CN112689622A

CN112689622A - Process for producing intermediate

Info

Publication number: CN112689622A
Application number: CN201980059201.XA
Authority: CN
Inventors: 坂本圭; 奥山久美
Original assignee: Zeon Corp
Current assignee: Zeon Corp
Priority date: 2018-09-19
Filing date: 2019-09-12
Publication date: 2021-04-20
Also published as: WO2020059634A1; JPWO2020059634A1; JP7327408B2

Abstract

The purpose of the present invention is to provide a method for efficiently producing an intermediate that can efficiently produce an intermediate containing a compound (I) at a high concentration. The method for producing an intermediate of the present invention comprises: (i) a step (α) of obtaining a solution (X) containing a compound (I) represented by the following formula (I) and a compound (II) represented by the following formula (II); and (II) a step (β) 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 86 mass% or more of the compound (I).

Description

Process for producing intermediate

Technical Field

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

Background

The retardation plate includes 1/4 wave plates for converting linearly polarized light into circularly polarized light, 1/2 wave plates for converting the plane of polarization oscillation of linearly polarized light by 90 degrees, and the like. These phase difference plates can accurately convert a specific monochromatic light into a phase difference of 1/4 λ or 1/2 λ in the wavelength of the light.

However, the conventional phase difference plate has a problem that the polarized light outputted from the phase difference plate is converted into the colored polarized light. This is due to the following reasons: since the material constituting the phase difference plate has wavelength dispersion in the phase difference, dispersion occurs in the polarization state at each wavelength with respect to white light of a composite wave in which light rays in the visible light region are mixed, and thus the phase difference of 1/4 λ or 1/2 λ cannot be accurately adjusted in all wavelength regions.

In order to solve such problems, a compound capable of obtaining an optical film capable of performing similar polarization conversion in a wide wavelength region and a method for producing the same have been studied (for example, refer to patent documents 1 to 4).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2009/116657;

patent document 2: international publication No. 2011/068138;

patent document 3: japanese patent laid-open publication No. 2016 and 216433;

patent document 4: international publication No. 2016/159193.

Disclosure of Invention

Problems to be solved by the invention

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

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

Means for solving the problems

The present inventors have intensively studied to solve the above problems, and as a result, they have found that an intermediate containing the compound (I) at a high concentration can be efficiently produced by adding a protic solvent to a solution (X) containing the compound (I) and the compound (II) to precipitate the compound (II) and removing the precipitated compound (II), and have completed the present invention.

Further, the present invention provides a method for producing an intermediate as shown below.

[1] A method for producing an intermediate, comprising the steps of:

(i) a step (alpha) for obtaining a solution (X) containing a compound (I) and a compound (II) represented by the formula (II); and

(ii) a step (β) 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),

the intermediate obtained by the step (β) contains the compound (I) in an amount of 86 mass% or more.

[ chemical formula 1]

[ in the formula (I), A²And B²Each independently represents a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent,

Y²and L²Each independently represents a single chemical bond, -O-, -C (═ O) -O-, -O-C (═ O) -, -NR²¹-C(＝O)-、-C(＝O)-NR²²-、-O-C(＝O)-O-、-NR²³-C(＝O)-O-、-O-C(＝O)-NR²⁴-or-NR²⁵-C(＝O)-NR²⁶-，R²¹～R²⁶Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

R³represents a hydrogen atom, a methyl group or a chlorine atom,

FG²represents a hydroxyl group, a carboxyl group or an amino group,

d represents an integer of 1 to 20,

e is 1 or 2

[ chemical formula 2]

[ in the formula (II), A²¹、B²¹And B²²Each independently represents a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent,

Y²¹、Y²²、L²¹and L²²Each independently represents a single chemical bond, -O-, -C (═ O) -O-, -O-C (═ O) -, -NR²¹-C(＝O)-、-C(＝O)-NR²²-、-O-C(＝O)-O-、-NR²³-C(＝O)-O-、-O-C(＝O)-NR²⁴-or-NR²⁵-C(＝O)-NR²⁶-，R²¹～R²⁶Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

R³¹and R³²Each independently represents 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. ]

In other words, the process for producing an intermediate of the above [1] is a process for producing an intermediate comprising the above compound (I), comprising the steps of:

(i) a step (α) of obtaining a solution (X) containing the compound (I) and the compound (II), and

(ii) and a step (β) 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 86 mass% or more of the compound (I).

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

[3] The process for producing an intermediate according to the above [1] or [2], wherein the compound (I) is a compound (I-1) represented by the following formula (I-1).

[ chemical formula 3]

[ in the formula (I-1), R³And d represents the same meaning as described above.]

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

[ chemical formula 4]

[ formula (II-1) wherein R³And d represents the same meaning as described above.]

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

[6]According to [5] above]The process for producing an intermediate, wherein the Hildebrand solubility parameter of the water-immiscible organic solvent is 14.0MPa^1/2Above and 22.0MPa^1/2The following.

[7] The process according to any one of [1] to [6], wherein the protic solvent is an alcohol.

Effects of the invention

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

Detailed Description

The present invention will be described in detail below. In the present invention, "may have a substituent" means "unsubstituted or substituted". When an organic group such as an alkyl group or an aromatic hydrocarbon ring group included in the general formula has a substituent, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent. For example, when an aromatic hydrocarbon ring group having 6 to 20 carbon atoms has a substituent, the number of carbon atoms of such substituent is not included in the number of carbon atoms of the aromatic hydrocarbon ring group having 6 to 20 carbon atoms. In the present invention, "alkyl" refers to a chain (linear or branched) saturated hydrocarbon group, and "cycloalkyl" as a cyclic saturated hydrocarbon group is not included in "alkyl". On the other hand, the "total number of pi electrons contained in the ring structure in Rf" also contains pi electrons of the ring structure contained in the substituent. Further, in the present invention, the "intermediate" may contain at least compound (I), either alone or as a mixture containing compound (I) and a component other than compound (I).

(Process for producing intermediate)

The method for producing the intermediate of the present invention will be described in detail below.

The method for producing an intermediate of the present invention at least comprises: a step (alpha) of obtaining a solution (X) containing a compound (I) and a compound (II); and a step (β) of adding a protic solvent to the solution (X) to precipitate a compound (II), and removing the precipitated compound (II) to obtain an intermediate containing the compound (I); other steps may be included as necessary.

[ chemical formula 5]

[ chemical formula 6]

< Process (. alpha.)

The step (α) is a step of obtaining a solution (X) containing the compound (I) and the compound (II).

< solution (X) >

The solution (X) contains at least the compound (I) and the compound (II), and further contains an organic solvent and other components as required.

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, and is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. If the concentration of the compound (I) in the solution (X) is not less than the lower limit and not more than the upper limit, the compound represented by the formula (II) can be removed with high selectivity.

The "concentration of compound (I) in the solution (X)" is calculated by the following formula.

The concentration (% by mass) of the compound (I) in the solution (X) is

(Mass of Compound (I)/[ (Mass of Compound (I) + Mass of solvent ]. times.100

The concentration of the compound (II) in the solution (X) is preferably 3.0% by mass or more, more preferably 3.5% by mass or more, and particularly preferably 4.0% by mass or more, and is preferably 10% by mass or less, more preferably 9.0% by mass or less, and particularly preferably 8.0% by mass or less. If the concentration of the compound (II) in the solution (X) is not less than the lower limit and not more than the upper limit, the compound represented by the formula (II) can be removed with high selectivity.

The "concentration of the compound (II) in the solution (X)" is calculated by the following formula.

Concentration of compound (II) in solution (X) ═ concentration

(Mass of Compound (II)/[ (Mass of Compound (II) + Mass of solvent ]. times.100

The ratio of the concentration of the compound (II) in the solution (X) to the concentration of the compound (I) in the solution (concentration of the compound (II) in the solution (X)/concentration of the compound (I) in the solution (X)) is preferably 20% or more, more preferably 25% or more, particularly preferably 30% or more, and preferably 60% or less, more preferably 55% or less, particularly preferably 50% or less. If the ratio of the concentration of the compound (II) in the solution (X) to the concentration of the compound (I) in the solution (X) (concentration of the compound (II) in the solution (X)/concentration of the compound (I) in the solution (X)) is not less than the lower limit value and not more than the upper limit value, the compound represented by the formula (II) can be removed with high selectivity.

[ Compound (I) ]

The compound (I) represented by the following formula (I) may be composed of only one compound, may be composed of two compounds, and is preferably composed of only one compound. When the compound (I) is composed of only one compound, the compound (II) described later is represented by A²¹Is symmetrical left and right in the center.

[ chemical formula 7]

[A²、B²]

In the formula (I), A²And B²Each independently represents a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent.

Among these, A²And B²Preferably, each independently represents a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent, or an aromatic group having 2 to 20 carbon atoms which may have a substituent.

Specific examples of the cyclic aliphatic group include: a cycloalkanediyl group having 5 to 20 carbon atoms such as a cyclopentane-1, 3-diyl group, a cyclohexane-1, 4-diyl group, a cycloheptane-1, 4-diyl group, a cyclooctane-1, 5-diyl group and the like; and a C5-20 bicycloalkane diyl group such as a decahydronaphthalene-1, 5-diyl group and a decahydronaphthalene-2, 6-diyl group. Among these, the cyclic aliphatic group is preferably a cycloalkanediyl group having 5 to 20 carbon atoms which may be substituted, more preferably a cyclohexanediyl group, particularly preferably a 1, 4-cyclohexylene group (cyclohexane-1, 4-diyl group), and still more preferably a trans-1, 4-cyclohexylene group.

Specific examples of the aromatic group include: an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as 1, 2-phenylene, 1, 3-phenylene, 1, 4-naphthylene, 1, 5-naphthylene, 2, 6-naphthylene, 4' -biphenylene, etc.; and an aromatic heterocyclic group having 2 to 20 carbon atoms such as furan-2, 5-diyl, thiophene-2, 5-diyl, pyridine-2, 5-diyl, pyrazine-2, 5-diyl, and the like. 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, a bromine atom, etc.; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and isopropoxy group; a nitro group; cyano, and the like. 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-mentioned substituents. In the case of having a plurality of substituents, the substituents may be the same or different.

Here, A is preferred²Is a cyclic aliphatic group which may have a substituent, B²Is an aromatic group which may have a substituent.

Furthermore, A is more preferable²Is a "trans-1, 4-cyclohexylene group which may have a substituent" represented by the formula (a), B²A combination of "1, 4-phenylene which may have a substituent" represented by the formula (b).

[ chemical formula 8]

In the formulae (a) and (b), R⁰Represents: a halogen atom; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; 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 trifluoromethyl group or a pentafluoroethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and the like; -OCF₃；-C(＝O)-O-R^a(ii) a or-O-C (═ O) -R^a. Herein, R is^aRepresents: may have a substituentAn alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent.

As R⁰From the viewpoint of improving solubility, it is preferable that: a halogen atom such as a fluorine atom or a chlorine atom; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; 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 trifluoromethyl group or a pentafluoroethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and the like. In addition, in R⁰In the case of plural, plural R⁰May be the same or different from each other. Further, p1 represents an integer of 0 to 4, preferably 0.

As R^aThe alkyl group having 1 to 20 carbon atoms which may have a substituent(s) is an alkyl group having 1 to 20 carbon atoms, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 1-methylpentyl, 1-ethylpentyl, sec-butyl, tert-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, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl, and the like. The alkyl group having 1 to 20 carbon atoms which may have a substituent preferably has 1 to 12 carbon atoms, more preferably 4 to 10 carbon atoms.

As R^aThe alkenyl group having 2 to 20 carbon atoms which may have a substituent(s) and which is an alkenyl group having 2 to 20 carbon atoms includes: vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, and eicosenyl, and the like.

The number of carbon atoms of the alkenyl group having 2 to 20 carbon atoms which may have a substituent is preferably 2 to 12.

As R^aThe substituent for the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms includes: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; an alkoxy group having 1 to 12 carbon atoms which is substituted with 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 and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group, a benzothiazol-2-ylthio group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; a cycloalkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group, a cyclohexyloxy group, or the like; tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, diyl

A cyclic ether group having 2 to 12 carbon atoms such as an alkyl group; aryloxy groups having 6 to 14 carbon atoms such as phenoxy groups and naphthoxy groups; trifluoromethyl, pentafluoroethyl, -CH₂CF₃A fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; a benzofuranyl group; a benzopyranyl group; benzodioxolyl group; and benzodi

Alkyl groups, and the like. Among these, as R^aThe substituent for the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of (b) is preferably: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as furyl group and thienyl group; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; trifluoromethyl, pentafluoroethyl, -CH₂CF₃Etc. at least one hydrogen atom is replaced by a fluorine atomA substituted fluoroalkyl group having 1 to 12 carbon atoms.

In addition, R^aThe C1-20 alkyl group and C2-20 alkenyl group of (a) may have a plurality of substituents selected from the above-mentioned substituents. At R^aWhen the alkyl group having 1 to 20 carbon atoms or the alkenyl group having 2 to 20 carbon atoms has a plurality of substituents, the plurality of substituents may be the same or different from each other.

As R^aThe cycloalkyl group having 3 to 12 carbon atoms which may have a substituent(s) includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl. Among these, cyclopentyl and cyclohexyl are preferable.

As R^aThe substituent of the cycloalkyl group having 3 to 12 carbon atoms includes: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group. Wherein, as R^aThe cycloalkyl group having 3 to 12 carbon atoms preferably has: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group.

In addition, R^aThe cycloalkyl group having 3 to 12 carbon atoms may have a plurality of substituents. At R^aWhen the cycloalkyl group having 3 to 12 carbon atoms has a plurality of substituents, the plurality of substituents may be the same or different from each other.

As R^aThe aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent(s) includes, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like. Among these, phenyl is preferred.

As carbon atoms which may have substituentsThe substituents of the aromatic hydrocarbon ring group having 5 to 12 numbers include: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; an alkoxy group having 1 to 12 carbon atoms which is substituted with 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 and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; a cycloalkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group, a cyclohexyloxy group, or the like; tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, diyl

A cyclic ether group having 2 to 12 carbon atoms such as an alkyl group; aryloxy groups having 6 to 14 carbon atoms such as phenoxy groups and naphthoxy groups; trifluoromethyl, pentafluoroethyl, -CH₂CF₃A fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; -OCF₃(ii) a A benzofuranyl group; a benzopyranyl group; benzodioxolyl group; benzodi (benzo-b)

Alkyl groups, and the like. Among them, as the substituent of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms, preferred are: a halogen atom selected from fluorine atom, chlorine atom and the like; a cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; trifluoromethyl, pentafluoroethyl, -CH₂CF₃A fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; -OCF₃At least one substituent in (1).

