining and deprotection.

<Reaction conditions>
The reaction conditions for the dicarboxylic acid compound and the hydroxyl group-containing vinyl compound described above are not particularly limited, and conventionally known reaction conditions for esterification can be appropriately adopted.
For example, the reaction temperature is preferably −10 to 150 ° C., more preferably −5 to 120 ° C., and still more preferably −5 to 100 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 30 minutes to 10 hours, and still more preferably 1 hour to 8 hours.

<Dicarboxylic acid diester body>
By the said diesterization process, the dicarboxylic acid diester body represented by following formula (3) is obtained. In the following formula (3), n, R ¹ , R ² , L ¹ and SP ¹ are all the same as those described in the above formulas (1) and (2).

Specifically as a compound represented by the said Formula (3), the compound represented by a following formula is mentioned suitably, for example.

[Monoesterification process]
In the monoesterification step included in the production method of the present invention, the dicarboxylic acid diester body represented by the above formula (3) is hydrolyzed using a base in a solvent containing a secondary or tertiary alcohol, and the above formula This is a step of producing a dicarboxylic acid monoester salt represented by (4).

<Solvent>
In the monoesterification step, a solvent containing a secondary or tertiary alcohol is used.
Here, the ratio of the secondary or tertiary alcohol in the solvent is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and still more preferably 50 to 100% by mass. .
Specific examples of the secondary alcohol include 2-propanol (isopropanol), sec-butanol, cyclopentanol, cyclohexanol and the like.
Specific examples of the tertiary alcohol include 1-ethynyl-1-cyclopropanol, 1-adamantanol, tert-butanol, t-amyl alcohol and the like.
In addition, solvents other than secondary alcohol or tertiary alcohol can be used together. Among the solvents exemplified as the organic solvent which can be used in each step, solvents other than primary alcohols are preferably mentioned as the solvent to be used in combination.

<Base>
The base used in the monoesterification step is preferably a Bronsted base from the viewpoints of availability, solubility, suppression of side reactions, and the like.
As a Br ス テ ッ ド nsted base, inorganic Br ス テ ッ ド nsted bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate and the like; pyridine, triethylamine, dimethylaminopyridine, diisopropylethylamine, N-methylmorpholine etc. Organic Br ス テ ッ ド nsted bases;
Among these, inorganic Br ス テ ッ ド nsted bases are preferable, and from the viewpoint of availability and solubility, sodium hydroxide, potassium hydroxide and lithium hydroxide are more preferable.
In practical use, it is also preferable to form the corresponding inorganic Bronsted base in the system by using a metal alkoxide in a secondary or tertiary alcohol and water. As the metal alkoxide, t-butoxy potassium, t-butoxy sodium, sodium methoxide and the like can be used.

<Reaction conditions>
The reaction conditions for producing the dicarboxylic acid monoester salt represented by the above formula (4) are not particularly limited except that the above-described solvent and base are used, and conventionally known hydrolysis reaction conditions are appropriately employed. be able to.
For example, the reaction temperature is preferably −30 to 100 ° C., more preferably −20 to 50 ° C., and still more preferably −10 to 40 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.

<Dicarboxylic acid monoester salt>
By the monoesterification process, a dicarboxylic acid monoester salt represented by the following formula (4) is obtained.

In the above formula (4), n, R ¹ , R ² , L ¹ and SP ¹ are all the same as those described in the above formulas (1) and (2).
Moreover, M represents an alkali metal atom or an alkaline earth metal atom, and m represents a valence number of M.

Specific examples of the alkali metal atom represented by M in the above formula (4) include sodium, potassium, lithium and cesium. Among them, sodium, potassium and lithium are preferable.
Further, specific examples of the alkaline earth metal atom represented by M include, for example, calcium, strontium and barium. Among them, calcium and barium are preferable.

Specifically as a compound represented by the said Formula (4), the compound represented by a following formula is mentioned suitably, for example. In the following formulas, Ma represents an alkali metal atom.

[Deprotection process]
The production method of the present invention imparts an acid to the dicarboxylic acid monoester salt represented by the above formula (4) after the above monoesterification step to form a devinylized compound represented by the formula (5) described later It is preferable to have a deprotecting step.

<Acid>
Examples of the acid to be imparted to the dicarboxylic acid monoester salt include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid or salts thereof; formic acid, acetic acid, propionic acid, oxalic acid Organic acids such as trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid or salts thereof; lithium tetrafluoroborate, boron trifluoride, boron trichloride, boron tribromide , Lewis acids such as aluminum trichloride, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, tin dichloride, titanium tetrachloride, titanium tetrabromide, trimethyliodosilane; alumina, silica gel, Oxides such as titania; minerals such as montmorillonite; etc. may be used alone or in combination of two or more. It may be.

<Reaction conditions>
The reaction conditions at the time of producing | generating the devinylization compound represented by Formula (5) mentioned later are not specifically limited, The reaction conditions of the deprotection reaction of the conventionally well-known vinyl group using an acid can be employ | adopted suitably.
For example, the reaction temperature is preferably −30 to 100 ° C., more preferably −20 to 50 ° C., and still more preferably −10 to 40 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.

By the above-mentioned deprotection step, a devinylized compound represented by the following formula (5) is obtained.

In the above formula (5), n, R ¹ , R ² and L ¹ and SP ¹ are all the same as described in the above formulas (1) and (2).

Specifically as a compound represented by the said Formula (5), the compound represented by a following formula is mentioned suitably, for example.

