Compound, electro-optical ink composition, film, electro-optical element, and method for producing compound

Abstract

To provide an EO compound containing an acceptor part capable of improving the degree of alignment in electric field poling.SOLUTION: A compound represented by the following formula (1): In the formula, A represents a group represented by the formula (1-A). R1 and R2 represent substituents other than hydrogen atoms, and m and n represent integers of 0 to 5. L represents a single bond or a divalent conjugated linking group, and D represents an electron-donating group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound, an electro-optical ink composition, a film, an electro-optical element, and a method for producing the compound. [Background technology]

[0002] The electro-optic (hereinafter sometimes abbreviated as "EO") effect refers to the phenomenon in which the refractive index of a material changes when a voltage is applied. Inorganic ferroelectric EO materials have traditionally been used as electro-optical materials for optical control devices (optical elements) such as optical modulators, optical switches, optical interconnects, optoelectronic circuits, wavelength conversion, electric field sensors, THz (terahertz) wave generation and detection, and optical phased arrays. However, inorganic ferroelectric EO materials have limitations in terms of high speed, miniaturization, and integration. Therefore, to realize next-generation ultra-high-speed optical communications, materials capable of high-speed operation and hybridization with silicon photonics are needed.

[0003] From this perspective, organic EO materials have attracted attention. Compared to inorganic ferroelectric EO materials, organic EO materials exhibit a larger electro-optic effect, are capable of high-speed operation, and can be miniaturized and integrated by hybridizing with silicon photonics. As a result, they are expected to be the materials that will play a key role in next-generation optical communications.

[0004] In general, organic EO materials contain compounds capable of exhibiting an electro-optic effect (hereinafter, sometimes referred to as "EO compounds"). EO compounds have a basic structure in which a donor and an acceptor are connected by a π-conjugated bridge (hereinafter, sometimes referred to as "linker"). It is known that the EO coefficient of an EO material can be increased by employing an EO compound with a highly electron-donating donor and a highly electron-withdrawing acceptor, thereby increasing the length of the π-conjugated bridge. Various EO compounds with such structures have been reported (e.g., Patent Document 1, Non-Patent Document 1, etc.).

[0005] When fabricating EO elements with optical waveguides formed from EO materials, the EO compound may be subjected to an alignment process to induce secondary EO activity in the EO material. The electric field poling method is commonly used to align EO compounds. This method involves applying an electric field to the EO material, and aligning the EO compound in the direction of the applied electric field due to the Coulomb force between the dipole moment of the EO compound and the applied electric field. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2004-501159 [Patent Document 2] International Publication No. 2023 / 174071 [Non-patent literature]

[0007] [Non-Patent Document 1] Chem.Mater.2008,120,6372-6377. Summary of the Invention [Problem to be solved by the invention]

[0008] However, EO compounds are prone to intermolecular association due to their large dipole moment and extensive π-conjugated backbone. It is known that intermolecular association of EO compounds inhibits alignment during electric field poling, leading to a deterioration in the performance of EO materials. Therefore, there is a need to design EO compounds that can suppress intermolecular association and suppress alignment during electric field poling.

[0009] Conventional EO compounds have been designed to suppress intermolecular association by introducing bulky substituents into the donor and linker moieties. However, even when bulky substituents are introduced into the donor and linker moieties of EO compounds, intermolecular association can still occur, leaving room for improvement in the degree of orientation of EO compounds during electric field poling.

[0010] In conventional EO compounds, the design of the acceptor moiety, for example, the introduction of a bulky substituent into the acceptor moiety to suppress intermolecular association of EO compounds, has not been studied. Patent Document 2 describes an EO compound in which a diaryl group having one fluoro group on the aryl group is introduced into the acceptor moiety, but does not describe the degree of orientation during electric field poling.

[0011] Therefore, an object of the present invention is to provide an EO compound containing an acceptor moiety that can improve the degree of orientation during electric field poling. [Means for solving the problem]

[0012] As a result of intensive research in light of the above-mentioned problems, the inventors have found that the degree of orientation of an EO compound during electric field poling can be improved by introducing a specific structure containing a carbon atom to which two aromatic rings are bonded into the acceptor portion of an EO compound having a donor / π-conjugated bridge / acceptor structure, and have thus completed the present invention.

[0013] The present invention provides the following compounds [1] to [5], an electro-optical polymer compound [6], an electro-optical ink composition [7] and [8], a film [9], an electro-optical element

[10] , and a method for producing

[11] .

[0014] [1] A compound represented by the following formula (1):

[0015] [ka]

[0016] In formula (1), A represents formula (1-A):

[0017] [ka]

[0018] [In formula (1-A), R 1 and R 2 each independently represents a substituent other than a hydrogen atom. m and n each independently represent an integer of 0 to 5, provided that m+n is not 0. When m is 2 to 5, multiple R 1 may be the same or different. When n is 2 to 5, a plurality of R 2 may be the same or different. (wherein R 1 and R 2 are both fluoro groups, and m and n are both 1), L represents a single bond or a divalent conjugated linking group; D represents an electron-donating group.

[0019] [2] All R contained in the group represented by formula (1-A) 1 and R 2 The compound according to [1], wherein the total molecular weight of the above is 40 to 600, preferably 60 to 300, more preferably 80 to 200, and particularly preferably 100 to 150.

[0020] [3] R satisfies the following condition A. 1 , R 2 , m and n. Condition A: In the compound represented by formula (2), the lowest unoccupied molecular orbital (LUMO) level calculated by density functional theory (DFT) is −0.081 eV or less, and may be, for example, −0.092 eV to −0.081 eV, −0.091 eV to −0.081 eV, −0.088 eV to −0.081 eV, or −0.085 eV to −0.082 eV. In one embodiment, the lowest unoccupied molecular orbital (LUMO) level may be, for example, −10.0 eV to −0.10 eV, or −7.0 eV to −0.30 eV, preferably −5.0 eV to −0.50 eV, more preferably −4.0 eV to −1.0 eV, even more preferably −3.0 to −1.5 eV, particularly preferably −2.5 to −2.0 eV, and especially preferably −2.4 to −2.2 eV.

[0021] [ka]

[0022] [4] R 1 and R 2 are each independently a halogeno group or a fluoroalkyl group.

[0023] [5] The compound according to any one of [1] to [4], wherein D is a group represented by formula (3).

[0024] [ka]

[0025] In formula (3), R 3 and R 4 each independently represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, -R 5 -OH(R 5 represents a divalent hydrocarbon group.) -R6 -NH2(R 6 represents a divalent hydrocarbon group.) -R 7 -SH(R 7 represents a divalent hydrocarbon group, or -R 8 -NCO(R 8 represents a divalent hydrocarbon group. These groups may have a substituent. These groups may have a crosslinkable group. R 3 and R 4 may be bonded to each other to form a ring together with the atoms to which they are bonded. 11 is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyloxy group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, an amino group, a sulfanyl group, an isocyanate group, -R 101 -OH(R 101 represents a divalent hydrocarbon group. 102 -OH(R 102 represents a divalent hydrocarbon group.) -R 103 -NH2(R 103 represents a divalent hydrocarbon group.) -R 104 -SH(R 104 represents a divalent hydrocarbon group.) -R 105 -NCO(R 105 represents a divalent hydrocarbon group, or -OC(=O)R 106 (R 106 represents a monovalent hydrocarbon group. These groups may have a crosslinkable group. R 11 When there are multiple R's, they may be the same or different. 11 is R 3 or R 4 may be bonded to each other to form a ring together with the atoms to which they are bonded. k represents an integer of 0 to 4. * represents the bonding position.

[0026] [6] An electro-optical polymer compound comprising an amorphous resin and the compound according to any one of [1] to [5], which is covalently bonded to the amorphous resin.

[0027] [7] An electro-optical ink composition comprising the compound according to any one of [1] to [5] or the electro-optical polymer compound according to [6].

[0028] [8] The electro-optical ink composition according to [7], further comprising an amorphous resin.

[0029] [9] A film formed from the electro-optical ink composition according to [7] or [8].

[0030]

[10] An electro-optical element comprising the film according to [9].

[0031]

[11] The process of: (1) a step of obtaining an acetal from an α-ketoester; (2) reacting the acetal with a compound represented by formula (A) to obtain a compound represented by formula (4A); and

[0032] [ka]

[0033] [In formula (A), M represents a group containing an alkali metal or an alkaline earth metal, and R 12 represents one or more substituents other than a hydrogen atom.]

[0034] [ka]

[0035] [In formula (4A), R 1 ' and R 2 Each of the ' independently represents a substituent other than a hydrogen atom. m' and n' each independently represent an integer of 0 to 5, provided that m'+n' is not 0. When m' is 2 to 5, a plurality of R 1 When n is 2 to 5, a plurality of R2 ' may be the same or different. (3) reacting the compound represented by formula (4A) with malononitrile to obtain a compound represented by formula (4);

[0036] [ka]

[0037] [In formula (4), R 1 ', R 2 ', m' and n' have the same meanings as in formula (4A). A method for producing a compound represented by formula (4), comprising: [Effects of the Invention]

[0038] According to the present invention, an EO compound containing an acceptor moiety that can improve the degree of orientation during electric field poling can be provided. Furthermore, the compound according to one embodiment of the present invention has high hyperpolarizability. Since the hyperpolarizability and degree of orientation affect the performance of EO devices, the use of the compound in EO devices can result in EO devices with high EO coefficients. DETAILED DESCRIPTION OF THE INVENTION

[0039] A preferred embodiment of this embodiment will be described in detail below.

[0040] <Explanation of common terms> Terms commonly used in this specification have the following meanings unless otherwise specified.

[0041] The "alkyl group" may be any of a linear alkyl group, a branched alkyl group, or a cyclic alkyl group (cycloalkyl group). The linear alkyl group usually has 1 to 20 carbon atoms, the branched alkyl group usually has 3 to 20 carbon atoms, and the cyclic alkyl group usually has 3 to 20 carbon atoms. The alkyl group may have a substituent. The number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent.

[0042] Examples of the straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, and an n-hexadecyl group.

[0043] Examples of branched alkyl groups include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, and a 2-decyltetradecyl group.

[0044] Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and an adamantyl group.

[0045] Examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, a perfluorohexyl group, and a chloromethyl group.

[0046] The "alkoxy group" may be any of a linear alkoxy group, a branched alkoxy group, or a cyclic alkoxy group (cycloalkoxy group). The linear alkoxy group usually has 1 to 30 carbon atoms, the branched alkoxy group usually has 3 to 30 carbon atoms, and the cyclic alkoxy group usually has 3 to 20 carbon atoms. The alkoxy group may have a substituent. The number of carbon atoms of the alkoxy group does not include the number of carbon atoms of the substituent.

[0047] Examples of the alkoxy group include linear alkoxy groups such as a methoxy group, an ethoxy group, an n-propyloxy group, an n-butyloxy group, an n-hexyloxy group, an n-octyloxy group, an n-dodecyloxy group, and an n-hexadecyloxy group; branched alkoxy groups such as an isopropyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a 2-ethylhexyloxy group, a 3,7-dimethyloctyloxy group, a 2-hexyldecyloxy group, a 2-octyldodecyloxy group, and a 2-decyltetradecyloxy group; and cyclic alkoxy groups such as a cyclopentyloxy group and a cyclohexyloxy group.

[0048] An "aryl group" is an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the aromatic hydrocarbon is usually 6 to 60, and preferably 6 to 20. The aryl group may have a substituent. Note that the number of carbon atoms in the aryl group does not include the number of carbon atoms in the substituent.

[0049] Aromatic hydrocarbons include compounds in which two or more members selected from the group consisting of benzene, fused ring hydrocarbon compounds containing benzene, and fused ring hydrocarbon compounds containing benzene are directly bonded to one another.

[0050] Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, and a 4-phenylphenyl group.

[0051] A "heteroaryl group" is an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring from an aromatic heterocyclic compound. The number of carbon atoms in an aromatic heterocyclic compound is usually 6 to 20. The heteroaryl group may have a substituent. Note that the number of carbon atoms in the heteroaryl group does not include the number of carbon atoms in the substituent.

[0052] Examples of heteroaryl groups include groups in which one hydrogen atom directly bonded to a carbon atom constituting the ring has been removed from an aromatic heterocyclic compound such as furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazan, triazole, thiadiazole, oxadiazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, isoquinoline, benzimidazole, benzothiazole, indazole, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, phenanthridine, acridine, β-carboline, perimidine, or phenanthroline.

[0053] An "aryloxy group" is a group having the above-mentioned "aryl group." In the aryloxy group, the number of carbon atoms of the aromatic hydrocarbon in the aryl group is usually 6 to 60, preferably 6 to 20 (i.e., the number of carbon atoms in the aryloxy group is usually 6 to 60, preferably 6 to 20). The aryl group in the aryloxy group may have a substituent (i.e., the aryloxy group may have a substituent). Note that the number of carbon atoms of the aryl group in the aryloxy group does not include the number of carbon atoms of the substituent (i.e., the number of carbon atoms of the aryloxy group does not include the number of carbon atoms of the substituent).

[0054] The "halogen atom" includes, for example, a fluorine atom, a chlorine atom, and a bromine atom.

[0055] Examples of the "halogeno group" include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0056] A "haloalkyl group" refers to an alkyl group in which at least one hydrogen atom in the above-mentioned "alkyl group" is substituted with a halogen atom. The haloalkyl group may have a substituent other than a halogen atom. Examples of haloalkyl groups include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 1,2-difluoroethyl group, a chloromethyl group, a 2-chloroethyl group, a 1,2-dichloroethyl group, a bromomethyl group, a 2-bromoethyl group, a 1-bromopropyl group, a 2-bromopropyl group, a 3-bromopropyl group, and an iodomethyl group.

[0057] A "fluoroalkyl group" refers to an alkyl group in which at least one hydrogen atom in the above-mentioned "alkyl group" is substituted with a fluorine atom. The fluoroalkyl group may have a substituent other than a fluorine atom. Examples of the fluoroalkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, and a 1,2-difluoroethyl group.

[0058] A "cyanoalkyl group" is an alkyl group in which at least one hydrogen atom in the above-mentioned "alkyl group" is substituted with a cyano group. The cyanoalkyl group may have a substituent other than a cyano group. Examples of cyanoalkyl groups include a cyanomethyl group, a dicyanomethyl group, and a cyanoethyl group.

[0059] The term "haloaryl group" refers to an aryl group in which at least one hydrogen atom in the above-mentioned "aryl group" is substituted with a halogen atom. The haloaryl group may have a substituent other than a halogen atom. Examples of haloaryl groups include pentafluorophenyl groups.

[0060] The "alkylthio group" may be any of a linear alkylthio group, a branched alkylthio group, or a cyclic alkylthio group (cycloalkylthio group). The linear alkylthio group usually has 1 to 30 carbon atoms, the branched alkylthio group usually has 3 to 30 carbon atoms, and the cyclic alkylthio group usually has 3 to 20 carbon atoms. The alkylthio group may have a substituent. The number of carbon atoms of the alkylthio group does not include the number of carbon atoms of the substituent.

[0061] Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, a cyclopropylthio group, a cyclopentylthio group, a cyclohexylthio group, and an adamantylthio group.

[0062] Examples of "monovalent heterocyclic groups" include thienyl, pyrrolyl, furyl, pyridyl, piperidinyl, quinolinyl, isoquinolinyl, pyrimidinyl, triazinyl, and groups in which some or all of the hydrogen atoms in these groups have been substituted with substituents (e.g., alkyl, cycloalkyl, alkoxy, cycloalkoxy groups). In this specification, monovalent heterocyclic groups are also referred to as heteroaryl groups.

[0063] The "amino group" may have a substituent, and is preferably a substituted amino group (i.e., a secondary amino group or a tertiary amino group, more preferably a tertiary amino group). The substituent that the amino group has is preferably an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group (heteroaryl group), and these groups may have a substituent. When the amino group has multiple substituents, they may be the same or different, and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded.

[0064] Examples of the "substituted silyl group" include a silyl group having an alkyl group which may have a substituent, or an aryl group which may have a substituent. Specific examples of the substituted silyl group include mono-substituted silyl groups such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group; di-substituted silyl groups such as a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group; and tri-substituted silyl groups such as a trimethylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a tri-tert-butylsilyl group, a tri-isobutylsilyl group, a tert-butyl-dimethylsilyl group, a tri-n-pentylsilyl group, and a tert-butyl-diphenylsilyl group.