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.

[Y²、L²]

In the formula (I), Y²And L²Each independently represents a single chemical bond, -O-, -C (═ O) -O-, -O-C (═ O) -, -NR²¹-C(＝O)-、-C(＝O)-NR²²-、-O-C(＝O)-O-、-NR²³-C(＝O)-O-、-O-C(＝O)-NR²⁴-or-NR²⁵-C(＝O)-NR²⁶-. Herein, R is²¹～R²⁶Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Among these, Y is difficult to synthesize and exhibits desired optical characteristics²preferably-O-, L²preferably-C (═ O) -O-or-O-C (═ O) -.

[R³]

In the formula (I), R³Represents a hydrogen atom, a methyl group or a chlorine atom.

Among these, R is from the viewpoint of ease of synthesis and polymerization rate³Preferably a hydrogen atom.

[FG²]

In the formula (I), FG²Represents a hydroxyl group, a carboxyl group or an amino group.

Among these, FG is difficult to synthesize and exhibits desired optical characteristics²Preferably a carboxyl group.

[d]

In the formula (I), d represents an integer of 1-20.

Among these, d is preferably an integer of 2 to 12, more preferably an integer of 4 to 12, and particularly preferably an integer of 4 to 10, from the viewpoint of ease of synthesis and development of desired optical properties.

[e]

In the formula (I), e is 1 or 2.

Among these, e is preferably 1.

In addition, in the case where e is 2, two B' s²May be the same or different, and 2L²May be the same or different.

As specific examples of the compound (I), there may be preferably mentioned, for example, a compound (I-1) represented by the following formula (I-1).

[ chemical formula 9]

In the formula (I-1), R³D has the same meaning as described above, and preferred examples thereof are also the same as described above.

[ preparation of Compound (I) ]

With respect to the production of the compound (I), the case where e is 1 and the case where e is 2 will be described.

In the case where e is 1, the compound (I) (the compound (I-a) represented by the following formula (I-a)) can be obtained, for example, by reacting the compound (a-0) represented by the following formula (a-0) with the compound (B-0) represented by the following formula (B-0), more specifically, by: a compound (A-1) represented by the following formula (A-1) is subjected to an esterification reaction with trans-1, 4-cyclohexanedicarboxylic acid chloride in a reaction solvent containing a base such as triethylamine, and then hydrolyzed. Further, the compound (A-1) can be obtained by reacting a compound represented by the following formula (A-1) with trans-1, 4-cyclohexanedicarboxylic acid in a reaction solvent in the presence of a dehydration condensation agent.

[ chemical formula 10]

In the formulae (A-0), (B-0) and (I-a), A²、B²、Y²、L²、R³、FG²And d each independently has the same meaning as described above, and preferred examples thereof are also the same as described above.

In the formula (A-0), Z represents a hydroxyl group, a carboxyl group or an amino group.

Among these, Z is preferably a hydroxyl group from the viewpoint of ease of synthesis.

In the formula (B-0), FQ is a group which reacts with Z to form L²And can be FG²The functional group of (a) represents-C (═ O) Cl, ClC (═ O) -, -COOH, HOOC-, -NH₂Or H₂N-。

Among these, FQ is preferably — C (═ O) Cl or ClC (═ O) -, -COOH, HOOC — from the viewpoint of ease of synthesis.

[ chemical formula 11]

In the formula (A-1), R³D has the same meaning as described above, and preferred examples thereof are also the same as described above.

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

[ chemical formula 12]

In the formulae (A-2), (B-0) and (I-B), A²、B²、Y²、L²、R³、FG²And d each independently has the same meaning as described above, and preferred examples thereof are also the same as described above.

In the formula (A-2), Z represents a hydroxyl group, a carboxyl group or an amino group.

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 of B in the formula (I-B)²Which may be the same or different, two L's in the formula (I-b)²May be the same or different.

Reaction solvent-

Examples of the reaction solvent include: ethers such as cyclopentyl methyl ether (CPME), tetrahydrofuran, methyl tert-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; alicyclic hydrocarbons such as cyclopentane and cyclohexane; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; nitriles such as acetonitrile and propionitrile; and mixed solvents thereof, and the like. These may be used alone or in combination of two or more in an arbitrary ratio.

The amount of the reaction solvent used in the reaction is preferably 10mL or more, more preferably 20mL or more, particularly preferably 40mL or more, and preferably 500mL or less, more preferably 250mL or less, particularly preferably 100mL or less, relative to 10g of the compound (A-0) or the compound (A-2). If the amount of the reaction solvent used is not less than the lower limit value and not more than the upper limit value, the selectivity of the compound represented by the formula (I) can be improved.

[ Compound (II) ]

The compound (II) represented by the following formula (II) may be represented by A²¹A is preferably a because it is symmetrical about the center or asymmetrical about the center, and it is easy to synthesize²¹Is symmetrical left and right (i.e. B)²¹And B²²Same, Y²¹And Y²²Same, L²¹And L²²Same, R³¹And R³²Identical, d1 and d2 identical, e1 and e2 identical).

[ chemical formula 13]

[A²¹、B²¹、B²²]

In the formula (II), A²¹、B²¹And B²²Each independently represents the same as A²、B²The same meanings as those of A above are also preferred²、B²The same is true.

[Y²¹、Y²²]

In the formula (II), Y²¹And Y²²Each independently represents the same as Y²The same meanings as those of Y are also preferred²The same is true.

[L²¹、L²²]

In the formula (II), L²¹And L²²Each independently represents the same as L²The same meanings as those of L are also preferred²The same is true.

[R³¹、R³²]

In the formula (II), R³¹And R³²Each independently represents the same as R³The same meanings as those of the above-mentioned preferred examples are also defined for R³The same is true.

[d1、d2]

In the formula (II), d1 and d2 each independently have the same meaning as d above, and preferred examples thereof are also the same as d above.

[e1、e2]

In the formula (II), e1 and e2 each independently have the same meaning as e above, and preferred examples thereof are also the same as e above.

As a specific example of the compound (II), there can be preferably mentioned, for example, a compound (II-1) represented by the following formula (II-1).

[ chemical formula 14]

[ formula (II-1) wherein R³D has 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 tertiary butyl ether, diethyl ether, dibutyl ether, diisopropyl ether, 1, 2-dimethoxyethane, 1, 4-bis (tert-butyl) ether

An alkyl, an aryl,Ethers such as 1, 3-dioxolane; 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; alicyclic hydrocarbons such as cyclopentane and cyclohexane; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; nitriles such as acetonitrile and propionitrile; and mixed solvents thereof, and the like. These may be used alone or in combination of two or more in an arbitrary ratio.

Among these, water-immiscible organic solvents are preferred. Here, the "water-immiscible organic solvent" is an organic solvent having the property of being immiscible with water and of phase separation 2. The solubility of the water-immiscible organic solvent in water is 40g (organic solvent)/100 mL (water) or less, preferably 30g (organic solvent)/100 mL (water) or less, and more preferably 15g (organic solvent)/100 mL (water) or less.

In the case where two or more kinds of mixed solvents are used, when the water-miscible solvent is added, the mixed solvent is a "water-immiscible organic solvent" when the solubility in water is satisfied with respect to the total of the water-miscible solvent and the water-immiscible organic solvent.

Specific examples of the water-immiscible organic solvent include: cyclopentyl methyl ether (CPME), 2-methyltetrahydrofuran, 1, 4-bis

Ethers such as alkane, 1, 3-dioxolane, tetrahydrofuran, methyl t-butyl ether, diethyl ether, dibutyl ether, 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; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclopentane and cyclohexane; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; nitriles such as acetonitrile and propionitrile; and mixed solvents thereof, and the like.

The Hildebrand solubility parameter of the water-immiscible organic solvent is excellentIs selected to be 14.0MPa^1/2Above, more preferably 14.3MPa^1/2Above, particularly preferably 14.5MPa^1/2Above, and preferably 22.0MPa^1/2Hereinafter, more preferably 20.0MPa^1/2Hereinafter, it is particularly preferably 19.5MPa^1/2The following. If the Hildebrand solubility parameter of the water-immiscible organic solvent is not less than the lower limit but not more than the upper limit, the compound represented by the formula (I) can be obtained with a high selectivity.

The Hildebrand solubility parameter is a value (δ) that is predicted from a Hildebrand-induced value that provides a numerical prediction of the degree of interaction between materials, as defined by the rule solution theory.

As Hildebrand solubility parameter of 14.0MPa^1/2Above and 22.0MPa^1/2The following organic solvents can be preferably exemplified: cyclopentyl methyl ether (CPME) (Hildebrand solubility parameter (. delta.): 17.2 MPa)^1/2) Tetrahydrofuran ((δ): 18.6MPa^1/2) Methyl tert-butyl ether ((δ): 15.6MPa^1/2) Diethyl ether ((δ): 15.1MPa^1/2) Dibutyl ether ((δ): 14.9MPa^1/2) Diisopropyl ether ((δ): 14.1MPa^1/2) 1, 2-dimethoxyethane ((δ): 19.2MPa^1/2) 2-butanone ((δ): 19.0MPa^1/2) Ethers and the like; chloroform (. delta.: 19.0 MPa)^1/2) Halogenated hydrocarbons, etc.; ethyl acetate ((delta): 18.6MPa^1/2) And the like esters; toluene ((delta): 18.2 MPa)^1/2) And the like aromatic hydrocarbons; cyclohexane ((delta): 16.7MPa^1/2) Alicyclic hydrocarbons; and mixed solvents thereof, and the like. In the case of using a mixed solvent, the solubility parameter thereof can be calculated by a summation 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, and particularly preferably 70% by mass or more, and is preferably 95% by mass or less, more preferably 93% by mass or less, and particularly preferably 90% by mass or less. If the content of the organic solvent in the solution (X) is not less than the lower limit and not more than the upper limit, the compound represented by the formula (II) can be removed with high selectivity.

[ other ingredients ]

Examples of other components include: triethylamine (Et)₃N), diisopropylethylamine, pyridine, N-dimethyl-4-dimethylaminopyridine, and the like; dehydration condensing agents such as dicyclohexylcarbodiimide, N-diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride; polymerization inhibitors such as 2, 6-di-t-butyl-p-cresol and p-methoxyphenol.

< step (. beta.)

The step (β) is 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).

< protic solvent >

The protic solvent is a solvent in which the compound (I) is easily dissolved and the compound (II) is not easily dissolved when added to the solution (X) containing the compound (I) and the compound (II) (i.e., a solvent which is a good solvent for the compound (I) in the solution (X) and a poor solvent for the compound (II) in the solution (X)).

Further, even if a single compound (I) is a good solvent, it is not necessarily a good solvent for the compound (I) in the solution (X), and even if a single compound (II) is a poor solvent, it is not necessarily a poor solvent for the compound (I) in the solution (X).

Examples of the protic solvent include alcohols such as ethanol, methanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol and cyclopentanol; glycerol; glycols such as ethylene glycol and propylene glycol; carboxylic acids such as formic acid and acetic acid; glycolic acid, 2-hydroxymalonic acid, glyceric acid and other hydroxy acids. These may be used alone or in combination of two or more in an arbitrary ratio.

Among these, alcohols are preferable, and methanol is more preferable, in terms of efficiently precipitating the compound (II).

The amount of the protic solvent to be used is preferably 0.1 times by mass or more, more preferably 0.2 times by mass or more, and particularly preferably 0.3 times by mass or more, and preferably 5 times by mass or less, more preferably 3 times by mass or less, and particularly preferably 2 times by mass or less, based on the compound (a-0) or the compound (a-2). When the amount of the protic solvent used is not less than the lower limit value and not more than the upper limit value, the compound represented by the formula (II) can be removed with high selectivity, and the purity of the compound represented by the formula (I) can be improved.

< removal >

Examples of a 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 preferable from the viewpoint of removal efficiency.

< intermediate >)

The intermediate contains at least the compound (I), and may be a single compound (I) or a mixture containing the compound (I) and other components (e.g., the compound (II)) other than the compound (I).

The content of the compound (I) in the intermediate is required to be 86 mass% or more, preferably 88 mass% or more, more preferably 90 mass% or more, and particularly preferably 92 mass% or more. If the content of the compound (I) in the intermediate is not less than the lower limit, a compound capable of obtaining an optical film capable of performing similar polarization conversion in a wide wavelength region can be efficiently produced.

In the step (β), in order to obtain the intermediate, after removing the compound (II), the intermediate containing the compound (I) is precipitated by cooling, filtered, and vacuum-dried.

The cooling temperature is preferably 20 ℃ or lower, more preferably 10 ℃ or lower, particularly preferably 5 ℃ or lower, and most preferably in the vicinity of 0 ℃. If the cooling temperature is not more than the above upper limit, the intermediate can be efficiently precipitated.

< other Process >

Examples of the other step include a step of preparing the above-mentioned compound (I) by drying or the like.

< polymerizable Compound >

An intermediate is produced by the method for producing an intermediate of the present invention, and a polymerizable compound produced from the intermediate will be described.

The polymerizable compound is, for example, a compound represented by the following formula (III) (hereinafter, may be referred to as "polymerizable compound (III)"), and can be advantageously used in the production of a polymer, an optical film and an optically anisotropic body, which will be described later.

[ chemical formula 15]

As described later, by using the compound represented by the formula (III), a polymerizable composition having excellent coating properties can be obtained, and an optical film or the like having excellent in-plane uniformity of film thickness and improved in-plane uniformity of optical characteristics can be advantageously produced.

<<Ar>>

In the formula (III), Ar is represented by the following formula (IV-1) or (IV-2), preferably by the following formula (IV-3) or (IV-4).

[ chemical formula 16]

(in the above formulae (IV-1) and (IV-2), R represents a group represented by the formula³Or Y⁴And (4) combining. )

[ chemical formula 17]

(in the above formulae (IV-3) and (IV-4), R represents a group represented by the formula³Or Y⁴And (4) combining. )

[R]

In the formulae (IV-1) to (IV-4), R represents an organic group having 1 to 60 carbon atoms which may have a substituent, preferably an organic group represented by Rf-K-Ga (Ga bonded to N) or an organic group represented by Gb.