[Polymerizable group introduction step]
It is preferable that the manufacturing method of this invention has a polymeric group introduce | transducing process of producing | generating the polymeric compound represented by following formula (6) after the said deprotection process.

In the above formula (6), n, R ¹ , R ² and L ¹ and SP ¹ are all the same as described in the above formulas (1) and (2).
Also, R ³ represents a hydrogen atom or a methyl group.

<Reaction conditions>
The reaction for forming the polymerizable compound represented by the above formula (6) is not particularly limited. For example, a method of reacting acryloyl chloride or methacryloyl chloride with the devinyl compound represented by the above formula (5); A method in which 3-chloropropionic acid chloride is reacted with a devinylized compound represented by the formula (5), and then dehydrochlorinated to give an acryloyl group or a methacryloyl group;
The reaction temperature is preferably −30 to 100 ° C., more preferably −20 to 50 ° C., and still more preferably −10 to 40 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.

Specifically as a compound represented by the said Formula (6), the compound represented by a following formula is mentioned suitably, for example.

[Dicarboxylic acid monoester salt]
The dicarboxylic acid monoester salt of the present invention is a dicarboxylic acid monoester salt represented by the following formula (4-1).

In the above formula (4-1), s represents an integer of 1 to 3 and is preferably an integer of 1 to 2. When s is 2 or 3, plural cyclohexylene groups are linked to each other by a single bond.
P represents an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.
Further, Ma represents an alkali metal atom, and preferably represents any of sodium, potassium and lithium.
Moreover, SP ¹ is the same as that described in the above equation (2).

Examples of the compound represented by the above formula (4-1) include the same compounds as those exemplified as the compound represented by the above formula (4).

[Method of producing polymerizable liquid crystal compound]
In the method for producing a polymerizable liquid crystal compound of the present invention, a polymerizable compound represented by the above formula (6) produced by the above-mentioned production method of the present invention is reacted with a compound having a hydroxyl group to obtain a polymerizable liquid crystal compound. It is a manufacturing method of a polymerizable liquid crystal compound to obtain.

[Compound having a hydroxyl group]
The compound having a hydroxyl group to be reacted with the polymerizable compound represented by the formula (6) is preferably a compound represented by the following formula (7).

In the above formula (7), Ar represents a divalent aromatic group.
Examples of the divalent aromatic group include, for example, an arylene group having 6 to 12 carbon atoms, and specific examples include a phenylene group and a naphthylene group.

In the present invention, Ar in the above formula (7) is preferably any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5) . In the following formulas (Ar-1) to (Ar-5), * represents a bonding position to a hydroxyl group in the above formula (7).

Here, in the above formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N (R ⁵ )-, and R ⁵ represents R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y ¹ is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or an aromatic complex having 3 to 12 carbon atoms Represents a ring group.
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁵ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. And n-pentyl and n-hexyl groups.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y ¹ include aryl groups such as phenyl group, 2,6-diethylphenyl group and naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y ¹ include heteroaryl groups such as thienyl group, thiazolyl group, furyl group and pyridyl group.
Moreover, as a substituent which Y ¹ may have, an alkyl group, an alkoxy group, a halogen atom etc. are mentioned, for example.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group) N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group and the like are more preferable, an alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group or an ethyl group is more preferable Is particularly preferred.
The alkoxy group is, for example, preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) More preferably, it is an alkoxy group of the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that it is a fluorine atom and a chlorine atom.

In the above formulas (Ar-1) to (Ar-5), Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon A monovalent alicyclic hydrocarbon group of 3 to 20, a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ , or represents -SR ^{9, R} 6 ~ R ⁹ each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, ^{Z 1} and ^{Z 2,} also form an aromatic ring bonded to each other Good.
The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group or an ethyl group , Isopropyl, tert-pentyl (1,1-dimethylpropyl), tert-butyl and 1,1-dimethyl-3,3-dimethyl-butyl are more preferable, and methyl, ethyl, tert-butyl Groups are particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, ethylcyclohexyl Monocyclic saturated hydrocarbon group such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as dienes; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, Tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1. 1 ^3,6 . 0 ^2,7 ] Polycyclic saturated hydrocarbon groups such as dodecyl and adamantyl; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, 2,6-diethylphenyl group, naphthyl group and biphenyl group, and the like. Aryl groups (especially phenyl groups) are preferred.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that it is a fluorine atom, a chlorine atom, a bromine atom.
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ to R ⁸ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group. Groups, tert-butyl group, n-pentyl group, and n-hexyl group.

In the above formulas (Ar-2) and (Ar-3), A ¹ and A ² are each independently selected from —O—, —N (R ¹⁰ ) —, —S— and —CO— And R ¹⁰ represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ¹⁰ include the same as the substituent which Y ¹ in the formula (Ar-1) may have.

Further, in the above formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom of Group 14 to 16 to which a substituent may be bonded.
Further, examples of the non-metallic atoms of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Specific examples of the substituent include Is, for example, an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (eg, phenyl group, naphthyl group etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group etc. Can be mentioned.

Also, in the above formula (Ar-3), D ⁵ and D ⁶ each independently represent a single bond, -CO-O-, -C (= S) O-, -CR ¹ R ^2- , -CR ^{1 R 2 -CR 3 R 4 -,} - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O-CO-CR 1 ^{R 2 -, - CR 1 R} 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 R 3 -, or, -CO Represents -NR ^1- . R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

In the above formula (Ar-3), SP ³ and SP ⁴ each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. A bivalent in which one or more of —CH ₂ — constituting a linear or branched alkylene group is substituted by —O—, —S—, —NH—, —N (Q) — or —CO— And Q represents a substituent. Examples of the substituent include those similar to the substituent which Y ¹ in the formula (Ar-1) may have.