[0065] An "aralkyl group" is an alkyl group in which at least one hydrogen atom in the above-mentioned "alkyl group" is substituted with the above-mentioned "aryl group." Specific examples of aralkyl groups include benzyl, 1-phenylethyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl groups.

[0066] Examples of the aralkyl group of the "aralkyloxy group" include the same as those of the above-mentioned "aralkyl group".

[0067] Examples of the "alkenyl group" include alkenyl groups having 2 to 20 carbon atoms. Specific examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl. The alkenyl group may have a substituent. The number of carbon atoms of the alkenyl group does not include the number of carbon atoms of the substituent.

[0068] The alkenyl group of the "alkenyloxy group" is exemplified by the same as the above-mentioned "alkenyl group."

[0069] Examples of the "alkynyl group" include alkynyl groups having 3 to 20 carbon atoms. Specific examples of the alkynyl group include a 2-propynyl group, a 1-methyl-2-propynyl group, a 1,1-dimethyl-2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, and a 4-pentynyl group. The alkynyl group may have a substituent. The number of carbon atoms of the alkynyl group does not include the number of carbon atoms of the substituent.

[0070] Examples of the alkynyl group of the "alkynyloxy group" include the same as those of the above-mentioned "alkynyl group".

[0071] The "alkylene group" may be any of a straight-chain alkylene group, a branched alkylene group, or a cyclic alkylene group (cycloalkylene group). The number of carbon atoms in a straight-chain alkylene group is usually 1 to 20, the number of carbon atoms in a branched alkylene group is usually 3 to 20, and the number of carbon atoms in a cyclic alkylene group is usually 3 to 20. The alkylene group may have a substituent. The number of carbon atoms in the alkylene group does not include the number of carbon atoms of the substituent.

[0072] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, an isobutylene group, a dimethylpropylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

[0073] An "arylene group" is an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the aromatic hydrocarbon is usually 6 to 20. The arylene group may have a substituent. Note that the number of carbon atoms in the arylene group does not include the number of carbon atoms in the substituent.

[0074] Examples of the arylene group include a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, a methylnaphthylene group, a dimethylnaphthylene group, a trimethylnaphthylene group, a vinylnaphthylene group, an ethenylnaphthylene group, a methylanthrylene group, and an ethylanthrylene group.

[0075] A "heteroarylene group" is an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic heterocyclic compound. The number of carbon atoms in an aromatic heterocyclic compound is usually 6 to 20. The heteroarylene group may have a substituent. Note that the number of carbon atoms in the heteroarylene group does not include the number of carbon atoms in the substituent.

[0076] Examples of heteroarylene groups include groups obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting the ring from aromatic heterocyclic compounds such as furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazan, triazole, thiadiazole, oxadiazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, isoquinoline, benzimidazole, benzothiazole, indazole, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, phenanthridine, acridine, β-carboline, perimidine, and phenanthroline.

[0077] Examples of the "substituent" include a halogen atom, a cyano group, an alkyl group, an aryl group, a monovalent heterocyclic group (heteroaryl group), an alkoxy group, an amino group, and a substituted amino group.

[0078] Examples of the "monovalent hydrocarbon group" include the above-mentioned alkyl groups, aryl groups, aralkyl groups, alkenyl groups, and alkynyl groups. A "divalent hydrocarbon group" is the atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom from the above-mentioned "monovalent hydrocarbon group." Examples of the "divalent hydrocarbon group" include the above-mentioned alkylene groups and arylene groups.

[0079] Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.

[0080] "Polymer compound" means a compound that contains two or more of the same "structural unit" in the molecule. So-called dimers also fall under the category of polymer compound. Two or more structural units contained in a polymer compound are generally also called "repeating units." The weight-average molecular weight of a polymer compound in polystyrene equivalent is usually 1 x 10 3 ~1×10 8 is.

[0081] The polymer compound may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, or may be in other forms.

[0082] [Compound] The compound of this embodiment is a compound represented by formula (1). The compound represented by formula (1) is an EO compound having a structure in which an electron-withdrawing group (acceptor moiety) represented by A and an electron-donating group (donor moiety) represented by D are linked by a linking group (linker moiety) represented by L.

[0083] <Electron-withdrawing group A> In the compound represented by formula (1) of this embodiment, the electron-withdrawing group A is a group represented by formula (1-A) and contains a carbon atom to which two aromatic rings are bonded. Since the electron-withdrawing group A is a group represented by formula (1-A), the compound of this embodiment exhibits a high degree of orientation during electric field poling. This is thought to be because the bulkiness of the group represented by formula (1-A) suppresses intermolecular association during electric field poling.

[0084] R 1 and R 2 R each independently represents a substituent other than a hydrogen atom. 1 and R 2 Examples of the substituent other than a hydrogen atom as the aryl group include an alkyl group, a haloalkyl group, a halogeno group, an aryl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and -SR 21 (R 21 represents a monovalent hydrocarbon group.) 22 (R 22 represents a monovalent hydrocarbon group.), a nitro group, -NR 23 3 + (ammonium group) (R 23 represents a monovalent hydrocarbon group. Examples include a —SO3H group, an amide group, etc. These groups may have a substituent.

[0085] R 1 and R 2 Examples of the acyloxy group as R include a benzoyloxy group. The number of carbon atoms in the acyloxy group is preferably 2 to 21, more preferably 2 to 20, even more preferably 2 to 10, and particularly preferably 2 to 7. The number of carbon atoms in the acyloxy group does not include the number of carbon atoms in the substituent. 1 and R 2 Examples of the alkoxycarbonyl group include a methoxycarbonyl group. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 21 (preferably 3 to 20), more preferably 2 to 10 (preferably 3 to 10), and even more preferably 2 to 7 (preferably 3 to 7). The number of carbon atoms in the alkoxycarbonyl group does not include the number of carbon atoms of the substituent.

[0086] R 1 and R 2 In R 21 , R 22 , and R 23 Examples of the monovalent hydrocarbon group as include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, and an alkynyl group.

[0087] R 1 and R 2 are each independently, from the viewpoint of ease of synthesis, thermal stability and material properties, preferably an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a halogeno group, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 3 to 20 carbon atoms, a cyano group, -SR 21 (R 21 represents an alkyl group having 1 to 20 carbon atoms, -SO2R 22 (R 22 represents an alkyl group having 1 to 20 carbon atoms, a nitro group, -NR 23 3 + (R 23 represents an alkyl group having 3 to 20 carbon atoms, a —SO3H group, or an amide group having 1 to 20 carbon atoms; more preferably, a haloalkyl group having 1 to 20 carbon atoms, a halogeno group, a cyano group, or —SO2R 22 (R 22 represents an alkyl group having 1 to 20 carbon atoms, a nitro group, -NR 23 3 + (R 23 represents an alkyl group having 3 to 20 carbon atoms, and a haloaryl group having 6 to 20 carbon atoms; more preferably, a halogeno group or a fluoroalkyl group. 1 and R 2 The halogeno group as R is more preferably a fluoro group or a chloro group. 1 and R 2 The number of carbon atoms in the alkyl group in the fluoroalkyl group represented by R may be, for example, 1 to 20, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 1 and R2 The fluoroalkyl group as is preferably a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group or a 1,2-difluoroethyl group, more preferably a trifluoromethyl group.

[0088] m and n each independently represent an integer of 0 to 5, provided that m+n is not 0. When m is 2 to 5, multiple R 1 may be the same or different. When n is 2 to 5, a plurality of R 2 may be the same or different. m and n are each independently an integer of preferably 1 to 5, more preferably an integer of 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0089] When m and n are 1, R 1 and R 2 The bonding position of is not particularly limited and may be, for example, the ortho, meta, or para position relative to the carbon atom to which the two benzene rings are bonded. In one embodiment, the bonding position is preferably the para position.

[0090] All R contained in the group represented by formula (1-A) 1 and R 2 The total molecular weight of R is preferably 40 to 600, more preferably 60 to 300, further preferably 80 to 200, and particularly preferably 100 to 150. For example, R 1 and R 2 are both trifluoromethyl groups, and m and n are both 2, all of the R 1 and R 2 The total molecular weight of the compound of the present embodiment is 276. The larger the total molecular weight, the bulkier the electron-withdrawing group A tends to be. Therefore, when the total molecular weight is equal to or greater than the lower limit, for example, equal to or greater than 40, intermolecular association during electric field poling is suppressed, and the degree of orientation during electric field poling of the compound of the present embodiment tends to be further improved.

[0091] The larger the molecular weight and bulkiness of the group represented by formula (1-A), the more intermolecular association is suppressed, and the degree of orientation during electric field poling tends to improve. The molecular weight of the group represented by formula (1-A) may be, for example, 335 to 500, preferably 350 to 490, more preferably 360 to 485, and even more preferably 372 to 482.

[0092] R in formula (1-A) 1 , R 2 From the viewpoint of easily ensuring the hyperpolarizability of the EO compound containing formula (1-A) as a partial structure, the combination of m and n may be such that the lowest unoccupied molecular orbital (LUMO) level in the compound represented by formula (2) calculated by density functional theory (DFT) is −0.081 eV or less, or −0.092 to −0.081 eV, or −0.091 to −0.081 eV, or −0.088 to −0.081 eV, or −0.085 to −0.082 eV. Furthermore, R in formula (1-A) 1 , R 2 From the viewpoint of easily ensuring the hyperpolarizability of the EO compound containing formula (1-A) as a partial structure, the combination of m and n may be such that the lowest unoccupied molecular orbital (LUMO) level in the compound represented by formula (2) calculated by density functional theory (DFT) is, for example, −10.0 eV to −0.10 eV, or −7.0 eV to −0.30 eV, preferably −5.0 eV to −0.50 eV, more preferably −4.0 eV to −1.0 eV, even more preferably −3.0 to −1.5 eV, particularly preferably −2.5 to −2.0 eV, and especially preferably −2.4 to −2.2 eV.

[0093] The LUMO level of the compound represented by formula (2) can be calculated using Gaussian 16, a quantum chemistry calculation program manufactured by Gaussian. Specifically, the LUMO in the optimal structure can be calculated by performing a structural optimization calculation using PCM calculation (specifying chloroform as the solvent) under the M062X / 6-31+g(d) conditions. Specifically, the calculation can be performed using the method described in the Examples.

[0094] Examples of formula (1-A) include formulas (a-1) to (a-15). Among these, formula (1-A) is preferably formulas (a-1) to (a-3) and formulas (a-8) to (a-10), and more preferably formula (a-1), from the viewpoint of ease of synthesis and the hyperpolarizability of an EO compound containing formula (1-A) as a partial structure.

[0095] In one embodiment, formula (1-A) is preferably formulas (a-1) to (a-4) and formulas (a-11) to (a-15), and more preferably formula (a-1), formula (a-2), formula (a-12), and formula (a-13).

[0096] [ka]

[0097] <Electron-donating group D> D is an electron-donating group (a group having a donor structure). The electron-donating group D can be a group that exhibits electron-donating properties relative to the group represented by formula (1-A) as the electron-withdrawing group A.

[0098] Examples of the electron-donating group D include an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, a hydroxy group, an amino group, a substituted amino group, and a substituted silyl group. The electron-donating group D may also be an alkenyl group, an aryl group, an alkynyl group, or a heteroaryl group substituted with at least one group selected from the group consisting of these groups (an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, a hydroxy group, an amino group, a substituted amino group, and a substituted silyl group). These groups may have a substituent.

[0099] Among these, the electron-donating group D is preferably an aryl group or heteroaryl group substituted with at least one group selected from the group consisting of an alkoxy group, an aryloxy group, an alkylthio group, a hydroxy group, an amino group, and a substituted amino group, more preferably an aryl group substituted with at least one group selected from the group, and even more preferably an aryl group substituted with at least one group selected from the group consisting of an alkoxy group and a substituted amino group. The number of substituted aryl or heteroaryl groups is preferably 1 from the viewpoint of synthesis, and preferably 2 or 3 from the viewpoint of improving hyperpolarizability.

[0100] The electron-donating group D is preferably a group represented by formula (3).

[0101] In formula (3), R 3 and R 4 each independently represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, -R 5 -OH(R 5 represents a divalent hydrocarbon group.) -R 6 -NH2(R 6 represents a divalent hydrocarbon group.) -R 7 -SH(R 7 represents a divalent hydrocarbon group, or -R 8 -NCO(R 8 represents a divalent hydrocarbon group. These groups may have a substituent. These groups may have a crosslinkable group. R 3 and R 4 may be bonded to each other to form a ring together with the atoms to which they are bonded. * indicates the bonding position.

[0102] R 3 and R 4Examples of the acyloxyalkyl group as R include an alkyl group substituted with one or more acyloxy groups. The number of carbon atoms in the acyloxyalkyl group is preferably 2 to 20, more preferably 3 to 10, and even more preferably 3 to 7. The number of carbon atoms in the acyloxyalkyl group does not include the number of carbon atoms in the substituent. 3 and R 4 In the acyloxyalkyl group as R, examples and preferred ranges of the acyloxy group are as follows: 1 and R 2 The examples and preferred ranges of the acyloxy group are the same as those of the acyloxy group.

[0103] R 3 and R 4 Examples of the trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group as mentioned above include an alkyl group substituted with one or more trialkylsilyloxy groups, an alkyl group substituted with one or more aryldialkylsilyloxy groups, and an alkyl group substituted with one or more alkyldiarylsilyloxy groups. The number of carbon atoms in the trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group is preferably 5 to 25, more preferably 10 to 22, and even more preferably 12 to 20. The number of carbon atoms in the trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group does not include the number of carbon atoms of the substituents.

[0104] R 3 and R 4 In R 5 , R 6 , R 7 , and R 8Examples of the divalent hydrocarbon group include alkylene groups such as alkanediyl and cycloalkanediyl. Specific examples of the alkanediyl group include linear alkanediyl groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylene; and branched alkanediyl groups such as propylene, isopropylene, isobutylene, 2-methyltrimethylene, isopentylene, isohexylene, isooctylene, 2-ethylhexylene, and isodecylene. Specific examples of the cycloalkanediyl group include cyclopropylene, cyclopentylene, cyclohexylene, and cyclododecylene. The number of carbon atoms in the alkanediyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The cycloalkanediyl group preferably has 3 to 20 carbon atoms.

[0105] R 3 and R 4 is preferably an alkyl group having 1 to 10 carbon atoms, an acyloxyalkyl group having 3 to 10 carbon atoms, a silyloxyalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, -R 5 -OH(R 5 represents an alkanediyl group having 1 to 10 carbon atoms), -R 6 -NH2(R 6 represents an alkanediyl group having 1 to 10 carbon atoms), -R 7 -SH(R 7 represents an alkanediyl group having 1 to 10 carbon atoms, or -R 8 -NCO(in the formula, R 8 represents an alkanediyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, an acyloxyalkyl group having 3 to 7 carbon atoms, a silyloxyalkyl group having 6 to 9 carbon atoms, -R 5 -OH(R 5 represents an alkanediyl group having 1 to 5 carbon atoms), -R 6 -NH2(R 6 represents an alkanediyl group having 1 to 5 carbon atoms), -R7 -SH(R 7 represents an alkanediyl group having 1 to 5 carbon atoms, or -R 8 -NCO(in the formula, R 8 represents an alkanediyl group having 1 to 5 carbon atoms.

[0106] R 3 and R 4 may have a crosslinkable group. The crosslinkable group refers to a group that reacts with the same or different groups of other molecules located nearby when exposed to heat and / or active energy rays to form a crosslinked structure (generate a new chemical bond). Examples of the crosslinkable group include radical polymerizable groups such as (meth)acryloyloxy groups and styryl groups (vinylphenyl groups), and Diels-Alder polymerizable groups that react with dienophile groups such as anthracenyl groups and benzocyclobutenyl groups.

[0107] R 3 and R 4 may be bonded to each other to form a ring together with the atoms to which they are bonded. 3 and R 4 When they are bonded to each other to form a ring, it is preferably a 5-membered or 6-membered ring from the viewpoint of ensuring stability. The ring is preferably an aliphatic ring.

