WO2020059634A1

WO2020059634A1 - Intermediate production method

Info

Publication number: WO2020059634A1
Application number: PCT/JP2019/035933
Authority: WO
Inventors: 坂本　圭; 久美奥山
Original assignee: 日本ゼオン株式会社
Priority date: 2018-09-19
Filing date: 2019-09-12
Publication date: 2020-03-26
Also published as: JPWO2020059634A1; JP7327408B2; CN112689622A

Abstract

The purpose of the present invention is to provide an intermediate production method capable of efficiently producing an intermediate containing a compound (I) at a high concentration. An intermediate production method according to the present invention includes: (i) a step (α) for obtaining a solution (X) containing a compound (I) represented by formula (I) and a compound (II) represented by formula (II); and (ii) a step (β) for obtaining an intermediate containing 86 mass% or more of the compound (I) by adding a protic solvent to the solution (X) to precipitate the compound (II) and by removing the precipitated compound (II).

Description

Production method of intermediate

The present invention relates to a method for producing an intermediate.

Examples of the retardation plate include a 板 wavelength plate that converts linearly polarized light into circularly polarized light, and a 波長 wavelength plate that converts the polarization oscillation plane of linearly polarized light by 90 degrees. These retardation plates are capable of accurately converting a specific monochromatic light into a phase difference of 光線 λ or λλ of the light wavelength.
However, the conventional retardation plate has a problem that polarized light output through the retardation plate is converted into colored polarized light. This is because the material constituting the retardation plate has a wavelength dispersion property with respect to the retardation, and distribution occurs in the polarization state for each wavelength with respect to white light, which is a composite wave in which light rays in the visible light region are mixed. It is impossible to accurately adjust the phase difference to 1 / 4λ or 1 / 2λ in all wavelength regions.
In order to solve such a problem, a compound capable of obtaining an optical film capable of performing uniform polarization conversion in a wide wavelength range and a production method thereof have been studied (for example, see Patent Documents 1 to 4).

International Publication No. 2009/116657 International Publication No. 2011/068138 JP 2016-216433 A International Publication No. WO 2016/159193

However, Patent Documents 1 to 3 have a problem that the number of steps in the manufacturing method is large and the manufacturing method is complicated. In Patent Document 4, an intermediate containing the target compound at a high concentration was not obtained, and the amount of the solvent used in the reaction was large, and there was room for improvement from the viewpoint of production efficiency.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for producing an intermediate which can efficiently produce an intermediate containing a predetermined compound (I) at a high concentration. And

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, added a protic solvent to a solution (X) containing the compound (I) and the compound (II) to precipitate the compound (II). The inventors have found that removing the precipitated compound (II) makes it possible to efficiently produce an intermediate containing the compound (I) at a high concentration, and has completed the present invention.
Thus, according to the present invention, there is provided the following method for producing an intermediate.

[1] (i) The following formula (I):

[In formula (I), A ² and B ² each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent;
Y ² and L ² are each independently a chemical single bond, —O—, —C (＝ O) —, —C (＝ O) —O—, —OC (＝ O) —, —NR ²¹ —C (＝ O) —, —C (＝ O) —NR ²² —, —OC (＝ O) —O—, —NR ²³ —C (＝ O) —O—, —O— Represents C (＝ O) —NR ²⁴ — or —NR ²⁵ —C (＝ O) —NR ²⁶ —, wherein R ²¹ to R ²⁶ are each independently a hydrogen atom or an alkyl having 1 to 6 carbon atoms. Represents a group,
R ³ represents a hydrogen atom, a methyl group or a chlorine atom,
FG ² represents a hydroxyl group, a carboxyl group or an amino group,
d represents an integer of 1 to 20,
e is 1 or 2. A compound (I) represented by the formula:
The following formula (II):

[In the formula (II), A ²¹ , B ²¹ and B ²² each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent. Represents
Y ²¹ , Y ²² , L ²¹ and L ²² are each independently a chemical single bond, —O—, —C (＝ O) —, —C (＝ O) —O—, —OC. ^{(= O) -, - NR} 21 -C (= O) -, - C (= O) -NR 22 -, - O-C (= O) -O -, - NR 23 -C (= O) - O—, —OC (＝ O) —NR ²⁴ — or —NR ²⁵ —C (＝ O) —NR ²⁶ —, wherein R ²¹ to R ²⁶ each independently represent a hydrogen atom or a carbon atom. Represents an alkyl group of Formulas 1 to 6,
R ³¹ and R ³² each independently represent a hydrogen atom, a methyl group or a chlorine atom;
d1 and d2 each independently represent an integer of 1 to 20,
e1 and e2 are each independently 1 or 2. A) obtaining a solution (X) containing the compound (II) represented by the formula:
(Ii) A protic solvent is added to the solution (X) to precipitate the compound (II), and the precipitated compound (II) is removed to obtain an intermediate containing the compound (I). A method for producing an intermediate comprising a step (β),
The method for producing an intermediate, wherein the intermediate obtained in the step (β) contains 86% by mass or more of the compound (I).
In other words, the method for producing an intermediate of the above [1] is a method for producing an intermediate containing the compound (I),
(I) a step (α) of obtaining a solution (X) containing the formula compound (I) and the compound (II);
(Ii) A protic solvent is added to the solution (X) to precipitate the compound (II), and the precipitated compound (II) is removed to contain the compound (I) at 86% by mass or more. Step (β) of obtaining an intermediate.

{[2]} The method for producing the intermediate of [1], wherein the concentration of the compound (I) in the solution (X) is 8.0% by mass or more.

[3] The method for producing the intermediate of [1] or [2], wherein the compound (I) is a compound (I-1) represented by the following formula (I-1).

[In the formula (I-1), R ³ and d represent the same meaning as described above. ]

[4] The method for producing an intermediate according to any one of [1] to [3], wherein the compound (II) is a compound (II-1) represented by the following formula (II-1).

[In the formula (II-1), R ³ and d represent the same meaning as described above. ]

{[5]} The method for producing an intermediate according to any one of the above [1] to [4], wherein the solution (X) further contains an organic solvent, and the organic solvent is a water-immiscible organic solvent.

[6] The method for producing an intermediate according to [5], wherein the water-immiscible organic solvent has a Hildebrand solubility parameter of 14.0 MPa ^1/2 or more and 22.0 MPa ^1/2 or less.

{[7]} The method for producing an intermediate according to any one of the above [1] to [6], wherein the protic solvent is an alcohol.

According to the present invention, there is provided a method for producing an intermediate which can efficiently produce an intermediate containing compound (I) at a high concentration.

Hereinafter, the present invention will be described in detail. In the present invention, “may have a substituent” means “unsubstituted or has a substituent”. Further, when an organic group such as an alkyl group or an aromatic hydrocarbon ring group included in the general formula has a substituent, the carbon number of the organic group having the substituent does not include the carbon number of the substituent. And For example, when the aromatic hydrocarbon ring group having 6 to 20 carbon atoms has a substituent, the carbon number of the aromatic hydrocarbon ring group having 6 to 20 carbon atoms does not include the carbon number of such a substituent. Shall be. In the present invention, the “alkyl group” means a chain (linear or branched) saturated hydrocarbon group, and the “alkyl group” includes a cyclic saturated hydrocarbon group “cyclo” "Alkyl group" is not included. On the other hand, the “total number of π electrons contained in the ring structure in Rf” includes the π electrons of the ring structure contained in the substituent. Further, in the present invention, the “intermediate” includes at least the compound (I), may be the compound (I) alone, or may be a compound other than the compound (I) and the compound (I). And a mixture containing

(Method for producing intermediate)
Hereinafter, the method for producing the intermediate of the present invention will be described in detail.
The process for producing an intermediate according to the present invention comprises a step (α) of obtaining a solution (X) containing a compound (I) and a compound (II), and adding a protic solvent to the solution (X) to obtain a compound (II) ), And removing the precipitated compound (II) to obtain an intermediate containing the compound (I) (β), and further including other steps as necessary.

<Step (α)>
Step (α) is a step of obtaining a solution (X) containing compound (I) and compound (II).

<< Solution (X) >>
Solution (X) contains at least compound (I) and compound (II), and further contains an organic solvent and other components as necessary.

The concentration of the compound (I) in the solution (X) is preferably 8.0% by mass or more, more preferably 8.5% by mass or more, and particularly preferably 9.0% by mass or more. The content is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the concentration of the compound (I) in the solution (X) is equal to or higher than the lower limit and equal to or lower than the upper limit, the compound represented by the formula (II) can be selectively removed.
The “concentration of compound (I) in solution (X)” is calculated by the following equation.
Concentration (% by mass) of compound (I) in solution (X) =
(Mass of compound (I)) / [(mass of compound (I)) + mass of solvent] × 100

The concentration of the compound (II) in the solution (X) is preferably at least 3.0% by mass, more preferably at least 3.5% by mass, particularly preferably at least 4.0% by mass. Preferably, it is preferably at most 10% by mass, more preferably at most 9.0% by mass, particularly preferably at most 8.0% by mass. When the concentration of the compound (II) in the solution (X) is equal to or higher than the lower limit and equal to or lower than the upper limit, the compound represented by the formula (II) can be selectively removed.
The “concentration of the compound (II) in the solution (X)” is calculated by the following equation.
Concentration of compound (II) in solution (X) =
(Mass of compound (II)) / [(mass of compound (II)) + mass of solvent] × 100

The ratio of the concentration of compound (II) in solution (X) to the concentration of compound (I) in solution (X) (concentration of compound (II) in solution (X) / compound (I) in solution (X) ) Is preferably 20% or more, more preferably 25% or more, particularly preferably 30% or more, and preferably 60% or less, and 55% or less. More preferably, it is particularly preferably at most 50%. The ratio of the concentration of the compound (II) in the solution (X) (the concentration of the compound (II) in the solution (X) / the concentration of the compound (I) in the solution (X)) is not less than the lower limit, When the content is equal to or less than the above upper limit, the compound represented by the formula (II) can be highly selectively removed.

[Compound (I)]
The compound (I) represented by the following formula (I) may be composed of only one kind of compound or may be composed of two kinds of compounds, but is composed of only one kind of compound. Is preferred. Here, when the compound (I) is composed of only one compound, the corresponding groups in the compounds (II) is a symmetrical about the A ^21.

[A ² , B ² ]
In the formula (I), A ² and B ² each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent.
Among these, A ² and B ² each independently represent a cycloaliphatic group having 5 to 20 carbon atoms which may have a substituent or 2 carbon atoms which may have a substituent. Up to 20 aromatic groups are preferred.

Specific examples of the cycloaliphatic group include cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group and the like. A cycloalkanediyl group having 5 to 20 carbon atoms; a bicycloalkanediyl group having 5 to 20 carbon atoms such as a decahydronaphthalene-1,5-diyl group and a decahydronaphthalene-2,6-diyl group. Among them, the cycloaliphatic group is preferably an optionally substituted cycloalkanediyl group having 5 to 20 carbon atoms, more preferably a cyclohexanediyl group, and particularly preferably a 1,4-cyclohexylene group (cyclohexane-1,4 -Diyl group), and a trans-1,4-cyclohexylene group is more preferable.

Specific examples of the aromatic group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group and 2,6-naphthylene group Aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, such as 4,4'-biphenylene group; furan-2,5-diyl, thiophen-2,5-diyl, pyridine-2,5-diyl, pyrazine- An aromatic heterocyclic group having 2 to 20 carbon atoms, such as 2,5-diyl; Among them, the aromatic group is preferably an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, more preferably a phenylene group, and particularly preferably a 1,4-phenylene group.

Examples of the substituent for the cyclic aliphatic group and the aromatic group include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; An alkoxy group having 1 to 5 carbon atoms such as a propoxy group; a nitro group; a cyano group; The cyclic aliphatic group, the cyclic aliphatic group having 5 to 20 carbon atoms, the aromatic group, and the aromatic group having 2 to 20 carbon atoms may have at least one substituent selected from the above-described substituents. Good. When a compound has a plurality of substituents, the substituents may be the same or different.

Here, A ² is preferably a cyclic aliphatic group which may have a substituent, and B ² is preferably an aromatic group which may have a substituent.
A ² is a “trans-1,4-cyclohexylene group optionally having a substituent” represented by the formula (a), and B ² is a “trans-1,4-cyclohexylene group” represented by the formula (b). The combination of "1,4-phenylene group which may have a substituent" is more preferable.

In the formulas (a) and (b), R ⁰ is a halogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a cyano group; a nitro group; An alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom such as an ethyl group is substituted by a halogen atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group; -OCF ₃ ; It represents a or -O-C (= O) -R a; (= O) -O-R a. Here, ^Ra is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. A cycloalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent.

As R ⁰ , a halogen atom such as a fluorine atom and a chlorine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a cyano group; a nitro group; An alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom such as a pentafluoroethyl group or a pentafluoroethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; . In the case R ⁰ is plural, a plurality of R ⁰ is may be the same or different from each other. Further, p1 represents an integer of 0 to 4, and is preferably 0.

^Examples of the alkyl group having 1 to 20 carbon atoms of the alkyl group having 1 to 20 carbon atoms which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl Group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like. The alkyl group having 1 to 20 carbon atoms which may have a substituent preferably has 1 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms.

Of R ^a, the alkenyl group having 2 to 20 carbon atoms alkenyl group substituents to 2 carbon atoms which may have a 20, a vinyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl Group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, and icosenyl group. Can be
The carbon number of the alkenyl group having 2 to 20 carbon atoms which may have a substituent is preferably 2 to 12.

Examples of the substituent for the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms for ^Ra include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; N, N-dialkylamino group; an alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group and butoxy group; an alkoxy group having 1 to 12 carbon atoms such as methoxymethoxy group and methoxyethoxy group Substituted alkoxy group having 1 to 12 carbon atoms; nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; triazolyl group, pyrrolyl group, furanyl group, thiophenyl group, benzothiazole group An aromatic heterocyclic group having 2 to 20 carbon atoms such as a 2-ylthio group; a C3 to C8 aromatic group such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group; A cycloalkyl group having 3 to 8 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group, and a dioxanyl group; a phenoxy group, an aryloxy group having 6 to 14 carbon atoms such as a naphthoxy group; trifluoromethyl group, pentafluoroethyl group, such as -CH ₂ CF _3, carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom A benzofuryl group; a benzopyranyl group; a benzodioxolyl group; and a benzodioxanyl group. Among these, as the substituent of the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of ^Ra , halogen atoms such as fluorine atom and chlorine atom; cyano group; methoxy group, ethoxy group, An alkoxy group having 1 to 20 carbon atoms such as a propoxy group or a butoxy group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; An aromatic heterocyclic group having from 20 to 20; a cycloalkyl group having from 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group; at least one group such as a trifluoromethyl group, a pentafluoroethyl group and -CH ₂ CF ₃ ; A fluoroalkyl group having 1 to 12 carbon atoms in which hydrogen atoms are substituted by fluorine atoms is preferred.
In addition, the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of ^Ra may have a plurality of substituents selected from the above-described substituents. When the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of ^Ra have a plurality of substituents, the plurality of substituents may be the same or different.

^Examples of the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. And the like. Among these, a cyclopentyl group and a cyclohexyl group are preferred.
Examples of the substituent of the cycloalkyl group having 3 to 12 carbon atoms of ^Ra include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; C1-C6 alkyl groups such as methyl group, ethyl group and propyl group; C1-C6 alkoxy groups such as methoxy group, ethoxy group and isopropoxy group; nitro group; and phenyl group and naphthyl group And an aromatic hydrocarbon ring group having 6 to 20 carbon atoms. Among them, examples of the substituent of the cycloalkyl group having 3 to 12 carbon atoms of ^Ra include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group. Groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro groups; and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group.
The cycloalkyl group having 3 to 12 carbon atoms of ^Ra may have a plurality of substituents. When the cycloalkyl group having 3 to 12 carbon atoms of ^Ra has a plurality of substituents, the plurality of substituents may be the same or different.