The organic group having 1 to 60 carbon atoms which may have a substituent as R 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: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 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, and n-butyl, n-hexyl, and n-octyl are more preferable, and n-hexyl is particularly preferable.

[ (ii) an 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, a butenyl group, and the like, and an alkenyl group having 2 to 12 carbon atoms is preferable.

[ (iii) alkynyl having 2 to 60 carbon atoms ]

Examples of the alkynyl group having 2 to 60 carbon atoms include propynyl group, propargyl group, butynyl group and the like, and an alkynyl group having 2 to 12 carbon atoms is preferable.

Examples of the substituent for 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, a bromine atom, etc.; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group; an alkoxy group having 1 to 6 carbon atoms which is substituted with an alkoxy group having 1 to 6 carbon atoms such as a methoxymethoxy group, a methoxyethoxy group, or an ethoxyethoxy group; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like; and substituted amino groups such as methylamino, ethylamino, acetylamino, and dimethylamino.

[Rf]

Rf represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.

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, a fluorene ring, and the like. Among these, benzene ring, naphthalene ring, anthracene ring, fluorene ring are preferable, and benzene ring and naphthalene ring are more preferable.

-aromatic heterocycles-

Examples of the aromatic heterocyclic ring include a 1H-isoindole-1, 3(2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring, and the like,

A diazole ring,

An azolyl ring,

An azolo pyrazine ring,

A pyrazolopyridine ring,

An oxazolopyridazine ring,

An oxazolopyrimidine ring, a quinazoline ring, a quinoxaline ring, a quinoline ring, a cinnoline ring, a thiadiazole ring, a thiazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a thiophene ring, a triazine ring, a triazole ring, a naphthyridine ring, a pyrazine ring, a pyrazole ring, a pyrone ring, a pyran ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrrole ring, a phenanthridine ring, a phthalazine ring, a furan ring, a benzo [ b ] ring]Thiophene ring, benzo [ c ]]Thiophene ring, benzisoxazines

Azole ring, benzisothiazole ring, benzimidazole ring, benzo

Diazole ring, benzo

An azole ring, a benzothiadiazole ring, a benzothiazole ring, a benzothiophene ring, a benzotriazine ring, a benzotriazole ring, a benzopyran ring, etc.

Among these, as the aromatic heterocyclic ring, preferred are a furan ring, a pyran ring, a thiophene ring, and a silicon,

An azolyl ring,

Monocyclic aromatic heterocycles such as a diazole ring, a thiazole ring and a thiadiazole ring; and a benzothiazole ring, a benzo

Azole 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, benzisoxazole

Azolyl ring, benzo

Fused aromatic heterocycles such as a diazole ring and a benzothiadiazole ring.

The aromatic hydrocarbon ring and the aromatic heterocyclic ring of Rf may have a substituent. Examples of the substituent include: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkenyl groups having 2 to 6 carbon atoms such as vinyl groups and allyl groups; 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 trifluoromethyl group or a pentafluoroethyl group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; methoxy, ethoxy, isopropylAn alkoxy group having 1 to 6 carbon atoms such as an oxy group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; -OCF₃；-C(＝O)-R^x；-C(＝O)-O-R^x；-O-C(＝O)-R^x(ii) a and-SO₂Rb and the like. Herein, R is^xThe aromatic hydrocarbon ring group is characterized by being represented by "(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent group", "(ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent group", "(iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent group", or "(iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent group". Further, Rb represents: alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; or an aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent, such as a phenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group.

Among these, the substituents of the aromatic hydrocarbon ring and the aromatic heterocyclic ring of Rf are preferably a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

Further, Rf may have a plurality of substituents selected from the above-mentioned 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(s) -

As R^xThe "alkyl group having 1 to 20 carbon atoms" of the "alkyl group having 1 to 20 carbon atoms which may have a substituent (i) includes: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 1-methylpentyl, 1-ethylpentyl, sec-butyl, tert-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, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the like.

The carbon number of the "alkyl group having 1 to 20 carbon atoms which may have a substituent (i)" is preferably 1 to 12, more preferably 1 to 10.

- - (ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent(s) - - - - - - - - (ii)

As R^xThe "alkenyl group having 2 to 20 carbon atoms" of the "alkenyl group having 2 to 20 carbon atoms which may have a substituent (ii) includes: vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl and the like.

The number of carbon atoms of the "(ii) alkenyl group having 2 to 20 carbon atoms which may have a substituent(s)", is preferably 2 to 12.

As R^xThe substituent for the "alkyl group having 1 to 20 carbon atoms" of the "(i) alkyl group having 1 to 20 carbon atoms which may have a substituent and the" alkenyl group having 2 to 20 carbon atoms "of the" (ii) alkenyl group having 2 to 20 carbon atoms which may have a substituent include: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; an alkoxy group having 1 to 12 carbon atoms which is substituted with 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 and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group, a benzothiazol-2-ylthio group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; a cycloalkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group, a cyclohexyloxy group, or the like; tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, diyl

A cyclic ether group having 2 to 12 carbon atoms such as an alkyl group; aryloxy group having 6 to 14 carbon atoms such as phenoxy group, naphthoxy group and the likeA group; trifluoromethyl, pentafluoroethyl, -CH₂CF₃A fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; a benzofuranyl group; a benzopyranyl group; benzodioxolyl group; benzodi (benzo-b)

Alkyl groups, and the like. Among these, as R^x(ii) a substituent of (i) an "alkyl group having 1 to 20 carbon atoms" which may have a substituted alkyl group having 1 to 20 carbon atoms and (ii) an "alkenyl group having 2 to 20 carbon atoms" which may have a substituted alkenyl group having 2 to 20 carbon atoms, preferably: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as furyl, thienyl, benzothiazol-2-ylthio and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; trifluoromethyl, pentafluoroethyl, -CH₂CF₃And fluoroalkyl groups having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

In addition, R^xThe "alkyl group having 1 to 20 carbon atoms" of the "(i) alkyl group having 1 to 20 carbon atoms which may have a substituent and the" alkenyl group having 2 to 20 carbon atoms "of the" (ii) alkenyl group having 2 to 20 carbon atoms which may have a substituent may have a plurality of substituents selected from the above-mentioned substituents. At R^xWhen the "alkyl group having 1 to 20 carbon atoms" of the "(i) alkyl group having 1 to 20 carbon atoms which may have a substituent and the" alkenyl group having 2 to 20 carbon atoms "of the" (ii) alkenyl group having 2 to 20 carbon atoms which may have a substituent have a plurality of substituents, the plurality of substituents may be the same or different from each other.

- - (iii) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent(s) - - - - - - (iii)

As R^x(iii) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent(s) "" has 3 to E carbon atomsExamples of the cycloalkyl group of 12 "include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl. Among these, cyclopentyl and cyclohexyl are preferable.

As R^x(iii) the substituent 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(s) includes: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group. Among these, as R^x(iii) a substituent of "cycloalkyl group having 3 to 12 carbon atoms" of the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, preferably: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group.

In addition, R^xThe "cycloalkyl group having 3 to 12 carbon atoms" of the "(iii) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent may have a plurality of substituents. At R^x(iii) the "cycloalkyl group having 3 to 12 carbon atoms" of the "cycloalkyl group having 3 to 12 carbon atoms which may have a substituent(s) has a plurality of substituents, and the plurality of substituents may be the same or different from each other.

- - (iv) an optionally substituted aromatic hydrocarbon ring group having 5 to 18 carbon atoms- - - - - - - - - - - (iv)

As R^xThe "aromatic hydrocarbon ring group having 5 to 18 carbon atoms" of the aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent (iv) includes phenyl, 1-naphthyl, 2-naphthyl and the like. Among these, phenyl and naphthyl are preferable, and phenyl, 1-naphthyl and 2-naphthyl are more preferable.

As R^x(iv) an optionally substituted aromatic hydrocarbon ring group having 5 to 18 carbon atoms"examples of the substituent include: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; an alkoxy group having 1 to 12 carbon atoms which is substituted with 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 and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; a cycloalkoxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group, a cyclohexyloxy group, or the like; tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, diyl

Alkyl groups, and the like. Among these, as R^x(iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent group ", and preferably: a halogen atom selected from fluorine atom, chlorine atom and the like; a cyano group; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, and the like; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a triazolyl group, a pyrrolyl group, a furyl group, a thienyl group and the like; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl and the like; trifluoromethyl, pentafluoroethyl, -CH₂CF₃A fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; -OCF₃At least one substituent in (1).

In addition, R^xThe "aromatic hydrocarbon ring group having 5 to 18 carbon atoms" of the "(iv) aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent may have a plurality of substituents. At R^x(iv) the aromatic hydrocarbon ring group having 5 to 18 carbon atoms "which may have a substituent(s)" in the case where the "aromatic hydrocarbon ring group having 5 to 18 carbon atoms" has a plurality of substituents, the substituents may be the same or different.

Here, the "number of carbon atoms" of the cyclic group having at least one of the aromatic hydrocarbon ring and the aromatic hetero ring of Rf means the number of carbon atoms of the organic group itself having at least one of the aromatic hydrocarbon ring and the aromatic hetero ring, which does not include a carbon atom of the substituent.

When Rf has a plurality of aromatic hydrocarbon rings and/or a plurality of aromatic heterocyclic rings, these plurality of groups may be the same or different.

The Rf is preferably a "cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle 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 heterocycle having 2 to 30 carbon atoms" of Rf are as follows. However, the present invention is not limited to the specific examples shown below. In the following formula, "-" represents a bond with K extending from an arbitrary position of the ring.

1) Specific examples of the hydrocarbon ring group which may have a substituent and has at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms include those represented by the following formulas (1-1) to (1-21), and those represented by the following formulas (1-8) to (1-21) are preferable. The groups represented by the following formulae (1-1) to (1-21) may have a substituent.

[ chemical formula 18]

[ chemical formula 19]

2) Specific examples of the heterocyclic group which may have a substituent and has at least one aromatic ring selected from an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms include structures represented by the following formulae (2-1) to (2-51), and the like, and heterocyclic groups having 2 to 16 carbon atoms represented by the formulae (2-11) to (2-51) and the like are preferable. The groups represented by the following formulae (2-1) to (2-51) may have a substituent.

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ in the formulae, A represents-CH₂-, -NRc-, oxygen atom, sulfur atom, -SO-or-SO₂-，

B and D each independently represent-NRc-, an oxygen atom, a sulfur atom, -SO-or-SO₂-，

E represents-NRc-, an oxygen atom or a sulfur atom.

Wherein Rc represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc. (wherein, in each formula,oxygen atom, sulfur atom, -SO-, -SO₂-each is not adjacent. )]

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

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

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

[ chemical formula 24]

(in the formula (i-4), J represents-CH₂-、-NR^d-, oxygen atom, sulfur atom, -SO-or-SO₂-、R^dRepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

The "cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms" of Rf may have one or more substituents. When a plurality of substituents are present, the plurality of substituents may be the same as or different from each other.

The substituent of "a cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms" of Rf includes, for example: a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; alkenyl groups having 2 to 6 carbon atoms such as vinyl groups and allyl groups; 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 trifluoromethyl group or a pentafluoroethyl group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group;alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; -OCF₃；-C(＝O)-R^x；-C(＝O)-O-R^x；-O-C(＝O)-R^x；-SO₂Rb and the like. Herein, R is^xAnd Rb represents the same meaning as described above, and preferred examples thereof are also the same as described above. When a plurality of substituents are present, the plurality of substituents may be the same or different from each other.

Among these, at least one substituent selected from the group consisting of 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 represents a single chemical bond, -O-, -S-, -C (═ O) -, -O-CRbRc-, -CRbRc-O-, -O-CH₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-C(＝O)-S-、-S-C(＝O)-、-NR¹⁴-C(＝O)-、-C(＝O)-NR¹⁴-、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-CRbRc-、-CRcRb-O-C(＝O)-、-O-C(＝O)-CRbRc-、-CRcRb-C(＝O)-O-、-O-C(＝O)-NR¹⁴-、-NR¹⁴-C(＝O)-O-、-O-C(＝O)-CH₂-S-、-S-CH₂-C (═ O) -O-or-O-C (═ O) -O-. Herein, R is¹⁴Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rc and Rb each independently represents a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 12 carbon atoms, or an optionally substituted aromatic heterocyclic group having 3 to 12 carbon atoms.

Among these, preferred are single chemical bonds, -O-CRbRc-, -CRcRb-O-, -O-CH₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-CRbRc-、-CRcRb-O-C(＝O)-、-O-C(＝O)-CRbRc-、-CRcRb-C(＝O)-O-、-O-C(＝O)-NR¹⁴-、-NR¹⁴-C(＝O)-O-、-O-C(＝O)-CH₂-S-、-S-CH₂-C (═ O) -O-, -O-C (═ O) -O-, more preferably a single chemical bond, -O-CRbRc-, -crcrrb-O-, -O-CH₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-C(＝O)-O-CRbRc-、-CRcRb-O-C(＝O)-、-O-C(＝O)-CRbRc-、-CRcRb-C(＝O)-O-、-O-C(＝O)-NR¹⁴-、-NR¹⁴-C(＝O)-O-、-S-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-S-, particularly preferably a single chemical bond, -O-CRbRc-, -CRcRb-O-, -O-CH₂-CH₂-、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-C(＝O)-O-CRbRc-、-CRcRb-O-C(＝O)-、-O-C(＝O)-CRbRc-、-CRcRb-C(＝O)-O-、-O-C(＝O)-NR¹⁴-、-NR¹⁴-C(＝O)-O-、-S-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-S-。

Herein, R is¹⁴Represents (i) a hydrogen atom or (ii) an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, wherein R is¹⁴Preferably a hydrogen atom.

Rc and Rb each independently represent a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 12 carbon atoms, or an optionally substituted aromatic heterocyclic group having 3 to 12 carbon atoms. Rc and Rb may be the same or different from each other.

Specific examples of the optionally substituted aromatic hydrocarbon ring group having 6 to 12 carbon atoms or the optionally substituted aromatic heterocyclic group having 3 to 12 carbon atoms of Rb and Rc include groups each having a predetermined carbon number among the same groups as those described above with respect to Rf. Examples of the substituent group of Rb and Rc include the same substituent groups as those of Rf, and preferred substituent groups thereof are also the same. When a plurality of substituents are present, they may be the same or different.

