Heterocyclic compound, polymer, composition containing the same, and methods for producing them

Abstract

To provide a heterocyclic compound having superior heat resistance (thermal stability) and useful as a material for electro-optical elements.SOLUTION: A heterocyclic compound is represented by the following formula (1). In formula (1), Q is a divalent monocyclic heterocycle (e.g., 1,3,4-oxadiazole-2,5-diyl) or a condensed-ring heterocycle (e.g., thieno[3,2-b]thiophene-2,5-diyl), which may have a substituent. R1 and R2 are each independently an alkyl group, -R21-OH or the like. R3 and R4 are each independently hydrogen, an alkyl group or the like. R21 is a divalent hydrocarbon group. k and m are each independently an integer of 0 to 4.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a heterocyclic compound having high heat resistance, a polymer, a composition containing the same, and methods for producing them.

Background Art

[0002] In addition to optical modulators (for ultra-high-speed applications, optical interconnect applications, optical signal processing applications, etc.), for example, it can be used in optical switches, optical memories, wavelength converters, electric field sensors such as microwaves, millimeter waves, and terahertz waves, bioelectric potential sensors such as electromyograms and electroencephalograms, optical spatial modulators, optical scanners, etc. Furthermore, organic electro-optic (hereinafter sometimes abbreviated as "organic EO") materials that can be used for optical signal transmission between electronic circuits by combination with electronic circuits are required. Conventionally, inorganic ferroelectric electro-optic materials have been used, but inorganic ferroelectric electro-optic materials have limitations in terms of high speed and miniaturization / integration. Therefore, in order to realize next-generation ultra-high-speed optical communication, materials that can operate at high speed and can be hybridized with silicon photonics are needed.

[0003] From such a perspective, organic EO materials have been attracting attention. Organic EO materials exhibit a large electro-optic effect compared to inorganic ferroelectric electro-optic materials, can operate at high speed, and can be miniaturized and integrated by hybridization with silicon photonics, and are therefore expected as materials for next-generation optical communication.

[0004] Organic EO materials are obtained by dispersing or bonding a compound having an electro-optic effect (hereinafter simply referred to as an "electro-optic compound") in a host material such as a polymer material.

[0005] An electro-optical compound has a structure in which a donor and an acceptor are linked by a π-conjugated bridge as a basic structure. In order to increase the electro-optical coefficient of an electro-optical material, it is known to employ a donor with high electron-donating property and an acceptor with high electron-withdrawing property of the electro-optical compound, and to increase the length of the π-conjugated bridge. As electro-optical compounds having such a structure, those having various structures have been reported (for example, Patent Documents 1 to 3, Non-Patent Document 1, etc.).

[0006] By the way, when manufacturing an electro-optical element in which an optical waveguide is formed by an electro-optical material, an alignment process may be performed on the electro-optical compound in order to generate second-order electro-optical activity of the electro-optical material. Generally, the electric field poling method is used as a method for aligning an electro-optical compound. The electric field poling method is a method of applying an electric field to an electro-optical material and aligning the electro-optical compound in the direction of the applied electric field by the Coulomb force between the dipole moment of the electro-optical compound and the applied electric field.

[0007] In such an electric field poling method, usually, heating is performed up to a temperature near the glass transition temperature of the host material, and an electric field is applied in a state where the molecular motion of the electro-optical compound is promoted. Therefore, in order to obtain an electro-optical element exhibiting excellent electro-optical performance, in addition to the electro-optical compound having excellent electro-optical characteristics, it is required that the electro-optical compound has heat resistance that does not deteriorate due to heating in the alignment process.

[0008] Furthermore, in order to improve the signal transmission speed by connecting between electronic circuits with an optical circuit due to the demand for high speed of electronic circuits, the use of an electro-optical element using an electro-optical material for the conversion of electrical signals and optical signals has been studied. At this time, since a high-speed operating electronic circuit becomes hot, the molecular motion of the non-linear optical compound becomes active, and there is a possibility that the alignment is relaxed. Therefore, a higher temperature is required for the glass transition temperature of the host material, and accordingly, the electro-optical compound is also required to have heat resistance (thermal stability) at a higher temperature.

Prior Art Documents

Patent Documents

[0009] [Patent Document 1] Japanese Translation of PCT International Publication No. 2004-501159 [Patent Document 2] Japanese Patent No. 5945905 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2022-97407 [Non-Patent Document]

[0010] [Non-Patent Document 1] Chem. Mater., 2008, 120, 6372-6377 [Summary of the Invention] [Problems to be Solved by the Invention]

[0011] Conventional electro-optical compounds do not have sufficient heat resistance (thermal stability) and tend to decompose under high-temperature conditions above a certain level. If the heat resistance of electro-optical compounds is not sufficient, there is a risk that processing process conditions such as device fabrication will be limited. Therefore, an object of the present invention is to provide a heterocyclic compound having excellent heat resistance. [Means for Solving the Problems]

[0012] The present invention has been proposed based on such findings and specifically has the following configurations.

[0013] As a result of intensive studies in view of the above problems, the present inventors have found that by introducing a predetermined monocyclic or condensed heterocyclic group and a predetermined linking group for linking the same in the π-conjugated bridge in the donor / π-conjugated bridge / acceptor structure, heterocyclic compounds A and B having high hyperpolarizability and excellent heat resistance can be provided, and the present invention has been completed. The present invention provides the following heterocyclic compounds [1] to [9], compositions

[10] and

[11] , and polymers

[12] to

[14] . [1]A heterocyclic compound represented by the following formula (1) (hereinafter referred to as "heterocyclic compound A").

[0014]

Chemical formula

[0015] [In formula (1), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent.

[0016] R 1 and R 2 each independently represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R 21 -OH (wherein R 21 represents a divalent hydrocarbon group), -R 22 -NH2 (wherein R 22 represents a divalent hydrocarbon group), -R 23 -SH (wherein R 23 represents a divalent hydrocarbon group), or -R 24 -NCO (wherein R 24 represents a divalent hydrocarbon group). These groups may have a crosslinkable group. R 1 and R 2 may be bonded to each other to form a ring together with the atoms to which they are attached.

[0017] R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (wherein R 31 represents a divalent hydrocarbon group), -O-R 32 -OH (wherein R 32represents a divalent hydrocarbon group.), -R 33 -NH2 (R 33 represents a divalent hydrocarbon group.), -R 34 -SH (R 34 represents a divalent hydrocarbon group.), -R 35 -NCO (R 35 represents a divalent hydrocarbon group.), or -OC(=O)R 5 (R 5 represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. R 3 and R 4 When there are a plurality of them, they may be the same or different. R 3 is, R 1 or R 2 may combine with each other to form a ring together with the atoms to which they are attached.

[0018] k and m each independently represent an integer from 0 to 4.] [2] The heterocyclic compound according to [1], wherein Q is represented by the following formulas (a1) to (a10).

[0019]

Chemical formula

[0020] [R 6 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a cyano group, an aryl group, or a haloaryl group.] [3] The heterocyclic compound according to [1] or [2], wherein R 6 , R 7 and R 8 are a hydrogen atom or a methyl group. [4] The heterocyclic compound according to any one of [1] to [3], wherein R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. [5] The heterocyclic compound according to any one of [1] to [4], wherein R 4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. [6]R 3 and R 4 is a hydrogen atom, the heterocyclic compound according to any one of [1] to [5]. [7]R 1 is an optionally branched alkyl group having 1 to 12 carbon atoms, an optionally branched haloalkyl group having 1 to 12 carbon atoms, an optionally branched acyloxyalkyl group having 1 to 12 carbon atoms, -R 21 -OH (R 21 represents a divalent hydrocarbon group.), -R 22 -NH2 (R 22 represents a divalent hydrocarbon group.), -R 23 -SH (R 23 represents a divalent hydrocarbon group.), or -R 24 -NCO (R 24 represents a divalent hydrocarbon group.), the heterocyclic compound according to any one of [1] to [6]. [8]R 1 is -R 21 -OH (R 21 represents a divalent hydrocarbon group.), the heterocyclic compound according to any one of [1] to [7]. [9]A heterocyclic compound represented by the following formulas (1A) to (1C) (hereinafter referred to as "heterocyclic compound B").

[0021] [Chemical formula]

[0022] [In formulas (1A) to (1C), Q represents an optionally substituted divalent monocyclic or condensed heterocyclic ring.

[0023] R 1 is an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R 21 -OH (R 21 represents a divalent hydrocarbon group.), -R 22 -NH2 (R 22represents a divalent hydrocarbon group.), -R 23 -SH (R 23 represents a divalent hydrocarbon group.), or -R 24 -NCO (R 24 represents a divalent hydrocarbon group.). These groups may have crosslinkable groups.

[0024] R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (R 31 represents a divalent hydrocarbon group.), -O-R 32 -OH (R 32 represents a divalent hydrocarbon group.), -R 33 -NH2 (R 33 represents a divalent hydrocarbon group.), -R 34 -SH (R 34 represents a divalent hydrocarbon group.), -R 35 -NCO (R 35 represents a divalent hydrocarbon group.), or -OC(=O)R 5 (R 5 represents a monovalent hydrocarbon group.). These groups may have crosslinkable groups. R 3 and R 4 If there are a plurality of them, they may be the same or different. R 3 is, R 1 may be bonded to each other to form a ring together with the atoms to which they are bonded.

[0025] k and m each independently represent an integer from 0 to 4.

[0026] Sp 1 、Sp 2 、and Sp 3each independently represents a single bond or an alkylene group which may be branched and has 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group are -OR b or may be substituted with a halogen atom, and each -CH2- contained in the alkylene group is independently -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)-, and the methine group contained in the alkylene group may be substituted with a nitrogen atom. R b and R f may be the same as or different from each other, and represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms.

[0027] A, B, and C each independently represent a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed aromatic ring, an alicyclic hydrocarbon ring, or a trivalent hydrocarbon group having atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as constituent atoms, and these monocyclic aromatic rings, polycyclic aromatic rings, condensed aromatic rings, alicyclic hydrocarbon rings, and trivalent hydrocarbon groups may have substituents, and the hydrogen atoms contained in the trivalent hydrocarbon group are -OR b or may be substituted with a halogen atom, and each -CH2- contained in the hydrocarbon group is independently -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)-, and the methine group contained in the hydrocarbon group may be substituted with a nitrogen atom.

[10] A composition containing the heterocyclic compound according to any one of [1] to [9] and a polymer.

[11] The composition according to

[10] , wherein the polymer is one or more polymers selected from the group consisting of poly(meth)acrylate, polyester, polyamide, polyimide, polycarbonate, polystyrene, polysulfone, polyethersulfone, polymaleimide, silicone resin, and epoxy resin.

[12] A polymer having a structure represented by the following formula (1‘).

[0028]

Chem.

[0029] In formula (1'), Q represents a divalent monocyclic or fused heterocyclic ring which may have a substituent.

[0030] R 1 represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R 21 -OH (where R 21 represents a divalent hydrocarbon group), -R 22 -NH2 (where R 22 represents a divalent hydrocarbon group), -R 23 -SH (where R 23 represents a divalent hydrocarbon group), or -R 24 -NCO (where R 24 represents a divalent hydrocarbon group). These groups may have a crosslinkable group.

[0031] R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (where R 31 represents a divalent hydrocarbon group), -O-R 32 -OH (where R 32 represents a divalent hydrocarbon group), -R 33 -NH2 (where R 33 represents a divalent hydrocarbon group), -R 34 -SH (where R 34 represents a divalent hydrocarbon group), -R 35 -NCO (where R 35represents a divalent hydrocarbon group.), or -OC(=O)R 5 (R 5 represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. R 3 and R 4 When there are a plurality of them, they may be the same or different. These groups may have a crosslinkable group. R 3 is, R 1 may combine with each other to form a ring together with the atoms to which they are attached.

[0032] k and m each independently represent an integer from 0 to 4.

[0033] Sp 1 represents a single bond or an optionally branched alkylene group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR b or a halogen atom, and each -CH2- contained in the alkylene group may independently be -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)-, and the methine groups contained in the alkylene group may be substituted with a nitrogen atom. R b , and R f may be the same as or different from each other, and represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. PM represents a polymer.]

[13] The polymer according to

[12] , wherein Q is represented by the following formulas (a1) to (a10).

[0034]

Chemical formula

[0035] [R 6 , R 7 and R 8Each independently represents a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a cyano group, an aryl group, or a haloaryl group. * indicates the bonding position to another structural unit.]

[14] The PM is the polymer described in "12" or

[13] , which is any one of poly(meth)acrylate, polyester, polyimide, and polymaleimide.

[15] A method for producing a heterocyclic compound represented by the following formula (1-1), which includes a step of subjecting a heterocyclic compound represented by the following formula (2) to a deprotection reaction.

[0036]

Chemical formula

[0037] [In formulas (2) and (1-1), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent.

[0038] R 8 represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, or an aralkyl group. These groups may have a crosslinkable group.