[0108] R 11 is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyloxy group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, an amino group, a sulfanyl group, an isocyanate group, -R 101 -OH(R 101 represents a divalent hydrocarbon group. 102 -OH(R 102 represents a divalent hydrocarbon group.) -R 103 -NH2(R 103 represents a divalent hydrocarbon group.) -R 104 -SH(R 104 represents a divalent hydrocarbon group.) -R105 -NCO(R 105 represents a divalent hydrocarbon group, or -OC(=O)R 106 (R 106 represents a monovalent hydrocarbon group. These groups may have a crosslinkable group. R 11 When there are multiple R's, they may be the same or different. 11 is R 3 or R 4 may be bonded to each other to form a ring together with the atoms to which they are bonded.

[0109] R 11 The trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group as R 3 and R 4 It may be the same as the trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group exemplified above.

[0110] R 11 In R 101 , R 102 , R 103 , R 104 , and R 105 The divalent hydrocarbon group as R 5 , R 6 , R 7 , and R 8 It may be the same as the divalent hydrocarbon group exemplified above.

[0111] R 11 In R 106 The monovalent hydrocarbon group as may be an alkyl group.

[0112] R 11 may have a crosslinkable group. The crosslinkable group is R 3 and R 4 The crosslinkable groups may be the same as those exemplified above.

[0113] k represents an integer of 0 to 4. k is preferably 0 or 1, and more preferably 0.

[0114] R 11 is R 3 or R 4 and may be bonded to each other to form a ring together with the atoms to which they are bonded. 11 and R 3 or R 4 When these are bonded to each other to form a ring, the ring is preferably a 5-membered or 6-membered ring from the viewpoint of ensuring stability. The ring is preferably an aliphatic ring.

[0115] <Linking group L> L represents a single bond or a divalent conjugated linking group. Here, the divalent conjugated linking group means a divalent linking group in which a conjugated system extends from one bonding position to another bonding position. L is preferably a divalent conjugated linking group.

[0116] Examples of the divalent conjugated linking group represented by L include linking groups represented by the following formula (x1).

[0117] [ka]

[0118] In formula (x1), X 1 represents an arylene group; a heteroarylene group; a divalent polycyclic fused ring group; -CR X1 =CR X2 -; -C≡C-; -N=N-; -arylene group -Y-; -heteroarylene group -Y-, etc. These groups may have a substituent. X 1 When there are multiple X's, they may be the same or different. 1 There are multiple -CR X1 =CR X2 -If they are adjacent to each other, their R X1 may be bonded to each other to form a ring together with the atoms to which they are bonded. kx represents an integer of 1 to 10. * represents the bonding position.

[0119] R X1and R X2 R each independently represents a hydrogen atom, an alkyl group, or an aryl group. X1 and R X2 may be bonded to each other to form a ring together with the atoms to which they are bonded.

[0120] Y is -O-, -S-, or -NR X3 - represents R X3 represents a hydrogen atom, an alkyl group, or an aryl group.

[0121] X 1 is preferably a divalent polycyclic fused ring group, a heteroarylene group, or -CR X1 =CR X2 -, more preferably -CR X1 =CR X2 -It is.

[0122] The divalent polycyclic fused ring group preferably has two or more thiophene rings. The number of thiophene rings is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6. In a fused thiophene having thiophenes fused thereto, the number of fused thiophenes is the number of thiophene rings. For example, in a thienothiophene having two thiophenes fused thereto, the number of thiophene rings is counted as two.

[0123] The divalent polycyclic fused ring group may have at least one constituent element selected from the group consisting of sp3 carbon atoms, nitrogen atoms, and silicon atoms. That is, the divalent polycyclic fused ring group has —C(R A )(R B )-, a group represented by -N(R C )- and a group represented by -Si(R D )(R E )-. A )(R B The carbon atom in - is R A and R B a tertiary carbon atom in which one of the carbon atoms is an alkyl group or the like and the other is a hydrogen atom, or R A and RB may be quaternary carbon atoms such as alkyl groups, and are preferably quaternary carbon atoms.

[0124] R A , R B , R C , R D , and R E each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, or a monovalent heterocyclic group (heteroaryl group), and these groups may have a substituent.

[0125] The heteroarylene group is preferably a group in which two hydrogen atoms directly bonded to carbon atoms constituting the ring have been removed from thiophene.

[0126] kx represents an integer of 1 to 10. kx is preferably 1 to 3, and more preferably 1 or 2.

[0127] Examples of the linking group L include formulae (L-1) to (L-13). Among these, from the viewpoint of ease of synthesis, the linking group L is preferably formulae (L-1) to (L-3) and formulae (L-9) to (L-13), and more preferably formulae (L-9) to (L-13). In formulae (L-1) to (L-13), * represents a bonding position. In formulae (L-1) to (L-13), R represents a substituent, and is preferably an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

[0128] [ka]

[0129] Examples of compounds represented by formula (1) include compounds represented by formulae (EO-1) to (EO-24). Among these, from the viewpoints of ease of synthesis and ensuring electro-optical properties, preferred are compounds represented by formulae (EO-1) to (EO-3), (EO-5) to (EO-13), (EO-15) to (EO-19), and (EO-21) to (EO-23), more preferred are compounds represented by formulae (EO-11), (EO-12), (EO-15) to (EO-19), and (EO-21) to (EO-23), and even more preferred are compounds represented by formulae (EO-16) to (EO-19), (EO-21), and (EO-22).

[0130] [ka]

[0131] [ka]

[0132] [Method of manufacturing the compound] The method for producing the compound represented by formula (1) is not particularly limited. Here, the production methods will be explained using the compound represented by formula (4) and the compound represented by formula (x) as examples.

[0133] <Manufacturing method A> Production method A is a method for producing a compound represented by formula (4). Production method A includes, for example, (1) a step of obtaining an acetal from an α-ketoester, (2) a step of reacting the acetal with a compound represented by formula (A) to obtain a compound represented by formula (4A), and (3) a step of reacting the compound represented by formula (4A) with malononitrile to obtain a compound represented by formula (4). Since production method A includes the above steps, the compound represented by formula (4) can be produced without using reagents that are flammable and toxic.

[0134] R in formula (4) and formula (4A) 1 ', R 2 ', m' and n' are R in formula (1).1 , R 2 , m and n have the same meaning.

[0135] In formula (A), M represents a group containing an alkali metal or alkaline earth metal.

[0136] In formula (A), R 12 represents one or more substituents other than hydrogen atoms. 12 As the organic group, R 1 and R 2 The substituents other than hydrogen atoms may be the same as those exemplified for R. 12 If there are two or more, there are multiple R 12 may be the same or different.

[0137] Specifically, production method A may include, for example, the steps of preparing compound (4-1), reacting compound (4-1) with an orthoester to obtain compound (4-2), reacting aryl metal compound (A) with compound (4-2) to obtain compound (4-3), converting the acetal of compound (4-3) to a ketone under acidic conditions to obtain compound (4A), and subjecting compound (4A) to a Knoevenagel condensation reaction with two molecules of malononitrile to obtain compound (4).

[0138] [ka]

[0139] <Manufacturing method B> Production method B is a method for producing a compound represented by formula (x). Production method B may include a step of aldol condensing compound (x-1) and compound (4) to obtain a compound represented by formula (x). By such production method B, the compound represented by formula (x) can be produced.

[0140] [ka]

[0141] D and L in the formula (x) and the formula (x-1) have the same meaning as D and L in the formula (1).

[0142] R in formula (x) 1 ', R 2 ', m' and n' are R in formula (4). 1 ', R 2 ', m' and n' have the same meaning.

[0143] [EO polymer compound] The present invention also encompasses an electro-optical polymer compound (hereinafter also referred to as "EO polymer compound") having an amorphous resin and a compound represented by formula (1) covalently bonded to the amorphous resin. An "electro-optical polymer compound" refers to a polymer compound capable of exhibiting an electro-optical effect. "Covalently bonded" means that a covalent bond exists between the bonded amorphous resin and the compound represented by formula (1). The amorphous resin and the compound represented by formula (1) may be bonded, for example, by a single bond or a linking group.

[0144] The compound represented by formula (1) preferably has a functional group capable of forming a covalent bond with the amorphous resin. In one embodiment, the compound represented by formula (1) preferably has an electron donating group D in formula (1) having a functional group capable of forming a covalent bond with the amorphous resin, and the electron donating group D is a group represented by formula (3), and R in formula (3) 3 and R 4 At least one of the following is -R 5 -OH(R 5 represents a divalent hydrocarbon group.) or -R 6 -NH2(R 6 represents a divalent hydrocarbon group.) is more preferable. The functional group may be, for example, at least one functional group selected from the group consisting of a hydroxy group, an amino group, and an alkoxycarbonyl group. Examples and preferred ranges of this alkoxycarbonyl group are given in R 1 and R 2 The examples and preferred ranges of the alkoxycarbonyl group are the same as those of the alkoxycarbonyl group.

[0145] The amorphous resin can function as a host material that holds the compound represented by formula (1) in the electro-optical ink composition described below. The amorphous resin is preferably a resin that exhibits high compatibility with the compound represented by formula (1).

[0146] In this specification, the "amorphous" nature of an amorphous resin can be determined by the presence or absence of a melting point (Tm) (an endothermic peak associated with melting observed by DSC (differential scanning calorimetry)), and "amorphous" refers to a resin that does not have a melting point (Tm). In other words, an amorphous resin refers to a resin that does not have a melting point (Tm).

[0147] Examples of amorphous resins include poly(meth)acrylates such as polymethyl methacrylate (PMMA), polyimides, polycarbonates, polystyrenes, polysulfones, polyethersulfones, silicone resins, and epoxy resins, which do not have a melting point (Tm). These resins have excellent compatibility with EO compounds, and when used in EO elements, they tend to have excellent transparency and moldability. Among these, the amorphous resin is preferably poly(meth)acrylate.

[0148] The amorphous resin poly(meth)acrylate may be a resin containing structural units derived from a (meth)acrylic monomer. Examples of the (meth)acrylic monomer include (meth)acrylic acid and (meth)acrylic acid esters. The (meth)acrylic monomer may have a reactive functional group and a crosslinkable functional group, which will be described later. From the viewpoint of making the poly(meth)acrylate amorphous, it is preferable that the (meth)acrylic monomer does not have a group with high crystallinity, such as an aromatic group. In this specification, "(meth)acrylate" refers to at least one selected from the group consisting of acrylate and methacrylate, and "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid.

[0149] The amorphous resin preferably has a reactive functional group capable of forming a covalent bond with the compound represented by formula (1). At least a portion of the compound represented by formula (1) is preferably bonded to the reactive functional group, for example, the reactive functional group of the amorphous resin is preferably bonded to a functional group of the compound represented by formula (1).

[0150] Examples of reactive functional groups include haloalkyl groups, halogenated acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, hydroxy groups, amino groups, isocyanate groups, epoxy groups, and carboxy groups. The reactive functional groups can react with functional groups such as hydroxy groups, amino groups, and alkoxycarbonyl groups in the compound represented by formula (1) to form covalent bonds. Examples and preferred ranges of alkoxycarbonyl groups in the reactive functional groups are given in R 1 and R 2 The examples and preferred ranges of the alkoxycarbonyl group are the same as those of the alkoxycarbonyl group.

[0151] When the EO compound has a crosslinkable group, the amorphous resin may have a crosslinkable functional group capable of reacting with the crosslinkable group of the EO compound to form a crosslinked structure. Furthermore, it is preferable that at least a portion of the EO compound forms a crosslinked structure with the crosslinkable functional group. Such an amorphous resin allows the EO compound to be present in the host material at a high density, thereby achieving high EO properties.

[0152] Examples of the crosslinkable functional group include radically polymerizable groups such as a (meth)acryloyloxy group and a styryl group (vinylphenyl group), and dienophile groups such as an anthracenyl group and a benzocyclobutenyl group. The crosslinkable functional group can react with a crosslinkable group in an EO compound to form a crosslinked structure.

[0153] The polystyrene-equivalent number average molecular weight (Mn) of the amorphous resin may be preferably 500 to 1,000,000, more preferably 1,000 to 100,000, still more preferably 5,000 to 70,000, and particularly preferably 10,000 to 50,000.

[0154] The weight average molecular weight (Mw) of the amorphous resin in terms of polystyrene may be preferably 1,000 to 2,000,000, more preferably 4,000 to 200,000, still more preferably 10,000 to 100,000, and particularly preferably 20,000 to 80,000.

[0155] The polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the amorphous resin can be determined by size exclusion chromatography (SEC), specifically, by the method described in the Examples.

[0156] The EO dye concentration of the EO polymer compound (the number of moles of the compound moiety represented by Formula (1) based on the mass of the EO polymer compound) is, for example, 0.1 to 0.8 mol / kg. If the concentration is less than 0.1 mol / kg, the EO effect is likely to be insufficient, while if it exceeds 0.8 mol / kg, the EO effect is likely to be reduced due to EO dye aggregation. The concentration is preferably 0.2 to 0.8 mol / kg, more preferably 0.3 to 0.77 mol / kg, and even more preferably 0.35 to 0.75 mol / kg. In one embodiment, the concentration is preferably 0.15 to 0.75 mol / kg, more preferably 0.2 to 0.7 mol / kg, even more preferably 0.21 to 0.5 mol / kg, and even more preferably 0.23 to 0.35 mol / kg. The EO dye concentration of the EO polymer compound can be calculated based on the amounts of raw materials used in the synthesis.

[0157] The method for producing the EO polymer compound is not particularly limited, and the compound can be produced, for example, by reacting a compound represented by formula (1) having a functional group capable of forming a covalent bond with an amorphous resin with an amorphous resin having a reactive functional group capable of forming a covalent bond with the compound represented by formula (1) by a known method.

[0158] [Electro-optical ink composition, film (electro-optical film), and electro-optical element] The EO ink composition, EO film, and EO element of this embodiment can be produced by known methods (e.g., the methods described in Ohe Tal., IEEE Journal on Selected Topics in Quantum Electronics, Vol. 7, No. 5, pp. 826-835, September / Oct. 2001; Dalton Tal., Journal of Materials Chemistry, 1999, 9, pp. 1905-1920; Kaino, Transactions of the Institute of Electronics, Information and Communication Engineers, CV Vol. J84-C, No. 9, pp. 744-755, September 2001; Maetal., Advanced Materials, 2002, 14, No. 19, 2002, pp. 1339-1365, etc.).

[0159] The EO ink composition of this embodiment contains the EO compound of this embodiment. The EO ink composition of this embodiment may further contain a host material that supports the EO compound of this embodiment. To exhibit excellent EO properties, it is preferable that the EO compound be present uniformly at a high concentration in the host material. Therefore, it is preferable that the host material exhibit high compatibility with the EO compound. The host material may form a covalent bond with the EO compound. In this case, the EO ink composition may contain the above-described EO polymer compound. Furthermore, the host material may react with the crosslinkable group of the EO compound to form a crosslinked structure. The EO ink composition of this embodiment can be suitably used for forming an EO film or an EO element. That is, the EO ink composition of this embodiment may be an ink composition for forming an EO film or an ink composition for forming an EO element.

[0160] Examples of host materials include resins such as poly(meth)acrylates such as polymethyl methacrylate (PMMA), polyimides, polycarbonates, polystyrenes, polysulfones, polyethersulfones, silicone-based resins, and epoxy-based resins. These resins have excellent compatibility with EO compounds, and when used in EO elements, they also have excellent transparency and moldability.

[0161] As a method for making the EO compound be held in the host material, for example, a method of dissolving the EO compound and the host material in an organic solvent at an appropriate mixing ratio can be mentioned.

[0162] The host material preferably contains a resin having a reactive functional group capable of forming a covalent bond with the EO compound. Furthermore, it is preferable that at least a portion of the EO compound is bonded to the resin having the reactive functional group. The EO ink composition of this embodiment allows the EO compound to be present in the host material at a high density, thereby achieving EO properties.

[0163] Examples of the reactive functional group include a haloalkyl group, a halogenated acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxy group, an amino group, an isocyanate group, an epoxy group, a carboxy group, etc. The reactive functional group can react with, for example, a hydroxy group, an amino group, an alkoxycarbonyl group, etc. in the EO compound to form a covalent bond.