Furthermore, in the above formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group.
As a monovalent organic group, an alkyl group, an aryl group, heteroaryl group etc. can be mentioned, for example. The alkyl group may be linear, branched or cyclic, preferably linear. The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but is preferably monocyclic. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable. The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom which comprises a heteroaryl group has a preferable nitrogen atom, a sulfur atom, and an oxygen atom. The carbon number of the heteroaryl group is preferably 6 to 18, and more preferably 6 to 12. In addition, the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include those similar to the substituent which Y ¹ in the formula (Ar-1) may have.

In the above formulas (Ar-4) to (Ar-5), Ax is an organic having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring Represents a group.
In the above formulas (Ar-4) to (Ar-5), Ay is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic group And an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of
Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
As Ax and Ay, those described in paragraphs [0039] to [0095] of Patent Document 3 (WO 2014/010325) can be mentioned.
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by Q ³ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. -Butyl group, n-pentyl group, n-hexyl group and the like, and as the substituent, those similar to the substituent which may be possessed by Y ¹ in the above formula (Ar-1) It can be mentioned.

[Reaction conditions]
The reaction conditions for the polymerizable compound represented by the above formula (6) and the compound having a hydroxyl group described above are not particularly limited, and conventionally known reaction conditions for esterification can be appropriately adopted.
For example, the reaction temperature is preferably −30 to 150 ° C., more preferably −20 to 100 ° C., and still more preferably −10 to 50 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

[Synthesis of Compound (I-1-a)]

As shown in the above scheme, after adding 125 g (0.462 mol) of dimethyl 4,4-biphenyldicarboxylate (S-1-a) to 1000 mL of acetic acid and adding 12.5 g of a palladium on carbon catalyst (wet product), The catalytic hydrogenation reaction was carried out in an autoclave at 130 ° C. and 2 MPa.
After completion of the reaction, the catalyst was removed by filtration after cooling to room temperature (23 ° C.).
Subsequently, after distilling off acetic acid under reduced pressure, ethyl acetate and sodium hydrogen carbonate aqueous solution were added. Then, the mixture was stirred, separated to remove the aqueous layer, and the organic layer was washed with 10% brine. Sodium sulfate was added to this solution to dry, and the solvent was concentrated to obtain dimethyl 4,4′-dicyclohexanedicarboxylate (S-1-b) (130 g).
No further purification is performed, and subsequently, dimethyl 4,4'-dicyclohexanedicarboxylate (130 g), potassium hydroxide pellets (manufactured by Aldrich, purity 90%) 86.3 g, cumene 1300 mL, and polyethylene glycol 2000 (Tokyo) 10 mL of made by Kasei Kogyo Co., Ltd. were mixed, fitted with a Dean-Stark tube, and heated and stirred at 120 ° C. After distilling off methanol, the temperature was adjusted to 180 ° C., and heating and refluxing were continued for 20 hours while distilling off the solvent. The progress of the reaction was confirmed by NMR (Nuclear Magnetic Resonance), and after completion of the reaction, the reaction solution was cooled, 1300 mL of ethanol was added to the reaction solution, and the precipitated potassium salt was collected by filtration.
The potassium salt was dissolved in 1300 ml of water, concentrated hydrochloric acid was added under ice cooling until the pH of the system reached 3, and the precipitated carboxylic acid was collected by filtration to recover a crude product.
The collected crude product was suspended in 500 mL of acetone, stirred at 50 ° C. for 30 minutes, cooled to room temperature, and collected by filtration. This reslurry operation is repeated twice to obtain 93.9 g (80% yield) of crystals of t, t-dicyclohexanedicarboxylic acid (I-1-a) having a trans content of almost 100%. The

Example 1
Compound (I-1), which is a dicarboxylic acid monoester, was synthesized according to the scheme shown below.

[Synthesis of Compound (I-1-c)]

As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a), 20 mL of toluene, and 6.7 mL of N, N-dimethylformamide (DMF) are mixed at room temperature (23 ° C.) And the internal temperature was cooled to 5 ° C. To the mixture was added dropwise 5.95 ml (82.6 mmol) of thionyl chloride (SOCl ₂ ) so that the internal temperature did not rise above 10 ° C. After stirring at 25 ° C. for 1 hour, the stirring was stopped and the resulting lower layer was removed to obtain a toluene solution of compound (I-1-b).
In a separate reaction vessel, 9.59 g (82.6 mmol) of trimethylene glycol monovinyl ether, 23.0 ml (165 mmol) of triethylamine, and 50 ml of ethyl acetate are mixed at room temperature (23 ° C.), and the internal temperature is 5 ° C. It cooled down. A toluene solution of compound (I-1-b) was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C., and the mixture was then stirred at 5 ° C. for 1 hour. After stirring, 50 ml of water was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give 15.9 g (35.4 mmol) of compound (I-1-c) (yield 90%) ).
The ¹ H-NMR of the obtained compound (I-1-c) is shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.4 (m, 4 H), 1.7-1.8 (m , 12H), 1.9-2.0 (m, 4H), 2.2-2.3 (m, 2H), 3.6-3.7 (m, 4H), 4.0 (dd, 2H) ), 4.0-4.1 (m, 4 H), 4.2 (dd, 2 H), 6.5 (dd, 2 H)