Each of Rc and Rb is independently preferably a hydrogen atom, an optionally substituted aromatic hydrocarbon ring group having 6 to 12 carbon atoms, further independently preferably a hydrogen atom, a phenyl group or a naphthyl group, and particularly preferably a combination in which both Rc and Rb are simultaneously a hydrogen atom, a combination of a hydrogen atom and a phenyl group, or a combination of a hydrogen atom and a naphthyl group.

As a preferred combination of Rf-K-,

preferably Rf is selected from the above formulae (i-1) to (i-6), and K is selected from the group consisting of a single chemical bond, -O-T, -O-CRbRc-T, -CRbRc-O-T and-O-CH₂-CH₂-T、-CH₂-CH₂-O-T、-C(＝O)-O-T、-O-C(＝O)-T、-CH₂-CH₂-C(＝O)-O-T、-O-C(＝O)-CH₂-CH₂-T、-C(＝O)-O-CRbRc-T、-CRbRc-O-C(＝O)-T、-O-C(＝O)-CRbRc-T、-CRbRc-C(＝O)-O-T、-NR¹⁴-C(＝O)-O-T、-S-CH₂-a combination of-C (═ O) -O-T.

More preferably, Rf is selected from the above general formulae (i-1) to (i-6), and K is selected from the group consisting of a single chemical bond, -O-T, -CRbRc-O-T, -CH₂-CH₂-O-T、-C(＝O)-O-T、-O-C(＝O)-T、-CH₂-CH₂-C(＝O)-O-T、-CRbRc-O-C(＝O)-T、-CRbRc-C(＝O)-O-T、-NR¹⁴-C(＝O)-O-T、-S-CH₂-a combination of-C (═ O) -O-T.

Further, Rf-K-is particularly preferably any one of the following formulas (ii-1) to (ii-45), and most preferably any one of (iii-1) to (iii-46). Rb and Rc are the same as defined above, and T is the direction in which Ga is bonded. ● (filled circles) in the groups represented by the following formulas (ii-1) to (ii-45) and (iii-1) to (iii-46) represent binding sites to Ga.

The groups represented by the following formulae (ii-1) to (ii-45) and the groups represented by the following formulae (iii-1) to (iii-46) may have a substituent.

In the following formulae (ii-26) to (ii-32) and the following formulae (iii-26) to (iii-32), J represents-CH₂-、-NR^d-, oxygen atom, sulfur atom, -SO-or-SO₂-，R^dRepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[ chemical formula 25]

[ chemical formula 26]

[Ga]

Ga is an optionally substituted organic group having a valence of 2 and having 1 to 20 carbon atoms, and preferably an optionally substituted organic group having a valence of 2 and having 3 to 20 carbon atoms.

Ga is more preferably-CH contained in (i) a 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms and (ii) a 2-valent aliphatic hydrocarbon group having 3 to 20 carbon atoms₂At least one of-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR¹⁵-C(＝O)-、-C(＝O)-NR¹⁵-、-NR¹⁵-or-C (═ O) -substituted group. However, the case where two or more adjacent-O-or 2 or more adjacent-S-are inserted is not included.

Herein, R is¹⁵Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, a hydrogen atom or a methyl group is preferable. Further, examples of the substituent group of the organic group of Ga include: alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy, ethoxy, propoxy and the like; a cyano group; a halogen atom such as a fluorine atom or a chlorine atom.

Examples of the substituent of Ga include: a hydroxyl group; alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl and propyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy, ethoxy, and isopropoxy; a cyano group; a halogen atom such as a fluorine atom or a chlorine atom.

Here, as for Ga, the "aliphatic hydrocarbon group having a valence of 2" is preferably a chain aliphatic hydrocarbon group having a valence of 2, and more preferably an alkylene group. The number of carbon atoms of the "aliphatic hydrocarbon group having a valence of 2" is preferably 3 to 20, more preferably 3 to 18. The "aliphatic hydrocarbon group having a valence of 2" is preferably an aliphatic hydrocarbon group having a valence of 2 to 20 carbon atoms, more preferably a chain-like aliphatic hydrocarbon group having a valence of 2 to 18 carbon atoms, and still more preferably an alkylene group having a carbon number of 2 to 18.

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

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, still more preferably an unsubstituted alkylene group having 6 to 12 carbon atoms, particularly preferably an unsubstituted alkylene group having 6 to 10 carbon atoms, and most preferably a n-hexylene group or a n-octylene group.

When the number of carbon atoms of Ga is 3 or more, both terminals of Ga are preferably-CH₂- (Ga having both ends not substituted). In addition, in the "(ii) carbon number is 3 ~ 20 of 2 valence aliphatic hydrocarbyl containing-CH₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR¹⁵-C(＝O)-、-C(＝O)-NR¹⁵-、-NR¹⁵In the group "substituted with — O" or — C (═ O) -, preferred are consecutive — CH in the group of-O-and-S-unsubstituted aliphatic hydrocarbon groups₂- (i.e. structures in which-O-and-S-are not formed) (that is, the case where insertion of two or more adjacent-O-or two or more adjacent-S-is not preferably included), preferably-C (═ O) -continuous-CH in unsubstituted aliphatic hydrocarbon group₂- (i.e. structures which do not form-C (═ O) -).

a-CH contained in a 2-valent aliphatic hydrocarbon group having 3 to 20 carbon atoms₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR¹⁵-C(＝O)-、-C(＝O)-NR¹⁵-、-NR¹⁵When the group-or-C (═ O) -is substituted, it is most preferably substituted with-O-, and it is preferable to use a so-called ethyleneoxy group substituted with-O-at every two carbon atoms as a repeating unit,Both ends of Ga are-CH₂-。

As Ga, (i) "a C1-18, preferably C3-18, 2-valent chain aliphatic hydrocarbon group and-CH contained in a C3-18, 2-valent chain aliphatic hydrocarbon group are preferable₂Any organic group of at least one group substituted with-O-, -S-, -O-C (-O) -, -C (-O) -O-or-C (-O) -, in which the adjacent 2 or more-O-or the adjacent 2 or more-S-is not included, more preferably (ii) "a 2-valent chain aliphatic hydrocarbon group having 3 to 18 carbon atoms", still more preferably (iii) "an alkylene group having 3 to 18 carbon atoms", still more preferably (iv) "an unsubstituted alkylene group having 4 to 16 carbon atoms", still more preferably (v) "an unsubstituted alkylene group having 5 to 14 carbon atoms", still more preferably (vi) "an unsubstituted alkylene group having 6 to 12 carbon atoms", particularly preferably, the "unsubstituted alkylene group having 6 to 10 carbon atoms" in (vii) "most preferably" n-hexylene group, n-octylene group or n-decylene group ".

[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-CH contained in (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) an aliphatic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR¹⁵-C(＝O)-、-C(＝O)-NR¹⁵-、-NR¹⁵-or-C (═ O) -substituted group. However, the case where two or more adjacent-O-or two or more adjacent-S-are inserted is not included.

Herein, R is¹⁵Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, a hydrogen atom or a methyl group is preferable.

In addition, as the substituent group of the organic group of Gb, there may be mentioned: a hydroxyl group; alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl and propyl; methoxy, ethoxy,C1-5 alkoxy groups such as propoxy groups; a cyano group; a halogen atom such as a fluorine atom or a chlorine atom; -O-C (═ O) -CRg ═ CH₂And other polymerizable groups. Herein, Rg represents a hydrogen atom, a methyl group, or a chlorine atom.

Here, the "aliphatic hydrocarbon group" is preferably a chain aliphatic hydrocarbon group, and more preferably an alkyl group, an alkynyl group, or an alkenyl group, with respect to Gb. The "aliphatic hydrocarbon group" is preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms, more preferably a chain-like aliphatic hydrocarbon group having 2 to 18 carbon atoms, and still more preferably an alkyl group having 2 to 18 carbon atoms (e.g., n-hexyl group), an alkynyl group having 2 to 18 carbon atoms (e.g., 2-butynyl group), or an alkenyl group having 2 to 18 carbon atoms (e.g., 1-butenyl group).

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

The Gb has preferably a structure of 4 to 16 carbon atoms in an unsubstituted alkyl group, 4 to 16 carbon atoms in an unsubstituted alkynyl group, or 4 to 16 carbon atoms in an unsubstituted alkenyl group, more preferably a carbon 4 to 14 unsubstituted alkyl group, a carbon 4 to 14 unsubstituted alkynyl group, or a carbon 4 to 14 unsubstituted alkenyl group, even more preferably a carbon 4 to 12 unsubstituted alkyl group, a carbon 4 to 12 unsubstituted alkynyl group, or a carbon 4 to 12 unsubstituted alkenyl group, particularly preferably a carbon 4 to 10 unsubstituted alkyl group, a carbon 4 to 10 unsubstituted alkynyl group, or a carbon 4 to 10 unsubstituted alkenyl group, even more preferably a carbon 4 to 10 unsubstituted alkyl group, and most preferably an n-hexyl group.

When the number of carbon atoms of Gb is 3 or more, it is preferable that one end of Gb (the side bonded to N) is-CH₂- (single end of Gb not substituted). In addition, in the "(ii) in the carbon number of 3 ~ 20 aliphatic hydrocarbyl containing-CH₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR¹⁵-C(＝O)-、-C(＝O)-NR¹⁵-、-NR¹⁵-, or-C (═ O) -substitutedAmong the groups of (A) is preferably continuous-CH in-O-and-S-unsubstituted aliphatic hydrocarbon groups₂- (i.e. structures in which-O-and-S-are not formed) (that is, the case where insertion of adjacent 2 or more-O-or adjacent 2 or more-S-is not preferably included), and preferably-C (═ O) -continuous-CH in unsubstituted aliphatic hydrocarbon group₂- (i.e. structures which do not form-C (═ O) -).

-CH contained in aliphatic hydrocarbon group having 3 to 20 carbon atoms₂At least one of-is-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR¹⁵-C(＝O)-、-C(＝O)-NR¹⁵-、-NR¹⁵In the case of substitution with-or-C (═ O) -, it is most preferable to substitute with-O-, and it is preferable that a repeating unit be a so-called ethyleneoxy group substituted with-O-at every 2 carbon atoms, and that one terminal (binding side to N) of Ga be-CH₂-。

The Gb is preferably (i) "a chain aliphatic hydrocarbon group having 1 to 18 carbon atoms, preferably 3 to 18 carbon atoms, which may have a substituent, or-CH contained in a chain aliphatic hydrocarbon group having 3 to 18 carbon atoms, which may have a substituent₂Any organic group of at least one group substituted with — O-, -S-, -O-C (═ O) -, -C (═ O) -O-, or-C (═ O) -, the case where no adjacent 2 or more-O-or adjacent 2 or more-S-is included, more preferably (ii) "a chain aliphatic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent", still more preferably (iii) "an alkyl group, an alkynyl group, or an alkenyl group having 3 to 18 carbon atoms which may have a substituent", still more preferably (iv) "an unsubstituted alkyl group having 4 to 16 carbon atoms, an unsubstituted alkynyl group having 4 to 16 carbon atoms, or an unsubstituted alkenyl group having 4 to 16 carbon atoms", and still more preferably (v) "an unsubstituted alkyl group having 4 to 14 carbon atoms, (vii) an unsubstituted alkynyl group having 4 to 14 carbon atoms or an unsubstituted alkenyl group having 4 to 14 carbon atoms ", more preferably (vi)" an unsubstituted alkyl group having 4 to 12 carbon atoms, an unsubstituted alkynyl group having 4 to 12 carbon atoms or an unsubstituted alkenyl group having 4 to 12 carbon atoms ", and particularly preferably (vii)" an unsubstituted alkyl group having 4 to 10 carbon atoms, an unsubstituted alkynyl group having 4 to 10 carbon atoms or an unsubstituted alkenyl group having 4 to 12 carbon atoms "An unsubstituted alkenyl group having 4 to 10 carbon atoms ", an unsubstituted alkyl group having 4 to 10 carbon atoms is particularly preferable, and (viii)" n-hexyl "is most preferable.

[Q]

In the formulae (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 which may have a substituent include methyl, ethyl, propyl, isopropyl and the like, and examples of the substituent include an aromatic hydrocarbon group having 6 to 12 carbon atoms such as phenyl, naphthyl and the like.

[R^I～R^IV]

In the formulae (IV-1) to (IV-4), R^I～R^IVEach independently represents a hydrogen atom; a halogen atom such as a fluorine atom or a chlorine atom; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; 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 trifluoromethyl group or a pentafluoroethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; -OCF₃；-C(＝O)-O-R^a(ii) a or-O-C (═ O) -R^a，R^aThe same meanings as above are given, and preferred examples thereof are also the same as above.

Among these, (i) R is preferable^I～R^IVAre each a hydrogen atom, or (ii) R^I～R^IVAt least one of them is an alkoxy group having 1 to 6 carbon atoms which may have a substituent, and the others are hydrogen atoms.

R^I～R^IVAt least one C-R which may be the same or different and form a ring^I～C-R^IVCan be substituted by nitrogen atoms.

C-R^I～C-R^IVSpecific examples of the group in which at least one of them is substituted with a nitrogen atom are shown below. However, C-R^I～C-R^IVThe group in which at least one of them is substituted with a nitrogen atom is not limited to these.

[ chemical formula 27]

[ in the formulae, R^I～R^IVThe same meanings as above are given, and preferred examples thereof are also the same as above.]

[R⁰、p、p1、p2]

In the formulae (IV-1) to (IV-4), R⁰Represents: a halogen atom; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; 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 trifluoromethyl group or a pentafluoroethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and the like; -OCF₃；-C(＝O)-O-R^a(ii) a or-O-C (═ O) -R^a，R^aThe same meanings as above are given, and preferred examples thereof are also the same as above.

As R⁰From the viewpoint of improving solubility, it is preferable that: a halogen atom such as a fluorine atom or a chlorine atom; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl; 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 trifluoromethyl group or a pentafluoroethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and the like. In addition, in R⁰In the case of plural, plural R⁰May be the same or different from each other. In the formulae (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 preferably, p1 and p2 are all 0.