[0164] The host material may be an amorphous resin. In this case, the degree of orientation of the EO compound during electric field poling is likely to be high, and the rate of change in absorbance before and after electric field poling is likely to be improved. The amorphous resin is preferably one of those described in the section on EO polymer compounds. These resins have excellent compatibility with EO compounds, and when used in EO elements, tend to have excellent transparency and moldability. Among these, the amorphous resin is preferably a poly(meth)acrylate such as PMMA.

[0165] The polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the amorphous resin that can be contained in the EO ink composition may be the polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the amorphous resin described in the section on EO polymer compounds, including preferred embodiments.

[0166] As a method for making the EO compound be held in the amorphous resin, for example, a method of dissolving the EO compound and the amorphous resin in an organic solvent at an appropriate mixing ratio can be mentioned.

[0167] The EO dye content of the EO ink composition (the number of moles of the compound represented by formula (1) based on the solid content mass of the EO ink composition) is, for example, 0.1 to 0.8 mol / kg. If the concentration is less than 0.1 mol / kg, the EO effect is likely to be insufficient, and if it exceeds 0.8 mol / kg, association of the EO dye is likely to occur. The concentration is preferably 0.2 to 0.8 mol / kg, more preferably 0.3 to 0.77 mol / kg, and even more preferably 0.35 to 0.75 mol / kg. In one embodiment, the concentration is preferably 0.15 to 0.75 mol / kg, more preferably 0.2 to 0.7 mol / kg, even more preferably 0.21 to 0.5 mol / kg, and even more preferably 0.23 to 0.35 mol / kg. The EO dye concentration of the EO polymer compound can be calculated based on the amount of raw material used in the preparation.

[0168] From the viewpoint of coatability, the content of the host material in the EO ink composition is preferably 10 to 10,000 parts by mass, more preferably 15 to 1,000 parts by mass, and even more preferably 20 to 500 parts by mass, relative to 100 parts by mass of the total amount of the EO compound of this embodiment and the EO polymer compound of this embodiment.

[0169] The EO film of this embodiment includes the EO compound or the EO polymer compound of this embodiment. The EO film of this embodiment can be formed using the EO ink composition. The EO film can be obtained, for example, by a method including a step of applying an organic solvent solution of the EO ink composition onto a substrate by spin coating and a step of heating and drying the resulting coating.

[0170] The thickness of the EO film may be, for example, 0.01 to 100 μm, and preferably 400 to 1000 nm.

[0171] The EO element of this embodiment includes the above-described EO film, and can be manufactured by a method including a step of poling the EO film while heating it.

[0172] In the method for producing an EO element, the temperature during poling treatment (poling temperature) is appropriately adjusted depending on the EO compound or EO polymer compound, for example, depending on the glass transition temperature of the EO compound, EO polymer compound, or EO film. The poling temperature may be, for example, 80 to 200°C, and preferably 150 to 190°C.

[0173] The EO film or EO element including the EO film of this embodiment exhibits a large change in absorbance before and after electric field poling. A large change in absorbance before and after electric field poling indicates a high degree of orientation of the EO compound during electric field poling. The change in absorbance at the maximum absorption wavelength λmax of the EO film or EO element before and after electric field poling at an electric field strength of 100 V / μm is preferably more than 14% and not more than 80%, more preferably 14.5 to 70%, and even more preferably 15 to 50%. Measurement of absorbance and calculation of the change in absorbance can be performed using the methods described in the Examples.

[0174] The application of the EO element of this embodiment is not limited to optical modulators, as long as it has the above-mentioned EO film. In addition to optical modulators (for ultrahigh-speed applications, optical interconnect applications, optical signal processing applications, etc.), the EO element of this embodiment can also be used in, for example, optical switches, optical memories, wavelength converters, electric field sensors for microwaves, millimeter waves, terahertz waves, etc., biopotential sensors for myoelectricity, electroencephalograms, etc., optical spatial modulators, optical scanners, etc. Furthermore, when combined with electronic circuits, it can also be used for optical signal transmission between electronic circuits, etc. [Example]

[0175] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0176] NMR was measured by the following method: Approximately 10 mg of a measurement sample was dissolved in 1 mL of deuterated chloroform (CDCl 3 ), and the measurement was performed using an NMR apparatus (manufactured by JEOL RESONANCE, trade name: JNM-ECZ400S / L1).

[0177] In the examples and comparative examples, the polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound were determined by one of the following size exclusion chromatography (SEC) methods using tetrahydrofuran as the mobile phase. The SEC measurement conditions were as follows:

[0178] <Measurement conditions> The polymer compound to be measured was dissolved in tetrahydrofuran at a concentration of approximately 0.05% by mass, and 0.001% by mass of ethanol relative to the polymer compound was added, followed by standing overnight. 10 μL of the resulting polymer compound solution was injected into the SEC. The mobile phase was run at a flow rate of 2.0 mL / min. The column used was a PLgel MIXED-B (manufactured by Polymer Laboratories). The detector used was an RI detector (manufactured by Shimadzu Corporation, product name: HLC-8220GPC).

[0179] Compound synthesis

[0180] (Example 1) Synthesis of Compound (4-7) To synthesize compound (4-7), compound (4-1) was acetalized to synthesize compound (4-2). Compound (4-5) was synthesized by reacting compound (4-2) with a Grignard reagent prepared from compound (4-4). Subsequently, compound (4-6) was synthesized by converting the acetal of compound (4-5) to a ketone under acidic conditions. Compound (4-7) was synthesized by the Knoevenagel condensation reaction of compound (4-6) with malononitrile.

[0181] Synthesis of compound (4-2) [ka]

[0182] Compound (4-2) was synthesized by acetalization of compound (4-1). A 200 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 15.16 g (130.6 mmol) of ethyl pyruvate (Tokyo Chemical Industry Co., Ltd.) and 31.2 mL (285 mmol) of trimethyl orthoformate (Tokyo Chemical Industry Co., Ltd.). A stirrer was then added, the atmosphere was purged with nitrogen, and the solution was cooled to 0 °C. 1.5 mL (41.5 mmol) of concentrated sulfuric acid (Kanto Chemical Co., Ltd.) was added dropwise, and the mixture was heated to room temperature (25 °C) and stirred with a magnetic stirrer for 6.5 hours. Aqueous sodium hydroxide solution was added until the reaction solution reached pH 10, and the reaction mixture was diluted with chloroform. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-2) as a transparent liquid. The obtained amount was 20.90 g (yield: 99.8%). 1 The results of the H-NMR spectrum measurement are as follows:

[0183] 1 H-NMR (400MHz, CDCl3): δ(ppm)=4.28(q,2H), 3.29(s,6H), 1.52(s,3H), 1.33(t,3H).

[0184] Synthesis of Compound (4-6) [ka]

[0185] First, compound (4-5) was synthesized by reacting compound (4-2) with the Grignard reagent prepared from compound (4-4). A 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 80 mL (160 mmol) of a 2 M solution of isopropyl magnesium chloride in tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) and 6.80 g of lithium chloride (Fujifilm Wako Pure Chemical Industries, Ltd.). A stirrer was then added and the inside of the flask was purged with nitrogen. After stirring the reaction solution at room temperature for 30 minutes, 22.1 mL of compound (4-4) was added and the mixture was stirred at room temperature (25 °C) for 2 hours to allow the reaction to proceed. The reaction solution was diluted with 200 mL of tetrahydrofuran and then cooled to -68 °C. 12.20 g (75.2 mmol) of compound (4-2) dissolved in 38 mL of tetrahydrofuran was added dropwise to the reaction solution cooled to -68 °C and allowed to react. The reaction mixture was warmed to 0°C, and then a saturated aqueous solution of ammonium chloride was added to terminate the reaction. The mixture was then diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-5) as a yellow liquid.

[0186] Next, compound (4-6) was synthesized by converting the acetal of compound (4-5) to a ketone under acidic conditions. The entire amount of compound (4-5) obtained in the previous step, 3.04 g (16 mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 288 mL of acetone (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added and the atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 15 hours, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate and diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (hexane / ethyl acetate = 40 / 1 → 20 / 1) to obtain compound (4-6) as a yellow oil. The amount obtained was 21.12 g (yield: 78%). 1 The results of the H-NMR spectrum measurement are as follows:

[0187] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.67(d,4H), 7.49(d,4H), 4.84(s,1H), 2.31(s,3H).

[0188] Synthesis of compound (4-7) [ka]

[0189] Compound (4-7) was synthesized by the Knoevenagel condensation reaction of compound (4-6) and malononitrile. A 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 7.82 g (21.6 mmol) of compound (4-6), 78 mL of ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.), 4.31 g (65.2 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 2.16 mL of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stir bar was added and the inside atmosphere was purged with nitrogen. The reaction solution was heated to 65 °C and reacted for 7 hours while stirring with a magnetic stirrer. An additional 2.84 g (43.0 mmol) of malononitrile was added, followed by heating and stirring at 65 °C for an additional 9 hours. After approximately 80% of the ethanol solvent was distilled off using a rotary evaporator, the reaction mixture was diluted with ion-exchanged water, and the aqueous layer was extracted six times with 70 mL of chloroform. The combined organic layers were dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The filtrate was concentrated and dried using a rotary evaporator to obtain a crude product. The obtained crude product was washed with 30 mL of methanol cooled to -30°C and then dried to obtain compound (4-7) as a white solid. The obtained amount was 5.51 g (yield: 56%). 1 The results of the H-NMR spectrum measurement are as follows:

[0190] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.78(d,4H), 7.33(d,4H), 2.46(s,3H).

[0191] (Example 2) Synthesis of Compound (4-11) Compound (4-9) was obtained by reacting compound (4-2) with an organometallic reagent prepared from compound (4-8). Subsequently, compound (4-10) was synthesized by converting the acetal of compound (4-9) to a ketone under acidic conditions. Compound (4-11) was synthesized by the Knoevenagel condensation reaction of compound (4-10) with malononitrile.

[0192] Synthesis of Compound (4-10) [ka]

[0193] First, compound (4-9) was synthesized by reacting compound (4-2) with organolithium species prepared from compound (4-8). 7.50 g (33.2 mmol) of compound (4-8) (Tokyo Chemical Industry Co., Ltd.) and 56 mL of dehydrated diethyl ether (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added and the inside atmosphere was purged with nitrogen. The reaction solution was then cooled to -68 °C, and 22.0 mL (33.2 mmol) of a 1.51 mol / L n-butyllithium hexane solution (Kanto Chemical Industry Co., Ltd.) was added dropwise using a gas-tight syringe. After the addition was complete, the reaction solution was stirred for 15 minutes. Then, 2.53 g (15.6 mmol) of compound (4-2) dissolved in 56 mL of dehydrated diethyl ether was added dropwise to the reaction solution at -68 °C and allowed to react. The reaction mixture was warmed to room temperature (25°C) and stirred for 2 hours. The reaction was then quenched by adding a saturated aqueous solution of ammonium chloride and diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-9) as a yellow liquid.

[0194] Next, compound (4-10) was synthesized by converting the acetal of compound (4-9) to a ketone under acidic conditions. The entire amount of compound (4-9) obtained in the previous step, 0.65 g (3.4 mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 60 mL of acetone (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added and the atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 2 hours, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate and diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (hexane / ethyl acetate = 20 / 1 → 10 / 1) to obtain compound (4-10) as a yellow oil. The amount obtained was 3.79 g (yield: 67%). 1 The results of the H-NMR spectrum measurement are as follows:

[0195] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.51-7.44(m,4H), 7.18-7.13(m,2H), 4.71(s,1H), 2.30(s,3H).

[0196] Synthesis of compound (4-11) [ka]

[0197] Compound (4-11) was synthesized by the Knoevenagel condensation reaction of compound (4-10) and malononitrile. A 200 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 3.79 g (10.4 mmol) of compound (4-10), 40 mL of ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.), 1.46 g (21.8 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 1.09 mL (1.09 mmol) of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stirrer was added and the atmosphere was purged with nitrogen. The reaction solution was heated to 65 °C and reacted for 7.5 hours while stirring with a magnetic stirrer. Approximately 80% of the ethanol solvent was removed using a rotary evaporator, and the reaction mixture was diluted with ion-exchanged water. The aqueous layer was extracted with 70 mL of chloroform. The combined organic layer was concentrated and dried using a rotary evaporator to obtain a crude product. 20 mL of methanol was added to the obtained crude product, and the mixture was stirred at room temperature, then cooled to -30°C, and the solid component was collected by filtration. The solid component on the filter was washed with 10 mL of methanol and dried to obtain compound (4-11) as a white solid. The obtained amount was 2.90 g (yield: 58%). 1 The results of the H-NMR spectrum measurement are as follows:

[0198] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.59(d,2H), 7.23(d,2H), 7.01(dd,2H), 2.43(s,3H).

[0199] (Example 3) Synthesis of Compound (4-15) Compound (4-13) was obtained by reacting compound (4-2) with an organometallic reagent prepared from compound (4-12). Subsequently, compound (4-14) was synthesized by converting the acetal of compound (4-13) to a ketone under acidic conditions. Compound (4-15) was synthesized by the Knoevenagel condensation reaction of compound (4-14) with malononitrile.

[0200] Synthesis of compound (4-14) [ka]

[0201] First, compound (4-13) was synthesized by reacting compound (4-2) with organolithium species prepared from compound (4-12). 4.05 g (33.4 mmol) of compound (4-12) (Tokyo Chemical Industry Co., Ltd.) and 53 mL of dehydrated diethyl ether (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added and the inside atmosphere was purged with nitrogen. The reaction solution was then cooled to -68 °C, and 22.1 mL (33.4 mmol) of a 1.51 mol / L n-butyllithium hexane solution (Kanto Chemical Industry Co., Ltd.) was added dropwise using a gas-tight syringe. After the addition was complete, the reaction solution was stirred for 10 minutes. Then, 2.55 g (15.7 mmol) of compound (4-2) dissolved in 15 mL of dehydrated diethyl ether was added dropwise to the reaction solution at -68 °C and reacted. The reaction mixture was warmed to 0°C and stirred for 45 minutes. The reaction was then quenched by adding a saturated aqueous solution of ammonium chloride and diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-13) as a yellow liquid.

[0202] Next, compound (4-14) was synthesized by converting the acetal of compound (4-13) to a ketone under acidic conditions. The entire amount of compound (4-13) obtained in the previous step, 0.68 g (3.6 mmol) of p-toluenesulfonic acid monohydrate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 56 mL of acetone (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the inside atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 30 minutes, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate, and the mixture was diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 300 mL recovery flask and concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (hexane / ethyl acetate = 20 / 1 → 10 / 1) to obtain compound (4-14) as a transparent oil. The obtained amount was 2.08 g (yield: 40%). 1 The results of the H-NMR spectrum measurement are as follows:

[0203] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.43(dd,2H), 7.18(dd,2H), 7.09-7.04(m,2H), 4.74(s,1H), 2.30(s,3H).

[0204] Synthesis of compound (4-15) [ka]

[0205] Compound (4-15) was synthesized by the Knoevenagel condensation reaction of compound (4-14) and malononitrile. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 2.08 g (10.4 mmol) of compound (4-14), 21 mL of ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.), 1.12 g (17.0 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 0.63 mL (0.63 mmol) of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stirrer was added and the atmosphere was purged with nitrogen. The reaction solution was heated to 65 °C and reacted for 6.5 hours while stirring with a magnetic stirrer. Approximately 80% of the ethanol solvent was removed using a rotary evaporator, after which the reaction mixture was diluted with ion-exchanged water, and the resulting aqueous layer was extracted with 70 mL of chloroform. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain a crude product. 20 mL of methanol was added to the obtained crude product, and the mixture was stirred at room temperature, and the solid component was collected by filtration. The solid component on the filter was washed with methanol and then dried to obtain compound (4-15) as a white solid. The amount obtained was 1.37 g (yield: 51%). 1 The results of the H-NMR spectrum measurement are as follows:

[0206] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.56(dd,2H), 6.98(dd,2H), 6.95-6.91(m,2H), 2.43(s,3H).

[0207] (Example 4) Synthesis of Compound (4-19) Compound (4-17) was obtained by reacting compound (4-2) with an organometallic reagent prepared from compound (4-16). Subsequently, compound (4-18) was synthesized by converting the acetal of compound (4-17) to a ketone under acidic conditions. Compound (4-19) was synthesized by the Knoevenagel condensation reaction of compound (4-18) with malononitrile.