Examples of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms of the optionally substituted aromatic hydrocarbon ring group having 5 to 12 carbon atoms for ^Ra include a phenyl group, a 1-naphthyl group, -Naphthyl group and the like. Among these, a phenyl group is preferred.
Examples of the substituent of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; N, N-dialkylamino group; C1-C20 alkoxy group such as methoxy group, ethoxy group, isopropoxy group, butoxy group; C1-C12 alkoxy group such as methoxymethoxy group, methoxyethoxy group A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group, a thiophenyl group or the like; An aromatic heterocyclic group having 2 to 20 carbon atoms; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group; a cyclopentyloxy group; A cycloalkyloxy group having 3 to 8 carbon atoms such as a rohexyloxy group; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group, a dioxanyl group; a phenoxy group, a naphthoxy group and the like An aryloxy group having 6 to 14 carbon atoms; a fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, such as a trifluoromethyl group, a pentafluoroethyl group, and -CH ₂ CF ₃ ; -OCF _3; benzofuryl; benzopyranyl group; benzodioxolyl group; benzodioxanyl group and the like. Among them, a substituent of an aromatic hydrocarbon ring group having 5 to 12 carbon atoms includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon atom having 1 carbon atom such as a methoxy group, an ethoxy group, an isopropoxy group and a butoxy group. Nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; aromatic group having 2 to 20 carbon atoms such as triazolyl group, pyrrolyl group, furanyl group and thiophenyl group A heterocyclic group; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; at least one hydrogen atom such as a trifluoromethyl group, a pentafluoroethyl group, and —CH ₂ CF ₃ Is preferably a fluoroalkyl group having 1 to 12 carbon atoms substituted with a fluorine atom; and at least one substituent selected from —OCF ₃ is preferable.
The aromatic hydrocarbon ring group having 5 to 12 carbon atoms may have a plurality of substituents. When the aromatic hydrocarbon ring group having 5 to 12 carbon atoms has a plurality of substituents, the substituents may be the same or different.

[Y ² , L ² ]
In the formula (I), Y ² and L ² are each independently a chemical single bond, —O—, —C (＝ O) —, —C (＝ O) —O—, —OC ^{(= O) -, - NR} 21 -C (= O) -, - C (= O) -NR 22 -, - O-C (= O) -O -, - NR 23 -C (= O) - Represents —O—, —OC (＝ O) —NR ²⁴ —, or —NR ²⁵ —C (＝ O) —NR ²⁶ —. Here, R ²¹ to R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Among these, Y ² is preferably -O-, and L ² is -C (= O) -O- or -OC (=, from the viewpoints of ease of synthesis and expression of desired optical properties. O)-.

[R ³ ]
In the formula (I), R ³ represents a hydrogen atom, a methyl group or a chlorine atom.
Among these, R ³ is preferably a hydrogen atom from the viewpoint of ease of synthesis and polymerization rate.

[FG ² ]
In the formula (I), FG ² represents a hydroxyl group, a carboxyl group or an amino group.
Among these, FG ² is synthesized from the standpoint of ease and desired optical properties expression is preferably a carboxyl group.

[D]
In the formula (I), d represents an integer of 1 to 20.
Among these, d is preferably an integer of 2 to 12, more preferably an integer of 4 to 12, and more preferably an integer of 4 to 10, from the viewpoints of ease of synthesis and expression of desired optical properties. Is particularly preferred.

[E]
In the formula (I), e is 1 or 2.
Among these, e is preferably 1.
Incidentally, in the case e is 2, the two B ² may be the same or different and also, the two L ² may be different even in the same.

Specific examples of the compound (I) include, for example, a compound (I-1) represented by the following formula (I-1).

In Formula (I-1), R ³ and d have the same meanings as described above, and preferred examples thereof are also the same as described above.

[Preparation of Compound (I)]
The preparation of compound (I) will be described separately for the case where e is 1 and for the case where e is 2.
When e is 1, compound (I) (compound (Ia) represented by the following formula (Ia)) includes, for example, compound (A-0) represented by the following formula (A-0) It can be obtained by reacting a compound (B-0) represented by the following formula (B-0), and more specifically, a compound (A-1) represented by the following formula (A-1) , And trans-1,4-cyclohexanedicarboxylic acid dichloride are subjected to an esterification reaction in a reaction solvent containing a base such as triethylamine, followed by hydrolysis. Further, a compound (A-1) represented by the following formula (A-1) and trans-1,4-cyclohexanedicarboxylic acid are reacted in a reaction solvent in the presence of a dehydration condensing agent. Can also.

In the formulas (A-0), (B-0) and (Ia), A ² , B ² , Y ² , L ² , R ³ , FG ² and d are each independently the same as defined above. The meaning is shown, and preferable examples are the same as described above.
In the formula (A-0), Z represents a hydroxyl group, a carboxyl group, or an amino group.
Among them, Z is preferably a hydroxyl group from the viewpoint of ease of synthesis.
Formula (B-0) in, FQ is the ^{L 2} formed by reaction with Z, and is a functional group which can be a ^{FG 2, -C (= O)} Cl, ClC (= O) -, - COOH , HOOC-, -NH ₂ , or H ₂ N-.
Among these, FQ is preferably —C (＝ O) Cl or ClC (＝ O) —, —COOH, or HOOC— from the viewpoint of ease of synthesis.

In Formula (A-1), R ³ and d have the same meanings as described above, and preferred examples thereof are also the same as described above.

When e is 2, the compound (I) (compound (Ib) represented by the following formula (Ib)) is, for example, a compound (A-2) represented by the following formula (A-2) It can be obtained by reacting with a compound (B-0) represented by the following formula (B-0).

In the formulas (A-2), (B-0) and (Ib), A ² , B ² , Y ² , L ² , R ³ , FG ² and d are each independently the same as defined above. Meaning is shown, and preferable examples are the same as described above.
In the formula (A-2), Z represents a hydroxyl group, a carboxyl group, or an amino group.
Among them, Z is preferably a hydroxyl group from the viewpoint of easy synthesis.
In the formula (B-0), FQ has the same meaning as described above, and preferred examples thereof are also the same as described above.
Two B ² in the formula (Ib) may be the same or different, and two L ² in the formula (Ib) may be the same or different.

-Reaction solvent-
Examples of the reaction solvent include ethers such as cyclopentyl methyl ether (CPME), tetrahydrofuran, methyl-t-butyl ether, diethyl ether, dibutyl ether, diisopropyl ether, and 1,2-dimethoxyethane; ketones such as 2-butanone and methyl isobutyl ketone Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; esters such as ethyl acetate and propyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; alicycles such as cyclopentane and cyclohexane Formula hydrocarbons; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; nitriles such as acetonitrile and propionitrile; and mixed solvents thereof. No. One of these may be used alone, or two or more of them may be used in any ratio.

The amount of the reaction solvent used in the above reaction is preferably 10 mL or more, more preferably 20 mL or more, and more preferably 40 mL or more, based on 10 g of the compound (A-0) or the compound (A-2). It is particularly preferable, and the volume is preferably 500 mL or less, more preferably 250 mL or less, and particularly preferably 100 mL or less. When the amount of the reaction solvent is at least the lower limit and at most the upper limit, the selectivity of the compound represented by the formula (I) can be improved.

[Compound (II)]
Compound represented by the following formula (II) (II) is, around the A ^21, even symmetrical, but may be asymmetrical in terms of ease of synthesis, the left and right around the A ²¹ Symmetric (ie, B ²¹ and B ²² are the same, Y ²¹ and Y ²² are the same, L ²¹ and L ²² are the same, R ³¹ and R ³² are the same, Preferably, d1 and d2 are the same, and e1 and e2 are the same.

[A ²¹ , B ²¹ , B ²² ]
In the formula (II), A ²¹ , B ²¹ and B ²² each independently represent the same meaning as A ² and B ^2, and preferred examples thereof are also the same as A ² and B ² .

[Y ²¹ , Y ²² ]
In Formula (II), Y ²¹ and Y ²² each independently represent the same meaning as Y ^2, and preferred examples thereof are also the same as Y ² .

[L ²¹ , L ²² ]
In Formula (II), L ²¹ and L ²² each independently represent the same meaning as L ^2, and preferred examples thereof are also the same as L ² .

[R ³¹ , R ³² ]
In Formula (II), R ³¹ and R ³² each independently represent the same meaning as R ^3, and preferred examples thereof are also the same as R ³ .

[D1, d2]
In formula (II), d1 and d2 each independently represent the same meaning as d, and preferred examples thereof are also the same as d.

[E1, e2]
In Formula (II), e1 and e2 each independently represent the same meaning as e, and preferred examples thereof are also the same as e.

Specific examples of the compound (II) include, for example, a compound (II-1) represented by the following formula (II-1).

[In the formula (II-1), R ³ and d represent the same meaning as described above, and preferred examples thereof are also the same as described above.

[Organic solvent]
Examples of the organic solvent include cyclopentyl methyl ether (CPME), tetrahydrofuran, methyl-t-butyl ether, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,4-dioxane, and 1,3-dioxolan. Ketones such as 2-butanone and methyl isobutyl ketone; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; esters such as ethyl acetate and propyl acetate; aromatics such as benzene, toluene and xylene Hydrocarbons; alicyclic hydrocarbons such as cyclopentane and cyclohexane; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; acetonitrile, propionitrile Nitriles such as; Beauty a mixed solvent thereof and the like. One of these may be used alone, or two or more of them may be used in any ratio.
Among these, a water-immiscible organic solvent is preferable. Here, the “water-immiscible organic solvent” is an organic solvent having a property of being separated into two phases without being compatible even when mixed with water. The solubility of the water-immiscible organic solvent in water is 40 g (organic solvent) / 100 mL (water) or less, preferably 30 g (organic solvent) / 100 mL (water) or less, more preferably 15 g (organic solvent) / 100 mL (water). Water).
In the case of using a mixed solvent of two or more, when adding a water-miscible solvent, when satisfying the solubility in water with respect to the sum of the water-miscible solvent and the water-immiscible organic solvent, The mixed solvent is a “water-immiscible organic solvent”.

Specific examples of the water-immiscible organic solvent include cyclopentyl methyl ether (CPME), 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, methyl-t-butyl ether, diethyl ether, dibutyl ether, Ethers such as diisopropyl ether and 1,2-dimethoxyethane; ketones such as 2-butanone; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; esters such as ethyl acetate and propyl acetate; Hydrocarbons such as cyclopentane and cyclohexane; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Acetonitrile, pro Nitriles such as Onitoriru; and mixed solvents thereof.

Solubility parameter of the water-immiscible organic solvent in Hildebrand is preferably at 14.0 MPa ^1/2 or more, more preferably 14.3MPa ^1/2 or more, is 14.5 MPa ^1/2 or more it is particularly preferred, also, is preferably 22.0MPa ^1/2 or less, more preferably 20.0 MPa ^1/2 or less, and particularly preferably 19.5MPa ^1/2 or less. When the solubility parameter of Hildebrand of the water-immiscible organic solvent is equal to or higher than the lower limit and equal to or lower than the upper limit, the compound represented by the formula (I) can be obtained with high selectivity.

Hildebrand solubility parameter is a value (δ) introduced by Hildebrand that provides a numerical prediction of the degree of interaction between materials, as defined by regular solution theory.

As the organic solvent having a Hildebrand solubility parameter of 14.0 MPa ^1/2 or more and 22.0 MPa ^1/2 or less, cyclopentyl methyl ether (CPME) (Hildebrand solubility parameter (δ): 17.2 MPa ^1/2 ) , Tetrahydrofuran ((δ): 18.6 MPa ^1/2 ), methyl-t-butyl ether ((δ): 15.6 MPa ^1/2 ), diethyl ether ((δ): 15.1 MPa ^1/2 ), dibutyl ether ((Δ): 14.9 MPa ^1/2 ), diisopropyl ether ((δ): 14.1 MPa ^1/2 ), 1,2-dimethoxyethane ((δ): 19.2 MPa ^1/2 ), 2-butanone ((δ): 19.0MPa ^1/2) ethers such as: chloroform ((δ): 19.0MPa ^1/2) halogen, such as Hydrocarbons; ethyl acetate ((δ): 18.6MPa ^1/2) esters such as: toluene ((δ): 18.2MPa ^1/2) aromatic hydrocarbons such as; cyclohexane (([delta]): Alicyclic hydrocarbons such as 16.7 MPa ^1/2 ); and mixed solvents thereof. When a mixed solvent is used, its solubility parameter can be calculated by the addition rule.

The content of the organic solvent in the solution (X) is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, and 95% by mass. Or less, more preferably 93% by mass or less, particularly preferably 90% by mass or less. When the content of the organic solvent in the solution (X) is equal to or more than the lower limit and equal to or less than the upper limit, the compound represented by the formula (II) can be removed with a high selectivity.

[Other ingredients]
Other components include, for example, bases such as triethylamine (Et ₃ N), diisopropylethylamine, pyridine, N, N-dimethyl-4-dimethylaminopyridine; dicyclohexylcarbodiimide, N, N-diisopropylcarbodiimide, 1- (3- Dehydration condensing agents such as dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride; and polymerization inhibitors such as 2,6-di-tert-butyl-p-cresol and paramethoxyphenol.

<Step (β)>
In the step (β), a step of adding a protic solvent to the solution (X) to precipitate the compound (II) and removing the precipitated compound (II) to obtain an intermediate containing the compound (I) It is.

<< Protic solvent >>
When the protic solvent is added to the solution (X) containing the compound (I) and the compound (II), the compound (I) is easily soluble, and the compound (II) is hardly soluble in the solvent (that is, the solution). (A solvent that is a good solvent for the compound (I) in (X) and a poor solvent for the compound (II) in the solution (X)).
Note that even if the solvent is a good solvent for the compound (I) alone, it is not necessarily a good solvent for the compound (I) in the solution (X), and the solvent is poor for the compound (II) alone. Even a solvent is not always a poor solvent for the compound (II) in the solution (X).
Examples of the protic solvent include alcohols such as ethanol, methanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol and cyclopentanol; glycols such as glycerin, ethylene glycol and propylene glycol; formic acid and acetic acid. Carboxylic acids; hydroxy acids such as glycolic acid, 2-hydroxymalonic acid and glyceric acid; and the like. One of these may be used alone, or two or more of them may be used in any ratio.
Among these, alcohol is preferable and methanol is more preferable in that the compound (II) can be efficiently precipitated.

The amount of the protic solvent to be used is preferably at least 0.1 times by mass, more preferably at least 0.2 times by mass, based on the compound (A-0) or the compound (A-2). It is particularly preferably at least 0.3 times by mass, more preferably at most 5 times by mass, even more preferably at most 3 times by mass, particularly preferably at most 2 times by mass. If the amount of the protic solvent used is greater than or equal to the lower limit and less than or equal to the upper limit, the compound represented by the formula (II) is removed with a high selectivity to remove the compound represented by the formula (I) Can be improved in purity.

<< Removal >>
Examples of the removal method for removing the precipitated compound (II) include filtration, centrifugation, and the like, and more specifically, suction filtration, pressure filtration, and the like as filtration. Among these, centrifugal separation and pressure filtration are preferred from the viewpoint of removal efficiency.