<<Y³、Y⁴>>

In the formula (III), Y³And Y⁴Each independently represents a single chemical bond, -O-CH₂-、-CH₂-O-、-O-CH₂-CH₂、-CH₂-CH₂-O-、-C(＝O)-O-、-O-C(＝O)-、-O-C(＝O)-O-、-C(＝O)-S-、-S-C(＝O)-、-NR¹³-C(＝O)-、-C(＝O)-NR¹³-、-CF₂-O-、-O-CF₂-、-CH₂-CH₂-、-CF₂-CF₂-、-O-CH₂-CH₂-O-、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-、-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-、-CH₂-CH₂-C(＝O)-O-、-O-C(＝O)-CH₂-CH₂-、-CH₂-CH₂-O-C(＝O)-、-C(＝O)-O-CH₂-CH₂-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝C(CH₃)-、-C(CH₃) N-, -N-or-C ≡ C-. Herein, R is¹³Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In these, Y³And Y⁴Each independently is preferably a single chemical bond, -O-C (═ O) -, -C (═ O) -O-, or-O-C (═ O) -O-.

<<A²³、A²⁴>>

In the formula (III), A²³And A²⁴Each independently represents the same as A²The same meanings as those of A above are also preferred²The same is true.

<<B²¹、B²²、Y²¹、Y²²、L²¹、L²²、R³¹、R³²、d1、d2、e1、e2>>

In the formula (III), B²¹、B²²、Y²¹、Y²²、L²¹、L²²、R³¹、R³²D1, d2, e1 and e2 have the same meanings as described above, and preferred examples thereof are also the same as described above.

The polymerizable compound (III) is not particularly limited, but preferably has a symmetrical structure (i.e., Y) with Ar as the center³And Y⁴Same, A²³And A²⁴Same, B²¹And B²²Same, Y²¹And Y²²Same, L²¹And L²²Same, R³¹And R³²Identical, d1 and d2 identical, e1 and e2 identical (symmetrical about Ar)).

The polymerizable compound (III) is preferably a polymerizable compound represented by any one of the following formulae (V-1) and (V-2), and more preferably the following formula (V-1).

[ chemical formula 28]

[ chemical formula 29]

(in formulae (V-1) and (V-2), R, Q, R^I～R^IV、R⁰、Y³、Y⁴、A²³、A²⁴、B²¹、B²²、Y²¹、Y²²、L²¹、L²²、R³¹、R³²D1, d2, e1, e2, p1 and p2 have the same meanings as described above, and preferred examples thereof are also the same as described above. )

The polymerizable compound represented by the formula (V-1) is preferably a polymerizable compound (iii-1) represented by the following formula (iii-1), more preferably a polymerizable compound (iii-2) represented by the following formula (iii-2), and particularly preferably any one of the following formulae (1) and (2).

[ chemical formula 30]

(in the formula (iii-1), R, Q, R^I～R^IV、R⁰、Y³、Y⁴、A²³、A²⁴、B²¹、B²²、Y²¹、Y²²、L²¹、L²²、R³¹、R³²D1, d2, e1, e2 and p have the same meanings as described above, and preferred examples thereof are also the same as described above. )

[ chemical formula 31]

(in the formula (iii-2))，R^I～R^IVQ and R are as defined above, and preferred examples thereof are as defined above. k and l each independently represent an integer of 1 to 18. )

[ chemical formula 32]

[ chemical formula 33]

The polymerizable compound (III) can be synthesized by combining known synthesis reactions. That is, it can be synthesized by referring to various documents (for example, International publication No. 2012/141245, International publication No. 2012/147904, International publication No. 2014/010325, International publication No. 2013/046781, International publication No. 2014/061709, International publication No. 2014/126113, International publication No. 2015/064698, International publication No. 2015-140302, International publication No. 2015/129654, International publication No. 2015/141784, International publication No. 2016/159193, International publication No. 2012/169424, International publication No. 2012/176679, International publication No. 2015/122385, Japanese patent laid-open No. 2016 190818, International publication No. 2017/150622) and the like).

For example, the polymerizable compound (iii-1) (Q is a hydrogen atom, and p is 0) can be obtained by reacting the compound (I) contained in the intermediate produced by the intermediate production method of the present invention with the benzaldehyde compound (AA) represented by the formula (AA) to obtain a compound (AB) represented by the following formula (AB), and then reacting the compound (AB) with the compound (AC) represented by the following formula (AC).

Further, details of the reaction conditions and the like can be set with reference to international publication No. 2014/010325, international publication No. 2015/064698, and international publication No. 2015/141784.

[ chemical formula 34]

[ chemical formula 35]

(formula (I), formula (AB), formula (AC) and formula (iii-1) wherein R³、Y²、B²、L²、A²、FG²、d、e、Y³、Y⁴、A²³、A²⁴、B²¹、B²²、Y²¹、Y²²、L²¹、L²²、R³¹、R³²D1, d2, e1, e2, R and R^I～R^IVThe same meanings as above are given, and preferred examples thereof are also the same as above. )

< polymerizable composition >

The polymerizable composition contains at least a polymerizable compound (III) and a polymerization initiator.

As described later, the polymerizable composition is useful as a raw material for producing polymers, optical films, and optically anisotropic bodies. Further, 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 carrying out the polymerization reaction of the polymerizable compound (III) contained in the polymerizable composition.

Examples of the polymerization initiator to be used include a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator.

As the radical polymerization initiator, it is possible to use: a thermal radical generator which generates an active species capable of initiating polymerization of the polymerizable compound by heating; the photo radical generator is any of compounds that generate an active species that can initiate polymerization of the polymerizable compound by exposure to visible light, ultraviolet light (i rays, etc.), far ultraviolet light, electron beams, X rays, or the like, and is preferably used.

Examples of the photoradical generator include: acetophenone compound, bisimidazole compound, triazine compound, O-acyloxime compound, and,

Salt-based compounds, acetophenone-based compounds, benzophenone-based compounds, α -diketone-based compounds, polyquinone-based compounds, xanthone-based compounds, diazo-based compounds, imide sulfonate-based compounds, and the like. These compounds are components that generate a reactive radical or a reactive acid, or both, upon exposure to light. The photo radical generators may be used singly or in combination of two or more.

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

Specific examples of the bisimidazole-based compound include: 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -bisimidazole, 2 ' -bis (2-bromophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -bisimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -bisimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -bisimidazole, 2 ' -bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -bisimidazole, 2 ' -bis (2-bromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -bisimidazole, 2 ' -bis (2, 4-dibromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -bisimidazole, 2 ' -bis (2,4, 6-tribromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -bisimidazole, and the like.

In addition, when a bisimidazole compound is used as a photopolymerization initiator (photo radical generator), it is preferable to use a hydrogen donor in combination in order to further improve sensitivity.

Here, the "hydrogen donor" refers to a compound capable of supplying a hydrogen atom to a radical generated from the bisimidazole compound by exposure. As the hydrogen donor, thiol compounds, amine compounds, and the like defined below are preferable.

Specific examples of the thiol compound include: 2-mercaptobenzothiazole, 2-mercaptobenzothiazole

Oxazole, 2-mercaptobenzimidazole, 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercapto-2, 5-dimethylaminopyridine, and the like. Examples of the amine compound include 4,4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, and 4-dimethylaminobenzoic acid nitrile.

Specific examples of the triazine compound include: 2,4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, triazine compounds having a halomethyl group such as 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, and 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine.

Specific examples of the O-acyloxime compound include: 1- [4- (phenylthio) phenyl ] -heptane-1, 2-dione-2- (O-benzoyloxime), 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-carbazol-3-yl ] -ethanone-1- (O-ethylglyoxyl) Acyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone-1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzoyl) -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-tetrahydrofurylbenzoyl) -9H-carboximide Oxazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydropyranyl-benzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) benzoyl } -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranyl-methoxybenzoyl) -9H-carbazol-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- Tetrahydropyranyl methoxybenzoyl) -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.

Further, as the photo radical generator, a commercially available product can be used as it is. Specific examples thereof include: trade name manufactured by BASF corporation: irgacure907, trade name: irgacure184, trade name: irgacure369, trade name: irgacure651, trade name: irgacure819, trade name: irgacure907 and trade name: irgacure OXE02 manufactured by ADEKA, trade name: ADEKA ARKLS N1919T, and the like.

Examples of the anionic polymerization initiator include: an alkyl lithium compound; mono-lithium or mono-sodium salts of biphenyl, naphthalene, pyrene, etc.; and polyfunctional initiators such as dilithium salts and trilithium salts.

Further, examples of the cationic polymerization initiator include: protonic acids such as sulfuric acid, phosphoric acid, perchloric acid, trifluoromethanesulfonic acid and the like; lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride and tin tetrachloride; aromatic compounds

Salts or aromatics

A combination system of a salt and a reducing agent.

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

In the polymerizable composition, the blending ratio of the polymerization initiator is usually 0.1 to 30 parts by mass, and preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound contained in the polymerizable composition.

In addition, a surfactant is preferably blended in the polymerizable composition for the purpose of adjusting the surface tension. The surfactant is not particularly limited, and a nonionic surfactant is generally preferred. As the nonionic surfactant, commercially available products may be used, and examples of the nonionic surfactant containing an oligomer containing a fluorine-containing group, a hydrophilic group and a lipophilic group include: surflon series (S242, S243, S386, S611, S651, etc.) manufactured by AGC Seimi Chemical, Megaface series (F251, F554, F556, F562, RS-75, RS-76-E, etc.) manufactured by DIC, Ftergent series (FTX601AD, FTX602A, FTX601ADH2, FTX650A, etc.) manufactured by Neos, and the like. These surfactants may be used alone or in combination of two or more at an arbitrary ratio.

Here, the compounding ratio of the surfactant in the polymerizable composition is usually 0.01 to 10 parts by mass, and preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the polymerizable compound contained in the polymerizable composition.

The polymerizable composition may further contain other components in addition to the polymerizable compound, the polymerization initiator, and the surfactant. Examples of 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, and the like.

In addition, other copolymerizable monomers may be used as the other component. Specific examples thereof are not particularly limited, but include, for example, 4 ' -methoxyphenyl 4- (2-methacryloyloxyethyloxy) benzoate, biphenyl 4- (6-methacryloyloxyhexyloxy) benzoate, 4 ' -cyanobiphenyl 4- (2-acryloyloxyethyloxy) benzoate, 4 ' -cyanobiphenyl 4- (2-methacryloyloxyethyloxy) benzoate, 3 ', 4 ' -difluorophenyl 4- (2-methacryloyloxyethyloxy) benzoate, naphthyl 4- (2-methacryloyloxyethyloxy) benzoate, 4-acryloyloxy-4 ' -decylbiphenyl, 4-acryloyloxy-4 ' -cyanobiphenyl, 4- (2-Acryloxyethyloxy) -4 '-cyanobiphenyl ester, 4- (2-methacryloyloxyethyloxy) -4' -methoxybenzyl ester, 4- (2-methacryloyloxyethyloxy) -4 '- (4 "-fluorobenzyloxy) -biphenyl ester, 4-acryloyloxy-4' -propylcyclohexylphenyl ester, 4-methacryloyl-4 '-butyldicyclohexyl ester, 4-acryloyl-4' -pentyltolane, 4-acryloyl-4 '- (3, 4-difluorophenyl) dicyclohexyl ester, 4- (2-acryloyloxyethyl) benzoic acid (4-pentylphenyl ester), 4- (2-acryloyloxyethyl) benzoic acid (4- (4' -propylcyclohexylcyclohexylphenyl ester) Phenyl ester) under the trade name "LC-242" (manufactured by BASF corporation), trans-1, 4-bis [4- [6- (acryloyloxy) hexyloxy ] phenyl ] cyclohexanedicarboxylate, and Japanese patent application laid-open Nos. 2007-002208, 2009-173893, 2009-274984, 2010-030979, 2010-031223, 2011-006360, 2010-24438, 2012/141245, 2012/147904, 2012/169424, 2012/76679, 2013/180217, 2014/010325, 2014/061709, 2014/065176, A copolymerizable monomer such as a compound disclosed in International publication No. 2014/126113, International publication No. 2015/025793, International publication No. 2015/064698, International publication No. 2015/122384 or International publication No. 2015/122385.

The blending ratio of these other components is usually 0.005 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound contained in the polymerizable composition.

The polymerizable composition can be usually prepared by mixing and dissolving predetermined amounts of the polymerizable compound, the polymerization initiator, and other components and the like which are blended as desired in an appropriate 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; 1, 4-di

And ethers such as alkane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and 1, 3-dioxolane.

< Polymer >

The polymer is obtained by polymerizing the polymerizable compound (III) or the polymerizable composition.

Here, "polymerization" means a chemical reaction in a broad sense including a crosslinking reaction in addition to a general polymerization reaction.

The polymer generally has a monomer unit derived from the polymerizable compound (III).

Since the polymer is produced using the polymerizable compound (III) or the polymerizable composition, the polymer can be suitably used as a constituent material of an optical film or the like.

The polymer can be used in any shape depending on the application, such as a film, a powder, a layer of a powder assembly, and the like, without particular limitation.

Specifically, the polymer film can be favorably used as a constituent material of an optical film and an optically anisotropic body described later, the polymer powder can be used for a paint, a counterfeit-proof article, a security article, and the like, and a layer formed of the polymer powder can be favorably used as a constituent material of an optically anisotropic body.

Specifically, the polymer can be preferably produced by the following method or the like: (α) a method in which a polymerization reaction of the polymerizable compound (III) or the polymerizable composition is carried out in the presence of an appropriate organic solvent, the target polymer is isolated, the obtained polymer is dissolved in an appropriate organic solvent to prepare a solution, the solution is coated on an appropriate substrate, the obtained coating film is dried, and then, the coating film is heated as desired; (β) the polymerizable compound (III) or the polymerizable composition is dissolved in an organic solvent, the solution is applied to a substrate by a known coating method, and then the solvent is removed, followed by heating or irradiation with an active energy beam to perform a polymerization reaction. The polymerizable compound (III) may be polymerized alone.

The organic solvent used for the polymerization reaction in the method (α) is not particularly limited as long as it is an inert organic solvent. Examples thereof include: aromatic hydrocarbons such as toluene, xylene, mesitylene, and the like; 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; and ethers such as cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and the like.