[0039] R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (R 31 represents a divalent hydrocarbon group.), -O-R 32 -OH (R 32 represents a divalent hydrocarbon group.), -R 33 -NH2 (R 33 represents a divalent hydrocarbon group.), -R 34 -SH (R 34represents a divalent hydrocarbon group.), -R 35 -NCO(R 35 represents a divalent hydrocarbon group.), or -OC(=O)R 5 (R 5 represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. R 3 and R 4 When there are a plurality of them, they may be the same or different. R 3 is, R 1 may combine with each other to form a ring together with the atoms to which they are attached.

[0040] k and m each independently represent an integer from 0 to 4.

[0041] Sp 4 represents a single bond or an optionally branched alkylene group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR b or a halogen atom, and each -CH2- contained in the alkylene group is independently -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)- may be substituted, and the methine group contained in the alkylene group may be substituted with a nitrogen atom. R b , and R f may be the same as or different from each other, and represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. X represents -NH-, -O-, or -NHC(=O)-. PG represents a protecting group. Y represents a hydroxy group, an amino group, or an isocyanato group.]

[16] The production method according to

[15] , wherein PG is a group represented by the following chemical formulas (Pg-1) to (Pg-19).

[0042]

Chemical formula

Advantages of the Invention

[0043] According to the present invention, heterocyclic compounds A and B having excellent heat resistance are provided. Further, the compounds A and B have a high hyperpolarizability. Therefore, by using the compounds A and B in the production of electro-optical elements, it is possible to improve the heat resistance required for high-temperature processes during poling, thermosetting processes for fixing film orientation, high-temperature processes during mounting, etc., and to increase the degree of freedom in the process of element production. Further, according to the present invention, an electro-optical composition, an electro-optical film, and an electro-optical element using such heterocyclic compounds A and B are provided.

Embodiments for Carrying Out the Invention

[0044] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "from" or "to" means a range including the numerical values described before and after "from" or "to" as the lower limit value and the upper limit value. [Heterocyclic Compound A] The heterocyclic compound A of the present invention is a heterocyclic compound represented by the following formula (1).

[0045]

Chemical Formula

[0046] In the heterocyclic compound A of the present embodiment (compound A represented by formula (1)), cis-trans isomers may exist. In the heterocyclic compound A of the present embodiment, the formation of the trans isomer tends to be dominant, but any of the cis isomer, the trans isomer, or a cis-trans isomer mixture can be used. Among them, the heterocyclic compound A of the present embodiment is preferably the trans isomer in terms of easily ensuring the polarizability.

[0047] R in formula (1) 1 and R 2Each independently represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R 21 -OH (where R 21 represents a divalent hydrocarbon group.), -R 22 -NH2 (where R 22 represents a divalent hydrocarbon group.), -R 23 -SH (where R 23 represents a divalent hydrocarbon group.), or -R 24 -NCO (where R 24 represents a divalent hydrocarbon group.).

[0048] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

[0049] Examples of the haloalkyl group include a chloromethyl group, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.

[0050] Examples of the acyloxyalkyl group include an acetyloxymethyl group, an acetyloxyethyl group, an acetyloxypropyl group, an acetyloxybutyl group, an acetyloxypentyl group, an acetyloxyhexyl group, an acetyloxyheptyl group, an acetyloxyoctyl group, an acetyloxynonyl group, an acetyloxydecyl group, a chloroacetyloxymethyl group, a chloroacetyloxyethyl group, a chloroacetyloxypropyl group, a chloroacetyloxybutyl group, a chloroacetyloxypentyl group, a chloroacetyloxyhexyl group, a chloroacetyloxyheptyl group, a chloroacetyloxyoctyl group, a chloroacetyloxynonyl group, a chloroacetyloxydecyl group, a trichloroacetyloxymethyl group, a trichloroacetyloxyethyl group, a trichloroacetyloxypropyl group, a trichloroacetyloxybutyl group, a trichloroacetyloxypentyl group, a trichloroacetyloxyhexyl group, a trichloroacetyloxyheptyl group, a trichloroacetyloxyoctyl group, a trichloroacetyloxynonyl group, a trichloroacetyloxydecyl group, a trifluoroacetyloxymethyl group, a trifluoroacetyloxyethyl group, a trifluoroacetyloxypropyl group, a trifluoroacetyloxybutyl group, a trifluoroacetyloxypentyl group, a trifluoroacetyloxyhexyl group, a trifluoroacetyloxyheptyl group, a trifluoroacetyloxyoctyl group, a trifluoroacetyloxynonyl group, and a trifluoroacetyloxydecyl group.

[0051] Examples of the trialkylsilyloxyalkyl group include trimethylsilyloxymethyl group, trimethylsilyloxyethyl group, trimethylsilyloxypropyl group, trimethylsilyloxybutyl group, trimethylsilyloxypentyl group, trimethylsilyloxyhexyl group, trimethylsilyloxyheptyl group, trimethylsilyloxyoctyl group, trimethylsilyloxynonyl group, trimethylsilyloxydecyl group, triethylsilyloxymethyl group, triethylsilyloxyethyl group, triethylsilyloxypropyl group, triethylsilyloxybutyl group, triethylsilyloxypentyl group, triethylsilyloxyhexyl group, triethylsilyloxyheptyl group, triethylsilyloxyoctyl group, triethylsilyloxynonyl group, triethylsilyloxydecyl group, tripropylsilyloxymethyl group, tripropylsilyloxyethyl group, tripropylsilyloxypropyl group, tripropylsilyloxybutyl group, tripropylsilyloxypentyl group, tripropylsilyloxyhexyl group, tripropylsilyloxyheptyl group, tripropylsilyloxyoctyl group, tripropylsilyloxynonyl group, tripropylsilyloxydecyl group, triisopropylsilyloxymethyl group, triisopropylsilyloxyethyl group, triisopropylsilyloxypropyl group, triisopropylsilyloxybutyl group, triisopropylsilyloxypentyl group, triisopropylsilyloxyhexyl group, triisopropylsilyloxyheptyl group, triisopropylsilyloxyoctyl group, triisopropylsilyloxynonyl group, triisopropylsilyloxydecyl group, tributylsilyloxymethyl group, tributylsilyloxyethyl group, tributylsilyloxypropyl group, tributylsilyloxybutyl group, tributylsilyloxypentyl group, tributylsilyloxyhexyl group, tributylsilyloxyheptyl group, tributylsilyloxyoctyl group, tributylsilyloxynonyl group, tributylsilyloxydecyl group, tri-tert-butylsilyloxymethyl group, tri-tert-butylsilyloxyethyl group, tri-tert-butylsilyloxypropyl group, tri-tert-butylsilyloxybutyl group, tri-tert-butylsilyloxypentyl group,A tri-tert-butylsilyloxyhexyl group, a tri-tert-butylsilyloxyheptyl group, a tri-tert-butylsilyloxyoctyl group, a tri-tert-butylsilyloxynonyl group, a tri-tert-butylsilyloxydecyl group, a tert-butyldimethylsilyloxymethyl group, a tert-butyldimethylsilyloxyethyl group, a tert-butyldimethylsilyloxypropyl group, a tert-butyldimethylsilyloxybutyl group, a tert-butyldimethylsilyloxypentyl group, a tert-butyldimethylsilyloxyhexyl group, a tert-butyldimethylsilyloxyheptyl group, a tert-butyldimethylsilyloxyoctyl group, a tert-butyldimethylsilyloxynonyl group, a tert-butyldimethylsilyloxydecyl group may be mentioned.

[0052] Examples of the aryldialkylsilyloxyalkyl group include a di-tert-butyl(phenyl)silyloxymethyl group, a di-tert-butyl(phenyl)silyloxyethyl group, a di-tert-butyl(phenyl)silyloxypropyl group, a di-tert-butyl(phenyl)silyloxybutyl group, a di-tert-butyl(phenyl)silyloxypentyl group, a di-tert-butyl(phenyl)silyloxyhexyl group, a di-tert-butyl(phenyl)silyloxyheptyl group, a di-tert-butyl(phenyl)silyloxyoctyl group, a di-tert-butyl(phenyl)silyloxynonyl group, a di-tert-butyl(phenyl)silyloxydecyl group.

[0053] Examples of the alkyldiarylsilyloxyalkyl group include a tert-butyldiphenylsilyloxymethyl group, a tert-butyldiphenylsilyloxyethyl group, a tert-butyldiphenylsilyloxypropyl group, a tert-butyldiphenylsilyloxybutyl group, a tert-butyldiphenylsilyloxypentyl group, a tert-butyldiphenylsilyloxyhexyl group, a tert-butyldiphenylsilyloxyheptyl group, a tert-butyldiphenylsilyloxyoctyl group, a tert-butyldiphenylsilyloxynonyl group, a tert-butyldiphenylsilyloxydecyl group.

[0054] Examples of the aryl group include a phenyl group and a tetrafluorophenyl group.

[0055] Examples of the aralkyl group include a benzyl group and a chlorobenzyl group.

[0056] -R 22 -NH2, -R 23 -SH, -R 24 R in -NCO 22 , R 23 , R 24 represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group.

[0057] Specific -R 22 Examples of -OH include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group, a hydroxydecyl group, a hydroxyundecyl group, and a hydroxydodecyl group.

[0058] Specific -R 22 Examples of -NH2 include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminoisopropyl group, an aminobutyl group, an aminopentyl group, an aminohexyl group, an aminoheptyl group, an aminooctyl group, an aminononyl group, an aminodecyl group, an aminoundecyl group, and an aminododecyl group.

[0059] Specific -R 23Examples of -SH include a mercaptomethyl group, a mercaptoethyl group, a mercaptopropyl group, a mercaptoisopropyl group, a mercaptobutyl group, a mercaptopentyl group, a mercaptohexyl group, a mercaptoheptyl group, a mercaptooctyl group, a mercaptononyl group, a mercapto decyl group, a mercaptoundecyl group, and a mercaptododecyl group.

[0060] Specific -R 24 Examples of -NCO include an isocyanatomethyl group, an isocyanatoethyl group, an isocyanatopropyl group, an isocyanatoisopropyl group, an isocyanatobutyl group, an isocyanatopentyl group, an isocyanatohexyl group, an isocyanatoheptyl group, an isocyanatooctyl group, an isocyanatononyl group, an isocyanatodecyl group, an isocyanatoundecyl group, and an isocyanatododecyl group.

[0061] These groups may have a crosslinkable group. Examples of the crosslinkable group include an azide group, an ethynyl group, a nitrile oxide group, an isocyanato group, a hydroxy group, a mercapto group, a cinnamoyl group, a chalcone group, an oxetanyl group, an epoxy group, an acrylic group, an acryloxy group, a methacrylic group, a methacryloxy group, a vinyl group, and a propargyl group.

[0062] Also, R 1 and R 2 may be bonded to each other to form a ring together with the atoms to which they are respectively bonded. Examples of the ring include a pyrrolidine ring and a piperidine ring.

[0063] Among these, R 1 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, or a hydroxyoctyl group, and particularly preferably a methyl group, a butyl group, or a hydroxyheptyl group.

[0064] R 2Examples thereof preferably include a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, and a hydroxyoctyl group, and particularly preferably include a methyl group, a butyl group, and a hydroxyheptyl group.

[0065] R in formula (1) 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (wherein R 31 represents a divalent hydrocarbon group), -O-R 32 -OH (wherein R 32 represents a divalent hydrocarbon group), -R 33 -NH2 (wherein R 33 represents a divalent hydrocarbon group), -R 34 -SH (wherein R 34 represents a divalent hydrocarbon group), -R 35 -NCO (wherein R 35 represents a divalent hydrocarbon group), or -OC(=O)R 36 (wherein R 36 represents a monovalent hydrocarbon group).

[0066] Examples of the alkyl group, aryl group, trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group include the same alkyl group, aryl group, trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group as those of R 1 and R 2 .

[0067] Examples of the alkyloxy group include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group.

[0068] Examples of the aryloxy group include a phenyloxy group and a chlorophenyloxy group.

[0069] Examples of the aralkyloxy group include a benzyloxy group and a paramethoxybenzyloxy group.

[0070] Examples of the alkenyloxy group include a vinyloxy group and an allyloxy group.

[0071] Examples of the alkynyloxy group include a propargyloxy group and an ethynyloxy group.

[0072] -R 31 -OH, -O-R 32 -OH, -R 33 R in -NH2 31 , R 32 , R 33 -R represents a divalent hydrocarbon group, and examples of the divalent hydrocarbon group can include the same divalent hydrocarbon groups as R1 and R2.

[0073] Specific -R 31 -OH, examples of -R 21 -OH can include the same ones as -OH.

[0074] Specific -O-R 32Examples of -OH include hydroxymethyloxy group, hydroxyethyloxy group, hydroxypropyloxy group, hydroxyisopropyloxy group, hydroxybutyloxy group, hydroxypentyloxy group, hydroxyhexyloxy group, hydroxyheptyloxy group, hydroxyoctyloxy group, hydroxynonyloxy group, hydroxydecyloxy group, hydroxyundecyloxy group, and hydroxydodecyloxy group.

[0075] Specific -R 33 Examples of -NH2 include -R 22 Those similar to -NH2 can be cited.