<<< intermediate >>>
The intermediate contains at least the compound (I), may be the compound (I) alone, or may contain the compound (I) and components other than the compound (I) (eg, the compound (II)). May be used as a mixture.
The content of the compound (I) in the intermediate must be 86% by mass or more, is preferably 88% by mass or more, more preferably 90% by mass or more, and is 92% by mass or more. Is particularly preferred. When the content of the compound (I) in the intermediate is not less than the above lower limit, a compound capable of obtaining an optical film capable of performing uniform polarization conversion in a wide wavelength range can be efficiently produced.

In the step (β), in order to obtain the above intermediate, after removing the compound (II), the mixture is cooled, an intermediate containing the compound (I) is precipitated, collected by filtration, and vacuum Drying and the like are performed.
The cooling temperature is preferably 20 ° C. or lower, more preferably 10 ° C. or lower, particularly preferably 5 ° C. or lower, and most preferably about 0 ° C. When the cooling temperature is equal to or lower than the upper limit, the intermediate can be efficiently precipitated.

<Other steps>
Other steps include, for example, a step of preparing the above-mentioned compound (I) such as drying.

<Polymerizable compound>
The polymerizable compound produced from the intermediate produced by the method for producing an intermediate of the present invention will be described.
The polymerizable compound is, for example, a compound represented by the following formula (III) (hereinafter, sometimes referred to as “polymerizable compound (III)”), and prepares a polymer, an optical film, and an optically anisotropic material described later. Can be used advantageously.

In addition, as described later, by using the compound represented by the formula (III), a polymerizable composition having excellent coatability is obtained, and excellent in-plane uniformity of film thickness and in-plane uniformity of optical characteristics are obtained. Can be advantageously produced.

<< Ar >>
Here, in the formula (III), Ar is represented by the following formula (IV-1) or (IV-2), and preferably by the following formula (IV-3) or (IV-4).

(In the above formulas (IV-1) and (IV-2), * represents binding to Y ³ or Y ^4. )

(In the above formulas (IV-3) and (IV-4), * represents binding to Y ³ or Y ^4. )

[R]
In the formulas (IV-1) to (IV-4), R represents an organic group having 1 to 60 carbon atoms which may have a substituent, and is represented by Rf-K-Ga (Ga is bonded to N). It is preferable that it is represented by Gb.

The organic group having 1 to 60 carbon atoms of the organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, and examples thereof include (i) an alkyl group having 1 to 60 carbon atoms. (Ii) an alkenyl group having 2 to 60 carbon atoms; (iii) an alkynyl group having 2 to 60 carbon atoms;

[(I) an alkyl group having 1 to 60 carbon atoms]
Examples of the alkyl group having 1 to 60 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. , N-heptyl, n-undecyl, n-dodecyl, 1-methylpentyl, 1-ethylpentyl and the like. Among these, an alkyl group having 1 to 12 carbon atoms is preferable, an n-butyl group, an n-hexyl group, and an n-octyl group are more preferable, and an n-hexyl group is particularly preferable.

[(Ii) Alkenyl group having 2 to 60 carbon atoms]
Examples of the alkenyl group having 2 to 60 carbon atoms include a vinyl group, an allyl group, an isopropenyl group and a butynyl group, and an alkenyl group having 2 to 12 carbon atoms is preferable.

[(Iii) Alkynyl group having 2 to 60 carbon atoms]
Examples of the alkynyl group having 2 to 60 carbon atoms include a propynyl group, a propargyl group and a butynyl group, and an alkynyl group having 2 to 12 carbon atoms is preferable.

Examples of the substituent of the organic group having 1 to 60 carbon atoms for R include a cyano group; a nitro group; a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; Alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group; methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group C1-C6 alkoxy group substituted by C1-C6 alkoxy group; C3-C8 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; methyl Substituted amino groups such as an amino group, an ethylamino group, an acetylamino group, and a dimethylamino group; and the like.

[Rf]
Rf represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Among these, an aromatic hydrocarbon ring group having 6 to 30 carbon atoms is more preferable.

-Aromatic hydrocarbon ring-
Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring. Among these, a benzene ring, a naphthalene ring, an anthracene ring and a fluorene ring are preferred, and a benzene ring and a naphthalene ring are more preferred.

-Aromatic heterocycle-
Examples of the aromatic heterocycle include a 1H-isoindole-1,3 (2H) -dione ring, a 1-benzofuran ring, a 2-benzofuran ring, an acridine ring, an isoquinoline ring, an imidazole ring, an indole ring, and an oxadiazole ring. , Oxazole ring, oxazolopyrazine ring, oxazolopyridin ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring, thia Zolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrrole ring, Phenanthridine ring, phthalazine Ring, furan ring, benzo [b] thiophene ring, benzo [c] thiophene ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, benzooxadiazole ring, benzoxazole ring, benzothiadiazole ring, benzothiazole ring Benzothiophene ring, benzotriazine ring, benzotriazole ring, benzopyrazole ring, benzopyranone ring and the like.
Among them, examples of the aromatic heterocyclic ring include monocyclic aromatic heterocyclic rings such as furan ring, pyran ring, thiophene ring, oxazole ring, oxadiazole ring, thiazole ring, and thiadiazole ring; and benzothiazole ring and benzoxazole Ring, quinoline ring, 1-benzofuran ring, 2-benzofuran ring, benzo [b] thiophene ring, 1H-isoindole-1,3 (2H) -dione ring, benzo [c] thiophene ring, thiazolopyridine ring, thia A condensed aromatic heterocyclic ring such as a zolopyrazine ring, a benzoisoxazole ring, a benzooxadiazole ring, or a benzothiadiazole ring is preferable.

The aromatic hydrocarbon ring and the aromatic hetero ring of Rf may have a substituent. Examples of such a substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; An alkenyl group having 1 to 6 carbon atoms, wherein at least one hydrogen atom such as a trifluoromethyl group and a pentafluoroethyl group is substituted with halogen; an N, N-dialkyl having 2 to 12 carbon atoms such as a dimethylamino group amino group; methoxy group, an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as an isopropoxy group, a nitro group, a phenyl group, an aromatic having 6 to 20 carbon atoms such as phenyl or naphthyl hydrocarbon ring group; -OCF _3; —C (＝ O) —R ^x ; —C (＝ O) —O—R ^x ; —OC (＝ O) —R ^x ; and —SO ₂ R ^b . Here, R ^x represents “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent” or “(ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent. ", (Iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent", or "(iv) an aromatic carbon atom having 5 to 18 carbon atoms which may have a substituent". A hydrogen ring group ". R ^b is an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; or an alkyl group having 1 to 6 carbon atoms such as a phenyl group, a 4-methylphenyl group or a 4-methoxyphenyl group; Represents an aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have an alkoxy group having 1 to 6 carbon atoms as a substituent.
Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable as the substituent of the aromatic hydrocarbon ring and the aromatic hetero ring of Rf.
Note that Rf may have a plurality of substituents selected from the above-described substituents. When Rf has a plurality of substituents, the substituents may be the same or different.

--- R ^x ---
--- (i) an alkyl group having 1 to 20 carbon atoms which may have a substituent ---
^Examples of the “alkyl group having 1 to 20 carbon atoms” of “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent” for R ^x include a methyl group, an ethyl group and an n-propyl group , Isopropyl, n-butyl, isobutyl, 1-methylpentyl, 1-ethylpentyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl , Isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n -Hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like.
The “(i) alkyl group having 1 to 20 carbon atoms which may have a substituent” preferably has 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms.

--- (ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent ---
^Examples of the “alkenyl group having 2 to 20 carbon atoms” of “(ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent” for R ^x include a vinyl group, a propenyl group, an isopropenyl group, Butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl And an icosenyl group.
The “(ii) alkenyl group having 2 to 20 carbon atoms which may have a substituent” preferably has 2 to 12 carbon atoms.

R ^{x represents} “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms”, and “(ii) an alkyl group having a substituent. Examples of the substituent of the "alkenyl group having 2 to 20 carbon atoms" of the "alkenyl group having 2 to 20 carbon atoms" include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; An alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group or a butoxy group; an alkoxy group having 1 to 12 carbon atoms such as a methoxymethoxy group or a methoxyethoxy group A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group, a thiophenyl group, a benzene group An aromatic heterocyclic group having 2 to 20 carbon atoms such as a zothiazol-2-ylthio group; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group; a cyclopentyloxy group and a cyclohexyloxy group A cycloalkyloxy group having 3 to 8 carbon atoms; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group, a dioxanyl group; and a 6 to 14 carbon atoms such as a phenoxy group and a naphthoxy group An aryloxy group; a trifluoromethyl group, a pentafluoroethyl group, a fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom, such as —CH ₂ CF ₃ ; a benzofuryl group; benzopyranyl Benzodioxolyl group; benzodioxanyl group; and the like. . Among them, R ^x has “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms” and “(ii) a substituent. The substituent of the "alkenyl group having 2 to 20 carbon atoms" of the "alkenyl group having 2 to 20 carbon atoms which may be substituted" includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a methoxy group, an ethoxy group, C1-C20 alkoxy groups such as isopropoxy group and butoxy group; nitro group; C6-C20 aromatic hydrocarbon ring groups such as phenyl group and naphthyl group; furanyl group, thiophenyl group, benzothiazole-2 An aromatic heterocyclic group having 2 to 20 carbon atoms, such as -ylthio group; a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group; trifluoromethyl group, pentafluoro group And a fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, such as a loethyl group or -CH ₂ CF ₃ .
In addition, ^Rx has “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms” and “(ii) a substituent. The “alkenyl group having 2 to 20 carbon atoms” of the “alkenyl group having 2 to 20 carbon atoms” which may have a plurality of substituents selected from the above-mentioned substituents. R ^{x represents} “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms”, and “(ii) an alkyl group having a substituent. When the “alkenyl group having 2 to 20 carbon atoms” of the “alkenyl group having a good carbon number of 2 to 20” has a plurality of substituents, the plurality of substituents may be the same or different.

--- (iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent ---
^Examples of the “cycloalkyl group having 3 to 12 carbon atoms” of “(iii) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” for R ^x include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl Group, cyclohexyl group, cyclooctyl group and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferred.
The substituent of the “cycloalkyl group having 3 to 12 carbon atoms” of the “(iii) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” for R ^x is a fluorine atom, a chlorine atom A halogen atom such as a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a methoxy group and an ethoxy group A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; and the like. Among them, the substituent of “(iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” of “(cycloalkyl group having 3 to 12 carbon atoms)” of R ^x is fluorine. Halogen atoms such as atoms and chlorine atoms; cyano groups; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group. A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group;
The “(3) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” of the “cycloalkyl group having 3 to 12 carbon atoms” of R ^x has a plurality of substituents. May be. When the “cycloalkyl group having 3 to 12 carbon atoms” of the “(iii) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” for R ^x has a plurality of substituents, The substituents may be the same or different.

--- (iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent
As the "(5) aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent (s)" for R ^x , the "aromatic hydrocarbon ring group having 5 to 18 carbon atoms" is a phenyl group , 1-naphthyl group, 2-naphthyl group and the like. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group, a 1-naphthyl group and a 2-naphthyl group are more preferable.
Examples of the substituent of “(iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent” for R ^x include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; An N, N-dialkylamino group having 2 to 12 carbon atoms such as a group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group and a butoxy group; a methoxymethoxy group, a methoxyethoxy group and the like; An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, An aromatic heterocyclic group having 2 to 20 carbon atoms such as a furanyl group and a thiophenyl group; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group; A cycloalkyloxy group having 3 to 8 carbon atoms such as an ethyloxy group and a cyclohexyloxy group; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group and a dioxanyl group; a phenoxy group and a naphthoxy group An aryloxy group having 6 to 14 carbon atoms, such as a trifluoromethyl group, a pentafluoroethyl group, a fluoro group having 1 to 12 carbon atoms, in which at least one hydrogen atom is substituted by a fluorine atom, such as —CH ₂ CF _3, etc. An alkyl group; —OCF ₃ ; a benzofuryl group; a benzopyranyl group; a benzodioxolyl group; a benzodioxanyl group; Among these, as the substituent of “(iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent” for R ^x , a halogen atom such as a fluorine atom and a chlorine atom; A C1-C20 alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group or a butoxy group; a nitro group; a C6-C20 aromatic hydrocarbon ring group such as a phenyl group or a naphthyl group; a triazolyl group An aromatic heterocyclic group having 2 to 20 carbon atoms, such as, a pyrrolyl group, a furanyl group, a thiophenyl group; a cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group; pentafluoroethyl group, such as _-CH 2 CF _3, has been having 1 to 12 carbon atoms fluoroalkyl group substituted with at least one hydrogen atom is a fluorine atom; a; -OCF ₃ At least one substituent barrel preferred.
The “(iv) aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent” of R ^x includes a plurality of “aromatic hydrocarbon ring groups having 5 to 18 carbon atoms”. May have a substituent. ^Rx is represented by “(iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent”, wherein “an aromatic hydrocarbon ring group having 5 to 18 carbon atoms” has a plurality of substituents; In the case of having, the substituents may be the same or different.

Here, the “carbon number” of the cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of Rf is at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring not containing a carbon atom of a substituent. Means the carbon number of the organic group itself having
When Rf has a plurality of aromatic hydrocarbon rings and / or a plurality of aromatic heterocycles, each may be the same or different.

Rf is preferably a “cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms”.

Preferred specific examples of the “cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms” of の Rf are shown below. However, it is not limited to the following. In the following formula, "-" represents a bond extending from an arbitrary position of the ring to K.

1) Specific examples of the optionally substituted hydrocarbon ring group having at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms include the following formulas (1-1) to (1-21) And a hydrocarbon ring group having 6 to 18 carbon atoms represented by formulas (1-8) to (1-21) is preferable. The groups represented by the following formulas (1-1) to (1-21) may have a substituent.

2) an optionally substituted heterocyclic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms; Specific examples include structures represented by the following formulas (2-1) to (2-51) and the like. Sixteen heterocyclic groups are preferred. The groups represented by the following formulas (2-1) to (2-51) may have a substituent.

[In each formula, A represents -CH _2- , -NR ^c- , an oxygen atom, a sulfur atom, -SO- or -SO _2- ,
B and D each independently represent -NR ^c- , an oxygen atom, a sulfur atom, -SO- or -SO _2- ,
E represents -NR ^c- , an oxygen atom or a sulfur atom.
Here, R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group. (However, in each formula, an oxygen atom, a sulfur atom, —SO—, and —SO ₂ — are not adjacent to each other.)]

Among the above, Rf is determined by the above formulas (1-8), (1-11), (1-12), (1-13), (1-14), (1-15), Formula (1-20), Formula (2-9) to Formula (2-11), Formula (2-24) to Formula (2-33), Formula (2-35) to Formula (2-43), Formula It is preferably any of groups represented by (2-47) and formulas (2-49) to (2-51).

The total number of π electrons contained in the ring structure in Rf is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and particularly preferably 10 or more. , 20 or less, more preferably 18 or less.

Further, it is preferable that Rf is any of the following (i-1) to (i-6). The groups represented by the following formulas (i-1) to (i-6) may have a substituent.

(In the formula (i-4), J represents —CH ₂ —, —NR ^d —, an oxygen atom, a sulfur atom, —SO— or —SO ₂ —, and R ^d represents a hydrogen atom or a carbon number of 1 to 6; Represents an alkyl group.)