[Synthesis of Compound (I-1-d)]

As shown in the above scheme, 10.0 g (22.2 mmol) of compound (I-1-c) and 100 mL of 2-propanol were mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. To the mixture was added 1.33 g (33.3 mmol) of sodium hydroxide and stirred at 25 ° C. for 3 hours. The resulting precipitate was filtered off, washed with 2-propanol and dried under reduced pressure to give 6.14 g (16.4 mmol) of compound (I-1-d) (yield 74%).
The ¹ H-NMR of the obtained compound (I-1-d) is shown below.
¹ H-NMR (solvent: D ₂ O) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.4 (m, 4 H), 1.7-1.8 ( m, 8 H), 1.8-2.0 (m, 4 H), 2.1 (tt, 1 H), 2.3 (tt, 1 H), 3.8 (t, 2 H), 4.1 (dd) , 1 H), 4.1 (t, 2 H), 4.3 (dd, 1 H), 6.5 (dd, 1 H)

[Synthesis of Compound (I-1)]

As shown in the above scheme, 5.0 g (13.4 mmol) of compound (I-1-d) and 20 mL of tetrahydrofuran (THF) were mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. . To the mixture, 20 ml of 1 N hydrochloric acid water was added dropwise so that the internal temperature did not rise above 15 ° C. After stirring at 25 ° C. for 2 hours, 20 ml of ethyl acetate was added to carry out liquid separation. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give compound (I-1-e).
The ¹ H-NMR of the obtained compound (I-1-e) is shown below.
¹ H-NMR (solvent: d ₆ -DMSO) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.4 (m, 4 H), 1.7-1.8 (M, 8 H), 1.8-2.0 (m, 4 H), 2.1 (tt, 1 H), 2.3 (tt, 1 H), 3.4 (t, 2 H), 4.0 ( t, 2H), 4.5 (s, 1 H), 12.0 (s, 1 H)

Next, 4.24 g of the obtained compound (I-1-e), 1.94 g (16.0 mmol) of N, N-dimethylaniline, and 30 mL of ethyl acetate are mixed at room temperature (23 ° C.), and the internal temperature is raised. Was cooled to 5 ° C. To the mixture, 1.46 g (16.0 mmol) of acrylic acid chloride was dropped so that the internal temperature did not rise to 10 ° C. or higher. After stirring at 25 ° C. for 2 hours, 20 ml of 1N aqueous hydrochloric acid was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 4.43 g (11.4 mmol) of compound (I-1) (yield: 85%).
The ¹ H-NMR of the obtained compound (I-1) is shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.5 (m, 4 H), 1.7-1.8 (m , 8H), 2.0-2.1 (m, 4H), 2.2 (tt, 1 H), 2.2 (tt, 1 H), 4.1 (t, 2 H), 4.2 (t, 2H), 5.8 (dd, 1 H), 6.1 (dd, 1 H), 6.4 (dd, 1 H)

Example 2
Compound (I-2), which is a dicarboxylic acid monoester, was synthesized according to the scheme shown below.

[Synthesis of Compound (I-2-c)]

As shown in the above scheme, 10.0 g (58.1 mmol) of compound (I-2-a), 20 mL of toluene, and 10.8 mL of N, N-dimethylformamide (DMF) are mixed at room temperature (23 ° C.) And the internal temperature was cooled to 5 ° C. To the mixture was added dropwise 8.80 ml (122 mmol) of thionyl chloride (SOCl2) so that the internal temperature did not rise to 10 ° C or more. After stirring for 1 hour at 25 ° C., the stirring was stopped and the resulting lower layer was removed to obtain a toluene solution of compound (I-2-b).
In a separate reaction vessel, 14.2 g (122 mmol) of trimethylene glycol monovinyl ether, 34.0 ml (244 mmol) of triethylamine, and 80 ml of ethyl acetate are mixed at room temperature (23 ° C.), and the internal temperature is cooled to 5 ° C. did. A toluene solution of compound (I-2-b) was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C., and the mixture was stirred at 5 ° C. for 1 hour. After stirring, 50 ml of water was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give 19.7 g (53.4 mmol) of compound (I-2-c) (yield 92%) ).
The ¹ H-NMR of the obtained compound (I-2-c) is shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.4-1.5 (m, 4 H), 1.7-1.8 (m, 8 H), 2.0-2.1 (m) , 4H), 2.2-2.3 (m, 2H), 3.7 (t, 4H), 4.0 (dd, 2H), 4.1 (t, 4H), 4.2 (dd, 2H), 6.5 (dd, 2H)

[Synthesis of Compound (I-2-d)]

As shown in the above scheme, 10.0 g (27.1 mmol) of compound (I-2-c) and 100 mL of 2-propanol were mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. To the mixture was added 1.63 g (40.7 mmol) of sodium hydroxide and stirred at 25 ° C. for 3 hours. The formed precipitate was separated by filtration, washed with 2-propanol and then dried under reduced pressure to obtain 5.39 g (18.4 mmol) of a compound (I-2-d) (yield: 68%).
The ¹ H-NMR of the obtained compound (I-2-d) is shown below.
¹ H-NMR (solvent: D ₂ O) δ (ppm): 1.2-1.3 (m, 4 H), 1.6 (m, 4 H), 1.8-1.9 (m, 4 H) , 2.0 (tt, 1 H), 2.2 (tt, 1 H), 3.7 (m, 2 H), 4.0 (m, 3 H), 4.2 (dd, 1 H), 6.4 ( dd, 1H)