[0208] Synthesis of compound (4-18) [ka]

[0209] First, compound (4-17) was synthesized by reacting compound (4-2) with organolithium species prepared from compound (4-16). 15.0 g (71.1 mmol) of compound (4-16) (Tokyo Chemical Industry Co., Ltd.) and 150 mL of dehydrated diethyl ether (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added and the inside atmosphere was purged with nitrogen. The reaction solution was then cooled to -68 °C, and 44.4 mL (71.1 mmol) of a 1.51 mol / L n-butyllithium hexane solution (Kanto Chemical Industry Co., Ltd.) was added dropwise using a gas-tight syringe. After the addition was complete, the reaction solution was stirred for 10 minutes. Then, 5.77 g (35.5 mmol) of compound (4-2) dissolved in 30 mL of dehydrated diethyl ether was added dropwise to the reaction solution at -68 °C and allowed to react. The reaction mixture was warmed to 0°C and stirred for 10 minutes. The reaction was then quenched by adding a saturated aqueous solution of ammonium chloride and diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-17) as a yellow liquid.

[0210] Next, compound (4-18) was synthesized by converting the acetal of compound (4-17) to a ketone under acidic conditions. The entire amount of compound (4-17) obtained in the previous step, 1.41 g (7.2 mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 120 mL of acetone (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 30 minutes, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate, and the mixture was diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (hexane / ethyl acetate = 20 / 1 → 9 / 1) to obtain compound (4-18) as a transparent oil in an amount of 6.55 g (yield: 59%).

[0211] Synthesis of compound (4-19) [ka]

[0212] Compound (4-19) was synthesized by the Knoevenagel condensation reaction of compound (4-18) and malononitrile. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 6.55 g (19.6 mmol) of compound (4-18), 26 mL of 2-ethoxyethanol (Tokyo Chemical Industry Co., Ltd.), 1.30 g (19.6 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 1.96 mL (1.96 mmol) of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stir bar was added and the inside atmosphere was purged with nitrogen. The reaction solution was heated to 65 °C and reacted for 1 hour while stirring with a magnetic stirrer. The reaction solution was then heated to 120 °C and reacted for 1 hour. After that, an additional 1.30 g (19.6 mmol) of malononitrile was added and the mixture was heated and stirred at 120 °C for an additional 3 hours. The reaction mixture was diluted with ion-exchanged water, and the aqueous layer was extracted with 70 mL of chloroform. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The remaining 2-ethoxyethanol was removed by azeotropy twice with n-heptane to obtain a crude product. 20 mL of methanol was added to the obtained crude product, and the mixture was stirred at room temperature, and the solid component was collected by filtration. The solid component on the filter was washed with methanol and then dried to obtain compound (4-19) as an off-white solid. The amount obtained was 1.78 g (yield: 21%). Compound (4-19) 1 The results of the H-NMR spectrum measurement are as follows:

[0213] 1 H-NMR (400MHz, acetone-d6): δ (ppm) = 7.48-7.39 (m, 4H), 2.61 (s, 3H).

[0214] (Example 5) Synthesis of Compound (4-23) The organometallic reagent prepared from compound (4-20) was reacted with compound (4-2) to obtain compound (4-21). Subsequently, compound (4-22) was synthesized by converting the acetal of compound (4-21) to a ketone under acidic conditions. Compound (4-23) was synthesized by the Knoevenagel condensation reaction of compound (4-22) with malononitrile.

[0215] Synthesis of compound (4-22) [ka]

[0216] First, compound (4-21) was synthesized by reacting compound (4-2) with an organolithium species prepared from compound (4-20). 5.00 g (19.2 mmol) of compound (4-20) (Kanto Chemical Industry Co., Ltd.) and 30 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 200 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the inside atmosphere was purged with nitrogen. The reaction solution was then cooled to 0 °C, and 9.6 mL (19.2 mmol) of a 2 mol / L solution of i-propylmagnesium chloride in tetrahydrofuran (Sigma-Aldrich) was added dropwise using a gas-tight syringe. After the addition was complete, the reaction solution was stirred for 15 minutes, then warmed to room temperature and stirred for another 15 minutes. Then, 1.47 g (9.1 mmol) of compound (4-2) dissolved in 30 mL of dehydrated tetrahydrofuran was added dropwise to the reaction solution and allowed to react. After stirring the reaction mixture for 30 minutes, a saturated aqueous solution of ammonium chloride was added to terminate the reaction, and diethyl ether was added to dilute the mixture. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 300 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-21) as a white solid.

[0217] Next, compound (4-22) was synthesized by converting the acetal of compound (4-21) to a ketone under acidic conditions. The entire amount of compound (4-21) obtained in the previous step, 0.37 g (1.9 mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 40 mL of acetone (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 35 minutes, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate, and the mixture was diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (hexane / ethyl acetate = 20 / 1 → 10 / 1) to obtain compound (4-22) as a white solid. The obtained amount was 2.00 g (yield: 51%). 1 The results of the H-NMR spectrum measurement are as follows:

[0218] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.36(s,4H), 4.63(s,1H), 2.34(s,3H).

[0219] Synthesis of compound (4-23) [ka]

[0220] Compound (4-23) was synthesized by the Knoevenagel condensation reaction of compound (4-22) and malononitrile. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 8.31 g (19.2 mmol) of compound (4-22), 8.3 mL of 2-ethoxyethanol (Tokyo Chemical Industry Co., Ltd.), 3.54 g (38.4 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 1.92 mL (1.92 mmol) of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stirrer was added and the atmosphere was purged with nitrogen. The reaction solution was heated to 120 °C and reacted for 1 hour while stirring with a magnetic stirrer. The reaction solution was then heated to 120 °C and reacted for 2 hours, after which it was diluted with saturated aqueous ammonium chloride, and the aqueous layer was extracted four times with 70 mL of chloroform. The combined organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain a crude product. 50 mL of methanol was added to the obtained crude product, and the mixture was stirred at room temperature, and the solid component was collected by filtration. The solid component on the filter was washed with methanol and then dried to obtain compound (4-23) as a white solid. The amount obtained was 0.86 g (yield: 10%). 1 The results of the H-NMR spectrum measurement are as follows:

[0221] 1 H-NMR (400MHz, acetone-d6): δ (ppm) = 7.77 (s, 4H), 2.66 (s, 3H).

[0222] (Example 6) Synthesis of Compound (4-27) The organometallic reagent prepared from compound (4-24) was reacted with compound (4-2) to obtain compound (4-25). Subsequently, compound (4-26) was synthesized by converting the acetal of compound (4-25) to a ketone under acidic conditions. Compound (4-27) was synthesized by the Knoevenagel condensation reaction of compound (4-26) with malononitrile.

[0223] Synthesis of compound (4-26) [ka]

[0224] First, compound (4-25) was synthesized by reacting compound (4-2) with organolithium species prepared from compound (4-24). 10.69 mL (63.1 mmol) of compound (4-24) (Tokyo Chemical Industry Co., Ltd.) and 37 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added and the inside atmosphere was purged with nitrogen. The reaction solution was then cooled to 0 °C, and 31.6 mL (63.2 mmol) of a 2 mol / L solution of i-propylmagnesium chloride in tetrahydrofuran (Sigma-Aldrich) was added dropwise using a gas-tight syringe. After the addition was complete, the reaction solution was stirred at 0 °C for 20 minutes and then cooled to -68 °C. Then, 4.81 g (29.7 mmol) of compound (4-2) dissolved in 37 mL of dehydrated tetrahydrofuran was added dropwise to the reaction solution and allowed to react. The reaction mixture was stirred at 0°C for 2 hours, and then a saturated aqueous solution of ammonium chloride was added to terminate the reaction, followed by dilution with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 300 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-25) as a yellow oil.

[0225] Next, compound (4-26) was synthesized by converting the acetal of compound (4-25) to a ketone under acidic conditions. The entire amount of compound (4-25) obtained in the previous step, 1.20 g (6.3 mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 148 mL of acetone (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 1 hour, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate, and the mixture was diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. 45 mL of hexane was added to the obtained oily crude product, and the mixture was cooled to 0°C. The resulting white solid was collected by filtration and washed with 15 mL of hexane cooled to 0°C to obtain compound (4-26) as a white solid. The obtained amount was 10.63 g (yield: 72%). 1 The results of the H-NMR spectrum measurement are as follows:

[0226] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.96(s,2H), 7.81(s,4H), 4.85(s,1H), 2.36(s,3H).

[0227] Synthesis of compound (4-27) [ka]

[0228] Compound (4-27) was synthesized by the Knoevenagel condensation reaction of compound (4-26) and malononitrile. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 8.85 g (17.8 mmol) of compound (4-26), 5.5 mL of 2-ethoxyethanol (Tokyo Chemical Industry Co., Ltd.), 2.63 g (39.7 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 1.81 mL (1.81 mmol) of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stirrer was added and the atmosphere was purged with nitrogen. The reaction solution was heated to 120 °C and reacted for 75 minutes. After that, the reaction mixture was diluted with aqueous ammonium chloride, and the aqueous layer was extracted with chloroform. The combined organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The remaining 2-ethoxyethanol was removed by azeotropy twice with n-heptane to obtain a crude product. Methanol was added to the obtained crude product, and the mixture was left to stand at room temperature. The precipitated white solid was collected by filtration. The solid component on the filter was washed with methanol and then dried to obtain compound (4-27) as a white solid. The filtrate was concentrated, and the solid was precipitated again by the same method to obtain a second crystal. The total amount obtained was 3.01 g (yield: 28%). Compound (4-27) 1 The results of the H-NMR spectrum measurement are as follows:

[0229] 1 H-NMR (400MHz, acetone-d6): δ(ppm)=8.29(s,2H), 8.23(s,4H), 2.71(s,3H).

[0230] (Example 7) Synthesis of Compound (4-31) Compound (4-29) was obtained by reacting compound (4-2) with Grignard reagent prepared from compound (4-28). Subsequently, compound (4-30) was synthesized by converting the acetal of compound (4-29) to a ketone under acidic conditions. Compound (4-31) was synthesized by the Knoevenagel condensation reaction of compound (4-30) with malononitrile.

[0231] Synthesis of compound (4-30) [ka]

[0232] First, compound (4-29) was obtained by reacting compound (4-2) with a Grignard reagent prepared from compound (4-28). 1.6 g (66.0 mmol) of magnesium powder (FUJIFILM Wako Pure Chemical Industries, Ltd.) and 117 mL of dehydrated tetrahydrofuran (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the inside of the flask was purged with nitrogen. Subsequently, 14.20 g (62.9 mmol) of compound (4-28) (Tokyo Chemical Industry Co., Ltd.) dissolved in 20 mL of dehydrated tetrahydrofuran was added dropwise to the reaction solution to prepare a Grignard reagent. After the addition was complete, the reaction solution was stirred for 2 hours and then cooled to -68 °C. 4.89 g (30.2 mmol) of compound (4-2) dissolved in 20 mL of dehydrated tetrahydrofuran was added dropwise to the reaction solution to allow the reaction to proceed. The reaction mixture was stirred at 0°C for 30 minutes, then a saturated aqueous solution of ammonium chloride was added to terminate the reaction, and the mixture was diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-29).

[0233] Next, compound (4-30) was synthesized by converting the acetal of compound (4-29) to a ketone under acidic conditions. The entire amount of compound (4-29) obtained in the previous step, 1.20 g (6.3 mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 114 mL of acetone (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 3 hours, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate, and the mixture was diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The obtained crude product was purified using a silica gel column (hexane / ethyl acetate = 30 / 1 → 20 / 1) to obtain compound (4-30) as a brown oil. The obtained amount was 10.00 g (yield: 90%). 1 The results of the H-NMR spectrum measurement are as follows:

[0234] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.40(t,2H), 7.22(d,4H), 4.69(s,1H), 2.33(s,3H).

[0235] Synthesis of compound (4-31) [ka]

[0236] Compound (4-31) was synthesized by the Knoevenagel condensation reaction of compound (4-30) and malononitrile. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 8.06 g (22.1 mmol) of compound (4-30), 48 mL of 2-ethoxyethanol (Tokyo Chemical Industry Co., Ltd.), 3.01 g (44.4 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 2.21 mL (2.21 mmol) of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stirrer was added and the atmosphere was purged with nitrogen. The reaction solution was heated to 100 °C and reacted for 4 hours. After that, it was diluted with distilled water, and the aqueous layer was extracted four times with 70 mL of chloroform. The combined organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 300 mL recovery flask and concentrated using a rotary evaporator to obtain a crude product as a brown oil. 150 mL of diethyl ether was added to the obtained crude product, and the mixture was stirred at room temperature, and the resulting solid was collected by filtration. The solid component on the filter was washed with methanol and diethyl ether, and then dried to obtain compound (4-31) as a white solid. The amount obtained was 1.01 g (yield: 10%). 1 The results of the H-NMR spectrum measurement are as follows:

[0237] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.56(t,2H), 7.02(d,4H), 2.45(s,3H).

[0238] (Example 8) Synthesis of compound (4-35) The organometallic reagent prepared from compound (4-32) was reacted with compound (4-2) to obtain compound (4-33). Subsequently, compound (4-34) was synthesized by converting the acetal of compound (4-33) to a ketone under acidic conditions. Compound (4-35) was synthesized by the Knoevenagel condensation reaction of compound (4-34) with malononitrile.

[0239] Synthesis of compound (4-34) [ka]

[0240] First, compound (4-33) was synthesized by reacting compound (4-2) with organolithium species prepared from compound (4-32). 12.0 g (53.3 mmol) of compound (4-32) (Tokyo Chemical Industry Co., Ltd.) and 80 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added and the inside atmosphere was purged with nitrogen. The reaction solution was then cooled to -68 °C, and 35.3 mL (53.3 mmol) of a 1.51 mol / L n-butyllithium hexane solution (Kanto Chemical Industry Co., Ltd.) was added dropwise using a gas-tight syringe. After the addition was complete, the reaction solution was stirred for 30 minutes. Then, 4.07 g (25.1 mmol) of compound (4-2) dissolved in 24 mL of dehydrated diethyl ether was added dropwise to the reaction solution at -68 °C and allowed to react. The reaction mixture was warmed to -20°C and stirred for 60 minutes. The reaction was then quenched by adding a saturated aqueous solution of ammonium chloride and diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator to obtain compound (4-33) as a yellow liquid.

[0241] Next, compound (4-34) was synthesized by converting the acetal of compound (4-33) to a ketone under acidic conditions. The entire amount of compound (4-33) obtained in the previous step, 1.01 g (5.3 mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 96 mL of acetone (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 300 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the atmosphere was purged with nitrogen. The reaction solution was reacted at room temperature (25 °C) for 30 minutes, after which the reaction was terminated by adding a saturated aqueous solution of sodium bicarbonate, and the mixture was diluted with diethyl ether. The aqueous layer was removed, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (hexane / ethyl acetate = 50 / 1 → 20 / 1) to obtain compound (4-34) as a transparent oil in an amount of 4.03 g (yield: 44%).

[0242] Synthesis of compound (4-35) [ka]

[0243] Compound (4-35) was synthesized by the Knoevenagel condensation reaction of compound (4-34) and malononitrile. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 4.17 g (11.5 mmol) of compound (4-34), 42 mL of ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.), 2.28 g (34.5 mmol) of malononitrile (Tokyo Chemical Industry Co., Ltd.), and 1.15 mL (1.15 mmol) of a 1 M ethanol solution of lithium ethoxide (Sigma-Aldrich). A stirrer was added and the atmosphere was purged with nitrogen. The reaction solution was heated to 65 °C and reacted for 24 hours. After that, the mixture was diluted with distilled water, and the aqueous layer was extracted four times with 50 mL of chloroform. The combined organic layer was dried over anhydrous magnesium sulfate. The insoluble matter was filtered off, and the filtrate was transferred to a 300 mL recovery flask and concentrated using a rotary evaporator to obtain a crude product as a brown oil. 32 mL of ethanol was added to the obtained crude product, and the mixture was stirred at room temperature, then cooled to -40°C, and the resulting solid was collected by filtration. The solid component on the filter was washed with 5 mL of ethanol at -40°C and then dried to obtain compound (4-35) as an off-white solid. The obtained amount was 1.80 g (yield: 34%). The amount of compound (4-35) was 1.80 g (yield: 34%). 1 The results of the H-NMR spectrum measurement are as follows:

[0244] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.82(d,2H), 7,67(t,2H), 7.40-7.34(m,4H), 2.43(s,3H).