The “cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms” of Rf may have one or more substituents. . When it has a plurality of substituents, the plurality of substituents may be the same or different from each other.

Examples of the substituent of “a cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms” of Rf include, for example, a fluorine atom, a chlorine atom and the like. A halogen atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group and an allyl group; a trifluoromethyl group and a pentafluoroethyl group A C1 to C6 alkyl group in which at least one hydrogen atom is substituted with halogen; a C2 to C12 N, N-dialkylamino group such as a dimethylamino group; a methoxy group, an ethoxy group, an isopropoxy group, etc. A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; —OCF ₃ ; —C (＝ O) —R ^x ; = O) -OR ^x ; -OC (= O) -R ^x ; -SO ₂ R ^b ; Here, ^Rx and ^Rb represent the same meaning as described above, and preferred examples thereof are also the same as described above. And when it has a plurality of substituents, the plurality of substituents may be the same or different.
Among these, at least one substituent selected from a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms is preferable.

[K]
K is a chemical single bond, —O—, —S—, —C (＝ O) —, —O—CRbRc—, —CRbRc—O—, —O—CH ₂ —CH ₂ —, —CH ₂ -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -C (= O) -S-, -SC (= O)-, -NR ¹⁴ —C (＝ O) —, —C (＝ O) —NR ¹⁴ —, —CH ＝ CH—C (＝ O) —O—, —OC (＝ O) —CH ＝ CH—, —CH ₂ —CH ₂ —C (＝ O) —O—, —OC (＝ O) —CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —OC (＝ O) —, —C (＝ O ) -O-CH ₂ -CH _2- , -C (= O) -O-CRbRc-, -CRcRb-OC (= O)-, -OC (= O) -CRbRc-, -CRcRb- C (= O) -O -, - O-C (= O) -NR 14 -, - NR ¹⁴ -C (= O) -O-, -OC (= O) -CH ₂ -S-, -S-CH ₂ -C (= O) -O-, or -OC (= O ) Represents -O-. Here, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb each independently represent a hydrogen atom or a substituent having 6 to 12 carbon atoms. It represents a good aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms.
The K, among these, chemical single bond, -O -, - O-CRbRc -, - CRcRb-O -, - O-CH 2 -CH 2 -, - CH 2 -CH 2 -O-, _{-C (= O) -O -,} - O-C (= O) -, - CH 2 -CH 2 -C (= O) -O -, - O-C (= O) -CH 2 -CH 2 -, -CH ₂ -CH ₂ -OC (= O)-, -C (= O) -O-CH ₂ -CH _2- , -C (= O) -O-CRbRc-, -CRcRb-O -C (= O) -, - O-C (= O) -CRbRc -, - CRcRb-C (= O) -O -, - O-C (= O) -NR 14 -, - NR 14 -C (= O) -O-, -OC (= O) -CH ₂ -S-, -S-CH ₂ -C (= O) -O-, -OC (= O) -O-, Is preferable, and a chemical single bond, -O-, -OC _{_{bRc -, - CRcRb-O -}} , - O-CH 2 -CH 2 -, - CH 2 -CH 2 -O -, - C (= O) -O -, - O-C (= O) -, - CH ₂ —CH ₂ —C (＝ O) —O—, —OC (＝ O) —CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —OC (＝ O) —, —C ( = O) -O-CH ₂ -CH _2- , -C (= O) -O-CRbRc-, -CRcRb-OC (= O)-, -OC (= O) -CRbRc-,- ^{CRcRb-C (= O) -O} -, - O-C (= O) -NR 14 -, - NR 14 -C (= O) -O -, - S-CH 2 -C (= O) -O —, —OC (＝ O) —CH ₂ —S— are more preferable, and a chemical single bond, —O—, —O—CRbRc—, —CRcRb—O—, —O—CH ₂ —CH ₂ _-, - CH ₂ -CH ₂ -O- _{-C (= O) -O -,} - O-C (= O) -, - CH 2 -CH 2 -C (= O) -O -, - O-C (= O) -CH 2 -CH 2 -, -C (= O) -O-CRbRc-, -CRcRb-OC (= O)-, -OC (= O) -CRbRc-, -CRcRb-C (= O) -O-, —OC (＝ O) —NR ¹⁴ —, —NR ¹⁴ —C (＝ O) —O—, —S—CH ₂ —C (＝ O) —O—, —OC (） O) — CH ₂ —S— is particularly preferred.
Here, R ¹⁴ represents (i) a hydrogen atom or (ii) an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, and among them, R ¹⁴ is preferably a hydrogen atom.
Rc and Rb each independently have a hydrogen atom, an aromatic hydrocarbon ring group which may have a substituent having 6 to 12 carbon atoms, or a substituent having 3 to 12 carbon atoms. Represents an aromatic heterocyclic group. Rc and Rb may be the same or different.
An aromatic hydrocarbon ring group of Rb and Rc which may have a substituent having 6 to 12 carbon atoms, or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms, Specific examples include those having the same defined number of carbon atoms among those similar to Rf described above. As the substituents of Rb and Rc, the same as the substituents of the above-mentioned Rf can be mentioned, and the preferable ones are also the same. When the compound has a plurality of substituents, they may be the same or different.
Rc and Rb are each independently preferably a hydrogen atom or an aromatic hydrocarbon ring group which may have a substituent having 6 to 12 carbon atoms, and further each independently is a hydrogen atom, a phenyl group or A naphthyl group is preferred, and a combination in which both Rc and Rb are simultaneously a hydrogen atom, a combination in which a hydrogen atom and a phenyl group, or a combination of a hydrogen atom and a naphthyl group are particularly preferred.
Preferred combinations of Rf-K- include:
Rf is selected from the general formulas (i-1) to (i-6), and K is a chemical single bond, -OT, -O-CRbRc-T, -CRbRc-OT,- O-CH ₂ -CH ₂ -T, -CH ₂ -CH ₂ -OT, -C (= O) -OT, -OC (= O) -T, -CH ₂ -CH _2- C (= O) -OT, -OC (= O) -CH ₂ -CH ₂ -T, -C (= O) -O-CRbRc-T, -CRbRc-OC (= O) -T, -OC (= O) -CRbRc-T, -CRbRc-C (= O) -OT, -NR ¹⁴ -C (= O) -OT, -S-CH ₂ -C A combination selected from (＝ O) —OT is preferred,
Rf is selected from the general formulas (i-1) to (i-6), and K is a chemical single bond, -OT, -CRbRc-OT, -CH ₂ -CH ₂ -O -T, -C (= O) -OT, -OC (= O) -T, -CH ₂ -CH ₂ -C (= O) -OT, -CRbRc-OC (= O) -T, -CRbRc-C (= O) -OT, -NR ¹⁴ -C (= O) -OT, -S-CH ₂ -C (= O) -OT Is more preferable,
Further, Rf-K- is particularly preferably one of the following formulas (ii-1) to (ii-45), and most preferably one of (iii-1) to (iii-46). preferable. Rb and Rc have the same meaning as described above, and T indicates the direction in which Ga is bonded. Further, in the groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by (iii-1) to (iii-46), ● (black circle) represents Ga and Indicates the binding site.
The groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by the following formulas (iii-1) to (iii-46) may have a substituent.
In the following formulas (ii-26) to (ii-32) and the following formulas (iii-26) to (iii-32), J represents —CH ₂ —, —NR ^d —, an oxygen atom, a sulfur atom, Represents —SO— or —SO ₂ —, and R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[Ga]
Ga is a divalent organic group having 1 to 20 carbon atoms which may have a substituent, and preferably a divalent organic group having 3 to 20 carbon atoms which may have a substituent. is there.
Ga is more preferably —CH ₂ contained in (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and (ii) a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms. - at least one of the, -O -, - S -, - O-C (= O) -, - C (= O) -O -, - O-C (= O) -O -, - NR 15 - C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - is a substituted group, the one of the organic groups. However, this excludes the case where two or more of -O- or -S- are adjacent to each other.
Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, a hydrogen atom or a methyl group is preferable. Examples of the substituent of the organic group represented by Ga include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. A cyano group; a halogen atom such as a fluorine atom and a chlorine atom;
Examples of the substituent for Ga include an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group and a propyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group; Group: a halogen atom such as a fluorine atom and a chlorine atom.
Here, with respect to Ga, the “divalent aliphatic hydrocarbon group” is preferably a divalent chain-like aliphatic hydrocarbon group, and more preferably an alkylene group. The “divalent aliphatic hydrocarbon group” preferably has 3 to 20 carbon atoms, more preferably 3 to 18 carbon atoms. The “divalent aliphatic hydrocarbon group” is preferably a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, and is preferably a divalent linear aliphatic hydrocarbon group having 2 to 18 carbon atoms. It is preferably a hydrogen group, more preferably an alkylene group having 2 to 18 carbon atoms.

The carbon number of Ga is preferably 4 to 16 carbon atoms, more preferably 5 to 14 carbon atoms, particularly preferably 6 to 12 carbon atoms, and most preferably 6 to 10 carbon atoms.

The structure of Ga is preferably an unsubstituted alkylene group having 4 to 16 carbon atoms, more preferably an unsubstituted alkylene group having 5 to 14 carbon atoms, and still more preferably an unsubstituted alkylene group having 6 to 12 carbon atoms. An unsubstituted alkylene group having 6 to 10 carbon atoms is particularly preferred, and an n-hexylene group and an n-octylene group are most preferred.

When Ga has 3 or more carbon atoms, it is preferable that both terminals of Ga be —CH ₂ — (both terminals of Ga are not substituted). Further, “(ii) at least one of —CH ₂ — contained in a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms is represented by —O—, —S—, —OC— (O) —, —C (＝ O) —O—, —OC (＝ O) —O—, —NR ¹⁵ —C (＝ O) —, —C (＝ O) —NR ¹⁵ —, —NR ¹⁵ —, or , —C (＝ O) —- substituted group ”, —O— and —S— do not substitute for consecutive —CH ₂ — in the aliphatic hydrocarbon group (ie, —O—O— and It is preferable not to form a structure of -SS- (that is, it is preferable to exclude a case where two or more of -O- or -S- are adjacent to each other), and -C (= O)- not replace - -CH ₂ consecutive aliphatic hydrocarbon group (i.e., -C (= O) -C ( = O) - does not form a structure) is preferably .
At least one of —CH ₂ — contained in the divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms is —O—, —S—, —OC (＝ O) —, or —C (＝ O); —O—, —OC (＝ O) —O—, —NR ¹⁵ —C (＝ O) —, —C (＝ O) —NR ¹⁵ —, —NR ¹⁵ —, or —C (＝ O When substituted with-)-, it is most preferably substituted with -O-, and a repeating unit is a so-called ethyleneoxy substituted with -O- every 2 carbon atoms, and both terminals of Ga are -CH _2- It is preferred that

Examples of Ga include (i) “a divalent linear aliphatic hydrocarbon group having 1 to 18 carbon atoms, preferably 3 to 18 carbon atoms, and a divalent linear aliphatic hydrocarbon group having 3 to 18 carbon atoms. At least one of —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —OC (＝ O) —, —C (＝ O) —O—, or —C (＝ O Or (ii) a group substituted with -O- or -S-, each of which is adjacent to two or more of them. " (Iii) an alkylene group having 3 to 18 carbon atoms, and (iv) an unsubstituted aliphatic hydrocarbon group having 4 to 16 carbon atoms. An alkylene group ”is still more preferable, and (v) an“ unsubstituted alkylene group having 5 to 14 carbon atoms ”is still more preferable, vi) “an unsubstituted alkylene group having 6 to 12 carbon atoms” is even more preferable, and (vii) an “unsubstituted alkylene group having 6 to 10 carbon atoms” is particularly preferable, and “n-hexylene group, n-octylene group” , N-decylene group "is most preferred.

[Gb]
Gb is an organic group having 1 to 20 carbon atoms which may have a substituent, and preferably an organic group having 3 to 20 carbon atoms which may have a substituent.
Gb is more preferably (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) 3 to 20 carbon atoms optionally having a substituent. At least one of —CH ₂ — contained in the aliphatic hydrocarbon group of the formula (1) is —O—, —S—, —OC (＝ O) —, —C (＝ O) —O—, —OC. A group substituted by (＝ O) —O—, —NR ¹⁵ —C (＝ O) —, —C (＝ O) —NR ¹⁵ —, —NR ¹⁵ —, or —C (＝ O) —, Any of the organic groups However, this excludes the case where two or more of -O- or -S- are adjacent to each other.
Here, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, a hydrogen atom or a methyl group is preferable.
Examples of the substituent of the organic group represented by Gb include a hydroxyl group; an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; A cyano group; a halogen atom such as a fluorine atom and a chlorine atom; and a polymerizable group such as —OC (＝ O) —CRgＣＨCH ₂ . Here, Rg represents a hydrogen atom, a methyl group, or a chlorine atom.
Here, regarding Gb, the “aliphatic hydrocarbon group” is preferably a chain-like aliphatic hydrocarbon group, and more preferably an alkyl group, an alkynyl group, or an alkenyl group. The “aliphatic hydrocarbon group” is preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms, and is preferably a linear aliphatic hydrocarbon group having 2 to 18 carbon atoms. More preferably, it is an alkyl group (eg, an n-hexyl group), an alkynyl group (eg, a 2-butynyl group), or an alkenyl group (eg, a 1-butenyl group) of Formulas 2 to 18.

The carbon number of Gb is preferably 4 to 16 carbon atoms, more preferably 4 to 14 carbon atoms, particularly preferably 4 to 12 carbon atoms, and most preferably 4 to 10 carbon atoms.

The structure of Gb is preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 16 carbon atoms, more preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 14 carbon atoms. And more preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 12 carbon atoms, particularly preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 10 carbon atoms. More particularly preferred are up to 10 unsubstituted alkyl groups, most preferably n-hexyl groups.

When Gb has 3 or more carbon atoms, it is preferable that one terminal of Gb (on the bonding side to N) is —CH ₂ — (one terminal of Gb is not substituted). Further, “(ii) at least one of —CH ₂ — contained in an aliphatic hydrocarbon group having 3 to 20 carbon atoms is represented by —O—, —S—, —OC (＝ O) —, —C ( ＝ O) —O—, —OC (＝ O) —O—, —NR ¹⁵ —C (＝ O) —, —C (＝ O) —NR ¹⁵ —, —NR ¹⁵ —, or —C In the "(O) -substituted group", -O- and -S- do not substitute a continuous -CH ₂ -in the aliphatic hydrocarbon group (that is, -OO- and -S- It is preferable that the compound does not form an S- structure (that is, it is preferable to exclude the case where two or more —O— or —S— are present adjacent to each other), and —C (＝ O) — It is preferable not to replace the continuous —CH ₂ — in the hydrogen group (that is, does not form a —C (＝ O) —C (＝ O) — structure).
At least one of —CH ₂ — contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms is —O—, —S—, —OC (＝ O) —, —C (＝ O) —O— ^{, -O-C (= O)} -O -, - NR 15 -C (= O) -, - C (= O) -NR 15 -, - NR 15 -, or, -C (= O) - in When substituted, it is most preferably substituted with -O-, and a repeating unit is a so-called ethyleneoxy substituted with -O- every 2 carbon atoms, and one terminal of Gb (the bond side to N) is —CH ₂ — is preferred.