[Synthesis of Compound (I-2)]

As shown in the above scheme, 5.0 g (17.1 mmol) of compound (I-2-d) and 25 mL of tetrahydrofuran (THF) were mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. . To the mixture, 25 ml of 1 N hydrochloric acid water was added dropwise so that the internal temperature did not rise above 15 ° C. After stirring at 25 ° C. for 2 hours, 25 ml of ethyl acetate was added to carry out liquid separation. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give compound (I-2-e).
The ¹ H-NMR of the obtained compound (I-2-e) is shown below.
¹ H-NMR (solvent: d ₆ -DMSO) δ (ppm): 1.3 to 1.4 (m, 4 H), 1.4 to 1.5 (m, 2 H), 1.5 to 1.6 (M, 2 H), 1.8-2.0 (m, 4 H), 2.1 (tt, 1 H), 2.3 (tt, 1 H), 3.4 (t, 2 H), 4.0 ( t, 2H), 4.5 (s, 1 H), 12.0 (s, 1 H)

Next, 3.76 g of the compound (I-2-e), 2.49 g (20.5 mmol) of N, N-dimethylaniline and 40 mL of ethyl acetate are mixed at room temperature (23 ° C.), and the internal temperature is raised. Was cooled to 5 ° C. To the mixture, 1.85 g (20.5 mmol) of acrylic acid chloride was dropped so that the internal temperature did not rise to 10 ° C. or higher. After stirring at 25 ° C. for 2 hours, 25 ml of 1N aqueous hydrochloric acid was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 4.08 g (13.7 mmol) of compound (I-2) (yield: 80%).
The ¹ H-NMR of the obtained compound (I-2) is shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 to 1.4 (m, 4 H), 1.4 to 1.5 (m, 2 H), 1.5 to 1.6 (m , 2H), 1.8-2.0 (m, 4H), 2.2 (tt, 1 H), 2.3 (tt, 1 H), 4.1 (t, 2 H), 4.2 (t, 2H), 5.8 (dd, 1 H), 6.1 (dd, 1 H), 6.4 (dd, 1 H)

[Example 3]
Compound (II-1), which is a dicarboxylic acid monoester, was synthesized according to the scheme shown below.

[Synthesis of Compound (II-1-a)]

As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a), 20 mL of toluene, and 6.7 mL of N, N-dimethylformamide (DMF) are mixed at room temperature (23 ° C.) And the internal temperature was cooled to 5 ° C. To the mixture was added dropwise 5.95 ml (82.6 mmol) of thionyl chloride (SOCl2) so that the internal temperature did not rise above 10 ° C. After stirring at 25 ° C. for 1 hour, the stirring was stopped and the resulting lower layer was removed to obtain a toluene solution of compound (I-1-b).
In a separate reaction vessel, 7.28 g (82.6 mmol) of ethylene glycol monovinyl ether, 23.0 ml (165 mmol) of triethylamine and 50 ml of ethyl acetate are mixed at room temperature (23 ° C.), and the internal temperature is increased to 5 ° C. It cooled. A toluene solution of compound (I-1-b) was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C., and the mixture was then stirred at 5 ° C. for 1 hour. After stirring, 50 ml of water was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give 14.1 g (35.8 mmol) of compound (II-1-a) (yield 91%) ).
The ¹ H-NMR of the obtained compound (II-1-a) is shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.4 (m, 4 H), 1.7-1.8 (m , 4H), 1.9-2.0 (m, 4H), 2.2-2.3 (m, 2H), 3.8-3.9 (m, 4H), 4.1 (dd, 2H) ), 4.1-4.2 (m, 4 H), 4.2 (dd, 2 H), 6.5 (dd, 2 H)

[Synthesis of Compound (II-1-b)]

As shown in the above scheme, 10.0 g (25.3 mmol) of compound (II-1-a) and 100 mL of 2-propanol were mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. To the mixture was added 1.52 g (38.0 mmol) of sodium hydroxide and stirred at 25 ° C. for 3 hours. The resulting precipitate was separated by filtration, washed with 2-propanol and then dried under reduced pressure to obtain 6.58 g (19.0 mmol) of compound (II-1-b) (yield 75%).
The ¹ H-NMR of the obtained compound (II-1-b) is shown below.
¹ H-NMR (solvent: D ₂ O) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.4 (m, 4 H), 1.7-1.8 ( m, 4 H), 1.9-2.0 (m, 4 H), 2.1 (tt, 1 H), 2.3 (tt, 1 H), 3.9 (t, 2 H), 4.1 (dd) , 1 H), 4.2 (t, 2 H), 4.2 (dd, 1 H), 6.5 (dd, 1 H)

[Synthesis of Compound (II-1)]

As shown in the above scheme, 5.0 g (14.4 mmol) of compound (II-1-b) and 22 mL of tetrahydrofuran (THF) were mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. . To the mixture, 22 ml of 1 N hydrochloric acid water was added dropwise so that the internal temperature did not rise to 15 ° C. or more. After stirring at 25 ° C. for 2 hours, 22 ml of ethyl acetate was added to carry out liquid separation. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give compound (II-1-c).
The ¹ H-NMR of the obtained compound (II-1-c) is shown below.
¹ H-NMR (solvent: d ₆ -DMSO) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.4 (m, 4 H), 1.7-1.8 (M, 4 H), 1.8-2.0 (m, 4 H), 2.1 (tt, 1 H), 2.3 (tt, 1 H), 3.5 (t, 2 H), 4.1 ( t, 2H), 4.4 (s, 1 H), 12.0 (s, 1 H)