[0076] -OC(=O)R 36 R in 36 represents a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Specific examples of -OC(=O)R 35 include acetyloxy group, ethanoyloxy group, propanoyloxy group, isopropanoyloxy group, butanoyloxy group, sec-butanoyloxy group, tert-butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, decanoyloxy group, undecanoyloxy group, and dodecanoyloxy group.

[0077] Also, R 3 is R 1 and R 2 may be bonded to each other to form a ring together with the atoms to which they are attached. Examples of the ring include pyrrolidine ring and piperidine ring.

[0078] Among these, R 3 and R 4 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

[0079] k and m each independently represent an integer from 0 to 4, preferably from 0 to 2, particularly preferably 0.

[0080] In formula (1), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent.

[0081] Examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, and a butyryl group.

[0082] As the divalent monocyclic or condensed heterocyclic ring which may have a substituent represented by Q, any of the groups represented by the following formulas (a1) to (a10) is preferable.

[0083]

Chemical formula

[0084] [R 6 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a cyano group, an aryl group, or a haloaryl group. * indicates the bonding position to another structural unit.] The alkyl group and the aryl group are R 1 and R 2Examples of the same alkyl group and aryl group can be given.

[0085] Examples of the haloalkyl group include a chloromethyl group, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.

[0086] Examples of the haloaryl group include a chlorophenyl group, a bromophenyl group, and an iodophenyl group.

[0087] Among these, R 6 is preferably a hydrogen atom, a methyl group, or an ethyl group, particularly preferably a hydrogen atom or a methyl group, and R 7 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably a hydrogen atom or a methyl group, and R 8 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably a hydrogen atom or a methyl group.

[0088] Specific examples of the heterocyclic compound A represented by the specific formula (1) include the following heterocyclic compounds (1-a1-1) to (1-a10-36).

[0089]

Chemical formula

[0090]

Chemical formula

[0091]

Chemical formula

[0092]

Chemical formula

[0093]

Chemical formula

[0094]

Chem.

[0095]

Chem.

[0096]

Chem.

[0097]

Chem.

[0098]

Chem.

[0099]

Chem.

[0100]

Chem.

[0101]

Chem.

[0102]

Chem.

[0103]

Chem.

[0104]

Chem.

[0105]

Chem.

[0106]

Chem.

[0107]

Chem.

[0108]

Chem.

[0109]

Chem.

[0110]

Chem.

[0111]

Chem.

[0112]

Chem.

[0113]

Chem.

[0114]

Chem.

[0115]

Chem.

[0116]

Chem.

[0117]

Chem.

[0118]

Chem.

[0119] In the above formulas (1-a1-1) to (1-a10-36), R 1a represents an optionally branched alkyl group having 1 to 12 carbon atoms. n represents an integer from 1 to 12.] Among these, (1-a2-1) to (1-a2-12), (1-a3-1) to (1-a3-12), (1-a3-13), and (1-a3-35) are preferred, and particularly preferred are (1-a2-1), (1-a3-1) to (1-a3-4), (1-a3-13), and (1-a3-35).

[0120] R 1a is an optionally branched alkyl group having 1 to 12 carbon atoms, and examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.

[0121] More specific examples of the heterocyclic compound A represented by the formula (1) include the following (1-a1-1-MeHep) to (1-a10-36-MeHep).

[0122] [Chemistry]

[0123] [Chemistry]

[0124] [Chemistry]

[0125] [Chemistry]

[0126] [Chemistry]

[0127] [Chemistry]

[0128] [Chemistry]

[0129] [Chemistry]

[0130] [Chemistry]

[0131] [Chemistry]

[0132] [Chemistry]

[0133]

Chem.

[0134]

Chem.

[0135]

Chem.

[0136]

Chem.

[0137]

Chem.

[0138]

Chem.

[0139]

Chem.

[0140]

Chem.

[0141]

Chem.

[0142]

Chem.

[0143]

Chem.

[0144]

Chem.

[0145]

Chem.

[0146]

Chem.

[0147]

Chem.

[0148]

Chem.

[0149]

Chem.

[0150]

Chem.

[0151]

Chem.

[0152] Among these, (1-a2-1-MeHep) to (1-a2-12-MeHep), (1-a3-1-MeHep) to (1-a3-12-MeHep), (1-a3-13-MeHep), and (1-a3-27-MeHep) are preferred, and particularly preferred are (1-a2-1-MeHep), (1-a3-1-MeHep) to (1-a3-4-MeHep), (1-a3-13-MeHep), and (1-a3-27-MeHep). [Heterocyclic Compound B] As one aspect of the present invention, there may be mentioned heterocyclic compound B represented by the following formulas (1A) to (1C) (hereinafter sometimes referred to as the heterocyclic compound B of the present invention).

[0153] [Chemical Formula]

[0154] [In formulas (1A) to (1C), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent.

[0155] R 1 represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R 21 -OH (where R 21 represents a divalent hydrocarbon group), -R 22 -NH2 (where R 22 represents a divalent hydrocarbon group), -R 23 -SH (where R 23 represents a divalent hydrocarbon group), or -R 24 -NCO (where R 24 represents a divalent hydrocarbon group). These groups may have a crosslinkable group.

[0156] R 3 and R 4Each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (where R 31 represents a divalent hydrocarbon group.), -O-R 32 -OH (where R 32 represents a divalent hydrocarbon group.), -R 33 -NH2 (where R 33 represents a divalent hydrocarbon group.), -R 34 -SH (where R 34 represents a divalent hydrocarbon group.), -R 35 -NCO (where R 35 represents a divalent hydrocarbon group.), or -OC(=O)R 5 (where R 5 represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. R 3 and R 4 When there are a plurality of them, they may be the same or different. R 3 may be bonded to R 1 to form a ring together with the atoms to which they are respectively bonded.

[0157] k and m each independently represent an integer from 0 to 4.

[0158] Sp 1 Sp 2 and Sp 3 each independently represent a single bond or an optionally branched alkylene group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR b or a halogen atom, and each -CH2- contained in the alkylene group is independently -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f-C(=O)- may be substituted, and the methine group contained in the alkylene group may be substituted with a nitrogen atom. R b , and R f may be the same as or different from each other, and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms.

[0159] A, B, and C each independently represent a monocyclic aromatic ring, a polycyclic aromatic ring, a condensed aromatic ring, or an aliphatic hydrocarbon ring having atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as constituent atoms, or a trivalent hydrocarbon group. These monocyclic aromatic rings, polycyclic aromatic rings, condensed aromatic rings, aliphatic hydrocarbon rings, and trivalent hydrocarbon groups may have substituents. The hydrogen atom contained in the trivalent hydrocarbon group may be substituted with -OR b or a halogen atom, and each -CH2- contained in the hydrocarbon group may independently be -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)- may be substituted, and the methine group contained in the hydrocarbon group may be substituted with a nitrogen atom. As the divalent monocyclic or condensed heterocyclic ring which may have a substituent represented by Q in the heterocyclic compound B of the present invention, any of the groups represented by the following formulas (a1) to (a10) is preferable.

[0160] [Chemical formula]

[0161] [R 6 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a cyano group, an aryl group, or a haloaryl group. * indicates the bonding position to another structural unit. Examples of the alkyl group and the aryl group include the same alkyl groups and aryl groups as those of R 1 and R 2 .

[0162] Examples of the haloalkyl group include a chloromethyl group, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.

[0163] Examples of the haloaryl group include a chlorophenyl group, a bromophenyl group, and an iodophenyl group.

[0164] Among these, R 6 is preferably a hydrogen atom, a methyl group, or an ethyl group, particularly preferably a hydrogen atom or a methyl group. R 7 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably a hydrogen atom or a methyl group. R 8 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably a hydrogen atom or a methyl group.

[0165] R 1 , R 2 , R 3 , R 4 , k, and m of the heterocyclic compound B of the present invention are the same as R 1 , R 2 , R 3 , R 4 , k, and m of the heterocyclic compound A.

[0166] Sp 1 , Sp 2 , and Sp 3 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms which may be branched. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a pentylene group, an iso-amylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, an undecanylene group, and a dodecanylene group.

[0167] The hydrogen atom contained in the alkylene group is -OR b(Or may be substituted with a halogen atom, and -CH2- contained in the alkylene group is each independently -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)- may be substituted, and the methine group contained in the alkylene group may be substituted with a nitrogen atom. R b and R f may be the same as or different from each other, and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms.

[0168] Specific examples of the heterocyclic compound B of the present invention can include structures represented by the following formulas (1A-a1-1) to (1C-a10-1).

[0169]

Chemical formula

[0170]

Chemical formula

[0171]

Chemical formula

[0172]

Chemical formula

[0173]

Chemical formula

[0174] [In the above formulas (1A-a1-1) to (1C-a10-1), R 1a represents an optionally branched alkyl group having 1 to 12 carbon atoms. n represents an integer from 1 to 12.] Among these, (1A-a2-1), (1A-a3-1), (1A-a5-1), (1A-a6-1), (1A-a7-1), (1A-a8-1), (1A-a9-1), and (1A-a10-1) are preferable, and particularly preferably (1A-a2-1) and (1A-a3-1).

[0175] R 1a is an optionally branched alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

[0176] More specific examples of the heterocyclic compound A represented by the formula (1) include the following (1A-a1-1-MeHep) to (1C-a10-1-MeHep).

[0177]

Chemical formula

[0178]

Chemical formula

[0179]

Chemical formula

[0180]

Chemical formula

[0181]

Chemical formula

[0182] Among these, (1A-a2-1-MeHep), (1A-a3-1-MeHep), (1A-a5-1-MeHep), (1A-a6-1-MeHep), (1A-a7-1-MeHep), (1A-a8-1-MeHep), (1A-a9-1-MeHep), and (1A-a10-1-MeHep) are preferred, and particularly preferred are (1A-a2-1-MeHep) and (1A-a3-1-MeHep).

[0183] The heterocyclic compounds A and B of the present embodiment have excellent heat resistance while having a high hyperpolarizability. Therefore, by using the compound in the production of an EO element, it is possible to improve the heat resistance required for high-temperature processes during poling, thermosetting processes for fixing film orientation, high-temperature processes during mounting, etc., and to increase the degree of freedom in the element production process. [Production Method of Heterocyclic Compound] The production method of the heterocyclic compound represented by the formula (1) is not particularly limited. Here, the production method will be described by taking the heterocyclic compound represented by the formula (1-1) and the heterocyclic compound represented by the formula (2) as examples.

[0184] The heterocyclic compound represented by the formula (1-1) of the present invention can be produced by deprotecting the protecting compound represented by the following formula (2).

[0185] [Chemical Formula]

[0186] [In the formulas (2) and (1-1), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent.

[0187] R 8 represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, or an aryl group. These groups may have a crosslinkable group.

[0188] R3 and R 4 is, independently of one another, a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (R 31 represents a divalent hydrocarbon group.), -O-R 32 -OH (R 32 represents a divalent hydrocarbon group.), -R 33 -NH2 (R 33 represents a divalent hydrocarbon group.), -R 34 -SH (R 34 represents a divalent hydrocarbon group.), -R 35 -NCO (R 35 represents a divalent hydrocarbon group.), or -OC(=O)R 5 (R 5 represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. R 3 and R 4 When a plurality of them are present, they may be the same or different. R 3 is, R 1 and R may be bonded to each other to form a ring together with the atoms to which they are each bonded.

[0189] k and m each independently represent an integer from 0 to 4.

[0190] Sp 4 represents a single bond or an optionally branched alkylene group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR b or a halogen atom, and each -CH2- contained in the alkylene group may be independently substituted with -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)-, and the methine groups contained in the alkylene group may be substituted with a nitrogen atom. Rb and R f may be the same as or different from each other and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. X represents -NH-, -O-, or -NHC(=O)-. PG represents a protecting group. Y represents a hydroxy group, an amino group, or an isocyanato group. When X in formula (2) is -O- and PG is a silyl-based protecting group, a heterocyclic compound represented by formula (1-1) in which Y is a hydroxy group can be produced by hydrolysis under acidic conditions or the action of a fluoride ion source.

[0191] Here, examples of the acid used for hydrolysis under acidic conditions include hydrochloric acid, sulfuric acid, acetic acid, chloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and the like.

[0192] Examples of the solvent used for hydrolysis under acidic conditions include tetrahydrofuran, methanol, ethanol, water, and the like.

[0193] Examples of the fluoride ion source include tetrabutylammonium fluoride, hydrofluoric acid, hydrogen fluoride-pyridine, triethylamine trihydrofluoride, and the like. It is preferable to use 1 to 10 equivalents, more preferably 1 to 3 equivalents, of the fluoride ion source relative to 1 equivalent of the silyl-based protecting group.

[0194] The solvent when the fluoride ion source is allowed to act is not particularly limited as long as it does not adversely affect the reaction.

[0195] The temperature when the fluoride ion source is allowed to act is preferably from -78°C to 50°C, more preferably from -10°C to 40°C. [Polymer] As one aspect of the present invention, there is provided a polymer having a structure represented by the following formula (1') (hereinafter sometimes referred to as the polymer of the present invention).