[0245] (Example 1-1) Synthesis of Compound (5) To synthesize compound (5), compound (5-1) was subjected to a Wittig reaction to synthesize compound (5-2), which was then subjected to aldol condensation to synthesize compound (5).

[0246] Synthesis of compound (5-2) [ka]

[0247] Compound (5-2) was synthesized by the Wittig reaction of compound (5-1) and tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide. Compound (5-1) was synthesized according to the description in International Publication No. 2022 / 131236. A 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 6.00 g (8.49 mmol) of compound (5-1), 120 mL of dehydrated tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3.47 g (9.40 mmol) of tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide (manufactured by BLDpharm), and 1.02 g (25.5 mmol) of sodium hydride (dispersed in liquid paraffin at 60%, manufactured by Tokyo Chemical Industry Co., Ltd.), and a stirrer was added. The inside of the flask was then purged with nitrogen. The reaction solution was stirred with a magnetic stirrer and reacted at room temperature (25°C) for 3 hours. The reaction solution was cooled to 0°C, and 1 mL of ion-exchanged water was added to stop the reaction. 120 mL of 10% hydrochloric acid was added to the reaction solution, and the reaction solution was warmed to room temperature and stirred for 3 hours. 180 mL of toluene was added to the reaction solution to separate the aqueous layer, which was then extracted three times with 60 mL of toluene. The combined organic layer was dried over anhydrous magnesium sulfate, and insoluble matter was filtered off. The filtrate was concentrated and dried using a rotary evaporator to obtain a crude product. The obtained crude product was purified using a silica gel column (hexane / chloroform = 50 / 50 → 0 / 100) to obtain compound (5-2) as a red solid. The obtained amount was 4.78 g (yield: 77%). 1 The results of the H-NMR spectrum measurement are as follows:

[0248] 1H-NMR (400MHz, CDCl3): δ(ppm)=9.57(d,1H), 7.62(d,4H), 7.58(d,1H), 7.47-7.32(m,8H), 7.19(s,1H), 6.99(s,1H), 6.57(d,2H), 6.45(dd,1H), 4.16(t,2H), 3.82(t,2H), 3.52(t,2H), 2.99(s,3H), 1.87(quint,2H), 1.38-1.18(m,10H), 1.03(s,9H), 0.85(t,3H).

[0249] Synthesis of compound (5) [ka]

[0250] Compound (5) was synthesized by aldol condensation reaction of compound (5-2) and compound (4-7). A 50 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 0.50 g (0.68 mmol) of the synthesized compound (5-2), 0.37 g (0.82 mmol) of compound (4-7), 5 mL of dehydrated ethanol, and 5 mL of dehydrated chloroform. A stirrer was then added, and the inside of the flask was purged with nitrogen. The reaction was carried out at 50°C for 18 hours while stirring with a magnetic stirrer. After the reaction was completed, the reaction mixture was concentrated using a rotary evaporator. Ethanol was added to the concentrate, and the precipitate was filtered off. The precipitate was then washed with ethanol to obtain a crude product. The crude product was purified by recycling gel permeation chromatography, and ethanol was added to the resulting solid. The precipitate was filtered off, and compound (5) was obtained as a reddish-black solid. The amount obtained was 0.468 g (yield: 58%). 1 The results of the H-NMR spectrum measurement are as follows:

[0251] 1H-NMR (400MHz, CD2Cl2): δ(ppm)=7.81-7.69(m,5H), 7.60(d,4H), 7.49-7.30(m,13H), 7.12(s,1H), 7.02(s,1H), 6.72-6.58(m,3 H), 6.27(d,1H), 4.13(t,2H), 3.81(t,2H), 3.54(t,2H), 3.00(s,3H), 1.84(m,2H), 1.36-1.17(m,10H), 1.00(s,9H), 0.82(t,3H).

[0252] (Comparative Example 1-1) Synthesis of Compound C5 Compound (5-2) was subjected to aldol condensation to synthesize compound (C5).

[0253] Synthesis of compound (C5) [ka]

[0254] Compound (C5) was synthesized by aldol condensation of compound (5-2) and 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile according to the description in WO 2022 / 131236. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 2.13 g (2.91 mmol) of the synthesized compound (5-2), 1.73 g (5.49 mmol) of 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile (manufactured by iChemical), 20 mL of dehydrated ethanol, and 20 mL of dehydrated chloroform. A stir bar was then added, and the inside of the flask was purged with nitrogen. The reaction was carried out at room temperature (25 °C) for 18 hours while stirring with a magnetic stirrer. 28 mL of ethanol was added to the reaction solution, and the resulting precipitate was filtered off and washed with ethanol. The collected precipitate was redissolved in 8.4 mL of chloroform and added dropwise to 42 mL of ethanol. The resulting precipitate was filtered off to obtain compound (C5) as a black solid. The obtained amount was 2.53 g (yield: 84%). 1 The results of the H-NMR spectrum measurement are as follows:

[0255] 1 H-NMR (400MHz, CD2Cl2): δ(ppm)=7.76(t,1H), 7.61(d,4H), 7.55-7.30(m,14H), 7.18(s,1H), 7.02(s,1H), 6.77-6.69(m,1H), 6.62(d,2) H), 6.33(d,1H), 4.13(t,2H), 3.81(t,2H), 3.55(t,2H), 3.00(s,3H), 1.90-1.78(m,2H), 1.36-1.15(m,10H), 1.00(s,9H), 0.83(t,3H).

[0256] (Example 1-2) Synthesis of Compound (6) Compound (6) was synthesized by aldol condensation of compound (6-1).

[0257] Synthesis of compound (6) [ka] Compound (6) was synthesized by aldol condensation reaction of compound (6-1) and compound (4-7). Compound (6-1) was synthesized according to the description in WO 2022 / 131236. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 1.25 g (1.71 mmol) of the synthesized compound (6-1), 0.861 g (1.87 mmol) of compound (4-7), 12.5 mL of dehydrated ethanol, and 12.5 mL of dehydrated tetrahydrofuran. A stirrer was then added and the inside atmosphere was purged with nitrogen. The reaction was carried out at 65 °C for 5 hours while stirring with a magnetic stirrer. After completion of the reaction, the reaction mixture was concentrated using a rotary evaporator. Ethanol was added to the concentrate, and the precipitate was filtered off. The precipitate was then washed with ethanol to obtain a crude product. The crude product was purified using a reversed-phase silica gel column (acetonitrile / ethyl acetate = 100 / 0 → 90 / 10) to obtain compound (6) as a green solid. The obtained amount was 1.81 g (yield: 91%). 1 The results of the H-NMR spectrum measurement are as follows:

[0258] 1 H-NMR (400MHz, CD2Cl2): δ(ppm)=7.74(d,4H), 7.72-7.62(m,1H), 7.59(d,4H), 7.45(d,4H), 7.42-7.28(m,8H), 6.88(s,1H), 6.81(s,1H), 6.59(d,2H), 6.54(d,1H), 3.80(t,2H), 3.53(t,2H), 2.99(s,3H), 1.88-1.75(m,6H), 1.00(s,9H), 0.82(t,12H).

[0259] (Comparative Example 1-2) Synthesis of Compound (C6) Compound (6-1) was subjected to aldol condensation to synthesize compound (C6).

[0260] Synthesis of compound (C6) [ka]

[0261] Compound (C6) was synthesized by aldol condensation of compound (6-1) and 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile according to the description in WO 2022 / 131236. A 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 4.92 g (6.81 mmol) of the synthesized compound (6-1), 2.58 g (8.18 mmol) of 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile (manufactured by iChemical), 64 mL of dehydrated ethanol, and 80 mL of dehydrated chloroform. A stir bar was then added, and the inside of the flask was purged with nitrogen. The reaction was carried out at room temperature (25 °C) for 30 hours while stirring with a magnetic stirrer. After the reaction was completed, the reaction mixture was concentrated using a rotary evaporator. Ethanol was added to the concentrate, and the precipitate was filtered off. The precipitate was then washed with ethanol to obtain a crude product. The crude product was purified using a reversed-phase silica gel column (acetonitrile / ethyl acetate = 100 / 0 to 90 / 10) to obtain compound (C6) as a green solid. The obtained amount was 6.30 g (yield: 70%). 1 The results of the H-NMR spectrum measurement are as follows:

[0262] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.61(dd,4H),7.55-7.47(m,5H),7.44-7.31(m,9H),6.90(s,1H),6.77(s,1H),6. 59-6.53(m,3H),3.80(t,2H),3.53(t,2H),3.00(s,3H),1.84-1.76(m,6H),1.03(s,9H),0.85(d,6H),0.83(d,6H).

[0263] (Example 1-3) Synthesis of polymer compound (P1) To obtain polymer compound (P1), compound (7-1) was silylated to synthesize compound (7-2). Subsequently, compound (7-2) was iodinated to synthesize compound (7-3) with an iodo group. The hydroxyl group of compound (7-3) was then protected with THP to obtain compound (7-4). The iodo group of compound (7-4) was then converted to a formyl group to synthesize compound (7-5). Compound (7-5) was then converted to compound (7-6) by condensation with isophorone, and compound (7-6) was subjected to a Wittig reaction to synthesize compound (7-7). Compound (7) was then synthesized by aldol condensation with compound (7-7). Polymer compound (P1) was obtained by reacting compound (7) with polymer compound (BP1).

[0264] Synthesis of compound (7-2) [ka] A 500 mL recovery flask equipped with a gas inlet tube and induction stirrer was charged with 30.06 g (165.6 mmol) of compound (7-1) (Tokyo Chemical Industry Co., Ltd.), 11.21 g (164.7 mmol) of imidazole (Tokyo Chemical Industry Co., Ltd.), and 210 mL of dehydrated N,N-dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.). The atmosphere was purged with nitrogen and the solution was cooled to 0 °C. 14.0 mL (54.6 mmol) of tert-butyldiphenylchlorosilane (TBDPSCl, Tokyo Chemical Industry Co., Ltd.; hereafter, tert-butyldiphenylsilyl group may be referred to as "TBDPS") was added, and the temperature was raised to room temperature (25 °C) and the reaction was allowed to proceed for 16 h. 600 mL of ion-exchanged water was added to the reaction mixture, and the aqueous layer was extracted twice with 150 mL of a 4:1 hexane / ethyl acetate mixed solvent. The combined organic layer was washed with ion-exchanged water. After washing, the organic layer was dried over anhydrous magnesium sulfate, and then insoluble matter was filtered off. The filtrate was concentrated and dried using a rotary evaporator to obtain compound (7-2) as a colorless oil. The obtained amount was 22.37 g (yield: 98%). 1The results of the H-NMR spectrum measurement are as follows:

[0265] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.63(d,4H), 7.42(t,2H), 7.35(t,4H), 7.16(t,2H), 6. 70(t,1H), 6.63(d,2H), 3.85-3.76(m,4H), 3.59-3.51(m,4H), 2.49(t,1H), 1.06(s,9H).

[0266] Synthesis of compound (7-3) [ka]

[0267] A 500 mL recovery flask equipped with a gas inlet tube and an induction stirrer was charged with 33.33 g (79.4 mmol) of compound (7-2), 117 mL of 1,2-dimethoxyethane (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 117 mL of pyridine (FUJIFILM Wako Pure Chemical Industries, Ltd.). The atmosphere was replaced with nitrogen and the solution was cooled to 0 °C. 35.02 g (138.0 mmol) of iodine (Tokyo Chemical Industry Co., Ltd.) was added, followed by stirring at 0 °C for 80 minutes. The temperature was then raised to room temperature (25 °C) and stirred for 2 hours. The reaction was terminated by adding saturated aqueous sodium sulfite to the reaction solution, and the organic solvent was then removed using a rotary evaporator. The remaining aqueous solution was diluted with ion-exchanged water, and the aqueous layer was extracted three times with chloroform. The combined organic layer was dried over anhydrous magnesium sulfate, and then insoluble matter was filtered off. The filtrate was transferred to a 500 mL recovery flask and concentrated using a rotary evaporator. The resulting crude product was purified using a silica gel column (hexane / ethyl acetate = 9 / 1 → 4 / 1) to obtain compound (7-3) as a transparent oil. The obtained amount was 27.90 g (yield: 64%). 1 The results of the H-NMR spectrum measurement are as follows:

[0268] 1H-NMR (400MHz, CDCl3): δ(ppm)=7.61(d,4H), 7.43(t,2H), 7.40-7.32(m,6H) 6.37(d,2H), 3.82-3.73(m,4H), 3.52-3.46(m,4H), 2.39(t,1H), 1.04(s,9H).

[0269] Synthesis of compound (7-4) [ka]

[0270] A 500 mL recovery flask equipped with a gas inlet tube and induction stirrer was charged with 26.87 g (49.3 mmol) of compound (7-3), 215 mL of dehydrated chloroform (Kanto Chemical Co., Inc.), 6.19 g (24.6 mol) of pyridinium p-toluenesulfonate (Tokyo Chemical Industry Co., Ltd.), and 18 mL of 3,4-dihydro-2H-pyran (Tokyo Chemical Industry Co., Ltd.). The atmosphere was replaced with nitrogen and the reaction was carried out at room temperature (25 °C) for 24 hours. The reaction was terminated by adding saturated aqueous sodium bicarbonate, and the aqueous layer was extracted three times with 54 mL of chloroform. The combined organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The filtrate was concentrated on a rotary evaporator. The oil obtained after concentration was dissolved in toluene and concentrated again on a rotary evaporator to obtain compound (7-4) as an orange oil. The amount obtained was 31.10 g (yield: 100%). 1 The results of the H-NMR spectrum measurement are as follows:

[0271] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.63(d,4H), 7.43(tt,2H), 7.36(t,4H), 7.30(d,2H), 6.29 (d,2H), 4.51(t,1H), 3.82-3.73(m,4H), 3.54-3.40(m,6H), 1.80-1.44(m,6H), 1.04(s,9H).

[0272] Synthesis of compound (7-5) [ka]

[0273] A 500 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 31.10 g (49.4 mmol) of compound (7-4) and 311 mL of dehydrated diethyl ether (Fujifilm Wako Pure Chemical Industries, Ltd.). The atmosphere was replaced with nitrogen, and the solution was cooled to -69 °C. 34.3 mL (51.9 mmol) of a 1.6 M hexane solution of n-butyl lithium (Kanto Chemical Co., Ltd.) was added dropwise, followed by stirring for 10 minutes to allow the reaction to proceed. 15.3 mL (198 mmol) of dehydrated N,N-dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised to room temperature (25 °C) over 90 minutes. The reaction mixture was quenched by adding saturated aqueous ammonium chloride, and the aqueous layer was extracted with diethyl ether. The combined organic layer was dried over anhydrous magnesium sulfate, and insoluble materials were filtered off. The filtrate was concentrated on a rotary evaporator to obtain the crude product. The obtained crude product was purified using a silica gel column (hexane / ethyl acetate = 9 / 1 → 4 / 1) to obtain compound (7-5) as a yellow oil. The obtained amount was 26.45 g (yield: 100%). 1 The results of the H-NMR spectrum measurement are as follows:

[0274] 1 H-NMR (400MHz, CDCl3): δ(ppm)=9.69(s,1H), 7.62(t,6H), 7.43(t,2H), 7.35(t,4H), 6.57(d,2H), 4. 53(t,1H), 3.90-3.73(m,4H), 3.67-3.53(m,5H), 3.48-3.41(m,1H), 1.78-1.47(m,6H), 1.04(s,9H).

[0275] Synthesis of compound (7-6) [ka]

[0276] A 200 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 8.00 g (15.0 mmol) of compound (7-5), 2.26 mL (15.0 mmol) of isophorone, and 80 mL of dehydrated ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the inside of the flask was replaced with nitrogen. After adding 1.02 g (15.0 mmol) of sodium ethoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), the reaction solution was heated to 60 °C and stirred at 60 °C for 14 hours to react. The reaction mixture was quenched by adding ion-exchanged water, and then concentrated using a rotary evaporator to obtain a crude product. The resulting crude product was purified using a reverse-phase silica gel column (ion-exchanged water / methanol = 9 / 1 → 10 / 0) ​​to obtain compound (7-6) as a red oil. The obtained amount was 4.31 g (yield: 44%). The amount of compound (7-6) was 1.02 g (15.0 mmol). 1 The results of the H-NMR spectrum measurement are as follows:

[0277] 1 H-NMR(400MHz,CD2Cl2):7.62(d,4H),7.42-7.31(m,6H),7.24(d,2H),6.90(d,1H),6.69(d,1H),6.53(d,2H),5.92(s,1H) ),4.49(t,1H),3.81-3.32(m,10H),2.44(s,1H),2.32(s,1H),2.22(s,2H),1.78-1.41(m,6H),1.06(s,6H),1.02(s,9H).