Then, 3.87 g of the compound (II-1-c), 2.09 g (17.2 mmol) of N, N-dimethylaniline and 33 mL of ethyl acetate are mixed at room temperature (23 ° C.), and the internal temperature is raised. Was cooled to 5 ° C. Into the mixture, 1.56 g (17.2 mmol) of acrylic acid chloride was dropped so that the internal temperature did not rise to 10 ° C. or more. After stirring at 25 ° C. for 2 hours, 22 ml of 1N aqueous hydrochloric acid was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 4.21 g (11.9 mmol) of a compound (II-1) (yield 83%).
The ¹ H-NMR of the obtained compound (II-1) is shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.1 (m, 6 H), 1.3-1.5 (m, 4 H), 1.7-1.8 (m , 4H), 2.0-2.1 (m, 4H), 2.2 (tt, 1 H), 2.2 (tt, 1 H), 4.2 (t, 2 H), 4.3 (t, 2H), 5.8 (dd, 1 H), 6.1 (dd, 1 H), 6.5 (dd, 1 H)

Example 4
The above compound (I-1) synthesized also in Example 1 was synthesized by the following procedure.

[Synthesis of Compound (I-1-c)]

As shown in the above scheme, 20.0 g (172 mmol) of 4-hydroxybutyl vinyl ether was dissolved in 100 mL of ethyl acetate, to which 52.8 g (518 mmol) of triethylamine was added at room temperature (23 ° C.). The solution was cooled with ice water, and 21.7 g (189 mmol) of methanesulfonyl chloride (MsCl) was added dropwise while maintaining the internal temperature at 10 ° C. or less. After dropping, the mixture was stirred at 5 ° C. or less for 1 hour, then the ice bath was removed and the reaction solution was returned to room temperature (23 ° C.). Thereafter, 50 ml of water was added to stop the reaction, and liquid separation was performed. The organic layer is washed with 10% aqueous sodium hydrogen carbonate solution and then with 10% brine, and dried over sodium sulfate, and the solvent is evaporated under reduced pressure to give 35.4 g of compound (I-1-f) (ethyl acetate 5) %) (172 mmol) was obtained as an oil (yield 100%).
Then, as shown in the above scheme, 15 g (59.0 mmol) of compound (I-1-a), 26.8 g (138 mmol) of compound (I-1-f), 19.6 g (142 mmol) of potassium carbonate, and 100 ml of N, N-dimethylacetamide was mixed, the internal temperature was heated to 100 ° C., and the mixture was stirred for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature and separated by adding ethyl acetate, 75 mL, hexane 75 mL, and water 75 ml. The organic layer is washed with 10% brine and then dried over sodium sulfate, and the solvent is evaporated under reduced pressure to give 25.1 g of compound (I-1-c) (containing 5% of ethyl acetate) (53.1 mmol) Obtained as an oil (yield 90%).

[Synthesis of Compound (I-1-d)]

As shown in the above scheme, 150 mL of t-butanol, 3.2 g (33.3 mmol) of t-butoxy sodium, and 0.6 mL of water were mixed and heated to dissolve.
To this solution, 10.0 g (22.2 mmol) of Compound (I-1-c) was added at room temperature (23 ° C.), and the mixture was stirred at 25 ° C. for 3 hours. The resulting precipitate was separated by filtration, washed with a mixed solution of t-butanol / THF (1/1), and dried under reduced pressure to obtain 6.2 g (16.6 mmol) of a compound (I-1-d) (16.6 mmol). Yield 75%).

[Synthesis of Compound (I-1)]

As shown in the above scheme, 6.2 g (16.6 mmol) of compound (I-1-d) and 30 mL of tetrahydrofuran (THF) and 30 mL of 2N aqueous hydrochloric acid (30 mL) are mixed at room temperature (23 ° C.), 1 Stir for hours. After completion of the reaction, 50 ml of ethyl acetate was added to carry out liquid separation. The organic layer was washed with 10% brine and then concentrated, without further purification, the next step was performed.
Then, Compound (I-1-e) and 30 mL of N, N-dimethylacetamide were mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. To the mixture was added dropwise 2.59 g (20.4 mmol) of 3-chloropropionyl chloride so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 50 ml of ethyl acetate and 50 ml of 1N aqueous hydrochloric acid were added to carry out liquid separation. The organic layer was washed with 10% aqueous sodium hydrogen carbonate solution and then with 10% brine, and the solvent was evaporated under reduced pressure. To this solution, 30 mL of acetonitrile and 2.03 g (20.4 mmol) of triethylamine were added, and stirred at room temperature (23 ° C.) for 2 hours. 50 ml of ethyl acetate and 50 ml of water were added to carry out liquid separation. The organic layer was washed with 10% brine, concentrated and recrystallized from ethyl acetate / hexane to give 5.58 g (14.7 mmol) of Compound (I-1) (yield: 88%).