[0196] [Chemical formula]

[0197] In formula (1'), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent.

[0198] R 1 represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R 21 -OH (where R 21 represents a divalent hydrocarbon group), -R 22 -NH2 (where R 22 represents a divalent hydrocarbon group), -R 23 -SH (where R 23 represents a divalent hydrocarbon group), or -R 24 -NCO (where R 24 represents a divalent hydrocarbon group). These groups may have a crosslinkable group.

[0199] R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31 -OH (where R 31 represents a divalent hydrocarbon group), -O-R 32 -OH (where R 32 represents a divalent hydrocarbon group), -R 33 -NH2 (where R 33 represents a divalent hydrocarbon group), -R 34 -SH (where R 34 represents a divalent hydrocarbon group), -R 35 -NCO (where R 35 represents a divalent hydrocarbon group), or -OC(=O)R5 (R 5 represents a monovalent hydrocarbon group.) represents. These groups may have a crosslinkable group. R 3 and R 4 When there are a plurality of them, they may be the same or different. R 3 may be bonded to R 1 to form a ring together with the atoms to which they are respectively bonded.

[0200] k and m each independently represent an integer from 0 to 4.

[0201] Sp 1 represents a single bond or an optionally branched alkylene group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR b or a halogen atom, and each -CH2- contained in the alkylene group is independently -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR f -C(=O)-, and the methine group contained in the alkylene group may be substituted with a nitrogen atom. R b , and R f may be the same as or different from each other, and represent a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. PM represents a polymer.] R in formula (1‘) 1 is an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R 21 -OH (R 21 represents a divalent hydrocarbon group.), -R 22 -NH2 (R 22 represents a divalent hydrocarbon group.), -R 23 -SH (R 23 represents a divalent hydrocarbon group.), or -R 24 -NCO (R 24 represents a divalent hydrocarbon group.).

[0202] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Examples of the haloalkyl group include a chloromethyl group, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.

[0203] Examples of the acyloxyalkyl group include an acetyloxymethyl group, an acetyloxyethyl group, an acetyloxypropyl group, an acetyloxybutyl group, an acetyloxypentyl group, an acetyloxyhexyl group, an acetyloxyheptyl group, an acetyloxyoctyl group, an acetyloxynonyl group, an acetyloxydecyl group, a chloroacetyloxymethyl group, a chloroacetyloxyethyl group, a chloroacetyloxypropyl group, a chloroacetyloxybutyl group, a chloroacetyloxypentyl group, a chloroacetyloxyhexyl group, a chloroacetyloxyheptyl group, a chloroacetyloxyoctyl group, a chloroacetyloxynonyl group, a chloroacetyloxydecyl group, a trichloroacetyloxymethyl group, a trichloroacetyloxyethyl group, a trichloroacetyloxypropyl group, a trichloroacetyloxybutyl group, a trichloroacetyloxypentyl group, a trichloroacetyloxyhexyl group, a trichloroacetyloxyheptyl group, a trichloroacetyloxyoctyl group, a trichloroacetyloxynonyl group, a trichloroacetyloxydecyl group, a trifluoroacetyloxymethyl group, a trifluoroacetyloxyethyl group, a trifluoroacetyloxypropyl group, a trifluoroacetyloxybutyl group, a trifluoroacetyloxypentyl group, a trifluoroacetyloxyhexyl group, a trifluoroacetyloxyheptyl group, a trifluoroacetyloxyoctyl group, a trifluoroacetyloxynonyl group, and a trifluoroacetyloxydecyl group.

[0204] Examples of the trialkylsilyloxyalkyl group include a trimethylsilyloxymethyl group, a trimethyloxysilylethyl group, a trimethyloxysilylpropyl group, a trimethyloxysilylbutyl group, a trimethyloxysilylpentyl group, a trimethyloxysilylhexyl group, a trimethyloxysilylheptyl group, a trimethyloxysilyloctyl group, a trimethyloxysilylnonyl group, a trimethyloxysilyldecyl group, a triethylsilyloxymethyl group, a triethylsilyloxyethyl group, a triethylsilyloxypropyl group, a triethylsilyloxybutyl group, a triethylsilyloxypentyl group, a triethylsilyloxyhexyl group, a triethylsilyloxyheptyl group, a triethylsilyloxyoctyl group, a triethylsilyloxynonyl group, a triethylsilyloxydodecyl group, a tripropylsilyloxymethyl group, a tripropylsilyloxyethyl group, a tripropylsilyloxypropyl group, a tripropylsilyloxybutyl group, a tripropylsilyloxypentyl group, a tripropylsilyloxyhexyl group, a tripropylsilyloxyheptyl group, a tripropylsilyloxyoctyl group, a tripropylsilyloxynonyl group, a tripropylsilyloxydodecyl group, a triisopropylsilyloxymethyl group, a triisopropylsilyloxyethyl group, a triisopropylsilyloxypropyl group, a triisopropylsilyloxybutyl group, a triisopropylsilyloxypentyl group, a triisopropylsilyloxyhexyl group, a triisopropylsilyloxyheptyl group, a triisopropylsilyloxyoctyl group, a triisopropylsilyloxynonyl group, a triisopropylsilyloxydodecyl group, a tributylsilyloxymethyl group, a tributylsilyloxyethyl group, a tributylsilyloxypropyl group, a tributylsilyloxybutyl group, a tributylsilyloxypentyl group, a tributylsilyloxyhexyl group, a tributylsilyloxyheptyl group, a tributylsilyloxyoctyl group, a tributylsilyloxynonyl group, a tributylsilyloxydodecyl group, a tritert-butylsilyloxymethyl group, a tritert-butylsilyloxyethyl group, a tritert-butylsilyloxypropyl group, a tritert-butylsilyloxybutyl group, a tritert-butylsilyloxypentyl group,A tri-tert-butylsilyloxyhexyl group, a tri-tert-butylsilyloxyheptyl group, a tri-tert-butylsilyloxyoctyl group, a tri-tert-butylsilyloxynonyl group, a tri-tert-butylsilyloxydecyl group, a tert-butyldimethylsilyloxymethyl group, a tert-butyldimethylsilyloxyethyl group, a tert-butyldimethylsilyloxypropyl group, a tert-butyldimethylsilyloxybutyl group, a tert-butyldimethylsilyloxypentyl group, a tert-butyldimethylsilyloxyhexyl group, a tert-butyldimethylsilyloxyheptyl group, a tert-butyldimethylsilyloxyoctyl group, a tert-butyldimethylsilyloxynonyl group, a tert-butyldimethylsilyloxydecyl group may be mentioned.

[0205] Examples of the aryldialkylsilyloxyalkyl group include a di-tert-butyl(phenyl)silyloxymethyl group, a di-tert-butyl(phenyl)silyloxyethyl group, a di-tert-butyl(phenyl)silyloxypropyl group, a di-tert-butyl(phenyl)silyloxybutyl group, a di-tert-butyl(phenyl)silyloxypentyl group, a di-tert-butyl(phenyl)silyloxyhexyl group, a di-tert-butyl(phenyl)silyloxyheptyl group, a di-tert-butyl(phenyl)silyloxyoctyl group, a di-tert-butyl(phenyl)silyloxynonyl group, a di-tert-butyl(phenyl)silyloxydecyl group.

[0206] Examples of the alkyldiarylsilyloxyalkyl group include a tert-butyldiphenylsilyloxymethyl group, a tert-butyldiphenylsilyloxyethyl group, a tert-butyldiphenylsilyloxypropyl group, a tert-butyldiphenylsilyloxybutyl group, a tert-butyldiphenylsilyloxypentyl group, a tert-butyldiphenylsilyloxyhexyl group, a tert-butyldiphenylsilyloxyheptyl group, a tert-butyldiphenylsilyloxyoctyl group, a tert-butyldiphenylsilyloxynonyl group, a tert-butyldiphenylsilyloxydecyl group.

[0207] Examples of the aryl group include a phenyl group and a tetrafluorophenyl group.

[0208] Examples of the aralkyl group include a benzyl group and a chlorobenzyl group.

[0209] -R 22 -NH2, -R 23 -SH, -R 24 R in -NCO 22 , R 23 , R 24 R represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group.

[0210] Specific -R 22 Examples of -OH include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group, a hydroxydecyl group, a hydroxyundecyl group, and a hydroxydodecyl group.

[0211] Specific -R 22 Examples of -NH2 include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminoisopropyl group, an aminobutyl group, an aminopentyl group, an aminohexyl group, an aminoheptyl group, an aminooctyl group, an aminononyl group, an aminodecyl group, an aminoundecyl group, and an aminododecyl group.

[0212] Specific -R 23Examples of -SH include a mercaptomethyl group, a mercaptoethyl group, a mercaptopropyl group, a mercaptoisopropyl group, a mercaptobutyl group, a mercaptopentyl group, a mercaptohexyl group, a mercaptoheptyl group, a mercaptooctyl group, a mercaptononyl group, a mercapto decyl group, a mercaptoundecyl group, and a mercaptododecyl group.

[0213] Specific -R 24 Examples of -NCO include an isocyanatomethyl group, an isocyanatoethyl group, an isocyanatopropyl group, an isocyanatoisopropyl group, an isocyanatobutyl group, an isocyanatopentyl group, an isocyanatohexyl group, an isocyanatoheptyl group, an isocyanatooctyl group, an isocyanatononyl group, an isocyanatodecyl group, an isocyanatoundecyl group, and an isocyanatododecyl group.

[0214] These groups may have a crosslinkable group, and examples of the crosslinkable group include an azide group, an ethynyl group, a nitrile oxide group, an isocyanato group, a hydroxy group, a mercapto group, a cinnamoyl group, a chalcone group, an oxetanyl group, an epoxy group, an acrylic group, an acryloxy group, a methacrylic group, a methacryloxy group, a vinyl group, and a propargyl group.

[0215] Among these, R 1 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, or a hydroxyoctyl group, and particularly preferably a methyl group, a butyl group, or a hydroxyheptyl group.

[0216] R in formula (1') 3 and R 4 are each independently a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R 31-OH (where R 31 represents a divalent hydrocarbon group), -O-R 32 -OH (where R 32 represents a divalent hydrocarbon group), -R 33 -NH2 (where R 33 represents a divalent hydrocarbon group), -R 34 -SH (where R 34 represents a divalent hydrocarbon group), -R 35 -NCO (where R 35 represents a divalent hydrocarbon group), or -OC(=O)R 35 (where R 35 represents a monovalent hydrocarbon group).

[0217] Examples of the alkyl group, aryl group, trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group include the same alkyl group, aryl group, trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, and alkyldiarylsilyloxyalkyl group as R 1 and R 2 in the heterocyclic compound A.

[0218] Examples of the alkyloxy group include methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, and dodecyloxy group.

[0219] Examples of the aryloxy group include phenyloxy group and chlorophenyloxy group.

[0220] Examples of the aralkyloxy group include benzyloxy group and paramethoxybenzyloxy group.

[0221] Examples of the alkenyloxy group include vinyloxy group and allyloxy group.

[0222] Examples of the alkynyloxy group include a propargyloxy group and an ethynyloxy group.

[0223] -R 31 -OH, -O-R 32 -OH, -R 33 R in -NH2 31 、R 32 、R 33 represents a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include the same divalent hydrocarbon groups as R1 and R2 of the heterocyclic compound A.

[0224] Specific -R 31 Examples of -OH include the same ones as -OH of the heterocyclic compound A. 21 can be mentioned.

[0225] Specific -O-R 32 Examples of -OH include a hydroxymethyloxy group, a hydroxyethyloxy group, a hydroxypropyloxy group, a hydroxyisopropyloxy group, a hydroxybutyloxy group, a hydroxypentyloxy group, a hydroxyhexyloxy group, a hydroxyheptyloxy group, a hydroxyoctyloxy group, a hydroxynonyloxy group, a hydroxydecyloxy group, a hydroxyundecyloxy group, and a hydroxydodecyloxy group.

[0226] Specific -R 33 Examples of -NH2 include the same ones as -NH2 of the heterocyclic compound A. 22 can be mentioned.

[0227] R in -OC(=O)R 35 represents a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Specific -OC(=O)R 35 35 ​Examples include methyloxycarbonyloxy, ethyloxycarbonyloxy, propyloxycarbonyloxy, isopropyloxycarbonyloxy, butyloxycarbonyloxy, sec-butyloxycarbonyloxy, tert-butyloxycarbonyloxy, pentyloxycarbonyloxy, hexyloxycarbonyloxy, heptyloxycarbonyloxy, octyloxycarbonyloxy, nonyloxycarbonyloxy, decyloxycarbonyloxy, undecyloxycarbonyloxy, and dodecyloxycarbonyloxy.

[0228] R 3 is R 1 and R 2 may be bonded to each other to form a ring together with the atoms to which they are bonded, and examples of the ring include a pyrrolidine ring and a piperidine ring.

[0229] Among these, R 3 and R 4 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

[0230] K and m each independently represent an integer of 0 to 4, preferably 0 to 2, and particularly preferably 0.

[0231] In formula (1'), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent.

[0232] Examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group. Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, and a butyryl group.