[0278] Synthesis of compound (7-7) [ka]

[0279] In a 200 mL recovery flask equipped with a three-way stopcock and a gas inlet tube, 5.43 g (7.67 mmol) of diethyl cyanomethylphosphonate (Tokyo Chemical Industry Co., Ltd.) was dissolved in 150 mL of dehydrated tetrahydrofuran, and the inside of the flask was then purged with nitrogen. 1.23 g (30.7 mmol) of sodium hydride (60% dispersion in liquid paraffin) was added and stirred at room temperature for 15 minutes. 5.00 g (7.67 mmol) of compound (7-6) was dissolved in 150 mL of dehydrated tetrahydrofuran, and the resulting solution was added to the reaction mixture. The temperature was raised to 60 °C and the mixture was stirred at 60 °C for 5 hours. The reaction mixture was cooled, and ion-exchanged water and chloroform were added. The organic layer was washed with ion-exchanged water and dried over magnesium sulfate, after which insoluble matter was filtered off. The resulting filtrate was concentrated using a rotary evaporator to obtain a crude product. The resulting crude product was purified using a silica gel column (chloroform / ethyl acetate = 9 / 1). 72 mL of dehydrated toluene was added to the resulting purified product to dissolve it. The interior was purged with nitrogen and then cooled to -70°C. 5.3 mL (5.3 mmol) of diisobutylaluminum hydride (1.0 M, Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated to 0°C over 1 hour. Methanol was then added to terminate the reaction. Chloroform was added to the reaction mixture, and the organic layer was washed with ion-exchanged water and dried over magnesium sulfate. The insoluble material was then filtered off. The filtrate was concentrated using a rotary evaporator. 25 mL of ethanol and 1.4 g of pyridinium paratoluenesulfonate were added to the resulting crude reaction product, and the mixture was heated to 60°C and stirred at 60°C for 1 hour. Chloroform was added to the reaction mixture, and the organic layer was washed with ion-exchanged water and dried over magnesium sulfate. The insoluble material was then filtered off. The filtrate was concentrated using a rotary evaporator, and the resulting crude product was purified using a silica gel column (chloroform) to obtain compound (7-7) as a red solid. The obtained amount was 0.76 g (yield: 36%). 1 The results of the H-NMR spectrum measurement are as follows:

[0280] 1H-NMR(400MHz, CDCl3):10.00(d,1H),7.62-7.58(m,4H),7.42-7.18(m,8H),6.75-6.72(m,2H),6.59-6.54(m ,2H),6.26(s,1H),5.84(d,1H),3.81-3.32(m,8H),2.66(s,1H),2.32-2.10(m,4H),1.03(s,6H),1.00(s,9H).

[0281] Synthesis of compound (7) [ka]

[0282] In a 100 mL recovery flask equipped with a three-way cock and a gas inlet tube at the top, 0.70 g (1.18 mmol) of compound (7-7), 7 mL of dehydrated ethanol, and 0.70 g (1.53 mmol) of compound (4-7) were dissolved, and then the inside of the flask was replaced with nitrogen. The reaction solution was heated to 60°C and reacted at 60°C for 3 hours. The reaction mixture was concentrated, and the crude product was purified by recycled gel permeation chromatography to obtain compound (7) as a black solid. The obtained amount was 0.57 g (yield: 47%). The amount of compound (7) was 1 The results of the H-NMR spectrum measurement are as follows:

[0283] 1 H-NMR (400MHz, CDCl3):7.88(dd,1H),7.72(d,4H),7.59(d,4H),7.44-7.27(m,12H),6.85(s,1H),6.74(d,1H),6.58(d,2H),6.3 5-6.27(m,3H),3.79(t,2H),3.74(td,2H),3.59(t,2H),3.54(t,2H),2.37-2.18(m,4H),2.05(t,1H),1.00(s,9H),0.93(s,6H).

[0284] Synthesis of polymer compound (BP1) A 200 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 4.00 g (18.16 mmol) of 1-adamantyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 3.64 g (36.31 mmol) of methyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 5.63 g (36.31 mmol) of 2-isocyanatoethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 0.15 g (0.91 mmol) of 2,2'-azodiisobutyronitrile (Tokyo Chemical Industry Co., Ltd.), and 58 mL of tetrahydrofuran (stabilizer-free) and dissolved. The atmosphere was then purged with nitrogen. The reaction solution was heated to 70 °C and reacted at 70 °C for 6 hours. The reaction mixture was cooled and then added dropwise to hexane under a nitrogen atmosphere. The resulting precipitate was collected by filtration, washed with hexane, and dried under reduced pressure to obtain polymer compound (BP1) as a white solid. The amount obtained was 9.07 g (yield: 68%). The molecular weight of polymer compound (BP1) under the above measurement condition 1 was Mw = 40,963 and Mn = 18,506. Differential scanning calorimetry was performed, and it was confirmed that polymer compound (BP1) did not have a melting point (Tm), that is, polymer compound (BP1) was an amorphous resin.

[0285] Synthesis of polymer compound (P1) Under a nitrogen atmosphere, 0.098 g of polymer compound (BP1), 0.053 g (0.06 mmol) of compound (7), and one drop of dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) were dissolved in 0.9 mL of tetrahydrofuran (stabilizer-free) and reacted at room temperature for 24 hours. After adding ethanol, the mixture was further reacted for an additional 18 hours. The resulting reaction mixture was added dropwise to methanol, and the resulting precipitate was collected by filtration and washed with hexane. The residue was dried under reduced pressure to obtain polymer compound (P1) as a black solid. The yield was 0.10 g (yield: 68%). The concentration of compound (7) in polymer compound (P1) (EO dye concentration of polymer compound (P1)) was calculated using absorption spectroscopy. Chloroform solutions of compound (7) were prepared at various concentrations, and a calibration curve was created from the absorbance at the maximum absorption wavelength of the absorption spectra of these solutions. The concentration of compound (7) in polymer compound (P1) (EO dye concentration) was calculated from the absorbance at λmax of the absorption spectrum of polymer compound (P1) using a calibration curve. The concentration of compound (7) in polymer compound (P1) was 0.23 mol / kg.

[0286] (Example 1-4) Synthesis of polymer compound (P2) The aldehyde compound (7-7) and compound (4-35) were converted to compound (8) by dehydration condensation. Subsequently, compound (8) was reacted with polymer compound (BP2) in a nitrogen atmosphere to obtain polymer compound (P2).

[0287] Synthesis of compound (8) [ka]

[0288] Compound (8) was synthesized by the condensation reaction of compound (7-7) and compound (4-35). 2.02 g (3.4 mmol) of the synthesized compound (7-7), 1.56 g (3.4 mmol) of the synthesized compound (4-35), and 40 mL of dehydrated ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube. A stirrer was then added, and the inside of the flask was purged with nitrogen. The reaction was carried out at 60°C for 1.5 hours while stirring with a magnetic stirrer. After completion of the reaction, the reaction mixture was concentrated using a rotary evaporator to obtain a crude product of compound (8). The crude product was purified by silica gel column chromatography, recycled preparative gel permeation chromatography, and reverse-phase silica gel column chromatography, in that order, to obtain the target compound (8) as a black solid. The amount obtained was 0.68 g (yield: 19%). Compound (8) 1 The results of the H-NMR spectrum measurement are as follows:

[0289] 1 H-NMR (400MHz, CD2Cl3): δ(ppm)=7.77(d,3H), 7.69-7.56(m,6H), 7.54-7.4 8(m,4H), 7.39(tt,2H), 7.36-7.25(m,6H), 6.86(d,1H), 6.75(d,1H), 6.57( d,2H), 6.40-6.18(m,3H), 3.80(t,2H), 3.78-3.72(m,2H), 3.59(t,2H), 3.5 4(t,2H), 2.36(s,2H), 2.15(s,2H), 2.04(t,1H), 1.00(s,9H), 0.92(s,6H).

[0290] Synthesis of polymer compound (BP2) A 200 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 5.00 g (22.70 mmol) of dicyclopentanyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 1.14 g (11.35 mmol) of methyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 3.52 g (22.70 mmol) of 2-isocyanatoethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 0.47 g (2.84 mmol) of 2,2'-azodiisobutyronitrile (Tokyo Chemical Industry Co., Ltd.), and 38 mL of anhydrous tetrahydrofuran (stabilizer-free, Fujifilm Wako Pure Chemical Industries Co., Ltd.). The reaction mixture was heated to 70 °C and reacted at 70 °C for 7 hours. The reaction mixture was cooled and then added dropwise to hexane under a nitrogen atmosphere. The resulting precipitate was collected by filtration, washed with hexane, and then dried under reduced pressure to obtain polymer compound (BP2) as a white solid. The obtained amount was 8.85 g (yield: 92%). The molecular weight of polymer compound (BP2) measured under the above conditions was Mw = 40,963 and Mn = 18,506. Differential scanning calorimetry was performed to confirm that polymer compound (BP2) did not have a melting point (Tm), i.e., polymer compound (BP2) was an amorphous resin.

[0291] Synthesis of polymer compound (P2) Under a nitrogen atmosphere, 0.060 g of polymer compound (BP2), 0.14 g (0.135 mmol) of compound (8), and one drop of dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) were dissolved in 1.2 mL of dehydrated tetrahydrofuran (stabilizer-free, Fujifilm Wako Pure Chemical Industries, Ltd.) and reacted at room temperature for 27 hours. Then, dehydrated ethanol was added and the reaction continued for an additional 20 hours. The resulting reaction mixture was added dropwise to methanol, and the resulting precipitate was collected by filtration and washed with hexane. The residue was dried under reduced pressure to obtain polymer compound (P2) as a black solid. The obtained amount was 0.144 g (yield: 72%). The EO dye concentration of polymer compound (P2) was calculated using the same method as in Example 1-3 and was found to be 57 wt% (0.64 mol / kg).

[0292] (Example 1-5) Synthesis of polymer compound (P3) Compound (9-1) was reacted with an organolithium species prepared from n-butyllithium and acetonitrile, and then converted to compound (9-2) under acidic conditions. The cyano group of compound (9-2) was reduced to an aldehyde using diisobutylaluminum hydride to obtain compound (9-3). Subsequently, compound (4-11) and the aldehyde compound (9-3) were converted to compound (9) by dehydration condensation. Finally, compound (9) was reacted with polymer compound (BP2) under a nitrogen atmosphere to obtain polymer compound (P3).

[0293] Synthesis of compound (9-2) [ka]

[0294] Compound (9-1) was synthesized according to the description in International Publication No. 2023 / 231528. Compound (9-1) was reacted with organolithium species prepared from n-butyllithium and acetonitrile, followed by acidic conditions to convert it to compound (9-2). A 200 mL three-neck flask equipped with a three-way stopcock and septum was charged with 0.43 mL (8.2 mmol) of dehydrated acetonitrile (Fujifilm Wako Pure Chemical Industries, Ltd.) and 44 mL of ultra-dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.). A stirrer was then added and the inside of the flask was purged with nitrogen. The reaction vessel was placed in an acetone bath at -70 °C, and 4.7 mL (7.5 mmol) of a 1.6 M n-butyllithium hexane solution (Kanto Chemical Industry Co., Ltd.) was added dropwise using a gas-tight syringe while stirring using a magnetic stirrer. After the addition was complete, the mixture was stirred for an additional 15 minutes while maintaining the temperature. Then, 3.02 g (3.87 mmol) of compound (9-1) dissolved in 10 mL of dehydrated tetrahydrofuran was added, and the mixture was warmed to room temperature (25 °C) over 1 hour. After stirring for another 2 hours at room temperature, 27 mL of aqueous ammonium chloride and 27 mL of 1 M hydrochloric acid were added to quench the reaction. The reaction mixture was extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. The insoluble material was filtered off, and the filtrate was concentrated using a rotary evaporator. 0.95 g (3.7 mmol) of pyridinium p-toluenesulfonate (Tokyo Chemical Industry Co., Ltd.) and 54 mL of dehydrated methanol (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the concentrate, and the mixture was immersed in an oil bath at 60 °C for an additional 1 hour. After the reaction was complete, the reaction vessel was returned to room temperature, and 50 mL of ion-exchanged water and 50 mL of chloroform were added to extract the product. The organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The filtrate was concentrated on a rotary evaporator to obtain the target compound (9-2) as a red oil. The entire amount of the concentrate was used in the next reaction step.

[0295] Synthesis of compound (9-3) [ka]

[0296] The cyano group of compound (9-2) was reduced to an aldehyde with diisobutylaluminum hydride to obtain compound (9-3). The entire crude product of compound (9-2) obtained in the previous step and 38 mL of dehydrated toluene (Kanto Chemical Industry Co., Ltd.) were added to a 100 mL three-neck flask equipped with a three-way stopcock and septum. A stirrer was then added and the inside atmosphere was purged with nitrogen. The reaction vessel was placed in an acetone bath at -70 °C, and 12 mL (12 mmol) of a 1.0 M hexane solution of diisobutylaluminum hydride (Tokyo Chemical Industry Co., Ltd.) was added via a gas-tight syringe while stirring using a magnetic stirrer. After the addition was complete, the mixture was heated to 0 °C and stirred for 20 minutes. The reaction was then quenched by adding 30 mL of tetrahydrofuran and saturated aqueous sodium potassium tartrate. The reaction mixture was extracted with a 1:1 mixture of tetrahydrofuran and diethyl ether, after which the organic layer was separated and washed twice with 20 mL of ion-exchanged water. After washing, the organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The filtrate was concentrated on a rotary evaporator to obtain a crude product. This crude product was redissolved in 100 mL of toluene, and 6 g of silica gel and 0.6 g of carborafine were added and stirred at room temperature. The insoluble matter was filtered off, and the filtrate was washed with approximately 200 mL of toluene. The filtrate was then concentrated to obtain the target compound (9-3) as a red viscous solid. The yield was 2.60 g (yield: 96%).

[0297] Synthesis of compound (9) [ka]

[0298] Compound (9) was synthesized by the condensation reaction of compound (9-3) and compound (4-11). A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 2.10 g (2.9 mmol) of the synthesized compound (9-3), 1.27 g (2.8 mmol) of the synthesized compound (4-11), 21 mL of dehydrated ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.), and 11 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.). A stirrer was added, and the inside atmosphere was purged with nitrogen. The reaction was carried out at 65 °C for 1.5 hours while stirring with a magnetic stirrer. After completion of the reaction, the reaction mixture was concentrated using a rotary evaporator to obtain crude compound (9). The crude product was purified by reprecipitation with chloroform / methanol (9 mL / 72 mL), yielding the target compound (9) as a black solid. The yield was 1.83 g (yield: 54%). Compound (9) 1 The results of the H-NMR spectrum measurement are as follows:

[0299] 1 H-NMR (400MHz, CD2Cl3): δ(ppm)=7.95(d,1H), 7.64-7.45(m,8H), 7.41-7.33(m,4H), 7.30- 7.24(m,5H), 7.13(dd,2H), 7.04(dd,1H), 6.47(s,1H), 6.38(d,1H), 3.83-3.70(m,4H), 3.64 -3.55(m,1H), 3.42-3.33(m,1H), 2.86-2.72(m,3H), 2.50-2.22(m,7H), 1.77(dd,1H), 1.60( t,1H), 1.51-1.45(m,1H), 1.33(s,3H), 1.26(d,3H), 1.20(s,3H), 0.97(s,9H), 0.91(s,6H).