Among these, from the viewpoint of excellent handling properties, an organic solvent having a boiling point of 60 to 250 ℃ is preferable, and an organic solvent having a boiling point of 60 to 150 ℃ is more preferable.

In addition, as the organic solvent for dissolving the polymer to be separated in the method (α) and the organic solvent used in the method (β), there may be mentioned: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane and the like; tetrahydrofuran, tetrahydropyran, 1, 2-dimethoxyethane, 1, 4-bis

Ether solvents such as alkane, cyclopentylmethyl ether, and 1, 3-dioxolane; n, N-dimethylformamide, N-diethylacetamide, dimethyl sulfoxide, gamma-butyrolactone,Aprotic polar solvents such as N-methylpyrrolidone (N-methyl-2-pyrrolidone). Among these, from the viewpoint of ease of handling, an organic solvent having a boiling point of 60 to 200 ℃ is preferred. These solvents may be used alone, or two or more of them may be used in combination.

As the substrate used in the methods (α) and (β), any of the substrates made of known and conventional materials can be used, regardless of organic or inorganic materials. Examples of the organic material include: polycycloolefins [ for example, ZEONEX, ZEONOR (registered trademark; manufactured by japan ryson corporation), ARTON (registered trademark; manufactured by JSR corporation) and APEL (registered trademark; manufactured by mitsui chemical corporation) ], polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose triacetate, polyether sulfone, and the like, and as inorganic materials, there can be mentioned: silicon, glass, calcite, and the like.

The substrate used may be a single layer or a laminate.

The substrate is preferably a substrate made of an organic material, and more preferably a resin film made of an organic material in a film form.

Examples of the substrate include substrates for producing optically anisotropic bodies described later.

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

Further, as the method for drying or desolvating in the above methods (α) and (β), natural drying, heat drying, drying under reduced pressure, heat drying under reduced pressure, or the like can be used.

The drying temperature is not particularly limited if the solvent can be desolventized, and the lower limit temperature is preferably 50 ℃ or higher, more preferably 70 ℃ or higher, from the viewpoint of stably obtaining a constant temperature.

The upper limit temperature of the drying temperature is preferably 200 ℃ or lower, and more preferably 195 ℃ or lower, from the viewpoint of not affecting the substrate adversely.

Further, as a method for polymerizing the polymerizable compound (III) or the polymerizable composition, a method of irradiating with an active energy beam, a thermal polymerization method, and the like can be mentioned, and a method of irradiating with an active energy beam is preferable from the viewpoint of not requiring heating and proceeding with a reaction at room temperature. Among them, a method of irradiating light such as ultraviolet light is preferable in view of easy operation.

The temperature at which light such as ultraviolet light is irradiated is not particularly limited if it is a temperature at which a liquid crystal phase can be maintained, and the lower limit temperature is preferably 15 ℃ or higher, more preferably 20 ℃ or higher, from the viewpoint of enabling photopolymerization to proceed stably.

The upper limit temperature of the temperature at which light such as ultraviolet light is irradiated is preferably 200 ℃ or lower, and more preferably 195 ℃ or lower, from the viewpoint of not affecting the substrate adversely.

Here, the temperature at the time of light irradiation is preferably 100 ℃. The intensity of light irradiation is usually 1W/m²～10kW/m²Preferably in the range of 5W/m²～2kW/m²The range of (1). The dose of the ultraviolet ray irradiation is preferably 0.1mJ/cm²Above, more preferably 0.5mJ/cm²Above, preferably 5000mJ/cm²More preferably 4000mJ/cm²The following.

The polymer obtained as described above can be used by transferring it onto a substrate, can be used singly by peeling it from a substrate, and can also be used as a constituent material of an optical film or the like without peeling it from a substrate.

The polymer peeled from the substrate can be pulverized by a known method and used in the form of powder.

The number average molecular weight of the polymer obtained as described above is preferably 500 to 500000, more preferably 5000 to 300000. When the number average molecular weight is in this range, high hardness can be obtained and handling properties are excellent, which is preferable. The number average molecular weight of the polymer can be measured by Gel Permeation Chromatography (GPC) using monodisperse polystyrene as a standard sample and tetrahydrofuran as an eluent.

Further, an optical film or the like having excellent in-plane uniformity of film thickness and improved in-plane uniformity of optical characteristics can be obtained from the polymer.

< optical film >

The optical film includes a layer having an optical function and formed using a polymer and/or a polymerizable compound. The optical function refers to simple transmission, reflection, refraction, birefringence, and the like. The optical film may be an optical film in which a polymer is 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. When the total constituent components of the layer having an optical function are 100% by mass, the proportion of the polymer in the optical film using the polymer as a constituent material is preferably more than 50% by mass. Further, it is preferable that the optical film containing the polymerizable compound contains 0.01% by mass or more of the polymerizable compound when the total constituent components of the layer having the optical function are 100% by mass.

Here, the optical film may be in any form of a form (alignment substrate/(alignment film)/optical film) which is left as it is after being formed on an alignment substrate which may have an alignment film, a form (transparent substrate film/optical film) in which the optical film is transferred to a transparent substrate film or the like different from the alignment substrate, or an optical film single layer form (optical film) in the case where the optical film has a self-supporting property.

As the alignment film and the alignment substrate, the same substrate and alignment film as those of optically different materials described later can be used.

Further, the optical film can be manufactured by the following method: (A) applying a solution containing a polymerizable compound or a solution of a polymerizable composition onto an alignment substrate, drying the obtained coating film, and performing heat treatment (alignment of liquid crystal) and light irradiation and/or heat treatment (polymerization); (B) applying a solution of a polymerizable compound or a liquid crystalline polymer obtained by polymerizing a polymerizable composition onto an alignment substrate, and optionally drying the resulting coating film; (C) a solution containing a polymerizable compound and a resin is applied to an alignment substrate, and the resulting coating film is dried.

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

The optical film can be obtained from the phase difference at a wavelength of 400nm to 800nm as measured by a Mueller Matrix Polarimeter Axoscan. The following α value and β value are preferably within the specified ranges. Specifically, the alpha value is preferably 0.70 to 0.99, and more preferably 0.75 to 0.90. The beta value is preferably 1.00 to 1.25, more preferably 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)

< optically Anisotropic article >

The optically anisotropic body has a layer made of a polymer.

The optically anisotropic body can be obtained by, for example, forming an alignment film on a substrate and further forming a layer (liquid crystal layer) made of a polymer on the alignment film. The optically anisotropic body may be one in which a layer (liquid crystal layer) made of a polymer is directly formed on a substrate, or one in which only a layer (liquid crystal layer) made of a polymer is formed.

The layer formed of a polymer may be formed of a film-like polymer or an aggregate of polymers in the form of powder.

Here, an alignment film is formed on the surface of the substrate in order to align the polymerizable compound in one direction in the plane.

The alignment film can be obtained by: a solution (composition for an alignment film) containing a polymer such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamideimide, or polyetherimide is applied to a substrate in a film form, dried, and then subjected to rubbing treatment or the like in one direction.

The thickness of the alignment film is preferably 0.001 to 5 μm, and more preferably 0.001 to 1.0 μm.

The method of rubbing treatment is not particularly limited, and examples thereof include a method of rubbing an alignment film in a certain direction with a roller wound with a cloth or felt made of synthetic fibers such as nylon or natural fibers such as kapok. In order to remove fine powder (foreign matter) generated during the rubbing treatment and to keep the surface of the alignment film clean, it is preferable to wash the alignment film with isopropyl alcohol or the like after the rubbing treatment.

In addition, the alignment film can be provided with a function of alignment control in one direction in the plane by a method of irradiating polarized ultraviolet rays to the surface of the alignment film in addition to a method of performing rubbing treatment.

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

Examples of the alicyclic olefin polymer include: examples of the hydrogenated polymer include a cyclic olefin random multipolymer described in Japanese patent application laid-open No. H05-310845 and U.S. Pat. No. 5179171, a hydrogenated polymer described in Japanese patent application laid-open No. H05-97978 and U.S. Pat. No. 5202388, a thermoplastic dicyclopentadiene ring-opened polymer described in Japanese patent application laid-open No. H11-124429 (International publication No. 99/20676), and a hydrogenated product thereof.

Examples of a method for forming a liquid crystal layer made of a polymer on an alignment film include the same methods as those described in the above-mentioned item of polymers (the above (α) and (β)).

The thickness of the liquid crystal layer obtained is not particularly limited, and is usually 1 to 10 μm.

Further, as one kind of optically different material, there is no particular limitation, and examples thereof include a retardation film, a viewing angle enlarging film and the like.

The optically different material can be obtained from the phase difference at a wavelength of 400nm to 800nm as measured by a Mueller Matrix Polarimeter Axoscan. The following α value and β value are preferably within the specified ranges. Specifically, the alpha value is preferably 0.70 to 0.99, and more preferably 0.75 to 0.90. The beta value is preferably 1.00 to 1.25, more preferably 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 a polarizing plate in which an optically anisotropic body is laminated on a polarizing film directly or via another layer (e.g., a glass sheet).

The method for producing the polarizing film is not particularly limited. Examples of the method for producing the PVA-based polarizing film include: the present invention relates to a method for uniaxially stretching a PVA-based film after adsorbing iodine ions, a method for simultaneously adsorbing iodine ions to a PVA-based film and uniaxially stretching the same, a method for uniaxially stretching a PVA-based film after dyeing a PVA-based film with a dichroic dye, a method for dyeing a PVA-based film with a dichroic dye after uniaxially stretching the same, and a method for simultaneously dyeing a PVA-based film with a dichroic dye and uniaxially stretching the same. Further, examples of the method for producing the polyolefin-based polarizing film include: a method of uniaxially stretching a PVA-based film and then heating and dehydrating the film in the presence of a dehydration catalyst; a method of uniaxially stretching a polyvinyl chloride-based film, and then heating and dehydrating the film in the presence of a deacidification catalyst.

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

Examples of the adhesive constituting the adhesive layer include: acrylic adhesives, urethane adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, polyvinyl alkyl ether adhesives, rubber adhesives, vinyl chloride-vinyl acetate adhesives, styrene-butadiene-styrene copolymer (SBS copolymer) adhesives, hydrogenated product thereof (SEBS copolymer) adhesives, ethylene adhesives such as ethylene-vinyl acetate copolymers and ethylene-styrene copolymers, and acrylate adhesives such as ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl methacrylate copolymers and ethylene-ethyl acrylate copolymers.

Since the polarizing plate uses an optically anisotropic material, it has reverse wavelength dispersibility and excellent in-plane uniformity of optical characteristics.

Further, by using the polarizing plate, a display device having a panel and an antireflection film can be preferably 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 having a polarizing plate and a liquid crystal panel, and an organic electroluminescence display device having a liquid crystal panel and an organic electroluminescence panel.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "%" and "part" of the amounts are based on mass unless otherwise specified.

Example 1 Synthesis of Compound 1

Compound 1 represented by the following structural formula is obtained through step 1 and step 2 described later.

[ chemical formula 36]

< step 1: synthesis of Compound A >

First, compound a represented by the following structural formula was synthesized by the method described in international publication No. 2017/150622 (step 1).

[ chemical formula 37]

< step 2: synthesis of Compound 1 >

Next, 83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) were placed in a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in the preceding step 1 was added thereto, and the reactor was immersed in an ice bath to bring the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. To the resulting reaction solution was added 250g of water, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.57% by mass. The reaction formula is shown below. In the organic layer at this stage, 44.9g of the compound X represented by the following structural formula was contained.

[ chemical formula 38]

[ chemical formula 39]

Further, 200g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The filtrate in which the above-mentioned washing solutions were combined was further stirred at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate to wash. After washing, the mixture was separated, and after the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again and stirred at 40 ℃ for 30 minutes. This operation was performed 5 times in total, liquid separation was performed, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was gradually cooled to 0 ℃ to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with n-hexane and then dried under vacuum to obtain 98.55g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 92.6% by mass. The yield of compound 1 was 57.64 mol% based on compound a.

Example 2 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The organic layer was further washed by stirring at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate. After washing, the mixture was separated, and after the aqueous layer was extracted, 416g of 1 mol/l composed ethanol was added againThe buffer solution of acid and sodium acetate (pH5.5) was stirred at 40 ℃ for 30 minutes. This operation was carried out 5 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.58% by mass. In addition, 44.8g of the compound X represented by the above structural formula was contained in the organic layer at this stage.

Further, 200g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The filtrate obtained by combining the above-mentioned washing solutions was washed by adding 250g of water thereto at 5 ℃ and stirring for 30 minutes. After the washing, liquid separation was performed, the aqueous layer was extracted, 250g of water was added again, the mixture was stirred for 30 minutes to wash and liquid separation, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was slowly cooled to 0 ℃ to precipitate a solid, and the precipitated solid was filtered. The filtrate was washed with n-hexane and then dried under vacuum to obtain 98.88g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 91.8% by mass. The yield of compound 1 was 57.33 mol% based on compound a.

Example 3 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the reaction solution was stirred at 5 deg.CStirred at 0 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.59 mass%. In addition, 45.0g of the compound X represented by the above structural formula was contained in the organic layer at this stage.

Further, 50g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The above-mentioned filtrate in which the washing solutions were combined was further stirred at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate to wash. After washing, the mixture was separated, and the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was performed 5 times in total, liquid separation was performed, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was gradually cooled to 0 ℃ to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with n-hexane and then dried under vacuum to obtain 99.22g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 92.5% by mass. The yield of compound 1 was 57.97 mol% based on compound a.

Example 4 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Next, while maintaining the internal temperature of the reaction solution at 10 ℃ or lower40.2g (0.397mol) of triethylamine (Et) are slowly added dropwise over a period of 20 minutes₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The organic layer was further washed with 416g of a 1 mol/liter buffer solution (pH5.5) formed of acetic acid and sodium acetate with stirring at 40 ℃ for 30 minutes. After washing, the mixture was separated, and the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was carried out 5 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.59 mass%. In the organic layer at this stage, 44.5g of the compound X represented by the above structural formula was contained.

Further, 50g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The filtrate obtained by combining the above-mentioned washing solutions was washed by adding 250g of water thereto at 5 ℃ and stirring for 30 minutes. After the washing, liquid separation was performed, the aqueous layer was extracted, 250g of water was added again, the mixture was stirred for 30 minutes to wash and perform liquid separation, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was slowly cooled to 0 ℃ to precipitate a solid, and the precipitated solid was filtered. The filtrate was washed with n-hexane and then dried under vacuum to obtain 99.88g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 92.5% by mass. The yield of compound 1 was 58.35 mol% based on compound a.