Examples of Gb include (i) “a linear aliphatic hydrocarbon group having 1 to 18 carbon atoms, preferably 3 to 18 carbon atoms which may have a substituent, At least one of —CH ₂ — contained in the chain aliphatic hydrocarbon group having a good carbon number of 3 to 18 is —O—, —S—, —OC (＝ O) —, —C (＝ O ) Is an organic group of either —O— or a group substituted with —C (＝ O) —, except that two or more —O— or —S— are adjacent to each other. (Ii) "It is preferably a linear aliphatic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent", and (iii) "It may have a substituent. An alkyl group, an alkynyl group, or an alkenyl group having a good carbon number of 3 to 18 "is more preferable; (Vi) Unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 14 carbon atoms are even more preferable, and (vi) unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 14 carbon atoms are more preferable; Even more preferred are "unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 12 carbon atoms", and (vii) "unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 10 carbon atoms" Is particularly preferable, and an unsubstituted alkyl group having 4 to 10 carbon atoms is more preferable, and (viii) an "n-hexyl group" is most preferable.

[Q]
In the formulas (IV-1) to (IV-4), Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, and an isopropyl group. And aromatic hydrocarbon groups having 6 to 12 carbon atoms such as phenyl and naphthalene groups.

[R ^I to R ^IV ]
In the formulas (IV-1) to (IV-4), R ^I to R ^IV each independently represent a hydrogen atom; a halogen atom such as a fluorine atom and a chlorine atom; a carbon atom such as a methyl group, an ethyl group and a propyl group. A cyano group; a nitro group; an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom such as a trifluoromethyl group and a pentafluoroethyl group is substituted by a halogen atom; a methoxy group, an ethoxy group group, an alkoxy group having 1 to 6 carbon atoms such as an isopropoxy _{group; -OCF 3; -C (= O} ) -O-R a; or represents -O-C (= O) -R a, R a Has the same meaning as described above, and preferred examples thereof are also the same as described above.
Among them, (i) all of R ^I to R ^IV are hydrogen atoms, or (ii) at least one of R ^I to R ^IV has 1 to 1 carbon atoms which may have a substituent. Preferably, it is an alkoxy group of No. 6 and the remainder is a hydrogen atom.

R ^I to R ^IV may be the same or different, and at least one of C R ^I to C R ^IV constituting the ring may be replaced by a nitrogen atom.
Specific examples of the group in which at least one of ^CR ^I to CR ^IV is replaced by a nitrogen atom are shown below. However, the group in which at least one of ^CR ^I to CR ^IV is replaced by a nitrogen atom is not limited to these.

[In each formula, R ^I to R ^IV represent the same meaning as described above, and preferred examples thereof are also the same as described above. ]

[R ⁰ , p, p1, p2]
In formulas (IV-1) to (IV-4), R ⁰ is an alkyl group having 1 to 6 carbon atoms such as a halogen atom, a methyl group, an ethyl group, and a propyl group; a cyano group; a nitro group; , at least one alkyl group of hydrogen atoms and 1 carbon atoms which is substituted with a halogen atom 6, such as pentafluoroethyl group; methoxy group, an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as a propoxy group, -OCF ₃ ; -C (= O) -O- R a; represents or -O-C (= O) -R a, R a are as defined above, the preferred examples are also the same as above.
As R ⁰ , a halogen atom such as a fluorine atom and a chlorine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a cyano group; a nitro group; And an alkyl group having 1 to 6 carbon atoms, in which at least one hydrogen atom is substituted with a halogen atom, such as a pentafluoroethyl group or a pentafluoroethyl group, or an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group. . In the case R ⁰ is plural, a plurality of R ⁰ is may be the same or different from each other. Further, in the formulas (IV-1) to (IV-4), p represents an integer of 0 to 3, p1 represents an integer of 0 to 4, p2 represents 0 or 1, and p, p1 and p2 represent Both are preferably 0.

<< ^Y ^3, ^Y 4 >>
In the formula (III), Y ³ and Y ⁴ are each independently a chemical single bond, —O—, —O—CH ₂ —, —CH ₂ —O—, —O—CH ₂ —CH ₂ , -CH ₂ -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= O)- ^{S -, - S-C (} = O) -, - NR 13 -C (= O) -, - C (= O) -NR 13 -, - CF 2 -O -, - O-CF 2 -, - CH ₂ —CH ₂ —, —CF ₂ —CF ₂ —, —O—CH ₂ —CH ₂ —O—, —CH ＝ CH—C (＝ O) —O—, —OC— (O) — CH = CH-, -CH ₂ -C (= O) -O-, -OC (= O) -CH _2- , -CH ₂ -OC (= O)-, -C (= O) —O—CH ₂ —, —CH ₂ —CH ₂ —C (＝ O) —O—, —OC (＝ O _{_{_{_{) -CH 2 -CH 2 -, -}}}} CH 2 -CH 2 -O-C (= O) -, - C (= O) -O-CH 2 -CH 2 -, - CH = CH -, - N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N-, or -C≡C-. Here, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Among these, Y ³ and Y ⁴ are each independently a chemical single bond, —O—, —OC (＝ O) —, —C (＝ O) —O—, or —O It is preferably —C (＝ O) —O—.

<< ^{^A 23,} ^A 24 >>
In Formula (III), A ²³ and A ²⁴ each independently and independently represent the same meaning as A ^2, and preferred examples thereof are also the same as A ² .

^{^{^{^{<< B 21, B 22, Y}}}} 21, Y 22, L 21, L 22, R 31, R 32, d1, d2, e1, e2 >>
In the formula (III), B ²¹ , B ²² , Y ²¹ , Y ²² , L ²¹ , L ²² , R ³¹ , R ³² , d 1, d 2, e 1 and e 2 have the same meanings as described above, and preferred examples thereof are also included. Same as above.

In addition, the polymerizable compound (III) has a symmetrical structure around Ar, although not particularly limited (that is, Y ³ and Y ⁴ , A ²³ and A ²⁴ , B ²¹ and B ²² , Y It is preferable that ²¹ and Y ²² , L ²¹ and L ²² , R ³¹ and R ³² , d 1 and d 2, e 1 and e 2 are the same (symmetric with respect to Ar).

Here, the polymerizable compound (III) is preferably a polymerizable compound represented by any of the following formulas (V-1) and (V-2), and is preferably the following formula (V-1) More preferred.

(In the formulas (V-1) and (V-2), R, Q, R ^I to R ^IV , R ⁰ , Y ³ , Y ⁴ , A ²³ , A ²⁴ , B ²¹ , B ²² , Y ²¹ , Y ²² , L ²¹ , L ²² , R ³¹ , R ³² , d1, d2, e1, e2, p, p1 and p2 have the same meaning as described above, and preferred examples thereof are also the same as described above.

Here, the polymerizable compound represented by the formula (V-1) is preferably a polymerizable compound (iii-1) represented by the following formula (iii-1), and is preferably a compound represented by the following formula (iii-2): And more preferably a polymerizable compound (iii-2) represented by the following formula (1) or (2).

(In the formula (iii-1), R, Q, R ^I to R ^IV , R ⁰ , Y ³ , Y ⁴ , A ²³ , A ²⁴ , B ²¹ , B ²² , Y ²¹ , Y ²² , L ²¹ , L ²² , R ³¹ , R ³² , d 1, d 2, e 1, e 2 and p have the same meaning as described above, and preferred examples thereof are also the same as described above.)

(In the formula (iii-2), R ^I to R ^IV , Q and R have the same meanings as described above, and preferred examples thereof are also the same as described above. K and l are each independently 1 to 18 Represents an integer.)

重合 The above-mentioned polymerizable compound (III) can be synthesized by combining known synthesis reactions. That is, various documents (for example, WO2012 / 141245, WO2012 / 147904, WO2014 / 010325, WO2013 / 0466781, WO2014 / 061709, WO WO 2014/126113, WO 2015/064698, WO 2015-140302, WO 2015/129654, WO 2015/141784, WO 2016/159193, WO 2012 / 169424, WO2012 / 176679, WO2015 / 122385, JP-A-2016-190818, WO2017 / 150622, and the like.

For example, by reacting the compound (I) contained in the intermediate produced by the production method of the intermediate of the present invention with the benzaldehyde compound (AA) represented by the formula (AA), the following formula (AB) Is obtained, and then the compound (AB) is reacted with a compound (AC) represented by the following formula (AC) to obtain the polymerizable compound (iii-1) ( Q is a hydrogen atom and p is 0).
The details of the reaction conditions and the like can be set with reference to International Publication No. WO 2014/010325, International Publication No. 2015/064698, and International Publication No. 2015/141784.

(In the formula (I), the formula (AB), the formula (AC) and the formula (iii-1), R ³ , Y ² , B ² , L ² , A ² , FG ² , d, e, Y ³ , Y ⁴ , A ²³ , A ²⁴ , B ²¹ , B ²² , Y ²¹ , Y ²² , L ²¹ , L ²² , R ³¹ , R ³² , d 1, d 2, e 1, e 2, R, and R ^I to R ^IV are as described above. And the preferred examples are also the same as above.)

<Polymerizable composition>
The polymerizable composition contains at least a polymerizable compound (III) and a polymerization initiator.
The polymerizable composition is useful as a raw material for producing a polymer, an optical film, and an optically anisotropic material, as described later. According to the polymerizable composition, an optical film or the like having excellent in-plane uniformity of film thickness and improved in-plane uniformity of optical characteristics can be favorably produced.

Here, the polymerization initiator is blended from the viewpoint of more efficiently performing the polymerization reaction of the polymerizable compound (III) contained in the polymerizable composition.
Examples of the polymerization initiator used include a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator.

Examples of the radical polymerization initiator include a thermal radical generator, which is a compound that generates an active species capable of initiating polymerization of a polymerizable compound when heated; A photo-radical generator, which is a compound that generates an active species capable of initiating polymerization of a polymerizable compound by exposure to exposure light such as X-rays and X-rays; Is preferred.

Examples of the photo-radical generator include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, and polynuclear quinone compounds. , A xanthone-based compound, a diazo-based compound, and an imidosulfonate-based compound. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure. The photoradical generator can be used alone or in combination of two or more.

Specific examples of the acetophenone-based compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime) and the like.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, , 2'-Bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2-bromophenyl) -4,4 ' 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bi Examples thereof include imidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

When a biimidazole-based compound is used as the photopolymerization initiator (photoradical generator), it is preferable to use a hydrogen donor together in that the sensitivity can be further improved.
Here, “hydrogen donor” means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound upon exposure. As the hydrogen donor, a mercaptan compound, an amine compound and the like defined below are preferable.

Specific examples of the mercaptan-based compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethyl Aminopyridine and the like can be mentioned. Examples of the amine compound include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, Examples thereof include 4-dimethylaminobenzoic acid and 4-dimethylaminobenzonitrile.

Specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxys) Triazine compounds having a halomethyl group such as (lyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Specific examples of the O-acyl oxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime) and 1- [4- (phenylthio) phenyl]- Octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl- 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole-3- Yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetyloxime), Tanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl- 6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5) -Tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dio) Solanyl) benzoyl {-9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9H-carbazol-3-yl] -1 -(O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9 -Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Can be.

市販 As the photoradical generator, a commercially available product can be used as it is. As specific examples, trade names: Irgacure 907, trade name: Irgacure 184, trade name: Irgacure 369, trade name: Irgacure 651, trade name: Irgacure 819, trade names: Irgacure 907, and trade names: Irgacure OAKEXAE02, manufactured by BASF Trade name: ADEKA ARKULS N1919T or the like.

Examples of the anionic polymerization initiator include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene and pyrene; and polyfunctional initiators such as dilithium salts and trilithium salts.

Examples of the cationic polymerization initiator include protonic acids such as sulfuric acid, phosphoric acid, perchloric acid, and trifluoromethanesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride; A combination system of an aromatic onium salt or an aromatic onium salt and a reducing agent.

These polymerization initiators can be used alone or in combination of two or more.

In the polymerizable composition, the mixing ratio of the polymerization initiator is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound contained in the polymerizable composition. Parts by weight.

Further, it is preferable to add a surfactant to the polymerizable composition in order to adjust the surface tension. The surfactant is not particularly limited, but is preferably a nonionic surfactant. As the nonionic surfactant, a commercially available product may be used. For example, a nonionic surfactant which is an oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group, such as Surflon manufactured by AGC Seimi Chemical Co., Ltd. Series (S242, S243, S386, S611, S651, etc.), DIC MegaFac series (F251, F554, F556, F562, RS-75, RS-76-E, etc.), Neos's Fuertgent series ( FTX601AD, FTX602A, FTX601ADH2, FTX650A, etc.). In addition, one of these surfactants may be used alone, or two or more thereof may be used in combination at an arbitrary ratio.
Here, in the polymerizable composition, the mixing ratio of the surfactant is usually 0.01 to 10 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound contained in the polymerizable composition. 2 parts by mass.

Further, the polymerizable composition may further contain other components in addition to the polymerizable compound, the polymerization initiator, and the surfactant. Other components include metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, Metal oxides such as titanium oxide are exemplified.
Other components include other copolymerizable monomers. Specific examples thereof include, but are not particularly limited to, for example, 4'-methoxyphenyl 4- (2-methacryloyloxyethyloxy) benzoate, biphenyl 4- (6-methacryloyloxyhexyloxy) benzoate, (2-acryloyloxyethyloxy) -4'-cyanobiphenyl benzoate, 4- (2-methacrylolyloxyethyloxy) -4'-cyanobiphenyl benzoate, 4- (2-methacrylolyloxyethyloxy) 3 ', 4'-difluorophenyl benzoate, naphthyl 4- (2-methacryloyloxyethyloxy) benzoate, 4-acryloyloxy-4'-decylbiphenyl, 4-acryloyloxy-4'-cyanobiphenyl, 4- (2-acryloyloxyethyloxy) -4′-cyanobiphenyl, 4- (2-methacrylic Yloxyethyloxy) -4′-methoxybiphenyl, 4- (2-methacryloyloxyethyloxy) -4 ′-(4 ″ -fluorobenzyloxy) -biphenyl, 4-acryloyloxy-4′-propylcyclohexylphenyl, 4-methacryloyl-4'-butylbicyclohexyl, 4-acryloyl-4'-amyltran, 4-acryloyl-4 '-(3,4-difluorophenyl) bicyclohexyl, 4- (2-acryloyloxyethyl) benzoic acid ( 4-amylphenyl), 4- (2-acryloyloxyethyl) benzoic acid (4- (4′-propylcyclohexyl) phenyl), trade name “LC-242” (manufactured by BASF), trans-1,4-bis [4- [6- (acryloyloxy) hexyloxy] phenyl] cyclohexanedical Boxylate, and JP-A-2007-002208, JP-A-2009-173893, JP-A-2009-274984, JP-A-2010-030979, JP-A-2010-031223, JP-A-2011-006360 JP-A-2010-24438, WO2012 / 141245, WO2012 / 147904, WO2012 / 169424, WO2012 / 76679, WO2013 / 180217, WO 2014/010325, WO 2014/061709, WO 2014/065176, WO 2014/126113, WO 2015/025793, WO 2015/064698, WO No. No. 015/122384, copolymerizable monomers such as compounds disclosed in WO 2015/122385 and the like.
The mixing ratio of these other components is usually 0.005 to 50 parts by mass based on 100 parts by mass of the polymerizable compound contained in the polymerizable composition.

The polymerizable composition can be usually prepared by mixing and dissolving a predetermined amount of a polymerizable compound, a polymerization initiator, and other components to be added as required in a suitable organic solvent. .

Examples of the organic solvent used for preparing the polymerizable composition include ketones such as cyclopentanone, cyclohexanone, and methyl ethyl ketone; acetates such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane; , 4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolan and the like; and the like.