[0233] As the divalent monocyclic or condensed heterocyclic ring represented by Q, any of the groups represented by the following formulas (a1) to (a10) is preferable.

[0234] [Chemical formula]

[0235] [R 6 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a cyano group, an aryl group, or a haloaryl group. * indicates the bonding position to another structural unit.] Examples of the alkyl group and the aryl group include the same alkyl groups and aryl groups as R 1 and R 2 in the heterocyclic compound A.

[0236] Examples of the haloalkyl group include a chloromethyl group, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.

[0237] Examples of the haloaryl group include a chlorophenyl group, a bromophenyl group, and an iodophenyl group.

[0238] Among these, R 6 is preferably a hydrogen atom, a methyl group, or an ethyl group, particularly preferably a hydrogen atom or a methyl group. For R 7 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably a hydrogen atom or a methyl group. For R 8 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably a hydrogen atom or a methyl group.

[0239] The polymer represented by PM includes poly(meth)acrylate, polyester, polyamide, polyimide, polycarbonate, polystyrene, polysulfone, polyethersulfone, polymaleimide, silicone resin, epoxy resin, etc. Among them, it is preferably any one of poly(meth)acrylate, polyester, and polyimide.

[0240] As the polymer having the structure represented by the specific formula (1'), the structures represented by the following formulas (1'-1-1-a1) to (1'-3-1-a10) can be exemplified.

[0241] [Chemical formula]

[0242] [Chemical formula]

[0243] [Chemical formula]

[0244] [Chemical formula]

[0245] [Chemical formula]

[0246]

Chem.

[0247]

Chem.

[0248]

Chem.

[0249]

Chem.

[0250]

Chem.

[0251]

Chem.

[0252]

Chem.

[0253]

Chem.

[0254]

Chem.

[0255]

Chem.

[0256] Among these, preferably (1’-1-1-a1) to (1’-1-1-a1), (1’-1-2-a3), (1’-1-3-a3), (1’-2-3-a3), (1’-3-1-a3), and particularly preferably (1’-1-1-a2), (1’-1-1-a3), (1’-1-2-a3), (1’-1-3-a3), (1’-1-3-a3), (1’-3-1-a3). [Composition] The composition of this embodiment contains the above heterocyclic compound, A, B, and a polymer. The polymer serves as a material for dispersing the compounds A and B. In order to exhibit excellent electro-optical properties, it is important that the heterocyclic compounds A and B are uniformly dispersed at a high concentration in the polymer. Therefore, the polymer preferably exhibits high compatibility with the heterocyclic compounds A and B.

[0257] Examples of the polymer include resins such as poly(meth)acrylate such as polymethyl methacrylate and polymethyl acrylate, polyester, polyamide, polyimide, polycarbonate, polystyrene, polysulfone, polyethersulfone, polymaleimide, silicone-based resin, and epoxy-based resin. Among them, preferably poly(meth)acrylate, polyester, polyamide, polyimide, and polystyrene, and particularly preferably poly(meth)acrylate, polyester, and polyimide. These polymers have excellent compatibility with the heterocyclic compounds A and B, and tend to have excellent transparency and moldability when used as electro-optical elements.

[0258] The composition may contain a resin having a reactive functional group capable of forming a covalent bond with the heterocyclic compounds A and B. Furthermore, it is preferable that at least a part of the heterocyclic compounds A and B is bonded to the resin having the reactive functional group. By including such a resin, it is possible to disperse the heterocyclic compounds A and B in the polymer at a high density, and high electro-optical properties can be achieved.

[0259] 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 isocyanato 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 heterocyclic compounds A and B to form a covalent bond.

[0260] The composition can be produced by polymer-dispersing the heterocyclic compounds A and B. Examples of the method for dispersing the compounds in a polymer include a method of dissolving the heterocyclic compounds A and B and the polymer in an organic solvent at an appropriate mixing ratio.

[0261] Examples of the organic solvent to be used include cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,3-dioxolane, methylcyclohexane, N-methyl-2-pyrrolidone, 1,1,1,3,3,3-hexafluoro-2-propanol, toluene, xylene, ethyl acetate, butyl acetate, chloroform, dichloromethane, etc.

[0262] The mixing ratio of A, B and the polymer is not particularly limited, but the mass ratio of the heterocyclic compound A or B to the polymer is preferably 10:90 to 90:10, more preferably 10:90 to 40:60.

[0263] The composition of this embodiment can be suitably used for forming an electro-optical film or for forming an electro-optical element. That is, the composition of this embodiment can be a composition for forming an electro-optical film or a composition for forming an electro-optical element.

[0264] As a method for using the composition of the present embodiment as an electro-optical film and an electro-optical device, a known method (for example, the methods described in Oh et al., IEEE Journal of Selected Topics in Quantum Electronics, Vol. 7, No. 5, pp. 826-835, 2001; Dalton et al., Journal of Materials Chemistry, 1999, Vol. 9, pp. 1905-1920; Toshikuni Kaino, Transactions of the Institute of Electronics, Information and Communication Engineers, Vol. J84-C, No. 9, pp. 744-755, September 2001; Ma et al., Advanced Materials, Vol. 14, No. 19, 2002, pp. 1339-1365, etc.) can be used for manufacturing.

[0265] The use of the electro-optical device of the present embodiment is not limited to an optical modulator as long as it has the above electro-optical film. In addition to an optical modulator (for ultra-high-speed applications, optical interconnect applications, optical signal processing applications, etc.), the electro-optical device of the present embodiment can be used, for example, in an optical switch, an optical memory, a wavelength converter, an electric field sensor for microwaves, millimeter waves, terahertz waves, etc., a bioelectric potential sensor for electromyogram, electroencephalogram, etc., an optical spatial modulator, an optical scanner, etc., and further, it can also be used for optical signal transmission between electronic circuits by combining with an electronic circuit.

Example

[0266] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited thereto. 1 [H-NMR measurement] 1 For the measurement of 1H-NMR, Bruker ASCEND 400 (400 MHz; manufactured by BRUKER) was used. Deuterated chloroform (CDCl3) or deuterated DMSO (DMSO-d6) was used as the measurement solvent, and trifluoroacetic acid-d (CF3CO2D) was added as needed to dissolve the heterocyclic compound. Tetramethylsilane (TMS) was used as the internal standard substance. [TG-DTA measurement] ​The measurement of the 5% weight loss temperature and decomposition temperature was carried out using a high-performance thermal analyzer NEXTA STA200 manufactured by Hitachi High-Tech Science Corporation. The measurement was performed while increasing the temperature at a rate of 5 °C / min under a nitrogen gas flow (0.1 L / min). [DSC measurement (glass transition temperature, crystallization temperature, melting point)] The measurement of the glass transition temperature, crystallization temperature, and melting point was performed using a high-sensitivity differential scanning calorimeter DSC7000X manufactured by Hitachi High-Tech Science Corporation. Aluminum oxide (Al2O3) was used as a reference in the DSC measurement.

[0267] The temperature of the sample was increased from 25 °C at a rate of 10 °C / min, and the glass transition temperature, crystallization temperature, and melting point were measured. [Example 1 of heterocyclic compound] [Synthesis of thieno[3,2-b]thiophene-2-carbaldehyde]

[0268] [Chemical formula]

[0269] Under an argon atmosphere, phosphorus oxychloride (13.7 mL, 150 mmol) was added dropwise to N,N-dimethylformamide (35 mL) cooled to 0 °C, and then stirred for 5 minutes to prepare a Vilsmeier reagent. Under an argon atmosphere, thieno[3,2-b]thiophene (7.01 g, 50.0 mmol) was dissolved in N,N-dimethylformamide (35 mL), and the previously prepared Vilsmeier reagent was added at 0 °C, and the temperature was raised to 60 °C and stirred for 7 hours. After cooling, the reaction solution was poured into ice (200 g), allowed to stand overnight, and then neutralized with a 48% aqueous sodium hydroxide solution. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to obtain a gray solid of thieno[3,2-b]thiophene-2-carbaldehyde (yield: 7.71 g, yield: 92%). 1 1H-NMR (400 MHz, CDCl3): δ 9.98 (s, 1H), 7.95 (d, J = 0.6 Hz, 1H), 7.70 (d, J = 5.4 Hz, 1H), 7.34 (dd, J = 5.4, 0.6 Hz, 1H). (Synthesis of 5 - Bromothieno[3,2 - b]thiophene - 2 - carbaldehyde)

[0270]

Chem.

[0271] Under an argon atmosphere, thiophene[3,2 - b]thiophene - 2 - carbaldehyde (3.36 g, 20.0 mmol) was dissolved in tetrahydrofuran (40 mL). N - Bromosuccinimide (4.98 g, 28.0 mmol) was added portionwise at 0 °C, and then the mixture was returned to room temperature and stirred for 20 hours. Water (200 mL) was added to the reaction mixture, and the precipitated solid was collected by filtration, washed with water, and dried under reduced pressure. The obtained solid was dissolved in chloroform and then filtered through silica gel. The filtrate was concentrated under reduced pressure, and the obtained solid was washed by slurry in hexane (50 mL) to obtain a pale - grayish - white solid of 5 - bromothieno[3,2 - b]thiophene - 2 - carbaldehyde (yield: 4.68 g, yield rate: 95%). 1 1H - NMR(400 MHz, CDCl3): δ 9.97 (s, 1H), 7.84 (d, J = 0.6 Hz, 1H), 7.36 (d, J = 0.6 Hz, 1H). (Synthesis of 4 - Bromo - N - (7 - hydroxyheptyl) - N - methylaniline)

[0272]

Chem.

[0273] Under an argon atmosphere, potassium carbonate (6.97 g, 50.4 mmol) and sodium iodide (1.89 g, 12.6 mmol) were suspended in acetonitrile (42 mL). 7-Bromo-1-heptanol (4.00 mL, 25.8 mmol) and 4-bromo-N-methylaniline (4.75 mL, 37.8 mmol) were added thereto, and the mixture was heated to reflux for 24 hours. The reaction solution was concentrated under reduced pressure, water (60 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL × 3). The combined organic layers were washed with water (75 mL) and saturated brine (75 mL), dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain a brown liquid of 4-bromo-N-(7-hydroxyheptyl)-N-methylaniline (yield: 5.44 g, yield: 70%). 1 1H-NMR (400 MHz, CDCl3): δ 7.30 - 7.24 (m, 2H), 6.56 - 6.51 (m, 2H), 3.67 - 3.60 (m, 2H), 3.26 (t, J = 7.5 Hz, 2H), 2.89 (s, 3H), 1.61 - 1.49 (m, 4H), 1.41 - 1.22 (m, 7H). (Synthesis of 4-bromo-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methylaniline)

[0274]

Chemical formula

[0275] Under an argon atmosphere, 4-bromo-N-(7-hydroxyheptyl)-N-methylaniline (5.43 g, 18.1 mmol) and imidazole (2.46 g, 36.2 mmol) were dissolved in N,N-dimethylformamide (50 mL). tert-Butyldimethylchlorosilane (4.09 g, 27.1 mmol) was added thereto, and the mixture was stirred at room temperature for 3 hours. Water (100 mL) was added to the reaction solution, and the mixture was extracted with a mixed solvent of hexane / ethyl acetate (volume ratio 1:1, 100 mL × 3). The combined organic layers were washed with water (100 mL × 3) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain a pale yellow liquid of 4-bromo-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methylaniline (yield: 6.13 g, yield: 82%). 1 1H-NMR (400 MHz, CDCl3): δ 7.29 - 7.24 (m, 2H), 6.56 - 6.55 (m, 2H), 3.59 (t, J = 6.6 Hz, 2H), 3.26 (t, J = 7.5 Hz, 2H), 2.89 (s, 3H), 1.57 - 1.45 (m, 4H), 1.38 - 1.23 (m, 6H), 0.89 (s, 9H), 0.04 (s, 6H). (Synthesis of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline)

[0276]

Chemical formula

[0277] Under an argon atmosphere, 4-bromo-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methylaniline (4.56 g, 11.0 mmol) was dissolved in tetrahydrofuran (45 mL) and cooled to -78 °C. n-Butyllithium (1.56 M hexane solution, 8.60 mL, 13.4 mmol) was added dropwise thereto, and the mixture was stirred at -78 °C for 1 hour. Then, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.00 mL, 14.8 mmol) was slowly added, and the mixture was stirred at -78 °C for 30 minutes and then returned to room temperature and stirred for 2 hours. Water (90 mL) was added to the reaction solution, and the mixture was extracted with a mixed solvent of hexane / ethyl acetate (volume ratio 1:1, 90 mL × 3). The combined organic layers were washed with saturated brine (150 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain a crude product of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (yield: 3.67 g). 1 1H-NMR (400 MHz, CDCl3): δ 7.70 - 7.63 (m, 2H), 6.67 - 6.61 (m, 2H), 3.59 (t, J = 6.6 Hz, 2H), 3.33 (t, J = 7.5 Hz, 2H), 2.95 (s, 3H), 1.61 - 1.45 (m, 4H), 1.38 - 1.23 (m, 6H), 1.32 (s, 12H), 0.89 (s, 9H), 0.04 (s, 6H). (Synthesis of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]phenyl]thieno[3,2-b]thiophene-2-carbaldehyde)