[Example 5]
The compound (I-1-c) was synthesized in the same manner as in Example 4 and used.
50 mL of t-butanol, 50 mL of acetonitrile, 2.99 g (26.6 mmol) of potassium t-butoxide, and 0.5 mL of water were mixed, heated and dissolved, and then cooled to room temperature. To this reaction solution, 10.0 g (22.2 mmol) of compound (I-1-c) was added at room temperature (23 ° C.), and the mixture was stirred at 25 ° C. for 3 hours.
After completion of the reaction, the solvent was partially distilled off under reduced pressure, 50 mL of tetrahydrofuran (THF) and 50 mL of 2N aqueous hydrochloric acid (50 mL) were added at room temperature (23 ° C.) and stirred for 1 hour. After completion of the reaction, 100 ml of ethyl acetate was added to carry out liquid separation. The organic layer was washed with 10% brine and concentrated, and the next step was performed without further purification.
The next step was carried out in the same manner as in Example 4 to obtain 6.08 g (16.0 mmol) of a compound (I-1). The yield from compound (I-1-c) was 72%.

[Example 6]

In the above scheme, compound (I-1-c) used was synthesized in the same manner as in Example 4.
As shown in the above scheme, 9.0 g (15.0 mmol) of compound (I-1-c), 30 mL of t-butanol, 30 mL of acetonitrile, and 0.4 mL of water are mixed and cooled to 0 to 5 ° C. It stirred. A solution of 2.52 g (22.5 mmol) of t-butoxy potassium in 45 mL of t-butanol was added dropwise to the reaction solution, and then stirred at 0-5 ° C. for 3 hours.
After completion of the reaction, 45 mL of acetonitrile was added, and the product was collected by filtration under reduced pressure and air-dried at 40 ° C. to obtain 4.70 g of a compound (I-1-dd). The yield from compound (I-1-c) was 72%.
Then, compound (I-1) was derived from compound (I-1-dd) in the same manner as in Example 4.

Comparative Example 1

As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a), 100 mL of ethyl acetate (EA), 18.2 mL of N, N-dimethylacetamide (DMAc), and 2,6- 433 mg of di-t-butyl-4-methylphenol was mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. To the mixture, 6.24 ml (86.5 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 5.67 g (39.3 mmol) of 4-hydroxybutyl acrylate was added. After dropwise addition of 37.7 ml (216 mmol) of N, N-diisopropylethylamine (DIPEA), the mixture was stirred at room temperature for 2 hours. After stirring, 100 ml of 1N aqueous hydrochloric acid was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 4.49 g (11.8 mmol) of a compound (I-1) (yield 30%).
From these results, it was found that the synthesis methods of Examples 1, 4 and 5 were superior to Comparative Example 1 in the production efficiency of compound (I-1).

Comparative Example 2

As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a), 100 mL of N, N-dimethylacetamide (DMAc), 8.0 ml (78.6 mmol) of triethylamine, and 2,6 433 mg of di-t-butyl-4-methylphenol were mixed at room temperature (23 ° C.). To the mixture, 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate was added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, 100 ml of 1N aqueous hydrochloric acid and 100 ml of ethyl acetate were added, and the mixture was stirred at room temperature (23 ° C.) for 10 minutes and filtered. The filtrate was separated, and the organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. To the residue was added 100 ml of chloroform, the resulting white crystals were filtered, and the filtrate was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 4.78 g (12.6 mmol) of compound (I-1) (yield 32%).
From these results, it was found that the synthesis methods of Examples 1, 4 and 5 were superior to Comparative Example 2 in the production efficiency of compound (I-1).

[Synthesis of Polymerizable Liquid Crystal Compound]
[Synthesis of Compound (L-1a)]
The compound (L-1a) having a hydroxyl group represented by the following formula (L-1a) was synthesized by referring to the method described in paragraphs [0161] and [0162] of JP-A-2010-254949. .
Specifically, 26.1 g (400 mmol) of 86% content potassium hydroxide was dissolved in 80 ml of isopropyl alcohol and 45 ml of water under a nitrogen stream. To this solution was added a solution of 13.21 g (200 mmol) of malononitrile dissolved in 10 ml of isopropyl alcohol at an internal temperature of 5 ° C. or less under ice-cooling and stirring. Subsequently, 15.23 g (200 mmol) of carbon disulfide was added dropwise at an internal temperature of 10 ° C. or less, and the mixture was stirred for 30 minutes under ice cooling. Acetic acid 3.43 ml (60 mmol) was added to the reaction solution to adjust the pH of the solution to 6, 71.07 g of 2-t-butyl-1,4-benzoquinone (purity 88%, 380 mmol), acetic acid 22. A mixed solution of 9 ml (400 mmol) and 290 ml of acetone was slowly added dropwise while keeping the internal temperature below 2 ° C. After stirring for 30 minutes at the same temperature, the temperature was raised to 25 ° C., 40 ml of water was added, and after stirring, the mixture was allowed to stand and the separated lower layer was removed. After raising the temperature to an internal temperature of 40-45 ° C., a mixed solution of 130 mL of acetonitrile / 130 mL of water was added dropwise, and the mixture was stirred for 30 minutes at the same temperature to precipitate crystals. Thereafter, 130 ml of water was further added and then cooled to 20 ° C., and the precipitated crystals were collected by filtration and washed with 130 ml of acetonitrile / 130 ml of water. The obtained crystals were dried at 50 ° C. under reduced pressure to obtain 47.6 g (yield 79%) of a compound (L-1a) as a pale yellow solid.