<Polymer>
The polymer is obtained by polymerizing the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition.
Here, “polymerization” means a chemical reaction in a broad sense including a cross-linking reaction in addition to a normal polymerization reaction.
The polymer usually has a monomer unit derived from the polymerizable compound (III).

Since the polymer is prepared using the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition, it can be used favorably as a constituent material of an optical film or the like.

Further, the polymer is not particularly limited, and can be used in an arbitrary shape according to the use such as a film, a powder, and a layer in which the powder is aggregated.
Specifically, a polymer film can be favorably used as a constituent material of an optical film and an optically anisotropic material described later, and a polymer powder is used for a paint, an anti-counterfeit article, a security article, and the like. The layer made of the polymer powder can be favorably used as a constituent material of the optically anisotropic body.

The polymer is specifically (α) subjected to the polymerization reaction of the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition in the presence of an appropriate organic solvent, and Isolating the polymer, dissolving the obtained polymer in a suitable organic solvent to prepare a solution, applying the solution on a suitable substrate, drying the obtained coating film, and optionally heating. (Β) dissolving the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition in an organic solvent, applying this solution on a substrate by a known coating method, and then removing the solvent. Then, it can be suitably produced by a method of performing a polymerization reaction by heating or irradiating with an active energy ray. In addition, you may polymerize the said polymerizable compound (III) independently.

The organic solvent used in the polymerization reaction in the method (α) is not particularly limited as long as it is inert. For example, aromatic hydrocarbons such as toluene, xylene and mesitylene; ketones such as cyclohexanone, cyclopentanone and methyl ethyl ketone; acetates such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; Ethers such as cyclopentyl methyl ether, tetrahydrofuran, and tetrahydropyran; and the like.
Among them, those having a boiling point of 60 to 250 ° C are preferable, and those having a boiling point of 60 to 150 ° C are more preferable from the viewpoint of excellent handling properties.

In the method (α), the organic solvent for dissolving the isolated polymer and the organic solvent used in the method (β) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, Ketone solvents such as cyclohexanone; ester solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as dichloromethane, chloroform and dichloroethane; tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, Ether solvents such as cyclopentyl methyl ether and 1,3-dioxolane; N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, N-methylpyrrolidone (N-methyl-2-pyrrolidone) and the like Non-proton Polar solvent; and the like. Among them, those having a boiling point of 60 to 200 ° C. are preferable from the viewpoint of easy handling. These solvents may be used alone or in combination of two or more.

As the substrate used in the methods (α) and (β), a substrate of a known and commonly used material can be used irrespective of organic or inorganic. For example, as an organic material, polycycloolefin [for example, ZEONEX, ZEONOR (registered trademark; manufactured by Nippon Zeon), ARTON (registered trademark; manufactured by JSR), and Apel (registered trademark; manufactured by Mitsui Chemicals, Inc.)], Polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose, cellulose triacetate, polyether sulfone, etc., and inorganic materials such as silicon, glass, calcite, etc. Is mentioned.
The substrate to be used may be a single layer or a laminate.
As the substrate, a substrate made of an organic material is preferable, and a resin film in which the organic material is formed into a film is more preferable.
Note that examples of the substrate include a substrate used for producing an optically anisotropic body described later.

As the method of applying the polymer solution to the substrate in the method (α) and the method of applying the polymerization reaction solution to the substrate in the method (β), known methods can be used. Specifically, for example, curtain coating, extrusion coating, roll coating, spin coating, dip coating, bar coating, spray coating, slide coating, print coating, gravure coating, die coating , A cap coating method or the like can be used.

Further, as the drying or desolvating method in the methods (α) and (β), natural drying, heat drying, reduced pressure drying, reduced pressure heat drying, and the like can be used.
The drying temperature is not particularly limited as long as the solvent can be removed, but the lower limit temperature is preferably 50 ° C or higher, and more preferably 70 ° C or higher, from the viewpoint that a constant temperature can be stably obtained. More preferably, there is.
The upper limit of the drying temperature is preferably 200 ° C. or lower, more preferably 195 ° C. or lower, from the viewpoint of not adversely affecting the substrate.

Examples of the method of polymerizing the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition include a method of irradiating with active energy rays and a thermal polymerization method. The method of irradiating with an active energy ray is preferable because of the progress of the process. Above all, a method of irradiating light such as ultraviolet light is preferable because of easy operation.
The temperature at which light such as ultraviolet light is irradiated is not particularly limited as long as the liquid crystal phase can be maintained. Preferably, the temperature is 20 ° C. or higher.
The upper limit of the temperature at which light such as ultraviolet rays is irradiated is preferably 200 ° C. or lower, more preferably 195 ° C. or lower, from the viewpoint of not adversely affecting the substrate.

Here, the temperature at the time of light irradiation is preferably 100 ° C. or less. The light irradiation intensity is usually in the range of 1 W / m ² to 10 kW / m ² , preferably in the range of 5 W / m ² to 2 kW / m ² . The dose of ultraviolet rays is preferably 0.1 mJ / cm ² or more, more preferably 0.5 mJ / cm ² or more, preferably 5000 mJ / cm ² or less, more preferably 4000 mJ / cm ² or less.

The polymer obtained as described above can be transferred from the substrate and used, or can be peeled off from the substrate and used alone, or can be used as it is as a constituent material of an optical film without peeling off the substrate You can also.
Further, the polymer peeled from the substrate can be used after being pulverized by a known method into powder.

The number average molecular weight of the polymer obtained as described above is preferably 500 to 500,000, more preferably 5,000 to 300,000. When the number average molecular weight is in such a range, high hardness is obtained and handleability is excellent, which is desirable. The number average molecular weight of the polymer can be measured by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard sample and tetrahydrofuran as an eluent.

According to the polymer, an optical film having excellent in-plane uniformity of film thickness and improved in-plane uniformity of optical characteristics can be obtained.

<Optical film>
The optical film is formed using a polymer and / or a polymerizable compound, and includes a layer having an optical function. The optical function simply means transmission, reflection, refraction, birefringence, and the like. The optical film may be an optical film using a polymer as a main constituent material of the layer having an optical function, or an optical film in which the layer having an optical function contains a polymerizable compound. Preferably, in the optical film using a polymer as a constituent material, the occupation ratio of the polymer is more than 50% by mass when all components of the layer having an optical function are 100% by mass. Preferably, the optical film containing the polymerizable compound contains the polymerizable compound in an amount of 0.01% by mass or more when all the components of the layer having an optical function are 100% by mass.

Here, the optical film is in the form as it is formed on the alignment substrate (orientation substrate / (alignment film) / optical film) which may have an alignment film, and is formed on a transparent substrate film different from the alignment substrate. It may be in the form of a transferred film (transparent substrate film / optical film) or, if the optical film has self-supporting properties, in the form of an optical film single layer (optical film).
In addition, as the alignment film and the alignment substrate, the same substrate and alignment film as an optical anisotropic body described later can be used.

Then, the optical film is obtained by applying a solution containing a polymerizable compound (A) or a solution of the polymerizable composition on an alignment substrate, drying the obtained coating film, and performing heat treatment (alignment of liquid crystal), and A method of performing light irradiation and / or heat treatment (polymerization), or (B) a solution of a liquid crystalline polymer obtained by polymerizing a polymerizable compound or a polymerizable composition is applied on an alignment substrate, and optionally obtained. It can be produced by a method of drying the obtained coating film, or a method of applying a solution containing the polymerizable compound and the resin (C) on an alignment substrate and drying the obtained coating film.

The optical film can be used for an optical anisotropic body, an alignment film for a liquid crystal display element, a color filter, a low-pass filter, a light polarizing prism, various optical filters, and the like.

The optical film is determined from the phase difference at a wavelength of 400 nm to 800 nm measured with a Mueller Matrix Polarimeter Axoscan. It is preferable that the following α value and β value are within a predetermined range. Specifically, the α value is preferably from 0.70 to 0.99, more preferably from 0.75 to 0.90. Further, the β value is preferably from 1.00 to 1.25, and more preferably from 1.01 to 1.20.
α = (Phase difference at 450 nm) / (Phase difference at 550 nm)
β = (phase difference at 650 nm) / (phase difference at 550 nm)

<Optical anisotropic body>
The optically anisotropic body has a layer containing a polymer as a constituent material.
The optically anisotropic body can be obtained, for example, by forming an alignment film on a substrate and further forming a polymer layer (liquid crystal layer) on the alignment film. Note that the optically anisotropic body may be a layer in which a polymer layer (liquid crystal layer) is directly formed on a substrate, or may be a layer only of a polymer layer (liquid crystal layer). .
The polymer layer may be a film-like polymer or may be a powdery polymer aggregate.

Here, the alignment film is formed on the surface of the substrate in order to regulate the alignment of the polymerizable compound in one direction within the plane.
For the alignment film, a solution (composition for alignment film) containing a polymer such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamide imide, or polyether imide is applied on a substrate in a film form, dried, and dried in one direction. Rubbing treatment or the like.
The thickness of the alignment film is preferably from 0.001 to 5 μm, more preferably from 0.001 to 1.0 μm.

The method of the rubbing treatment is not particularly limited, and examples thereof include a method of rubbing the alignment film in a certain direction with a roll made of synthetic fiber such as nylon or natural fiber such as cotton, or a roll around which felt is wound. After the rubbing treatment, the alignment film is preferably washed with isopropyl alcohol or the like in order to remove the fine powder (foreign matter) generated during the rubbing treatment and to keep the surface of the alignment film clean.
In addition to the rubbing method, a method of irradiating polarized ultraviolet light to the surface of the alignment film can also have a function of regulating the alignment in one direction in the plane.

基板 Examples of the substrate on which the alignment film is formed include a glass substrate and a substrate made of a synthetic resin film. As the synthetic resin, acrylic resin, polycarbonate resin, polyether sulfone resin, polyethylene terephthalate resin, polyimide resin, polymethyl methacrylate resin, polysulfone resin, polyarylate resin, polyethylene resin, polystyrene resin, polyvinyl chloride resin, cellulose diacetate , Cellulose triacetate, and thermoplastic resins such as alicyclic olefin polymers.

Examples of the alicyclic olefin polymer include cyclic olefin random multi-component copolymers described in JP-A-05-310845 and US Pat. No. 5,179,171, JP-A 05-97978, and US Pat. No. 5,202,388. A hydrogenated polymer described in JP-A-11-124429 (International Publication No. WO 99/20676), and a hydrogenated product of the thermoplastic dicyclopentadiene-based ring-opened polymer described in JP-A-11-124429. .

As a method for forming a liquid crystal layer made of a polymer on the alignment film, the same method (the above (α) and (β)) as described in the section of the polymer can be used.
The thickness of the obtained liquid crystal layer is not particularly limited, but is usually 1 to 10 μm.

In addition, as a kind of optical anisotropic body, there is no particular limitation, and a retardation plate, a viewing angle widening plate, and the like can be given.

The optically anisotropic body is obtained from a phase difference at a wavelength of 400 nm to 800 nm measured by a Mueller Matrix Polarimeter Axoscan. It is preferable that the following α value and β value are within a predetermined range. Specifically, the α value is preferably from 0.70 to 0.99, more preferably from 0.75 to 0.90. Further, the β value is preferably from 1.00 to 1.25, and more preferably from 1.01 to 1.25.
α = (Phase difference at 450 nm) / (Phase difference at 550 nm)
β = (phase difference at 650 nm) / (phase difference at 550 nm)

<Polarizing plate, etc.>
The polarizing plate includes an optically anisotropic body and a polarizing film.
Specific examples of the polarizing plate include those obtained by laminating an optically anisotropic body on a polarizing film directly or via another layer (such as a glass plate).

方法 The method for producing the polarizing film is not particularly limited. As a method of producing a PVA-based polarizing film, a method of uniaxially stretching after adsorbing iodine ions to the PVA-based film, a method of adsorbing iodine ions after uniaxially stretching the PVA-based film, A method of simultaneously performing iodine ion adsorption and uniaxial stretching, a method of uniaxially stretching a PVA-based film after dyeing it with a dichroic dye, a method of uniaxially stretching a PVA-based film and then dyeing it with a dichroic dye, PVA-based A method of simultaneously dyeing a film with a dichroic dye and uniaxially stretching the film is exemplified. In addition, as a method for producing a polyene-based polarizing film, a method in which a PVA-based film is uniaxially stretched and then heated and dehydrated in the presence of a dehydration catalyst, and a method in which a polyvinyl chloride-based film is uniaxially stretched and then subjected to a dehydrochlorination catalyst And a known method such as a method of heating and dewatering.

において In the polarizing plate, the polarizing film and the optically anisotropic body may be in contact with each other via an adhesive layer made of an adhesive (including an adhesive). The average thickness of the adhesive layer is usually 0.01 μm to 30 μm, preferably 0.1 μm to 15 μm. The adhesive layer is preferably a layer having a tensile breaking strength of 40 MPa or less according to JIS K7113.

Examples of the adhesive constituting the adhesive layer include an acrylic adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl alcohol adhesive, a polyolefin adhesive, a modified polyolefin adhesive, a polyvinyl alkyl ether adhesive, a rubber adhesive, and vinyl chloride. Vinyl acetate adhesive, styrene / butadiene / styrene copolymer (SBS copolymer) adhesive, hydrogenated product (SEBS copolymer) adhesive, ethylene / vinyl acetate copolymer, ethylene-styrene copolymer, etc. Ethylene adhesives, and acrylate ester adhesives such as ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl methacrylate copolymer and ethylene-ethyl acrylate copolymer, etc. Is mentioned.

Since the polarizing plate uses an optically anisotropic body, it has excellent in-plane uniformity of optical characteristics while having reverse wavelength dispersion.

表示 Further, by using a polarizing plate, a display device having a panel and an antireflection film can be suitably manufactured. Examples of the panel include a liquid crystal panel and an organic electroluminescence panel. Examples of the display device include a flat panel display device including a polarizing plate and a liquid crystal panel, and an organic electroluminescence display device including a liquid crystal panel and an organic electroluminescence panel.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the following description, “%” and “parts” representing amounts are based on mass unless otherwise specified.

Example 1 Synthesis of Compound 1
Through Step 1 and Step 2 described below, Compound 1 represented by the following structural formula was obtained.

<Step 1: Synthesis of compound A>
First, a compound A represented by the following structural formula was synthesized by the method described in WO 2017/150622 (Step 1).

<Step 2: Synthesis of compound 1>
Next, in a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in the previous step 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.57% by mass. The reaction formula is shown below. Note that the organic layer at this stage contained 44.9 g of the compound X represented by the following structural formula.

(4) Further, 200 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. The filtrate combined with this washing solution was further washed with 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter by stirring at 40 ° C. for 30 minutes. After washing, liquid separation was carried out, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed 5 times in total, liquids were separated, the aqueous layer was extracted, and 1200 g of normal hexane was added to the organic layer (oil layer), which was gradually cooled to 0 ° C. to precipitate a solid. The solid thus obtained was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 98.55 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 92.6 mass. %Met. The yield of compound 1 was 57.64 mol% based on compound A.

(Example 2: Synthesis of compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed five times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.58% by mass. Note that the organic layer at this stage contained 44.8 g of the compound X represented by the above structural formula.

(4) Further, 200 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. At 5 ° C., 250 g of water was added to the filtrate combined with the washing solution, and the mixture was stirred for 30 minutes and washed. After washing, liquid separation was performed to extract an aqueous layer. Then, 250 g of fresh water was added, and the mixture was stirred for 30 minutes, washed, separated, and 1200 g of normal hexane was added to an organic layer (oil layer) obtained by extracting the aqueous layer. Was added, and the mixture was gradually cooled to 0 ° C. to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 98.88 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 91.8 mass. %Met. The yield of compound 1 was 57.33 mol% based on compound A.