[0278]

Chemical formula

[0279] Under an argon atmosphere, 5-bromothieno[3,2-b]thiophene-2-carbaldehyde (1.54 g, 6.22 mmol) and the crude product of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3.77 g, about 7.46 mmol) were dissolved in 1,4-dioxane (48 mL), 2M aqueous potassium carbonate solution (16 mL) was added, and argon gas was bubbled into the reaction solution for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (359 mg, 0.311 mmol) was added thereto, and argon gas was bubbled into the reaction solution for 5 minutes, followed by stirring at 90 °C for 15 hours. The reaction solution was concentrated under reduced pressure, water (80 mL) was added, and the mixture was extracted with chloroform (90 mL × 2). The combined organic layers were washed with water (100 mL) and saturated brine (100 mL), and the dried mixture over anhydrous sodium sulfate was filtered through silica gel. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane / chloroform) to obtain a crude product of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]phenyl]thieno[3,2-b]thiophene-2-carbaldehyde (yield: 2.80 g). 1 1H-NMR (400 MHz, CDCl3): δ 9.91 (s, 1H), 7.86 (d, J = 0.5 Hz, 1H), 7.54 - 7.49 (m, 2H), 7.34 (d, J = 0.5 Hz, 1H), 6.72 - 6.66 (m, 2H), 3.60 (t, J = 6.6 Hz, 2H), 3.36 (t, J = 7.5 Hz, 2H), 3.00 (s, 3H), 1.66 - 1.45 (m, 4H), 1.40 - 1.28 (m, 6H), 0.89 (s, 9H), 0.05 (s, 6H). Synthesis of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-([5-[(E)-4-(nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0280]

Chemical formula

[0281] Under an argon atmosphere, sodium hydride (about 55% mineral oil dispersion, 314 mg, 6.30 mmol) was suspended in tetrahydrofuran (20 mL) and cooled to 0 °C. Diethyl (4-nitrobenzyl)phosphonate (1.40 mL, 6.30 mmol) was added thereto, and the mixture was stirred at 0 °C for 15 minutes. Then, a solution of the crude product of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]phenyl]thieno[3,2-b]thiophene-2-carbaldehyde (2.43 g, about 4.50 mmol) in tetrahydrofuran (40 mL) was added, and the mixture was returned to room temperature and stirred for 2 hours. Since the reaction was incomplete, sodium hydride (about 55% mineral oil dispersion, 158 mg, 3.62 mmol) and diethyl (4-nitrobenzyl)phosphonate (0.700 mL, 3.62 mmol) were added at 0 °C, and the mixture was returned to room temperature and stirred for 1 hour. Water (150 mL) was added to the reaction mixture, and the mixture was extracted with chloroform (150 mL × 4). The combined organic layers were washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was slurried and washed with a mixed solvent of hexane / ethyl acetate (volume ratio 1:1, 90 mL) to obtain a brown solid of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (yield: 2.56 g, yield: 76% in two steps). 1 1H-NMR (400 MHz, CDCl3): δ 8.24 - 8.18 (m, 2H), 7.61 - 7.55 (m, 2H), 7.52 - 7.46 (m, 2H), 7.42 (d, J = 15.8 Hz, 1H), 7.29 - 7.25 (m, 2H), 6.89 (d, J = 15.8 Hz, 1H), 6.72 - 6.66 (m, 2H), 3.60 (t, J = 6.5 Hz, 2H), 3.34 (t, J = 7.6 Hz, 2H), 2.98 (s, 3H), 1.65 - 1.46 (m, 4H), 1.40 - 1.28 (m, 6H), 0.90 (s, 9H), 0.05 (s, 6H). (Synthesis of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0282] [Chemistry]

[0283] N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (2.01 g, 3.24 mmol) was suspended in a mixed solvent of dichloromethane / methanol (volume ratio 3:1, 136 mL), 4M hydrogen chloride (1,4-dioxane solution, 34 mL) was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, 1M aqueous sodium hydroxide solution (100 mL) was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was washed with water and ethyl acetate and dried under reduced pressure to obtain a brown solid (yield: 1.60 g, yield: 98%) of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (compound 1). 1 1H-NMR (400 MHz, CDCl3 + CF3CO2D (1 drop)): δ 8.27 - 8.21 (m, 2H), 7.85 - 7.78 (m, 2H), 7.67 - 7.60 (m, 2H), 7.56 (s, 1H), 7.55 - 7.49 (m, 2H), 7.46 (d, J = 15.8 Hz, 1H), 7.35 (s, 1H), 6.99 (d, J = 15.8 Hz, 1H), 3.78 (t, J = 6.4 Hz, 2H), 3.67 (brm, 1H), 3.46 (brm, 1H), 3.34 (s, 3H), 1.78 - 1.41 (m, 4H), 1.41 - 1.22 (m, 6H). As a result of measuring the TG-DTA of the obtained compound (compound 1, 2.1 mg), the 5% weight loss temperature was 306 °C. Also, as a result of measuring the DSC of the obtained compound (compound 1, 2.5 mg), the glass transition temperature, melting point, and crystallization temperature were not detected. [Example 2 of Heterocyclic Compound] (Synthesis of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-3-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0284] [Chemical formula]

[0285] Under an argon atmosphere, diethyl (3-methyl-4-nitrobenzyl)phosphonate (1.66 g, 5.78 mmol) was dissolved in tetrahydrofuran (20 mL) and cooled to 0 °C. Sodium hydride (about 60% mineral oil dispersion, 645 mg, 10.7 mmol) was added thereto, and the mixture was stirred at 0 °C for 30 minutes. Subsequently, a solution of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]phenyl]thieno[3,2-b]thiophene-2-carbaldehyde (2.07 g, 4.12 mmol) in tetrahydrofuran (52 mL) was added, and the mixture was returned to room temperature and stirred for 2 hours. Then, water (70 mL) was added to stop the reaction. The precipitated solid was collected by filtration, washed with water and hexane, and dried to obtain a reddish-brown solid of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-3-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (yield: 2.50 g, yield: 96%). 1 1H-NMR (400 MHz, CDCl3): δ 8.02 (d, J = 8.7 Hz, 1H), 7.51 - 7.46 (m, 2H), 7.44 - 7.35 (m, 3H), 7.28 - 7.23 (m, 2H), 6.83 (d, J = 16.1 Hz, 1H), 6.72 - 6.66 (m, 2H), 3.60 (t, J = 6.6 Hz, 2H), 3.35 (t, J = 7.5 Hz, 2H), 2.98 (s, 3H), 2.66 (s, 3H), 1.66 - 1.46 (m, 4H), 1.40 - 1.28 (m, 6H), 0.90 (s, 9H), 0.05 (s, 6H). (Synthesis of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-3-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0286] [Chemical formula]

[0287] N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-3-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (127 mg, 0.199 mmol) was suspended in a mixed solvent of dichloromethane / methanol (volume ratio 3:1, 8.8 mL), 4 M hydrogen chloride (1,4-dioxane solution, 2.1 mL) was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure, 1 M aqueous sodium hydroxide solution (6.7 mL) was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was washed with water and hexane and dried under reduced pressure. The obtained solid was washed successively with ethyl acetate and hexane and dried to obtain a brown solid (yield: 80.5 mg, yield: 78%) of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-3-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (compound 2). 1 1H-NMR (400 MHz, CDCl3): δ 8.03 (d, J = 8.5 Hz, 1H), 7.51 - 7.46 (m, 2H), 7.44 - 7.35 (m, 3H), 7.28 - 7.23 (m, 2H), 6.83 (d, J = 15.9 Hz, 1H), 6.72 - 6.66 (m, 2H), 3.65 (td, J = 6.5, 5.5 Hz, 2H), 3.35 (t, J = 7.5 Hz, 2H), 2.98 (s, 3H), 2.66 (s, 3H), 1.66 - 1.50 (m, 4H), 1.44 - 1.30 (m, 6H), 1.20 (d, J = 5.5 Hz, 1H). As a result of measuring the TG-DTA of the obtained compound (compound 2, 3.47 mg), the 5% weight loss temperature was 300 °C. [Example 3 of heterocyclic compound] (Synthesis of 4-[(tert-Butoxycarbonyl)(methyl)amino]benzoic acid)

[0288]

Chem.

[0289] Di-tert-butyl dicarbonate (6.52 g, 29.9 mmol) was added dropwise to a 1M aqueous sodium hydroxide solution (20.8 mL) of 4-(methylamino)benzoic acid (3.01 g, 19.9 mmol) over 10 minutes. After the reaction mixture was stirred at room temperature for 23 hours, it was cooled to 0 °C, and 1M hydrochloric acid (20 mL) was added to adjust the pH to 7. The precipitated solid was collected by filtration, washed with water, and dried to obtain 4-[(tert-butoxycarbonyl)(methyl)amino]benzoic acid (yield: 3.27 g, yield rate: 65%). 1 H-NMR (400 MHz, CDCl3): δ 8.07 (d, J = 8.8 Hz, 2H), 7.38 (d, J = 8.8 Hz, 2H), 3.32 (s, 3H), 1.49 (s, 9H). (Synthesis of N-[(E)-3-(4-Nitrophenyl)-2-propenoyl]hydrazine)

[0290]

Chem.

[0291] Under an argon atmosphere, 1-hydroxybenzotriazole monohydrate (5.32 g, 33.7 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (6.47 g, 33.7 mmol) were added to a DMF (70 mL) solution of 4-nitrocinnamic acid (5.43 g, 28.1 mmol), and the mixture was stirred at room temperature for 3 hours. The resulting suspension was added dropwise over 40 minutes to a DMF (70 mL) solution of hydrazine monohydrate (2.70 mL, 56.2 mmol) cooled to 0 °C. After stirring the reaction mixture at 0 °C for 1 hour, water (380 mL) was added to stop the reaction. The precipitated solid was collected by filtration, washed with water (100 mL) and ethanol (20 mL), and then dried to obtain a pale yellow solid of N-[(E)-3-(4-nitrophenyl)-2-propenoyl]hydrazine (yield: 4.51 g, yield: 77%). 1 1H-NMR (400 MHz, DMSO-d6): δ 9.54 (s, 1H), 8.27 (d, J = 8.8 Hz, 2H), 7.84 (d, J = 8.8 Hz, 2H), 7.56 (d, J = 15.9 Hz, 1H), 6.74 (d, J = 15.9 Hz, 1H), 4.56 (br, 2H). (Synthesis of N-[4-[(tert-butoxycarbonyl)(methyl)amino]benzoyl]-N'-[(E)-3-(4-nitrophenyl)-2-propenoyl]hydrazine)

[0292] [Chemical formula]

[0293] To a solution of N-[(E)-3-(4-nitrophenyl)-2-propenoyl]hydrazine (0.830 g, 4.01 mmol) in DMF (40 mL) were added triethylamine (1.40 mL, 10.0 mmol), 4-[(tert-butoxycarbonyl)(methyl)amino]benzoic acid (1.01 g, 4.01 mmol), 1-hydroxybenzotriazole monohydrate (0.633 g, 4.01 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.863 g, 4.41 mmol), and the mixture was stirred at room temperature for 18 h. After adding water (80 mL) to stop the reaction, the precipitated solid was collected by filtration and dried to obtain a pale yellow solid of N-[4-[(tert-butoxycarbonyl)(methyl)amino]benzoyl]-N’-[(E)-3-(4-nitrophenyl)-2-propenoyl]hydrazine (yield: 1.52 g, 86%). 1 1H-NMR (400 MHz, CDCl3): δ 10.2 (br, 1H), 9.54 (br, 1H), 8.20 (d, J = 8.8 Hz, 2H), 7.86 (d, J = 8.8 Hz, 2H), 7.74 (d, J = 15.7 Hz, 1H), 7.59 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 8.7 Hz, 2H), 6.83 (d, J = 15.7 Hz, 1H), 3.32 (s, 3H), 1.50 (s, 9H). (Synthesis of tert-butyl N-methyl-N-[4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]phenyl]carbamate)

[0294]

Chemical Structure

[0295] To a solution of N-[4-[(tert-butoxycarbonyl)(methyl)amino]benzoyl]-N’-[(E)-3-(4-nitrophenyl)-2-propenoyl]hydrazine (3.61 g, 8.20 mmol) in acetonitrile (138 mL) were added diisopropylethylamine (4.00 mL, 23.0 mmol) and p-toluenesulfonyl chloride (5.78 g, 30.3 mmol), and the mixture was stirred at room temperature for 1 hour. After adding water (300 mL) to stop the reaction, the resulting solid was collected by filtration and dried to obtain a pale yellow solid of tert-butyl N-methyl-N-[4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]phenyl]carbamate (yield: 3.45 g, quantitative yield). 1 1H-NMR (400 MHz, DMSO-d6): δ 8.31 (d, J = 8.8 Hz, 2H), 8.11 - 8.07 (m, 4H), 7.92 (d, J = 16.4 Hz, 1H), 7.67 (d, J = 16.4 Hz, 1H), 7.59 (d, J = 8.8 Hz, 2H), 3.28 (s, 3H), 1.45 (s, 9H). (Synthesis of N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline)