[Synthesis of Polymerizable Liquid Crystal Compound (L-1)]

As shown in the above scheme, 2.53 g (6.65 mmol) of compound (I-1c), 15 mL of ethyl acetate (EA), 4.5 mL of N, N-dimethylacetamide (DMAc), 2,6-di-t- 33 mg of butyl-4-methylphenol was mixed at room temperature, and the internal temperature was cooled to 5 ° C. To the mixture, 0.58 ml (7.98 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise to 10 ° C. or more. After stirring at 5 ° C. for 1 hour, a solution of compound (L-1a) 0.92 g (3.02 mmol) in tetrahydrofuran (THF) (5 ml) was added. After dropwise addition of 2.90 ml (16.6 mmol) of N, N-diisopropylethylamine (DIPEA), the mixture was stirred at room temperature for 6 hours. After stirring, 15 ml of 1 N hydrochloric acid water and 15 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine and then dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 2.65 g (2.58 mmol) of a compound (L-1) (yield: 85%).
The ¹ H-NMR of the obtained compound (L-1) is shown below.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.2 (m, 12 H), 1.3 (s, 9 H), 1.3-1.5 (m, 4 H), 1.5-1.6 (m, 4H), 1.7-1.8 (m, 8 H), 1.8-2.0 (m, 8 H), 2.0-2.1 (m, 4 H) ), 2.1-2.3 (m, 6 H), 2.5 (tt, 1 H), 2.6 (tt, 1 H), 4.1 (m, 4 H), 4.2 (m, 4 H) , 5.8 (dd, 2 H), 6.1 (dd, 2 H), 6.4 (dd, 2 H), 7.3 (s, 1 H)

Claims (10)

The di-esterification which makes the dicarboxylic acid compound represented by following formula (1), and the hydroxyl-containing vinyl compound represented by following formula (2) react, and produces the dicarboxylic acid diester body represented by following formula (3) Process,
A monoesterification step of hydrolyzing the dicarboxylic acid diester body using a base in a solvent containing a secondary or tertiary alcohol to form a dicarboxylic acid monoester salt represented by the following formula (4);
The manufacturing method of the dicarboxylic acid monoester body which has.

Here, in the formulas (1) to (4),
n represents an integer of 0 to 2;
R ¹ and R ² each independently represent a ring structure, L ¹ represents a single bond or a divalent linking group, and when n is 2, plural L ^{1 s} may be identical to each other It may be different, and multiple R ^{2 s} may be the same or different.
In SP ¹ , one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms is — It represents a divalent linking group substituted by O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent.
M represents an alkali metal atom or an alkaline earth metal atom, and m represents a valence of M. The dicarboxylic acid according to claim 1, further comprising a deprotection step of applying an acid to the dicarboxylic acid monoester salt to form a devinylized compound represented by the following formula (5) after the monoesterification step. Method for producing an acid monoester body.

Here, in the formula (5),
n represents an integer of 0 to 2;
R ¹ and R ² each independently represent a ring structure, L ¹ represents a single bond or a divalent linking group, and when n is 2, plural L ^{1 s} may be identical to each other It may be different, and multiple R ^{2 s} may be the same or different.
In SP ¹ , one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms is — It represents a divalent linking group substituted by O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent. Furthermore, the manufacturing method of the dicarboxylic acid monoester body of Claim 2 which has a polymeric group introduce | transducing process of producing | generating the polymeric compound represented by following formula (6) after the said deprotection process.

Here, in the formula (6),
n represents an integer of 0 to 2;
R ¹ and R ² each independently represent a ring structure, L ¹ represents a single bond or a divalent linking group, and when n is 2, plural L ^{1 s} may be identical to each other It may be different, and multiple R ^{2 s} may be the same or different.
In SP ¹ , one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms is — It represents a divalent linking group substituted by O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent.
R ³ represents a hydrogen atom or a methyl group. The hydroxyl group-containing vinyl compound represented by the said Formula (2) is a compound any one of represented by following formula (2-1)-(2-3), The manufacturing method of the dicarboxylic acid monoester body of description.

The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 4, wherein the base is a Bronsted base. The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 5, wherein the base is any one of sodium hydroxide, potassium hydroxide and lithium hydroxide. The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 6, wherein the dicarboxylic acid compound represented by the formula (1) is a compound represented by the following formula (1-1) .

Here, in the formula (1-1),
s represents an integer of 1 to 3, and p represents an integer of 0 to 3. The dicarboxylic acid monoester salt represented by following formula (4-1).

Here, in the formula (4-1),
s represents an integer of 1 to 3, and p represents an integer of 0 to 3.
Ma represents an alkali metal atom.
In SP ¹ , one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms is — It represents a divalent linking group substituted by O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent. The dicarboxylic acid monoester salt according to claim 8, wherein Ma in the formula (4-1) represents any of sodium, potassium and lithium. A polymerizable liquid crystal compound is obtained by reacting a polymerizable compound represented by the following formula (6) produced by the method for producing a dicarboxylic acid monoester according to claim 3 with a compound having a hydroxyl group to obtain a polymerizable liquid crystal compound Method of producing a compound.

Here, in the formula (6),
n represents an integer of 0 to 2;
R ¹ and R ² each independently represent a ring structure, L ¹ represents a single bond or a divalent linking group, and when n is 2, plural L ^{1 s} may be identical to each other It may be different, and multiple R ^{2 s} may be the same or different.
In SP ¹ , one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms is — It represents a divalent linking group substituted by O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent.
R ³ represents a hydrogen atom or a methyl group.