Example 5 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.56% by mass. In the organic layer at this stage, 44.2g of the compound X represented by the above structural formula was contained.

Further, 300g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The above-mentioned filtrate in which the washing solutions were combined was further stirred at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate to wash. After washing, the mixture was separated, and the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was performed 5 times in total, liquid separation was performed, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was gradually cooled to 0 ℃ to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with n-hexane and then dried under vacuum to obtain 100.1g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 91.8% by mass. The yield of compound 1 was 58.04 mol% based on compound a.

Example 6 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. To this was added 100.0g (0.378mol) of compound a synthesized in step 1 of example 1, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The organic layer was further washed with 416g of a 1 mol/liter buffer solution (pH5.5) formed of acetic acid and sodium acetate with stirring at 40 ℃ for 30 minutes. After washing, the mixture was separated, and the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was carried out 5 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.57% by mass. In the organic layer at this stage, 45.2g of the compound X represented by the above structural formula was contained.

Further, 300g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The filtrate obtained by combining the above-mentioned washing solutions was washed by adding 250g of water thereto at 5 ℃ and stirring for 30 minutes. After the washing, liquid separation was performed, the aqueous layer was extracted, 250g of water was added again, the mixture was stirred for 30 minutes to wash and perform liquid separation, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was slowly cooled to 0 ℃ to precipitate a solid, and the precipitated solid was filtered. The filtrate was washed with n-hexane and then dried under vacuum to obtain 98.9g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 89.8% by mass. The yield of compound 1 was 56.09 mol% based on compound a.

Comparative example 1 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.59 mass%. In the organic layer at this stage, 44.3g of the compound X represented by the above structural formula was contained.

The obtained organic layer was slowly cooled and slowly stirred at 0 ℃ for 1 hour, whereby a solid was precipitated. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of CPME prepared separately, cooled to 0 ℃, and the wash obtained by this washing was combined with the previous filtrate. The above-mentioned filtrate in which the washing solutions were combined was further stirred at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate to wash. After washing, the mixture was separated, and the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was performed 5 times in total, liquid separation was performed, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was gradually cooled to 0 ℃ to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with n-hexane and then dried under vacuum to obtain 73.8g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 91.5% by mass. The yield of compound 1 was 42.65 mol% based on compound a.

Comparative example 2 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The organic layer was further washed with 416g of a 1 mol/liter buffer solution (pH5.5) formed of acetic acid and sodium acetate with stirring at 40 ℃ for 30 minutes. After washing, the mixture was separated, and the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was carried out 5 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.57% by mass. In the organic layer at this stage, 44.8g of the compound X represented by the above structural formula was contained.

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

Comparative example 3 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the mixture was stirred at 10 ℃ or lower for 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.55% by mass. In the organic layer at this stage, 44.6g of the compound X represented by the above structural formula was contained.

Further, 550g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The filterability at this time is very poor as a whole. The above-mentioned filtrate in which the washing solutions were combined was further stirred at 40 ℃ for 30 minutes using 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate to wash. After washing, the mixture was separated, and the aqueous layer was extracted, 416g of a 1 mol/L buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was performed 5 times in total, liquid separation was performed, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was gradually cooled to 0 ℃ to precipitate a solid, and the precipitated solid was collected by filtration. The filtrate was washed with n-hexane and then dried under vacuum to obtain 82.3g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 85.5% by mass. The yield of compound 1 was 44.44 mol% based on compound a.

Comparative example 4 Synthesis of Compound 1

83.05g (0.397mol) of trans-1, 4-cyclohexanedicarboxylic acid chloride and 830g of cyclopentyl methyl ether (CPME) are introduced into a 3-port reactor with a thermometer in a nitrogen stream. 100.0g (0.378mol) of Compound A synthesized in step 1 of example 1 was added thereto, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ℃. Then, 40.2g (0.397mol) of triethylamine (Et) was slowly added dropwise over 20 minutes while keeping the internal temperature of the reaction mixture at 10 ℃ or lower₃N). After the end of the dropwise addition, the entire contents were returned to 25 ℃ and stirred for a further 1 hour. 250g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ℃ for 2 hours. After the liquid separation, the aqueous layer was extracted, 250g of water was added again, and the mixture was stirred at 50 ℃ for 2 hours. This operation was carried out 3 times in total. The organic layer was further washed with 416g of a 1 mol/liter buffer solution (pH5.5) formed of acetic acid and sodium acetate with stirring at 40 ℃ for 30 minutes. Cleaning ofThen, liquid separation was carried out, and after the aqueous layer was extracted, 416g of a 1 mol/liter buffer solution (pH5.5) composed of acetic acid and sodium acetate was added again, and the mixture was stirred at 40 ℃ for 30 minutes. This operation was carried out 5 times in total. The concentration of compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography, and as a result, it was 10.58% by mass. In the organic layer at this stage, 44.4g of the compound X represented by the above structural formula was contained.

Further, 550g of methanol was added to the obtained organic layer, and the mixture was slowly cooled to 0 ℃ and slowly stirred for 1 hour, thereby precipitating a solid. The precipitated solid was removed by filtration to obtain a filtrate. The filtrate in the filter was washed with 100g of methanol prepared separately and cooled to 0 ℃, and the washing liquid obtained by the washing was combined with the previous filtrate. The filterability at this time is very poor as a whole. The filtrate obtained by combining the above-mentioned washing solutions was washed by adding 250g of water thereto at 5 ℃ and stirring for 30 minutes. After the washing, liquid separation was performed, the aqueous layer was extracted, 250g of water was added again, the mixture was stirred for 30 minutes to wash and perform liquid separation, 1200g of n-hexane was added to the organic layer (oil layer) obtained by extracting the aqueous layer, and the mixture was slowly cooled to 0 ℃ to precipitate a solid, and the precipitated solid was filtered. The filtrate was washed with n-hexane and then dried under vacuum to obtain 82.2g of a white solid (mixture Y of Compound 1 and Compound X) as an intermediate. The obtained white solid (mixture Y of compound 1 and compound X) was quantified by high performance liquid chromatography, and as a result, the content of compound 1 relative to the white solid (mixture Y of compound 1 and compound X) was 85.3% by mass. The yield of compound 1 was 44.29 mol% based on compound a.

Comparative example 5 comparative example 1 to International publication No. 2011/068138

[ chemical formula 40]

Toluene and 24.68g of trans-1, 4-cyclohexanedicarboxylic acid were mixed. To the resulting solution were added 74.91g of oxalyl chloride and 0.5mL of N, N-dimethylformamide. The resulting solution was stirred under nitrogen to react. The resulting reaction mixture was concentrated under reduced pressure to remove toluene and unreacted oxalyl chloride. The resulting solution and chloroform were mixed to give a solution containing trans-1, 4-cyclohexanedicarboxylic acid chloride.

Chloroform and 12g of the compound represented by the above formula (A-IV) were mixed. The obtained solution and 12.6g of pyridine were added dropwise to the previously obtained solution containing trans-1, 4-cyclohexanedicarboxylic acid chloride under ice-cooling. The resulting mixture was stirred under nitrogen. The precipitate was removed by filtration, and the resulting filtrate was concentrated under reduced pressure. The concentrated solution was added dropwise to a water/methanol solution (volume ratio: 1/1). The resulting precipitate was pulverized and then filtered. The precipitate was washed with pure water. The precipitate was filtered and dried in vacuo. The obtained powder was pulverized and heptane was added. After stirring the resulting mixture, the precipitate was taken out. The precipitate was mixed with toluene and the insoluble components were removed by filtration. The filtrate was concentrated under reduced pressure, and heptane was added to the resulting concentrated solution. The precipitate was collected by filtration and dried in vacuo to obtain 7.8g 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) relative to the obtained powder was 70.0 mass%.

Comparative example 6 comparative example 2 of International publication No. 2011/068138

24.68g of trans-1, 4-cyclohexanedicarboxylic acid, 74.91g of oxalyl chloride and 0.5mL of N, N-dimethylformamide were mixed. The resulting solution was stirred under nitrogen to react. The resulting reaction mixture was concentrated under reduced pressure to remove toluene and unreacted oxalyl chloride. The resulting solution and chloroform were mixed to give a solution containing trans-1, 4-cyclohexanedicarboxylic acid chloride.

Chloroform and 12g of the compound represented by the above formula (6-a) were mixed. The obtained solution and 12.6g of pyridine were added dropwise to the previously obtained solution containing trans-1, 4-cyclohexanedicarboxylic acid chloride under ice-cooling. The resulting solution was stirred under nitrogen. The precipitate was removed by filtration and the filtrate was concentrated under reduced pressure. The concentrated solution was added dropwise to water, and the resulting precipitate was pulverized and then filtered. The precipitate was mixed with purified water and filtered. The precipitate was dried in vacuo. The obtained powder was pulverized and added to a water/methanol solution (volume ratio: 1/1). The precipitate was pulverized and then filtered. Heptane was added to the precipitate, the resulting mixture was stirred, and insoluble components were removed by filtration. The insoluble matter was mixed with toluene and then filtered. The obtained filtrate was concentrated under reduced pressure, and heptane was added to the obtained concentrated solution. The precipitate was collected by filtration and dried in vacuo to obtain 2.1g 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) relative to the obtained powder was 85.0 mass%.

[ Table 1]

Example 7 Synthesis of polymerizable Compound 1

[ chemical formula 41]

< step 1: synthesis of Compound B >

[ chemical formula 42]

In a 3-port reactor with a thermometer under a nitrogen stream, 100g (0.605mol) of 2-hydrazinobenzothiazole were added to 750g of N, N-dimethylformamide, followed by 119.9g (0.726mol) of 1-bromohexane. To this solution, 192.72g (0.908mol) of tripotassium phosphate was added, and the whole was stirred at 100 ℃ for 3 hours. After the reaction is finished, the reaction liquid is cooled to 60 ℃, and then the temperature is reducedAfter adding 750g of toluene and 750g of water to the reaction mixture of (1), the mixture was stirred for 15 minutes while maintaining the temperature at 60 ℃. When the reaction solution was allowed to stand, it was separated into three layers. The two layers of the lower layer are drawn out. To the toluene layer thus obtained, 430g of a 10 mass% aqueous solution of sodium chloride was added, and the mixture was stirred at 60 ℃ for 15 minutes. The toluene layer (organic layer) obtained by extracting the aqueous layer was concentrated under reduced pressure, and 560g of toluene was extracted. The concentrated toluene layer (organic layer) was heated to 60 ℃ and 500g of water was added thereto, and the mixture was slowly cooled with vigorous stirring. After reaching 0 ℃, the mixture was stirred vigorously at this temperature for 1 hour. The slurry solution was filtered. The obtained wet solid was sprayed with 500g of a mixed solution of water/methanol (mass ratio) 1/4 cooled to 5 ℃ or lower, and washed. The obtained wet solid was dried under reduced pressure using a vacuum dryer, whereby 132.8g of compound B was obtained as a white solid. The yield thereof was found to be 88 mol%. Structural use of Compound B¹And H-NMR identification.¹The H-NMR spectrum data are shown below.

¹H-NMR(500MHz,CDCl₃,TMS,δppm)：7.60(dd、1H、J＝1.0,8.0Hz)、7.53(dd,1H,J＝1.0,8.0Hz)、7.27(ddd,1H,J＝1.0,8.0,8.0Hz)、7.06(ddd,1H,J＝1.0,8.0,8.0Hz)、4.22(s,2H)、3.74(t,2H,J＝7.5Hz)、1.69-1.76(m,2H)、1.29-1.42(m,6H)、0.89(t,3H,J＝7.0Hz)。

< step 2: synthesis of polymerizable Compound 1 >

In a nitrogen stream, 10.80g (10.00 g (23.90mmol) of the white solid (mixture Y of Compound 1 and Compound X) as the intermediate synthesized in example 1 above, 100g of chloroform and 3.49g of Dimethylformamide (DMF)) were charged in a 3-port reactor equipped with a thermometer, and cooled to 10 ℃ or less. The reaction temperature was controlled to 10 ℃ or lower, and 3.27g (27.48mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After the reaction, the reaction mixture was concentrated by an evaporator until the amount of the reaction mixture became one fourth. Thereafter, 25g of chloroform was added to obtain a chloroform solution of the acid chloride of compound 1. In a further 3-port reactor with a thermometer, 1.50g (10.86mmol) of 2, 5-dihydroxybenzaldehyde and 6.98g (65.17 m) were reacted in a stream of nitrogenmol) of 2, 6-lutidine as a base was dissolved in 50g of chloroform, and the resulting solution was cooled to 10 ℃ or lower. The whole amount of the chloroform solution of the acid chloride of compound 1 synthesized before was slowly added dropwise while keeping the internal temperature of the reaction solution at 10 ℃ or lower. After completion of the dropwise addition, the reaction mixture was further reacted for 1 hour while being kept at 10 ℃ or lower. Thereafter, 40g of a 1.0 equivalent aqueous hydrochloric acid solution was further added thereto, and the mixture was stirred at 10 ℃ or lower for 30 minutes to effect a reaction. After the reaction was completed, 3.52g (14.12mmol) of compound B synthesized in the above step 1 was further added to the obtained reaction solution at 10 ℃ or lower. Thereafter, the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours. After the reaction, the reaction mixture was cooled to 25 ℃ and subjected to a liquid separation operation. To the obtained organic layer was added 0.50g of Rokahelp #479 (manufactured by Mitsui Metal mining Co., Ltd.), and after stirring for 30 minutes, Rokahelp #479 was filtered off. Then, about 80% of the total mass was extracted from the obtained reaction solution by an evaporator, and the reaction solution was concentrated. After 20g of THF was added to the solution, the mixture was stirred for 1 hour. Then, 80g of n-hexane was added dropwise to the solution, and then the solution was cooled to 0 ℃ to precipitate crystals. Thereafter, the precipitated crystals were collected by filtration. To the resulting crystals were added 108g of THF, 1.8g of Rokahelp #479 and 100mg of 2, 6-di-t-butyl-4-methylphenol, and after stirring for 30 minutes, Rokahelp #479 was filtered off. Then, 36g of THF was distilled off from the obtained reaction solution by an evaporator. 117g of methanol was added dropwise to the obtained solution, and then cooled to 0 ℃ to precipitate crystals. Thereafter, the precipitated crystals were collected by filtration. The filtrate was washed with methanol and then dried under vacuum to obtain 11.7g of polymerizable compound 1. The isolated yield was 92.0 mol% (2, 5-dihydroxybenzaldehyde basis). Structural use of polymerizable Compound 1¹And H-NMR identification.¹The H-NMR spectrum data are shown below.