[0296]

Chemical formula

[0297] A solution of tert-butyl N-methyl-N-[4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]phenyl]carbamate (0.910 g, 2.16 mmol) in dichloromethane (36 mL) was cooled to 0 °C, and trifluoroacetic acid (3.2 mL) was added dropwise over 5 minutes. After stirring the reaction mixture for 4 hours while returning it to room temperature, saturated aqueous sodium hydrogen carbonate solution (67 mL) was added to stop the reaction, and dichloromethane was distilled off under reduced pressure. The precipitated solid was collected by filtration, washed with water (50 mL), and dried to obtain a brown solid of N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline (yield: 0.625 g, 90% yield).1 1H-NMR (400 MHz, DMSO-d6): δ 8.28 (d, J = 8.9 Hz, 2H), 8.07 (d, J = 8.9 Hz, 2H), 7.84 - 7.78 (m, 3H), 7.60 (d, J = 16.5 Hz, 1H), 6.70 (d, J = 8.9 Hz, 2H), 6.60 (q, J = 5.0 Hz, 1H), 2.77 (d, J = 5.0 Hz, 3H). (Synthesis of N-[7-[(tert-butyldiphenylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline)

[0298] [Chemical Structure]

[0299] Under an argon atmosphere, acetic acid (2.7 mL) was added to a solution of N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline (1.53 g, 4.76 mmol) and 7-[(tert-butyldiphenylsilyl)oxy]heptanal (5.26 g, 14.3 mmol) in dichloromethane (48 mL), and the mixture was stirred at room temperature for 10 minutes. Then, sodium triacetoxyborohydride (3.33 g, 15.7 mmol) was added, and the mixture was stirred at room temperature for 1 hour. A saturated aqueous sodium hydrogen carbonate solution (50 mL) was added to the reaction mixture, and the mixture was concentrated under reduced pressure. The residue was extracted with ethyl acetate (60 mL × 3), and the obtained organic layer was dried over magnesium sulfate and then concentrated under reduced pressure. The obtained crude product was washed with hexane (60 mL) and then dried to obtain an orange solid of N-[7-[(tert-butyldiphenylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline (yield: 2.96 g, yield rate: 92%). 1H-NMR(400MHz, DMSO-d6): δ 8.29 (d, J = 8.8 Hz, 2H), 7.95 (d, J = 9.1 Hz, 2H), 7.71 (d, J = 8.8 Hz, 2H), 7.68 - 7.65 (m, 4H), 7.58 (d, J = 16.4 Hz, 1H), 7.43 - 7.35 (m, 6H), 7.23 (d, J = 16.4 Hz, 1H), 6.73 (d, J = 9.1 Hz, 2H), 3.66 (t, J = 6.5 Hz, 2H), 3.40 (t, J = 7.6 Hz, 2H), 3.04 (s, 3H), 1.61 - 1.54 (m, 4H), 1.40 - 1.30 (m, 6H), 1.05 (s, 9H). (Synthesis of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline)

[0300] [Chemical formula]

[0301] Under an argon atmosphere, a 1.0 M tetrahydrofuran solution of tetrabutylammonium fluoride (6.50 mL, 6.50 mmol) was added to a solution of N-[7-[(tert-butyldiphenylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline (2.93 g, 4.34 mmol) in tetrahydrofuran (43 mL), and the mixture was stirred at room temperature for 1 hour. Water (45 mL) was added to stop the reaction, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with a saturated aqueous ammonium chloride solution and saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting crude product was washed with hexane (100 mL) and then purified by silica gel column chromatography (chloroform / methanol) to obtain an orange solid of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-4-nitrostyryl]-1,3,4-oxadiazol-2-yl]aniline (compound 3) (yield: 1.70 g, yield rate: 90%). 11H-NMR (400 MHz, CDCl3): δ 8.32 - 8.26 (m, 2H), 7.98 - 7.92 (m, 2H), 7.75 - 7.69 (m, 2H), 7.59 (d, J = 16.5 Hz, 1H), 7.17 (d, J = 16.5 Hz, 1H), 6.76 - 6.71 (m, 2H), 3.65 (td, J = 6.5, 5.3 Hz, 2H), 3.41 (t, J = 7.5 Hz, 2H), 3.05 (s, 3H), 1.69 - 1.52 (m, 4H), 1.45 - 1.31 (m, 6H), 1.23 (t, J = 5.3 Hz, 1H). As a result of measuring the TG-DTA of the obtained compound (compound 3, 1.6 mg), the temperature at 5% weight loss was 310 °C. [Example 4 of Heterocyclic Compound] (Synthesis of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0302] [Chemical Structure]<

[0303] Under an argon atmosphere, diethyl (2-methyl-4-nitrobenzyl)phosphonate (1.45 g, 5.06 mmol) was dissolved in tetrahydrofuran (18 mL) and cooled to 0 °C. Sodium hydride (approx. 60% mineral oil dispersion, 0.560 g, 9.40 mmol) was added thereto, and the mixture was stirred at 0 °C for 30 minutes. Subsequently, a solution of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]phenyl]thieno[3,2-b]thiophene-2-carbaldehyde (1.81 g, 3.62 mmol) in tetrahydrofuran (45 mL) was added, and after returning to room temperature and stirring for 3 hours, water (120 mL) was added to stop the reaction. The precipitated solid was collected by filtration, washed with water and hexane, and then recrystallized from a mixed solvent of chloroform / hexane to obtain a brown solid of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (yield: 1.83 g, yield rate: 80%). 1 1H-NMR (400 MHz, CDCl3): δ 8.06−8.03 (m, 2H), 7.69 (d, J = 9.3 Hz, 1H), 7.49 (d, J = 8.9 Hz, 2H), 7.33 (d, J = 15.8 Hz, 1H), 7.27−7.26 (m, 2H), 7.04 (d, J = 15.8 Hz, 1H), 6.69 (d, J = 8.9 Hz, 2H), 3.60 (t, J = 6.5 Hz, 2H), 3.35 (t, J = 7.4 Hz, 2H), 2.98 (s, 3H), 2.52 (s, 3H), 1.63−1.50 (m, 4H), 1.35−1.32 (m, 6H), 0.90 (s, 9H), 0.05 (s, 6H). (Synthesis of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0304]

Chemical Structure

[0305] N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (1.65 g, 2.60 mmol) was suspended in a mixed solvent of dichloromethane / methanol (volume ratio 3:1, 114 mL), 4 M hydrogen chloride (1,4-dioxane solution, 27.3 mL) was added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was concentrated under reduced pressure, 1 M aqueous sodium hydroxide solution (90 mL) was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was washed with water and hexane and dried under reduced pressure. The obtained solid was washed again with hexane and dried to obtain a brown solid of N-(7-hydroxyheptyl)-N-methyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (compound 4) (yield: 1.26 g, yield: 93%). 1 1H-NMR (400 MHz, CDCl3): δ 8.06−8.04 (m, 2H), 7.69 (d, J = 9.3 Hz, 1H), 7.49 (d, J = 8.9 Hz, 2H), 7.34 (d, J = 15.7 Hz, 1H), 7.27−7.26 (m, 2H), 7.05 (d, J = 15.7 Hz, 1H), 7.49 (d, J = 8.9 Hz, 2H), 3.67−3.63 (m, 2H), 3.35 (t, J = 7.4 Hz, 2H), 2.99 (s, 3H), 2.52 (s, 3H), 1.64−1.51 (m, 4H), 1.37 (br, 6H), 1.20 (t, J = 5.4 Hz, 1H). As a result of measuring the TG-DTA of the obtained compound (compound 4, 5.45 mg), the 5% weight loss temperature was 311 °C. [Example 5 of Heterocyclic Compounds] (Synthesis of N-(4-bromo-3-methylphenyl)acetamide)

[0306]

Chemical Structure

[0307] Under an argon atmosphere, triethylamine (5.6 mL, 40.5 mmol) was added dropwise to a solution of 4-bromo-3-methylaniline (5.02 g, 27.0 mmol) in dichloromethane (135 mL), and the mixture was stirred for 30 minutes. Then acetic anhydride (3.8 mL, 40.5 mmol) was added dropwise, and the mixture was stirred for 2 hours. The reaction solution was concentrated under reduced pressure, ethyl acetate (50 mL) and saturated aqueous ammonium chloride solution (70 mL) were added thereto, and after stirring for a while, extraction was performed with ethyl acetate (70 mL × 2). The obtained organic layer was washed with saturated brine (200 mL × 2), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 62:38 to 41:59) to obtain an ivory solid of the title compound (yield: 5.94 g, yield: 97%). 1 1H-NMR (400 MHz, CDCl3): δ 7.45 - 7.43 (m, 2H), 7.26 - 7.17 (m, 2H), 2.37 (s, 3H), 2.16 (s, 3H). (Synthesis of N-(4-bromo-3-methylphenyl)-N-methylacetamide)

[0308]

Chemical Structure

[0309] Under an argon atmosphere, methyl iodide (1.8 mL, 28.2 mmol) was added to a solution of N-(4-bromo-3-methylphenyl)acetamide (5.35 g, 23.5 mmol) in DMF (60 mL), and the mixture was cooled in ice. Sodium hydride (about 60% mineral oil dispersion, 1.69 g, 28.2 mmol) was added thereto, and the mixture was stirred at room temperature for 2 hours. The reaction solution was cooled in ice, and water (180 mL) was added to stop the reaction. This was extracted with a mixed solvent of hexane / ethyl acetate (volume ratio 4:1, 150 mL × 3), and the obtained organic layer was washed with water (300 mL) and saturated brine (300 mL), and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crystals were washed with hexane (100 mL) to obtain white crystals of the title compound (yield: 4.29 g). The filtrate was collected and purified by silica gel column chromatography (chloroform:ethyl acetate = 100:0 to 0:100) to further obtain white crystals of the title compound (yield: 0.997 g). The total yield was 5.29 g, and the yield was 93%. 1 1H-NMR (400 MHz, CDCl3): δ 7.56 (d, J = 8.3 Hz, 1H), 7.07 (d, J = 2.3 Hz, 1H), 6.89 (dd, J = 8.3, 2.3 Hz, 1H), 3.23 (s, 3H), 2.42 (s, 3H), 1.88 (s, 3H). (Synthesis of N-methyl-4-bromo-3-methylaniline)

[0310]

Chemical Structure

[0311] To a solution of N-(4-bromo-3-methylphenyl)-N-methylacetamide (0.151 g, 0.622 mmol) in ethanol (5.2 mL) was added 6 M aqueous sodium hydroxide solution (1.2 mL), and the mixture was refluxed for 2 hours. After cooling to room temperature, ethyl acetate (15 mL) was added and the layers were separated. The organic layer was washed with water (20 mL) and saturated brine (20 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform:ethyl acetate = 100:0 to 0:100) to obtain the title compound as a yellow oil (yield: 0.103 g, yield: 83%). 1 1H-NMR (400 MHz, CDCl3): δ 7.28 (d, J = 8.6 Hz, 1H), 6.48 (d, J = 2.9 Hz, 1H), 6.32 (dd, J = 8.6, 2.9 Hz, 1H), 3.65 (brs, 1H), 2.80 (s, 3H), 2.32 (s, 3H). (Synthesis of 7-[(4-bromo-3-methylphenyl)methylamino]-1-heptanol)

[0312] [Chemical formula]

[0313] Under an argon atmosphere, 7-bromo-1-heptanol (1.8 mL, 11.6 mmol) was added to a suspension of N-methyl-4-bromo-3-methylaniline (3.42 g, 17.1 mmol), potassium carbonate (3.14 g, 22.7 mmol), and sodium iodide (0.84 g, 5.63 mmol) in acetonitrile (17 mL), and the mixture was refluxed for 23 hours. After completion of the reaction, water (50 mL) was added under ice-cooling to stop the reaction, and the mixture was extracted with ethyl acetate (30 mL × 3). The resulting organic layer was washed with water (100 mL) and saturated brine (100 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 100:0 to 85:15) to obtain the title compound as a brown oil (yield: 3.46 g, yield: 65%). 1H-NMR (400 MHz, CDCl3): δ 7.29 (d, J = 8.8 Hz, 1H), 6.53 (d, J = 3.3 Hz, 1H), 6.39 (dd, J = 8.8, 3.3 Hz, 1H), 3.64 (t, J = 6.3 Hz, 2H), 3.25 (t, J = 7.3 Hz, 2H), 2.88 (s, 3H), 2.34 (s, 3H), 1.60 - 1.51 (m, 4H), 1.38 - 1.28 (m, 6H), 1.23 (brs, 1H). (Synthesis of 4-Bromo-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-3-methyl-N-methylaniline)

[0314] [Chemical Structure]

[0315] Under an argon atmosphere, imidazole (1.50 g, 22.0 mmol) and tert-butyldimethylchlorosilane (2.49 g, 16.5 mmol) were sequentially added to a solution of 7-[(4-bromo-3-methylphenyl)methylamino]-1-heptanol (3.46 g, 11.0 mmol) in DMF (30 mL). After stirring the reaction mixture for 1 hour, water (60 mL) was added to stop the reaction, and the mixture was extracted with a mixed solvent of hexane / ethyl acetate (volume ratio 4:1, 60 mL × 3). The obtained organic layer was washed with water (200 mL) and saturated brine (200 mL), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 100:0 to 90:10) to obtain the title compound as a yellow oil (yield: 4.52 g, yield rate: 96%). 1 H-NMR (400 MHz, CDCl3): δ 7.29 (d, J = 8.9 Hz, 1H), 6.53 (d, J = 3.0 Hz, 1H), 6.39 (dd, J = 8.9, 3.0 Hz, 1H), 3.59 (t, J = 6.6 Hz, 2H), 3.25 (t, J = 7.5 Hz, 2H), 2.88 (s, 3H), 2.34 (s, 3H), 1.57 - 1.47 (m, 4H), 1.32 (brs, 6H), 0.891 (s, 9H), 0.0438 (s, 6H). (Synthesis of 1-[3-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methylaniline)

[0316]

Chem.