(Example 3: Synthesis of compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.59% by mass. The organic layer at this stage contained 45.0 g of the compound X represented by the above structural formula.

(5) Further, 50 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. The filtrate combined with this washing solution was further washed with 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter by stirring at 40 ° C. for 30 minutes. After washing, liquid separation was carried out, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed 5 times in total, liquids were separated, the aqueous layer was extracted, and 1200 g of normal hexane was added to the organic layer (oil layer), which was gradually cooled to 0 ° C. to precipitate a solid. The solid thus obtained was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 99.22 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 92.5 mass%. %Met. The yield of Compound 1 was 57.97 mol% based on Compound A.

(Example 4: Synthesis of compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed five times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.59% by mass. In addition, 44.5 g of the compound X represented by the above structural formula was contained in the organic layer at this stage.

(5) Further, 50 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. At 5 ° C., 250 g of water was added to the filtrate combined with the washing solution, and the mixture was stirred for 30 minutes and washed. After washing, liquid separation was performed to extract an aqueous layer. Then, 250 g of fresh water was added, and the mixture was stirred for 30 minutes, washed, separated, and 1200 g of normal hexane was added to an organic layer (oil layer) obtained by extracting the aqueous layer. Was added, and the mixture was gradually cooled to 0 ° C. to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 99.88 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 92.5 mass%. %Met. The yield of compound 1 was 58.35 mol% based on compound A.

(Example 5: Synthesis of compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.56% by mass. In addition, 44.2 g of the compound X represented by the above structural formula was contained in the organic layer at this stage.

(4) Further, 300 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. The filtrate combined with this washing solution was further washed with 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter by stirring at 40 ° C. for 30 minutes. After washing, liquid separation was carried out, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed 5 times in total, liquids were separated, the aqueous layer was extracted, and 1200 g of normal hexane was added to the organic layer (oil layer), which was gradually cooled to 0 ° C. to precipitate a solid. The solid thus obtained was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 100.1 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 91.8 mass. %Met. The yield of compound 1 was 58.04 mol% based on compound A.

(Example 6: Synthesis of compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed five times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.57% by mass. Note that the organic layer at this stage contained 45.2 g of the compound X represented by the above structural formula.

(4) Further, 300 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. At 5 ° C., 250 g of water was added to the filtrate combined with the washing solution, and the mixture was stirred for 30 minutes and washed. After washing, liquid separation was performed to extract an aqueous layer. Then, 250 g of fresh water was added, and the mixture was stirred for 30 minutes, washed, separated, and 1200 g of normal hexane was added to an organic layer (oil layer) obtained by extracting the aqueous layer. Was added, and the mixture was gradually cooled to 0 ° C. to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 98.9 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 89.8 mass%. %Met. The yield of compound 1 was 56.09 mol% based on compound A.

(Comparative Example 1: Synthesis of Compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.59% by mass. In addition, 44.3 g of the compound X represented by the above structural formula was contained in the organic layer at this stage.

Furthermore, the obtained organic layer was gradually cooled, and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of separately prepared CPME cooled to 0 ° C., and the washing solution obtained by this washing and the previous filtrate were combined. The filtrate combined with this washing solution was further washed with 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter by stirring at 40 ° C. for 30 minutes. After washing, liquid separation was carried out, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed 5 times in total, liquids were separated, the aqueous layer was extracted, and 1200 g of normal hexane was added to the organic layer (oil layer), which was gradually cooled to 0 ° C. to precipitate a solid. The solid thus obtained was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 73.8 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 91.5 mass%. %Met. The yield of compound 1 was 42.65 mol% based on compound A.

(Comparative Example 2: Synthesis of Compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed five times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.57% by mass. Note that the organic layer at this stage contained 44.8 g of the compound X represented by the above structural formula.

Furthermore, the obtained organic layer was gradually cooled, and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of separately prepared CPME cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. The filtrate combined with the washing liquid was separated, and the organic layer (oil layer) obtained by extracting the aqueous layer was added with 1200 g of normal hexane and gradually cooled to 0 ° C. to precipitate a solid. The solid was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 74.7 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 91.1 mass. %Met. The yield of compound 1 was 42.98 mol% based on compound A.

(Comparative Example 3: Synthesis of Compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.55% by mass. Note that the organic layer at this stage contained 44.6 g of the compound X represented by the above structural formula.

Further, 550 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol, which was separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. The filterability at this time was generally very poor. The filtrate combined with this washing solution was further washed with 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter by stirring at 40 ° C. for 30 minutes. After washing, liquid separation was carried out, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed 5 times in total, liquids were separated, the aqueous layer was extracted, and 1200 g of normal hexane was added to the organic layer (oil layer), which was gradually cooled to 0 ° C. to precipitate a solid. The solid thus obtained was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 82.3 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 85.5 mass%. %Met. The yield of compound 1 was 44.44 mol% based on compound A.

(Comparative Example 4: Synthesis of Compound 1)
In a nitrogen stream, 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer. Thereto, 100 g (0.378 mol) of the compound A synthesized in Step 1 of Example 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C. Next, 40.2 g (0.397 mol) of triethylamine (Et ₃ N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower. After the completion of the dropwise addition, the whole volume was returned to 25 ° C., and further stirred for 1 hour. 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours. After liquid separation and extraction of the aqueous layer, 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total. The organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted. Then, 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed five times in total. The concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.58% by mass. The organic layer at this stage contained 44.4 g of the compound X represented by the above structural formula.

Further, 550 g of methanol was added to the obtained organic layer, and the mixture was gradually cooled and slowly stirred at 0 ° C. for 1 hour to precipitate a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100 g of methanol, which was separately prepared and cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate. The filterability at this time was generally very poor. At 5 ° C., 250 g of water was added to the filtrate combined with the washing solution, and the mixture was stirred for 30 minutes and washed. After washing, liquid separation was performed to extract an aqueous layer. Then, 250 g of fresh water was added, and the mixture was stirred for 30 minutes, washed, separated, and 1200 g of normal hexane was added to an organic layer (oil layer) obtained by extracting the aqueous layer. Was added, and the mixture was gradually cooled to 0 ° C. to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with normal hexane and then dried under vacuum to obtain 82.2 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate. When the obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 85.3 mass. %Met. The yield of compound 1 was 44.29 mol% based on compound A.

(Comparative Example 5: Comparative Example 1 of International Publication No. 2011/068138)

24.68 g of trans-1,4-cyclohexanedicarboxylic acid and toluene were mixed. To the resulting solution, 74.91 g of oxalyl dichloride and 0.5 mL of N, N-dimethylformamide were added. The resulting solution was stirred and reacted under a nitrogen atmosphere. The obtained reaction mixture was concentrated under reduced pressure to remove toluene and unreacted oxalyl dichloride. The obtained solution and chloroform were mixed to obtain a solution containing trans-1,4-cyclohexanedicarboxylic acid dichloride.
12 g of the compound represented by the above formula (A-IV) and chloroform were mixed. The obtained solution and 12.6 g of pyridine were added dropwise to the previously obtained solution containing trans-1,4-cyclohexanedicarboxylic acid dichloride under ice cooling. The resulting mixture was stirred under a nitrogen atmosphere. The precipitate was removed by filtration, and the obtained filtrate was concentrated under reduced pressure. The concentrate was dropped into a water / methanol solution (volume ratio = 1/1). The resulting precipitate was pulverized and filtered. The precipitate was washed with pure water. The precipitate was filtered and dried under vacuum. After pulverizing the obtained powder, heptane was added. After stirring the obtained mixture, the precipitate was taken out. The precipitate was mixed with toluene, and the insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure, and heptane was added to the obtained concentrate. The precipitate was taken out by filtration and dried under vacuum to obtain 7.8 g of a powder (intermediate) containing the compound represented by the above formula (6-a) (compound (I)). The yield of the compound represented by the above formula (6-a) was 40.00 mol% based on the compound represented by the above formula (A-IV). The content (purity) of the compound represented by the above formula (6-a) with respect to the obtained powder was 70.0% by mass.

(Comparative Example 6: Comparative Example 2 of International Publication No. 2011/068138)
24.68 g of trans-1,4-cyclohexanedicarboxylic acid, 74.91 g of oxalyl dichloride and 0.5 mL of N, N-dimethylformamide were mixed. The resulting solution was stirred and reacted under a nitrogen atmosphere. The obtained reaction mixture was concentrated under reduced pressure to remove toluene and unreacted oxalyl dichloride. The obtained solution and chloroform were mixed to obtain a solution containing trans-1,4-cyclohexanedicarboxylic acid dichloride.
12 g of the compound represented by the above formula (6-a) and chloroform were mixed. The obtained solution and 12.6 g of pyridine were added dropwise to the previously obtained solution containing trans-1,4-cyclohexanedicarboxylic acid dichloride under ice cooling. The resulting solution was stirred under a nitrogen atmosphere. The precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was dropped into water, and the resulting precipitate was pulverized and then filtered. The precipitate was mixed with pure water and filtered. The precipitate was dried under vacuum. After the obtained powder was pulverized, it was added to a water / methanol solution (volume ratio = 1/1). The precipitate was ground and then filtered. Heptane was added to the precipitate, the resulting mixture was stirred, and insolubles were removed by filtration. After the insoluble matter was mixed with toluene, the mixture was filtered. The obtained filtrate was concentrated under reduced pressure, and heptane was added to the obtained concentrate. The precipitate was taken out by filtration and dried under vacuum to obtain 2.1 g of a powder (intermediate) containing the compound represented by the above formula (6-a) (compound (I)). The yield of the compound represented by the above formula (6-a) was 12.00 mol% based on the compound represented by the above formula (A-IV). The content (purity) of the compound represented by the above formula (6-a) with respect to the obtained powder was 85.0% by mass.

(Example 7: Synthesis of polymerizable compound 1)

In a three-necked reactor equipped with a thermometer, 100 g (0.605 mol) of 2-hydrazinobenzothiazole was added to 750 g of N, N-dimethylformamide in a nitrogen stream, and then 119.9 g (0.1 g) of 1-bromohexane. 726 mol). To this solution, 192.72 g (0.908 mol) of tripotassium phosphate was added, and the whole volume was stirred at 100 ° C. for 3 hours. After the completion of the reaction, the reaction solution was cooled to 60 ° C., and 750 g of toluene and 750 g of water were added to the cooled reaction solution, and the mixture was stirred at 60 ° C. for 15 minutes. When the reaction solution was allowed to stand, it was separated into three layers. Two lower layers were extracted. To the obtained toluene layer, 430 g of a 10% by mass aqueous sodium chloride solution was added, and the mixture was stirred at 60 ° C. for 15 minutes. The liquid layer was separated, the aqueous layer was extracted, and the toluene layer (organic layer) obtained was concentrated under reduced pressure to extract 560 g of toluene. The temperature of the toluene layer (organic layer) after concentration was raised to 60 ° C., 500 g of water was added, and the mixture was gradually cooled with vigorous stirring. After reaching 0 ° C., the mixture was vigorously stirred at the same temperature for 1 hour. This slurry solution was filtered. The obtained wet solid was washed by splashing it with 500 g of a mixed solvent of water / methanol = 1/4 (mass ratio) cooled to 5 ° C. or lower. The obtained wet solid was dried under reduced pressure using a vacuum drier to obtain 132.8 g of Compound B as a white solid. The yield was 88 mol%. The structure of Compound B was identified by ¹ H-NMR. ^{The 1} H-NMR spectrum data is shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.60 (dd, 1 H, J = 1.0, 8.0 Hz), 7.53 (dd, 1 H, J = 1.0, 8. 0 Hz), 7.27 (ddd, 1H, J = 1.0, 8.0, 8.0 Hz), 7.06 (ddd, 1H, J = 1.0, 8.0, 8.0 Hz), 4 .22 (s, 2H), 3.74 (t, 2H, J = 7.5 Hz), 1.69-1.76 (m, 2H), 1.29-1.42 (m, 6H), 0 .89 (t, 3H, J = 7.0 Hz).

<Step 2: Synthesis of polymerizable compound 1>
In a three-necked reactor equipped with a thermometer, in a nitrogen stream, 10.80 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 (as a pure amount of compound 1) 10.00 g (23.90 mmol)), 100 g of chloroform and 3.49 g of dimethylformamide (DMF) were added, and the mixture was cooled to 10 ° C or lower. To the solution, 3.27 g (27.48 mmol) of thionyl chloride was added dropwise while controlling the reaction temperature to 10 ° C. or lower. After completion of the dropwise addition, the reaction solution was returned to 25 ° C and stirred for 1 hour. After the completion of the reaction, the reaction solution was concentrated by an evaporator until the amount of the reaction solution became 1/4. Thereafter, 25 g of chloroform was added to obtain a chloroform solution of the acid chloride of Compound 1. Separately, in a three-necked reactor equipped with a thermometer, 1.50 g (10.86 mmol) of 2,5-dihydroxybenzaldehyde and 6.98 g (65.17 mmol) of 2,6-lutidine as a base were placed in a nitrogen stream. And 50 g of chloroform, and the resulting solution was cooled to 10 ° C. or lower. To this solution, the whole amount of the chloroform solution of the acid chloride of Compound 1 synthesized previously was slowly added dropwise while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the reaction was further performed for 1 hour while maintaining the reaction solution at 10 ° C. or lower. Thereafter, 40 g of a 1.0 N aqueous hydrochloric acid solution was further added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to perform a reaction. After the completion of the reaction, 3.52 g (14.12 mmol) of the compound B synthesized in Step 1 was added to the obtained reaction solution while keeping the temperature at 10 ° C. or lower. Thereafter, the reaction solution was heated to 40 ° C. and reacted for 4 hours. After the completion of the reaction, the reaction solution was cooled to 25 ° C., and a liquid separation operation was performed. To the obtained organic layer, 0.50 g of LocaHelp # 479 (manufactured by Mitsui Mining & Smelting Co., Ltd.) was added, and after stirring for 30 minutes, LocaHelp # 479 was filtered off. Next, a total mass of about 80% was extracted from the obtained reaction solution with an evaporator and concentrated. After adding 20 g of THF to this solution, the mixture was stirred for 1 hour. Next, 80 g of normal hexane was dropped into this solution, and then cooled to 0 ° C. to precipitate crystals. Thereafter, the precipitated crystals were collected by filtration. To the obtained crystals were added 108 g of THF, 1.8 g of LocaHelp # 479, and 100 mg of 2,6-di-t-butyl-4-methylphenol, and the mixture was stirred for 30 minutes. Then, LokaHelp # 479 was filtered off. Next, 36 g of THF was distilled off from the obtained reaction solution using an evaporator. After 117 g of methanol was added dropwise to the resulting solution, the solution was cooled to 0 ° C. to precipitate crystals. Thereafter, the precipitated crystals were collected by filtration. The filtrate was washed with methanol and dried under vacuum to obtain 11.7 g of polymerizable compound 1. The isolation yield was 92.0 mol% (based on 2,5-dihydroxybenzaldehyde). The structure of the polymerizable compound 1 was identified by ¹ H-NMR. ^{The 1} H-NMR spectrum data is shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 7.75 (d, 1H, J = 2.5 Hz), 7.67-7.70 (m, 3H), 7.34 (ddd, 1H) , J = 1.0 Hz, 7.0 Hz, 7.5 Hz), 7.17 (ddd, 1H, J = 1.0 Hz, 7.5 Hz, 7.5 Hz), 7.12 (d, 1H, J = 9) 0.0 Hz), 7.10 (dd, 1H, J = 2.5 Hz, 9.0 Hz), 6.99 (d, 2H, J = 9.0 Hz), 6.98 (d, 2H, J = 9. 0 Hz), 6.88 (d, 4H, J = 9.0 Hz), 6.40 (dd, 2H, J = 1.5 Hz, 17.0 Hz), 6.13 (dd, 2H, J = 10.5 Hz) , 17.5 Hz), 5.82 (dd, 2H, J = 1.5 Hz, 10.5 Hz), 4.30 (t, 2H, J = 8.0 Hz) 4.18 (t, 4H, J = 6.5 Hz), 3.95 (t, 4H, J = 6.5 Hz), 2.58-2.70 (m, 4H), 2.31-2. 35 (m, 8H), 1.66-1.82 (m, 18H), 1.31-1.54 (m, 14H), 0.90 (t, 3H, J = 7.0 Hz).