[0300] Synthesis of polymer compounds (P3) Under a nitrogen atmosphere, 0.150 g of polymer compound (BP2), 0.350 g (0.34 mmol) of compound (9), and one drop of dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) were dissolved in 3.0 mL of dehydrated tetrahydrofuran (stabilizer-free, Fujifilm Wako Pure Chemical Industries, Ltd.) and reacted at room temperature for 29 hours. Then, dehydrated ethanol was added and the reaction continued for an additional 20 hours. The resulting reaction mixture was added dropwise to methanol, and the resulting precipitate was collected by filtration and washed with hexane. The residue was dried under reduced pressure to obtain polymer compound (P3) as a black solid. The obtained amount was 0.45 g (yield: 89%). The EO dye concentration of polymer compound (P3) was calculated using the same method as in Example 1-3 and was found to be 81 wt% (0.69 mol / kg).

[0301] (Comparative Example 1-3) Synthesis of polymer compound (CP1) Compound (C7) was synthesized by aldol condensation of compound (7-7). Compound (C7) was reacted with polymer compound (BP1) to obtain polymer compound (CP1).

[0302] Synthesis of compound (C7) [ka]

[0303] In a 50 mL recovery flask equipped with a three-way cock and a gas inlet tube at the top, 0.50 g (0.8 mmol) of compound (7-7), 10 mL of dehydrated ethanol, and 0.70 g (1.53 mmol) of 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile were added, and the inside of the flask was replaced with nitrogen, followed by reaction at room temperature for 3 hours. The reaction mixture was concentrated, and the crude product was purified by silica gel chromatography to obtain compound (C7) as a black solid. The obtained amount was 0.45 g (yield: 50%). 1 The results of the H-NMR spectrum measurement are as follows:

[0304] 1 H-NMR (400MHz, CDCl3):7.92(dd,1H),7.72(d,4H),7.44-7.27(m,13H),6.90(d,1H),6.74(d,1H),6.58(d,2H),6.35-6.27(m,3H) ),3.80(t,2H),3.75(td,2H),3.60(t,2H),3.55(t,2H),2.39-2.14(m,4H),2.04(t,1H),1.00(s,9H),0.99(s,3H),0.92(s,3H).

[0305] Synthesis of polymer compound (CP1) Polymer compound (CP1) was synthesized in the same manner as in the synthesis of polymer compound (P1), except that "compound (7)" was replaced with "compound (C7)". The obtained amount was 0.11 g (yield: 73%). The EO dye concentration of polymer compound (CP1) was calculated in the same manner as in Example 1-3, and was found to be 0.36 mol / kg.

[0306] (Comparative Example 1-4) Synthesis of polymer compound (CP2) The aldehyde compound (9-3) was converted to compound (C9) by dehydration condensation with 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile. Subsequently, compound (C9) was reacted with polymer compound (BP2) under a nitrogen atmosphere to obtain polymer compound (CP2).

[0307] Synthesis of compound (C9) [ka]

[0308] Compound (C9) was synthesized by the condensation reaction of compound (9-3) with 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile. A 100 mL recovery flask equipped with a three-way stopcock and a gas inlet tube was charged with 0.876 g (1.2 mmol) of the synthesized compound (9-3), 0.37 g (1.2 mmol) of 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)-2(5H)-furanylidene)-propanedinitrile (iChemical), 17 mL of dehydrated ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.), and 9 mL of dehydrated tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.). A stir bar was added, and the inside atmosphere was replaced with nitrogen. The reaction was carried out at room temperature (25 °C) for 16 hours while stirring with a magnetic stirrer. After the reaction was completed, the reaction mixture was concentrated using a rotary evaporator to obtain a crude product of compound (C9). The obtained crude product was purified using recycle preparative gel permeation chromatography to obtain the target compound (C9) as a solid. The obtained amount was 0.51 g (yield: 41%). 1 The results of the H-NMR spectrum measurement are as follows:

[0309] 1 H-NMR (400MHz, CD2Cl3): δ(ppm)=7.96(d,1H), 7.68-7.24(m,19H), 6.50-6.42(m ,2H), 3.85-3.69(m,4H), 3.66-3.54(m,1H), 3.43-3.33(m,1H), 2.87-2.78(m,1H) ), 2.74(t,2H), 2.52-2.14(m,7H), 1.77(dd,1H), 1.61(br,1H), 1.51-1.46(m,1H ), 1.33(s,3H), 1.26(d,3H), 1.20(s,3H), 0.98(s,9H), 0.93(s,3H), 0.84(s,3H).

[0310] Synthesis of polymer compound (CP2) Under a nitrogen atmosphere, 0.225 g of polymer compound (BP2), 0.275 g (0.27 mmol) of compound (C9), and one drop of dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) were dissolved in 3.0 mL of dehydrated tetrahydrofuran (stabilizer-free, Fujifilm Wako Pure Chemical Industries, Ltd.) and reacted at room temperature for 24 hours. Then, dehydrated ethanol was added and the reaction continued for an additional 22 hours. The resulting reaction mixture was added dropwise to methanol, and the resulting precipitate was collected by filtration and washed with hexane. The residue was dried under reduced pressure to obtain polymer compound (CP2) as a black solid. The obtained amount was 0.44 g (yield: 87%). The EO dye concentration of polymer compound (CP2) was calculated using the same method as in Example 1-3 and was found to be 57 wt% (0.57 mol / kg).

[0311] 2. Evaluation of the degree of orientation of the compound The degree of orientation of an EO element can be evaluated by measuring the change in absorbance before and after poling based on a known method (LR Dalton et al., Chem. Mater. 2011, 23, 430). It is known that the higher the degree of orientation, the greater the change in absorbance.

[0312] (Example 2-1) Evaluation of Compound (5) <Preparation of electro-optical (EO) films> Compound (5) and the amorphous resin polymethyl methacrylate (PMMA) were adjusted to the EO dye concentration ρ listed in Table 1, and dissolved in cyclopentanone to prepare a coating solution. The coating solution was applied to a cleaned substrate (glass with ITO or quartz glass) at 500 to 3,000 rpm using a spin coater MS-A100 (Mikasa Co., Ltd.), and then vacuum dried for 1 hour at a temperature near the glass transition temperature (Tg) of the resulting EO film. The type of solvent, solution concentration, and spin coater rotation speed were appropriately selected to produce an EO film with a thickness of 400 to 1,000 nm.

[0313] <Calculation of absorbance change rate> The fabricated EO film was subjected to poling treatment at an electric field strength of 100 V / μm, and the absorbance at the maximum absorption wavelength λmax of the EO film before and after the poling treatment was measured. Based on the following formula, the absorbance change rate at the maximum absorption wavelength λmax was calculated. For the measurement of absorbance, a UV-VIS-NIR spectrophotometer Agilent Cary 5000 (manufactured by Agilent Technologies, Inc.) was used. The absorbance change rate of compound (5) was 19.7%. Absorbance change rate (%) = [(Absorbance of the EO film after poling treatment - Absorbance of the EO film before poling treatment) / Absorbance of the EO film before poling treatment] × 100

[0314] (Example 2-2) Evaluation of compound (6) An EO film was fabricated in the same manner as in Example 2-1, except that compound (5) was changed to compound (6), and the absorbance change rate at the maximum absorption wavelength λmax of the EO film was calculated. The absorbance change rate of the EO film in Example 2-2 was 15.3%.

[0315] (Example 2-3) Evaluation of polymer compound (P1) <Fabrication of EO film> The polymer compound (P1) and polymethyl methacrylate (PMMA), which is an amorphous resin, were adjusted to the EO dye concentration ρ described in Table 1, and a coating solution was prepared by dissolving them in cyclopentanone. Using a spin coater MS-A100 (manufactured by Mikasa Co., Ltd.), the coating solution was applied to a cleaned substrate (glass with ITO, quartz glass) under the condition of 500 - 3000 revolutions per minute, and then vacuum dried for 1 hour near the glass transition temperature (Tg) of the fabricated EO film. The type of solvent, the concentration of the solution, and the rotation speed condition of the spin coater were appropriately selected so that the film thickness was 400 - 1000 nm to fabricate the EO film.

[0316] <Calculation of absorbance change rate> The calculation of the absorbance change rate was performed in the same manner as in Example 2-1. The absorbance change rate of the EO film in Example 2-3 was 19.7%.

[0317] (Example 2-4) Evaluation of polymer compound (P2) An EO film of Example 2-4 was prepared in the same manner as in Example 2-3, except that the polymer compound (P1) was replaced with the polymer compound (P2), and the absorbance change rate of the EO film was calculated. The absorbance change rate of the EO film of Example 2-4 was 14.7%.

[0318] (Example 2-5) Evaluation of polymer compound (P3) An EO film of Example 2-5 was prepared in the same manner as in Example 2-3, except that the polymer compound (P1) was replaced with the polymer compound (P3), and the absorbance change rate of the EO film was calculated. The absorbance change rate of the EO film of Example 2-5 was 19.1%.

[0319] (Comparative Example 2-1) Evaluation of Compound (C5) An EO film of Comparative Example 2-1 was prepared in the same manner as in Example 2-1, except that compound (5) was replaced with compound (C5), and the absorbance change rate of the EO film was calculated. The absorbance change rate of the electro-optical film of Comparative Example 2-1 was 14.0%.

[0320] (Comparative Example 2-2) Evaluation of Compound (C6) An EO film of Comparative Example 2-2 was prepared in the same manner as in Example 2-1, except that compound (5) was replaced with compound (C6), and the absorbance change rate of the EO film was calculated. The absorbance change rate of the electro-optical film of Comparative Example 2-2 was 13.1%.

[0321] (Comparative Example 2-3) Evaluation of polymer compound (CP1) An EO film of Comparative Example 2-3 was prepared in the same manner as in Example 2-3, except that the polymer compound (P1) was replaced with the polymer compound (CP1), and the absorbance change rate of the EO film was calculated. The absorbance change rate of the EO film of Comparative Example 2-3 was 8.7%.

[0322] (Comparative Example 2-4) Evaluation of polymer compound (CP2) An EO film of Comparative Example 2-4 was prepared in the same manner as in Example 2-3, except that the polymer compound (P1) was replaced with the polymer compound (CP2), and the absorbance change rate of the EO film was calculated. The absorbance change rate of the EO film of Comparative Example 2-4 was 12.9%.

[0323]

Table 1

[0324] The dye concentration in Table 1 represents the EO dye content of the coating solution (the number of moles of the compound represented by Formula (1) based on the solid content mass of the coating solution). As shown in Table 1, the absorbance change rates of the EO films prepared using compounds (5) and (6), and polymer compounds (P1), (P2) and (P3) are larger than those of the EO films prepared using compounds (C5) and (C6), and polymer compounds (CP1) and (CP2). That is, it can be said that the degrees of orientation of compounds (5) and (6), and polymer compounds (P1), (P2) and (P3) during field poling are higher than those of compounds (C5) and (C6), and polymer compounds (CP1) and (CP2).

[0325] 3. Measurement of the EO coefficient r33 of the EO film (Examples 3-1 to 3-5) The EO coefficient r33 of the EO film was measured using compounds (5) and (6), and polymer compounds (P1), (P2) and (P3). The EO film was prepared in the same manner as the method described in Examples 2-1 to 2-5.

[0326] <Measurement of the EO coefficient of the EO film> Using the prepared film, the EO coefficient r33 of the EO film was measured in the same manner as the method described in the reference paper (“Transmission ellipsometric method without an aperture for simpIe and reIiabIe evaluation of electro-optic properties”, Toshiki Yamada and Akira Otomo, Optics Express, voI.21, pages29240-48(2013)). The laser light sources used were LP1310-SAD2 (1310 nm) and LP1550-SAD2 (1550 nm) of a semiconductor DFB laser (manufactured by THORLABS). The results are shown in Table 2.

[0327] [Table 2]

[0328] As shown in Table 2, the EO coefficients r33 of the EO films containing compounds (5) and (6) and polymer compounds (P1), (P2) and (P3) all showed sufficiently high values. These results demonstrate that the compounds of the present invention have an excellent degree of orientation and, when used in EO devices, also show high EO coefficients.

[0329] 4. Calculation of the lowest unoccupied molecular orbital (LUMO) level The calculated LUMOs of the compounds of formula (2) corresponding to compounds (5) and (6) and polymer compounds (P1), (P2), and (P3) were calculated using Gaussian 16, a quantum chemistry calculation program manufactured by Gaussian. Geometry optimization calculations were performed using PCM calculations (specifying chloroform as the solvent) under the M062X / 6-31+g(d) conditions, and the LUMOs of the optimized structures were calculated. The calculated LUMO levels of the compounds (5) and (6) and the compound of formula (2) corresponding to the polymer compound (P1) were −2.30 eV. The calculated LUMO level of the compound of formula (2) corresponding to the polymer compound (P2) was −2.28 eV. The calculated LUMO level of the compound of formula (2) corresponding to the polymer compound (P3) was −2.31 eV.

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 In formula (1), A represents formula (1-A): 【Chemistry 2】 [In formula (1-A), R １ and R ２ each independently represents a substituent other than a hydrogen atom. m and n each independently represent an integer of 0 to 5, provided that m+n is not 0. When m is 2 to 5, a plurality of R １ may be the same or different. When n is 2 to 5, there are multiple R ２ may be the same or different. (wherein R １ and R ２ are both fluoro groups, and m and n are both 1), L represents a single bond or a divalent conjugated linking group; D represents an electron-donating group.

2. All R contained in the group represented by formula (1-A) １ and R ２ The compound according to claim 1, wherein the total molecular weight of

3. R satisfies the following condition A １ , R ２ 10. The compound of claim 1 having m and n. Condition A: In the compound represented by formula (2), the lowest unoccupied molecular orbital (LUMO) level calculated by density functional theory (DFT) is −0.081 eV or less. 【Transformation 3】

4. R １ and R ２ The compound according to claim 1 , wherein each of is independently a halogeno group or a fluoroalkyl group.

5. The compound according to claim 1 , wherein D is a group represented by formula (3): 【Chemistry 4】 In formula (3), R ３ and R ４ each independently represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, -R ５ -OH(R ５ represents a divalent hydrocarbon group), —R ６ -NH ２ (R ６ represents a divalent hydrocarbon group), —R ７ -SH(R ７ represents a divalent hydrocarbon group, or —R ８ -NCO(R ８ represents a divalent hydrocarbon group. These groups may have a substituent. These groups may have a crosslinkable group. R ３ and R ４ may be bonded to each other to form a ring together with the atoms to which they are bonded. R １１ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyloxy group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, an amino group, a sulfanyl group, an isocyanate group, -R １０１ -OH(R １０１ represents a divalent hydrocarbon group.), —O—R １０２ -OH(R １０２ represents a divalent hydrocarbon group), —R １０３ -NH ２ (R １０３ represents a divalent hydrocarbon group), —R １０４ -SH(R １０４ represents a divalent hydrocarbon group), —R １０５ -NCO(R １０５ represents a divalent hydrocarbon group, or —OC(═O)R １０６ (R １０６ represents a monovalent hydrocarbon group. These groups may have a crosslinkable group. １１ When there are a plurality of R, they may be the same or different. １１ is R ３ or R ４ may be bonded to each other to form a ring together with the atoms to which they are bonded. k represents an integer of 0 to 4. * represents a bonding position.

6. An electro-optical polymer compound comprising an amorphous resin and the compound according to claim 1 covalently bonded to the amorphous resin.

7. 10. An electro-optical ink composition comprising the compound according to claim 1 or the electro-optical polymer compound according to claim 6.

8. The electro-optical ink composition according to claim 7 , further comprising an amorphous resin.

9. A film formed from the electro-optical ink composition according to claim 7.

10. An electro-optical element comprising the film according to claim 9.

11. The following steps: (1) a step of obtaining an acetal from an α-ketoester; (2) reacting the acetal with a compound represented by formula (A) to obtain a compound represented by formula (4A); and 【Transformation 5】 [In formula (A), M represents a group containing an alkali metal or an alkaline earth metal, and R １２ represents one or more substituents other than a hydrogen atom. 【Transformation 6】 [In formula (4A), R １ ' and R ２ Each of the ' independently represents a substituent other than a hydrogen atom. m' and n' each independently represent an integer of 0 to 5, provided that m'+n' is not 0. When m' is 2 to 5, a plurality of R １ ' may be the same or different. When n is 2 to 5, there are multiple R ２ ' may be the same or different. (3) reacting the compound represented by formula (4A) with malononitrile to obtain a compound represented by formula (4); 【Transformation 7】 [In formula (4), R １ ', R ２ ', m' and n' have the same meanings as in formula (4A). A method for producing a compound represented by formula (4), comprising:

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