¹H-NMR(400MHz,CDCl₃,TMS,δppm)：7.75(d,1H,J＝2.5Hz)、7.67-7.70(m,3H)、7.34(ddd,1H、J＝1.0Hz,7.0Hz,7.5Hz)、7.17(ddd,1H,J＝1.0Hz,7.5Hz,7.5Hz)、7.12(d,1H,J＝9.0Hz)、7.10(dd,1H,J＝2.5Hz,9.0Hz)、6.99(d,2H,J＝9.0Hz)、6.98(d,2H,J＝9.0Hz)、6.88(d,4H,J＝9.0Hz)、6.40(dd,2H,J＝1.5Hz,17.0Hz)、6.13(dd,2H,J＝10.5Hz,17.5Hz)、5.82(dd,2H、J＝1.5Hz,10.5Hz)、4.30(t,2H,J＝8.0Hz)、4.18(t,4H,J＝6.5Hz)、3.95(t,4H,J＝6.5Hz)、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＝7.0Hz)。

Example 8 Synthesis of polymerizable Compound 1

In the above example 7, the synthesis of the polymerizable compound 1 was carried out in the same manner as in example 7 except that in step 2, 10.89g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 2 was used instead of 10.80g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 1. As a result, 11.6g of the polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 based on 2, 5-dihydroxybenzaldehyde was 91.3 mol%.

Example 9 Synthesis of polymerizable Compound 1

In the above example 7, a polymerizable compound 1 was synthesized in the same manner as in example 7 except that 10.81g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 3 was used in step 2 instead of 10.80g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 1. As a result, 11.7g of the 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 the above example 7, a polymerizable compound 1 was synthesized in the same manner as in example 7 except that 10.81g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 4 was used in step 2 instead of 10.80g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 1. As a result, 11.8g of the polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 based on 2, 5-dihydroxybenzaldehyde was 92.8 mol%.

Example 11 Synthesis of polymerizable Compound 1

In the above example 7, a polymerizable compound 1 was synthesized in the same manner as in example 7 except that 10.89g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 5 was used in step 2 instead of 10.80g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 1. As a result, 11.5g of the 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 the above example 7, a polymerizable compound 1 was synthesized in the same manner as in example 7 except that 11.14g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 6 was used in step 2 instead of 10.80g (10.00 g (23.90mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 1. As a result, 11.6g of the polymerizable compound 1 was obtained. The isolation yield of the polymerizable compound 1 based on 2, 5-dihydroxybenzaldehyde was 91.3 mol%.

Example 13 Synthesis of polymerizable Compound 2

[ chemical formula 43]

< step 1: synthesis of Compound C >

[ chemical formula 44]

500.5g (2.69mol) of 1-naphthylacetic acid and 1049g of toluene were charged into a 3-port reactor having a thermometer under a nitrogen stream. 349.5g (2.56mol) of 6-chloro-1-hexanol and 48.6g (0.26mol) of p-toluenesulfonic acid monohydrate were further added to prepare a solution. The prepared solution was heated using a Dean-Stark apparatus, and azeotropic dehydration was carried out for 2 hours while discharging the produced water from the outside of the reaction system (inner temperature: about 95 ℃ C.). After completion of the reaction, 742g of a 5.8 mass% aqueous solution of sodium hydrogencarbonate was added to the reaction mixture cooled to 25 ℃ to separate the solution, followed by washing. After the washing, the organic layer obtained by extracting the aqueous layer was further washed with 500g of water. After the washing, 7g of a filter aid (trade name: Rokahelp #479, manufactured by Mitsui Metal mining 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, followed by filtration to remove the filter aid. The solvent was removed from the organic layer using a rotary evaporator to give 755g of a pale brown oil containing compound C. As a result of quantitative determination by high performance liquid chromatography, the pale brown oil containing compound C contained 93.0 mass% of compound C. This pale brown oil was used as such in the next reaction without purification (step 2: synthesis of compound D).

< step 2: synthesis of Compound D >

[ chemical formula 45]

59.52g (55.35 g (0.182mol) of a pale brown oil containing the compound C synthesized in the above step 1 and 235g of N-methyl-2-pyrrolidone were charged into a 3-port reactor equipped with a thermometer under a nitrogen flow to prepare a uniform solution. To this homogeneous solution was added 25.0g (0.151mol) of 2-hydrazinobenzothiazole. Next, 48.18g (0.227mol) of phosphorus were addedTripotassium phosphate, the entire contents were stirred at 100 ℃ for 3 hours. After the reaction, the reaction mixture was cooled to 60 ℃ and 312.5g of ethyl acetate was added to the cooled reaction mixture, and then the mixture was filtered while maintaining the temperature at 60 ℃. The organic layer as a filtrate was slowly dropped into 250g of a 0.5 equivalent aqueous solution of citric acid, stirred at an internal temperature of 60 ℃ for 30 minutes, and then the aqueous layer was extracted. Furthermore, 275g of a 9.1 mass% aqueous sodium chloride solution was added to the organic layer, and after stirring at an internal temperature of 60 ℃ for 30 minutes, the mixture was allowed to stand for 30 minutes, and the aqueous layer was extracted. Then, 262.5g of a 4.76 mass% aqueous solution of sodium hydrogencarbonate was added to the organic layer, and after stirring at an internal temperature of 60 ℃ for 30 minutes, the mixture was allowed to stand for 30 minutes, and the aqueous layer was extracted. Further, 250g of water was added to the organic layer, and after stirring at an internal temperature of 60 ℃ for 30 minutes, the mixture was allowed to stand for 30 minutes, and the aqueous layer was extracted. The resulting organic layer was slowly cooled to 0 ℃ and stirred at 0 ℃ for 30 minutes. The resulting solid was taken up by filtration. Thereafter, 150g of ethyl acetate was added to the obtained solid, and the mixture was heated to 60 ℃ to prepare a uniform solution, and stirred for 30 minutes. Thereafter, the ethyl acetate solution was slowly cooled to 0 ℃ and stirred at 0 ℃ for 1 hour. The resulting solid was collected by filtration and dried under reduced pressure, whereby 36.9g of compound D was obtained as a white solid. The yield of compound D was 56.4 mol%. Structural use of Compound D¹And H-NMR identification.¹The H-NMR spectrum data are shown below.

¹H-NMR(500MHz,CDCl₃,TMS,δppm)：8.00(d,1H,J＝8.5Hz)、7.85(dd,1H、J＝1.0Hz、8.0Hz)、7.78(dd,1H,J＝1.5Hz,7.5Hz)、7.60(dd,1H,J＝1.0Hz,7.5Hz)、7.54-7.51(m,2H)、7.49-7.40(m,3H)、7.28(ddd,1H,J＝1.0Hz,7.5Hz,7.5Hz)、7.07(ddd,1H,J＝1.0Hz,7.5Hz,7.5Hz)、4.16(br,2H)、4.08(t,2H,J＝6.5Hz)、4.06(s,2H)、3.66(t,2H,J＝7.0Hz)、1.63-1.54(m,4H)、1.32-1.22(m,4H)。

< step 3: synthesis of polymerizable Compound 2 >

32.43g (30.00 g (71.7mmol) of the pure amount of Compound 1, i.e., the white solid (mixture Y of Compound 1 and Compound X) synthesized in example 3 above as an intermediate, 300g of chloroform and 10.5g (143.4mmol) of N, N-Dimethylformamide (DMF) were charged in a nitrogen stream into a 3-port reactor equipped with a thermometer, and cooled to 10 ℃ or less. The reaction temperature was controlled to 10 ℃ or lower, and 9.81g (82.44mmol) of thionyl chloride was added dropwise thereto. After the completion of the dropwise addition, the reaction solution was returned to 25 ℃ and stirred for 1 hour. After completion of the reaction, 225g of chloroform was extracted by an evaporator and concentrated to synthesize an acid chloride of compound 1 as a chloroform solution. In a separate 3-port reactor with a thermometer in a nitrogen stream, 4.5g (32.58mmol) of 2, 5-dihydroxybenzaldehyde and 19.78g (195.5mmol) of triethylamine as a base were dissolved in 150g of chloroform, and the resulting solution was cooled to 10 ℃ or lower. The total amount of the chloroform solution of the acid chloride of compound 1 synthesized before slowly dropping while keeping the internal temperature of the reaction solution at 10 ℃ or lower. After the completion of the dropwise addition, the entire contents were further stirred at 5 to 10 ℃ for 1 hour to effect a reaction. After the reaction, 120g of a 1.0 equivalent hydrochloric acid aqueous solution was added to the reaction mixture while keeping the temperature at 10 ℃ or lower, and the mixture was stirred at 10 ℃ or lower for 30 minutes to effect a reaction. After the reaction was completed, 18.38g (42.4mmol) of the compound D synthesized in the above step 2 and 0.3g of 2, 6-di-t-butyl-p-cresol were further added to the obtained reaction solution at 10 ℃ or lower. Thereafter, the reaction solution was heated to 40 ℃ to carry out a reaction for 4 hours.

After the reaction, the aqueous layer was extracted to obtain an organic layer. 105g of distilled water was put into the obtained organic layer, and the organic layer was stirred at 40 ℃ for 30 minutes and washed. The organic layer obtained by extracting the aqueous layer was cooled to 25 ℃ and 1.5g of Rokahelp #479 was added and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. 180g of chloroform was extracted from the organic layer obtained by removing Rokahelp #479 by a rotary evaporator and concentrated. To the organic layer obtained by the concentration was added 210g of hexane over 1 hour to precipitate a solid, which was then filtered to obtain a pale yellow solid. The resulting pale yellow solid was dissolved in 120g of tetrahydrofuran at 25 ℃ and 1.5g of Rokahelp #479 was added thereto and stirred for 30 minutes. Thereafter, Rokahelp #479 was removed by filtration using a Tung mountain funnel paved with 1g of Rokahelp # 479. To the organic layer obtained by removing Rokahelp #479 was slowly dropped 165g of methanol at 15 ℃ to precipitate a solid, followed by filtration to obtainTo a solid. The obtained solid was dried by a vacuum dryer to obtain 40.2g of polymerizable compound 2 as a pale yellow solid. The yield of the polymerizable compound 2 was 91.0 mol% based on 2, 5-dihydroxybenzaldehyde. Structural use of polymerizable Compound 2¹And H-NMR identification.¹The H-NMR spectrum data are shown below.

¹H-NMR(500MHz,CDCl₃,TMS,δppm)：7.97(dd,1H,J＝0.5Hz,8.5Hz)、7.80(ddd,1H,J＝0.5Hz,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＝1.0Hz,6.5Hz,8.5Hz)、7.42(ddd,1H,J＝1.5Hz,7.0Hz,7.0Hz)、7.33-7.39(m,3H)、7.18(ddd,1H,J＝1.0Hz,7.5Hz,8.0Hz)、7.10-7.14(m,2H)、6.95-7.01(m,4H)、6.85-6.90(m,4H)、6.405(dd,1H,J＝1.5Hz,17.5Hz)、6.402(dd,1H,J＝1.5Hz,17.5Hz)、6.127(dd,1H,J＝10.5Hz,17.5Hz)、6.124(dd,1H,J＝10.5Hz,17.5Hz)、5.822(dd,1H,J＝1.5Hz,10.5Hz)、5.819(dd,1H,J＝1.5Hz,10.5Hz)、4.16-4.22(m,6H)、4.08(t,2H,J＝6.5Hz)、4.03(s,2H)、3.95(t,2H,J＝6.5Hz)、3.93(t,2H,J＝6.5Hz)、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 the above example 13, a polymerizable compound 2 was synthesized in the same manner as in example 13 except that 32.43g (30.00 g (71.7mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 4 was used as a pure amount of the compound 1) in step 3 instead of 32.43g (30.00 g (71.7mmol) of the white solid (mixture Y of the compound 1 and the compound X) as the intermediate synthesized in the above example 3. As a result, 40.6g of the polymerizable compound 2 was obtained. The isolation yield of the polymerizable compound 2 based on 2, 5-dihydroxybenzaldehyde was 92.1 mol%.

From the results of examples 7 to 14, it is clear that the intermediate containing the compound (I) at a high concentration obtained by the production method of the present invention can be preferably used for the production of a polymerizable compound.

Industrial applicability

Claims

1. A process for producing an intermediate comprising a compound (I) represented by the following formula (I), which comprises the steps of:

(i) a step (alpha) for obtaining a solution (X) containing the compound (I) and a compound (II) represented by the following formula (II); and

(ii) a step (β) 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 86 mass% or more of the compound (I);

in the formula (I), A²And B²Each independently represents a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent,

R³represents a hydrogen atom, a methyl group or a chlorine atom,

FG²represents a hydroxyl group, a carboxyl group or an amino group,

d represents an integer of 1 to 20,

e is a number of 1 or 2,

in the formula (II), A²¹、B²¹And B²²Each independently represents a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent,

d1 and d2 each independently represent an integer of 1 to 20,

e1 and e2 are each independently 1 or 2.

2. The intermediate production method according to claim 1, wherein the concentration of the compound (I) in the solution (X) is 8.0 mass% or more.

3. The process for producing an intermediate according to claim 1 or 2, wherein the compound (I) is a compound (I-1) represented by the following formula (I-1),

in the formula (I-1), R³And d represents the same meaning as described above.

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

in the formula (II-1), R³And d represents the same meaning as described above.

5. The intermediate production method according to any one of claims 1 to 4, wherein the solution (X) further comprises an organic solvent, which is a water-immiscible organic solvent.

6. The process for producing an intermediate according to claim 5, wherein the Hildebrand solubility parameter of the water-immiscible organic solvent is 14.0MPa^1/2Above and 22.0MPa^1/2The following.

7. The intermediate production method according to any one of claims 1 to 6, wherein the protic solvent is an alcohol.