(Example 8: Synthesis of polymerizable compound 1)
In Example 7, in Step 2, a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)) instead of using: 10.89 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 2 (10.00 g (23. A polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.6 g of the polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 was 91.3 mol% based on 2,5-dihydroxybenzaldehyde.

(Example 9: Synthesis of polymerizable compound 1)
In Example 7, in Step 2, a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)) instead of using: 10.81 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 3 (10.00 g (23. A polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.7 g of polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 was 92.0 mol% based on 2,5-dihydroxybenzaldehyde.

(Example 10: Synthesis of polymerizable compound 1)
In Example 7, in Step 2, a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). Instead of using (.90 mmol)), a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 4: 10.81 g (10.00 g (23. A polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.8 g of the polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 was 92.8 mol% based on 2,5-dihydroxybenzaldehyde.

(Example 11: Synthesis of polymerizable compound 1)
In Example 7, in Step 2, a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)), instead of using: 10.89 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 5 (10.00 g (23. A polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.5 g of polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 was 90.5 mol% based on 2,5-dihydroxybenzaldehyde.

(Example 12: Synthesis of polymerizable compound 1)
In Example 7, in Step 2, a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)), 11.14 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 6 (10.00 g of pure compound 1 (23.90 mmol)). A polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.6 g of the polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 was 91.3 mol% based on 2,5-dihydroxybenzaldehyde.

(Example 13: Synthesis of polymerizable compound 2)

In a nitrogen gas stream, 500.5 g (2.69 mol) of 1-naphthylacetic acid and 1049 g of toluene were charged into a three-necked reactor equipped with a thermometer. Further, 349.5 g (2.56 mol) of 6-chloro-1-hexanol and 48.6 g (0.26 mol) of paratoluenesulfonic acid monohydrate were added to prepare a solution. Using a Dean-Stark apparatus, the prepared solution was heated, and azeotropic dehydration (internal temperature: about 95 ° C.) was performed for 2 hours while discharging generated water out of the reaction system. After the reaction was completed, 742 g of a 5.8% by mass aqueous sodium bicarbonate solution was added to the reaction solution cooled to 25 ° C., and the mixture was separated and washed. After washing, the organic layer obtained by extracting the aqueous layer was further washed with 500 g of water. After washing, 7 g of a filter aid (trade name: RocaHelp # 479, manufactured by Mitsui Mining & Smelting Co., Ltd.) was added to the organic layer obtained by extracting the aqueous layer, and the mixture was stirred at room temperature for 30 minutes, filtered, and filtered. The agent was removed. The solvent was distilled off from the organic layer using a rotary evaporator to obtain 755 g of a light brown oil containing Compound C. Determination by high performance liquid chromatography revealed that the light brown oil containing Compound C contained 93.0% by mass of Compound C. This light brown oil was not purified and used as it was in the next reaction (Step 2: synthesis of compound D).

In a three-necked reactor equipped with a thermometer, in a nitrogen stream, 59.52 g (55.35 g (0.182 mol) as a net amount of compound C) of the light brown oil containing compound C synthesized in the above step 1 and N 235 g of -methyl-2-pyrrolidone was charged to obtain a uniform solution. 25.0 g (0.151 mol) of 2-hydrazinobenzothiazole was added to the homogeneous solution. Next, 48.18 g (0.227 mol) of tripotassium phosphate was added, and the whole volume was stirred at 100 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to 60 ° C., and after adding 312.5 g of ethyl acetate to the cooled reaction solution, filtration was performed while maintaining the temperature at 60 ° C. The organic layer, which was the filtrate, was slowly dropped into 250 g of a 0.5 N aqueous citric acid solution, stirred at an internal temperature of 60 ° C. for 30 minutes, and then the aqueous layer was extracted. Further, 275 g of a 9.1 mass% aqueous sodium chloride solution was added to the organic layer, and the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract an aqueous layer. Next, 262.5 g of a 4.76% by mass aqueous sodium hydrogen carbonate solution was added to the organic layer, and the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then left standing for 30 minutes to extract an aqueous layer. Further, 250 g of water was added to the organic layer, and the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then left standing for 30 minutes to extract an aqueous layer. The obtained organic layer was gradually cooled to 0 ° C and stirred at 0 ° C for 30 minutes. The resulting solid was obtained by filtration. Thereafter, 150 g of ethyl acetate was added to the obtained solid, and the mixture was heated to 60 ° C. to form a homogeneous solution and stirred for 30 minutes. Thereafter, the ethyl acetate solution was gradually cooled to 0 ° C and stirred at 0 ° C for 1 hour. The resulting solid was obtained by filtration and dried under reduced pressure to obtain 36.9 g of Compound D as a white solid. The yield of compound D was 56.4 mol%. The structure of compound D was identified by ¹ H-NMR. ^{The 1} H-NMR spectrum data is shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 8.00 (d, 1 H, J = 8.5 Hz), 7.85 (dd, 1 H, J = 1.0 Hz, 8.0 Hz), 7 .78 (dd, 1H, J = 1.5 Hz, 7.5 Hz), 7.60 (dd, 1H, J = 1.0 Hz, 7.5 Hz), 7.54-7.51 (m, 2H), 7.49-7.40 (m, 3H), 7.28 (ddd, 1H, J = 1.0 Hz, 7.5 Hz, 7.5 Hz), 7.07 (ddd, 1H, J = 1.0 Hz, 7.5 Hz, 7.5 Hz), 4.16 (br, 2H), 4.08 (t, 2H, J = 6.5 Hz), 4.06 (s, 2H), 3.66 (t, 2H, J = 7.0 Hz), 1.63-1.54 (m, 4H), 1.32-1.22 (m, 4H).

<Step 3: Synthesis of polymerizable compound 2>
In a three-necked reactor equipped with a thermometer, in a nitrogen stream, a white solid as an intermediate synthesized in Example 3 (mixture Y of compound 1 and compound X): 32.43 g (as a pure amount of compound 1) 30.00 g (71.7 mmol)), 300 g of chloroform and 10.5 g (143.4 mmol) of N, N-dimethylformamide (DMF) were added, and the mixture was cooled to 10 ° C. or lower. Thereto, 9.81 g (82.44 mmol) of thionyl chloride was added dropwise while controlling the reaction temperature to 10 ° C. or lower. After completion of the dropwise addition, the reaction solution was returned to 25 ° C and stirred for 1 hour. After completion of the reaction, 225 g of chloroform was extracted with an evaporator and concentrated, and the acid chloride of Compound 1 was synthesized as a chloroform solution. Separately, in a three-necked reactor equipped with a thermometer, 4.5 g (32.58 mmol) of 2,5-dihydroxybenzaldehyde and 19.78 g (195.5 mmol) of triethylamine as a base were added to 150 g of nitrogen in a nitrogen stream. It was dissolved in chloroform, and the obtained solution was cooled to 10 ° C or lower. To this solution, the whole amount of the chloroform solution of the acid chloride of Compound 1 synthesized previously was slowly added dropwise while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the whole volume was further stirred at 5 to 10 ° C. for 1 hour to carry out a reaction. After completion of the reaction, while maintaining the temperature at 10 ° C. or lower, 120 g of a 1.0 N aqueous hydrochloric acid solution was added to the reaction solution, and the reaction was stirred at 10 ° C. or lower for 30 minutes. After the completion of the reaction, 18.38 g (42.4 mmol) of the compound D synthesized in Step 2 and 2,6-di-tert-butyl-para-cresol 0 were added to the resulting reaction solution at 10 ° C. or lower. .3 g were added. Thereafter, the reaction solution was heated to 40 ° C. and reacted for 4 hours.
After completion of the reaction, the aqueous layer was extracted to obtain an organic layer. 105 g of distilled water was added to the obtained organic layer, and the organic layer was washed by stirring at 40 ° C. for 30 minutes. The organic layer obtained by extracting the aqueous layer was cooled to 25 ° C., 1.5 g of LocaHelp # 479 was added, and the mixture was stirred for 30 minutes. Thereafter, filtration was performed with a Kiriyama funnel covered with 1 g of LocaHelp # 479 to remove LocaHelp # 479. 180 g of chloroform was extracted with a rotary evaporator from the organic layer obtained by removing LocaHelp # 479, and concentrated. 210 g of hexane was added to the organic layer obtained by concentration over 1 hour to precipitate a solid, and a pale yellow solid was obtained by filtration. The obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of LocaHelp # 479 was added, and the mixture was stirred for 30 minutes. Thereafter, filtration was performed with a Kiriyama funnel covered with 1 g of LocaHelp # 479 to remove LocaHelp # 479. 165 g of methanol was slowly dropped at 15 ° C. to the organic layer obtained by removing LocaHelp # 479 to precipitate a solid, which was filtered to obtain a solid. The obtained solid was dried with a vacuum drier to obtain 40.2 g of the polymerizable compound 2 as a pale yellow solid. The yield of the polymerizable compound 2 was 91.0 mol% based on 2,5-dihydroxybenzaldehyde. The structure of the polymerizable compound 2 was identified by ¹ H-NMR. ^{The 1} H-NMR spectrum data is shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.97 (dd, 1 H, J = 0.5 Hz, 8.5 Hz), 7.80 (ddd, 1 H, J = 0.5 Hz, 0. 5Hz, 8.0Hz), 7.73-7.76 (m, 2H), 7.67-7.71 (m, 2H), 7.61 (s, 1H), 7.49 (ddd, 1H, J = 1.0 Hz, 6.5 Hz, 8.5 Hz), 7.42 (ddd, 1H, J = 1.5 Hz, 7.0 Hz, 7.0 Hz), 7.33-7.39 (m, 3H) , 7.18 (ddd, 1H, J = 1.0 Hz, 7.5 Hz, 8.0 Hz), 7.10-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.90 (m, 4H), 6.405 (dd, 1H, J = 1.5 Hz, 17.5 Hz), 6.402 (dd, H, J = 1.5 Hz, 17.5 Hz), 6.127 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 6.124 (dd, 1H, J = 10.5 Hz, 17.5 Hz) 5.822 (dd, 1H, J = 1.5 Hz, 10.5 Hz), 5.819 (dd, 1H, J = 1.5 Hz, 10.5 Hz), 4.16-4.22 (m, 6H) ), 4.08 (t, 2H, J = 6.5 Hz), 4.03 (s, 2H), 3.95 (t, 2H, J = 6.5 Hz), 3.93 (t, 2H, J) = 6.5 Hz), 2.56-2.67 (m, 4H), 2.28-2.36 (m, 8H), 1.59-1.83 (m, 20H), 1.42-1 .56 (m, 8H), 1.24-1.36 (m, 4H).

(Example 14: Synthesis of polymerizable compound 2)
In Example 13, in Step 3, a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 3: 32.43 g (30.00 g (71 in pure amount of compound 1) Instead of using 0.7 mmol), a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 4: 32.43 g (30.00 g (71.7 mmol as a pure amount of compound 1) )), Except that polymerizable compound 2 was synthesized in the same manner as in Example 13. As a result, 40.6 g of polymerizable compound 2 was obtained. Was 92.1 mol% based on 2,5-dihydroxybenzaldehyde.

From the results of Examples 7 to 14, it was found that the intermediate containing Compound (I) at a high concentration obtained by the production method of the present invention can be suitably used for producing a polymerizable compound. Was.

According to the present invention, there is provided a method for producing an intermediate, which can efficiently produce an intermediate containing compound (I) at a high concentration.

Claims

The following formula (I):

[In formula (I), A 2 and B 2 each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent;
Y 2 and L 2 are each independently a chemical single bond, —O—, —C (＝ O) —, —C (＝ O) —O—, —OC (＝ O) —, —NR 21 —C (＝ O) —, —C (＝ O) —NR 22 —, —OC (＝ O) —O—, —NR 23 —C (＝ O) —O—, —O— Represents C (＝ O) —NR 24 — or —NR 25 —C (＝ O) —NR 26 —, wherein R 21 to R 26 are each independently a hydrogen atom or an alkyl having 1 to 6 carbon atoms. Represents a group,
R 3 represents a hydrogen atom, a methyl group or a chlorine atom,
FG 2 represents a hydroxyl group, a carboxyl group or an amino group,
d represents an integer of 1 to 20,
e is 1 or 2. A method for producing an intermediate comprising a compound (I) represented by the formula:
(I) the compound (I);
The following formula (II):

[In the formula (II), A 21 , B 21 and B 22 each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent. Represents
Y 21 , Y 22 , L 21 and L 22 are each independently a chemical single bond, —O—, —C (＝ O) —, —C (＝ O) —O—, —OC. (= O) -, - NR 21 -C (= O) -, - C (= O) -NR 22 -, - O-C (= O) -O -, - NR 23 -C (= O) - O—, —OC (＝ O) —NR 24 — or —NR 25 —C (＝ O) —NR 26 —, wherein R 21 to R 26 each independently represent a hydrogen atom or a carbon atom. Represents an alkyl group of Formulas 1 to 6,
R 31 and R 32 each independently represent a hydrogen atom, a methyl group or a chlorine atom;
d1 and d2 each independently represent an integer of 1 to 20,
e1 and e2 are each independently 1 or 2. A) obtaining a solution (X) containing the compound (II) represented by the formula:
(Ii) A protic solvent is added to the solution (X) to precipitate the compound (II), and the precipitated compound (II) is removed to contain the compound (I) at 86% by mass or more. A method for producing an intermediate, comprising a step (β) of obtaining an intermediate.
The method for producing an intermediate according to claim 1, wherein the concentration of the compound (I) in the solution (X) is 8.0% by mass or more.
3. The method for producing an intermediate according to claim 1, wherein the compound (I) is a compound (I-1) represented by the following formula (I-1).

[In the formula (I-1), R 3 and d represent the same meaning as described above. ]
4. The method for producing an intermediate according to claim 1, wherein the compound (II) is a compound (II-1) represented by the following formula (II-1).

[In the formula (II-1), R 3 and d represent the same meaning as described above. ]
(5) The method for producing an intermediate according to any one of (1) to (4), wherein the solution (X) further contains an organic solvent, and the organic solvent is a water-immiscible organic solvent.
The method for producing an intermediate according to claim 5, wherein the water-immiscible organic solvent has a Hildebrand solubility parameter of 14.0 MPa 1/2 or more and 22.0 MPa 1/2 or less.
方法 The method for producing an intermediate according to any one of claims 1 to 6, wherein the protic solvent is an alcohol.