[0317] Under an argon atmosphere, a solution of 4-bromo-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-3-methyl-N-methylaniline (4.22 g, 9.85 mmol) in THF (40 mL) was cooled to -78 °C. To this was added dropwise a 1.6 M hexane solution of n-butyllithium (7.8 mL, 11.8 mmol), and the mixture was stirred for 1 hour. Then, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.8 mL, 13.8 mmol) was added dropwise, and after stirring for 30 minutes, the temperature was raised to room temperature and stirring was continued for 2 hours. After completion of the reaction, water (80 mL) was added under ice-cooling to stop the reaction, and the mixture was extracted with a mixed solvent of hexane / ethyl acetate (volume ratio 1:1, 50 mL × 3). The obtained organic layer was washed with water (150 mL) and saturated brine (150 mL), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 100:0 to 82:18) to obtain the title compound as a brown oily substance (yield: 4.31 g, yield: 92%). 1 1H-NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.0 Hz, 1H), 6.48 - 6.45 (m, 2H), 3.59 (t, J = 6.8 Hz, 2H), 3.31 (t, J = 7.6 Hz, 2H), 2.93 (s, 3H), 2.50 (s, 3H), 1.54 - 1.46 (m, 4H), 1.32 (brs, 6H), 1.30 (s, 12H), 0.892 (s, 9H), 0.0436 (s, 6H). (Synthesis of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]-3-methylphenyl]thieno[3,2-b]thiophene-2-carbaldehyde)

[0318]

Chem.

[0319] Under an argon atmosphere, an aqueous solution of 2M potassium carbonate (2.1 mL) was added to a solution of 1-[3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methylaniline (0.207 g, 0.839 mmol) in 1,4-dioxane (6.5 mL), and the mixture was stirred. This was added to 5-bromothieno[3,2-b]thiophene-2-carboxaldehyde (0.479 g, 1.01 mmol), and argon gas was bubbled through the reaction solution for 15 minutes. Then, tetrakis(triphenylphosphine)palladium(0) (48.5 mg, 0.0420 mmol) was added, and argon gas was further bubbled through the reaction solution for 15 minutes. Thereafter, the temperature was raised to 90 °C and the mixture was stirred for 22 hours, and water (12 mL) was added to stop the reaction. This was extracted with chloroform (15 mL × 3), and the obtained organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The obtained residue was dissolved in chloroform and filtered through silica gel (50 mL), and eluted slowly with chloroform (200 mL). The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (hexane:ethyl acetate = 94:6 to 73:27) to obtain the title compound as a brown oily substance (yield: 370 mg, yield: 85%). 1 1H-NMR (400 MHz, CDCl3): δ 9.94 (s, 1H), 7.89 (d, J = 0.6 Hz, 1H), 7.34 - 7.31 (m, 1H), 7.18 (d, J = 0.6 Hz, 1H), 6.58 - 6.56 (m, 2H), 3.60 (t, J = 6.6 Hz, 2H), 3.34 (t, J = 7.8 Hz, 2H), 2.98 (s, 3H), 2.47 (s, 3H), 1.64 - 1.49 (m, 4H), 1.35 (brs, 6H), 0.894 (s, 9H), 0.0471 (s, 6H). (Synthesis of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-3-methylphenyl-4-[5-[(E)-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0320] [Chemical formula]

[0321] Under an argon atmosphere, diethyl (4-nitrobenzyl)phosphonate (1.64 g, 5.99 mmol) was dissolved in tetrahydrofuran (20 mL) and cooled in ice. Sodium hydride (approx. 60% mineral oil dispersion, 668 mg, 11.1 mmol) was added thereto, and the mixture was stirred for 30 minutes under ice cooling. Subsequently, a solution of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]-3-methylphenyl]thieno[3,2-b]thiophene-2-carbaldehyde (2.21 g, 4.28 mmol) in tetrahydrofuran (54 mL) was added, and after returning to room temperature and stirring for 1 hour, water (80 mL) was added to stop the reaction. The precipitated solid was collected by filtration, washed with water and hexane, and then reprecipitated with chloroform / methanol to obtain a reddish-brown solid (yield: 2.13 g, yield: 78%) of the title compound. 1 1H-NMR (400 MHz, CDCl3): δ 8.21 (d, J = 8.8 Hz, 2H), 7.59 (d, J = 8.8 Hz, 2H), 7.44 (d, J = 16.0 Hz, 1H), 7.33 - 7.30 (m, 1H), 7.29 (s, 1H), 7.10 (s, 1H), 6.91 (d, J = 16.0 Hz, 1H), 6.58 - 6.56 (m, 2H), 3.61 (t, J = 7.02 Hz, 2H), 3.34 (t, J = 7.41 Hz, 2H), 2.97 (s, 3H), 2.47 (s, 3H), 1.64 - 1.49 (m, 4H), 1.35 (brs, 6H), 0.896 (s, 9H), 0.0495 (s, 6H). (Synthesis of N-(7-hydroxyheptyl)-N-methyl-3-methylphenyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0322] [Chemical formula]

[0323] N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-3-methylphenyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (1.99 g, 3.13 mmol) was suspended in a mixed solvent of dichloromethane / methanol (volume ratio 3:1, 137 mL), and a 1,4-dioxane solution of 4 M hydrogen chloride (33 mL) was added. The mixture was stirred at room temperature for 1.5 hours. The reaction solution was concentrated under reduced pressure, 1 M aqueous sodium hydroxide solution (100 mL) was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was washed with water and hexane and dried under reduced pressure to obtain the title compound as a black solid (yield: 1.51 g, yield: 93%). 1 H-NMR (400 MHz, CDCl3): δ 8.21 (d, J = 8.8 Hz, 2H), 7.59 (d, J = 8.8 Hz, 2H), 7.44 (d, J = 16 Hz, 1H), 7.33 - 7.31 (m, 1H), 7.29 (s, 1H), 7.10 (s, 1H), 6.91 (d, J = 16 Hz, 1H), 6.58 - 6.55 (m, 2H), 3.65 (dt, J = 5.3, 6.7 Hz, 2H), 3.34 (t, J = 7.3 Hz, 2H), 2.98 (s, 3H), 2.47 (s, 3H), 1.65 - 1.54 (m, 4H), 1.38 (brs, 6H), 1.20 (t, J = 5.3 Hz, 1H). As a result of measuring the TG-DTA of the obtained compound (compound 5, 5.94 mg), the 5% weight loss temperature was 316 °C. [Example 6 of Heterocyclic Compound] (Synthesis of N-(4-bromo-3-hydroxyphenyl)acetamide)

[0324] [Chemical formula]

[0325] Under an argon atmosphere, 3-(acetamido)phenol (5.04 g, 33.3 mmol) was dissolved in a mixed solvent of dichloromethane / methanol (volume ratio 1:1, 330 mL), and benzyltrimethylammonium tribromide (13.6 g, 35.0 mmol) was added little by little. After stirring at room temperature for 30 minutes, water (200 mL) was added to stop the reaction, and the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography (hexane:ethyl acetate = 36:64 to 15:85) to obtain a white solid of the title compound (yield: 3.97 g, yield: 52%). 1 H-NMR (400 MHz, DMSO): δ10.2 (brs, 1H), 9.95 (s, 1H), 7.47 (d, J = 2.3 Hz, 1H), 7.34 (d, J = 8.8 Hz, 1H), 6.87 (dd, J = 2.3, 8.8 Hz, 1H), 2.03 (s, 3H). (Synthesis of N-(4-bromo-3-benzyloxyphenyl)acetamide)

[0326]

Chemical Structure

[0327] Under an argon atmosphere, potassium carbonate (3.26 g, 23.6 mmol) and benzyl bromide (1.4 mL, 11.8 mmol) were added to a solution of N-(4-bromo-3-hydroxyphenyl)acetamide (2.71 g, 11.8 mmol) in DMF (24 mL), and the mixture was stirred at room temperature for 1.5 hours. Water (80 mL) was added to stop the reaction, and the precipitated solid was collected by filtration to obtain a white solid of the title compound (yield: 3.55 g, yield: 94%). 1 H-NMR (400 MHz, DMSO-d6): δ10.1 (s, 1H), 7.56 (d, J = 2.2 Hz, 1H), 7.50 - 7.48 (m, 3H), 7.44 - 7.40 (m, 2H), 7.37 - 7.33 (m, 1H), 7.12 (dd, J = 2.2, 8.6 Hz, 1H), 5.15 (s, 2H), 2.04 (s, 3H). (Synthesis of N-(4-bromo-3-benzyloxyphenyl)-N-methylacetamide)

[0328] [Chemistry]

[0329] Under an argon atmosphere, methyl iodide (0.83 mL, 13.3 mmol) was added to a solution of N-(4-bromo-3-benzyloxyphenyl)acetamide (3.55 g, 11.1 mmol) in DMF (28 mL), and the mixture was cooled in ice. Sodium hydride (about 60% mineral oil dispersion, 0.799 g, 13.3 mmol) was added thereto, and the temperature was raised to room temperature and stirred for one and a half hours. Water (90 mL) was added to stop the reaction, and the precipitated solid was washed with water and hexane. The obtained solid was purified by silica gel column chromatography (hexane:ethyl acetate = 50:50 to 29:71) to obtain a white solid of the title compound (yield: 3.36 g, yield: 91%). 1 H-NMR (400 MHz, CDCl3): δ 7.59 (d, J = 8.3 Hz, 1H), 7.46 - 7.44 (m, 2H), 7.41 - 7.37 (m, 2H), 7.34 - 7.31 (m, 1H), 6.70 - 6.68 (m, 2H), 5.18 (s, 2H), 3.20 (s, 3H), 1.76 (s, 3H). (Synthesis of 4-bromo-3-benzyloxy-N-methylaniline)

[0330] [Chemistry]

[0331] To a solution of N-(4-bromo-3-benzyloxyphenyl)-N-methylacetamide (3.26 g, 9.76 mmol) in ethanol (80 mL) was added 6 M aqueous sodium hydroxide solution (19.5 mL, 117 mmol), and the mixture was refluxed for 6 hours. The reaction solution was concentrated under reduced pressure, water (80 mL) was added, and the mixture was extracted with ethyl acetate (80 mL × 3). The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 96:4 to 75:25) to obtain a brown oil of the title compound (yield: 2.70 g, yield: 95%). 1H-NMR (400 MHz, CDCl3): δ 7.49 - 7.47 (m, 2H), 7.40 - 7.36 (m, 2H), 7.33 - 7.28 (m, 2H), 6.20 (d, J = 2.5 Hz, 1H), 6.12 (dd, J = 8.5, 2.5 Hz, 1H), 5.11 (s, 2H), 3.72 (brs, 1H), 2.78 (s, 3H). (Synthesis of 4-Bromo-N-(7-hydroxyheptyl)-3-benzyloxy-N-methylaniline)

[0332] [Chemical Formula]

[0333] Under an argon atmosphere, 7-bromo-1-heptanol (55 μL, 0.356 mmol) was added to a suspension of 4-bromo-3-benzyloxy-N-methylaniline (0.114 g, 0.391 mmol), potassium carbonate (98.3 mg, 0.711 mmol), and sodium iodide (27.0 mg, 0.180 mmol) in acetonitrile (0.4 mL), and the mixture was refluxed for 22 hours. After cooling to room temperature, water (5 mL) was added to stop the reaction, and then the mixture was extracted with ethyl acetate (5 mL × 3). The obtained organic layer was washed with saturated brine (10 mL × 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 77:23 - 56:44) to obtain the title compound as a brown oil (yield: 24.8 mg, yield rate: 76%). 1 H-NMR (400 MHz, CDCl3): δ 7.49 - 7.47 (m, 2H), 7.40 - 7.36 (m, 2H), 7.32 - 7.29 (m, 2H), 6.23 (d, J = 2.8 Hz, 1H), 6.18 (dd, J = 9.3, 2.8 Hz, 1H), 5.14 (s, 2H), 3.64 (t, J = 6.6 Hz, 2H), 3.21 (t, J = 7.4 Hz, 2H), 2.86 (s, 3H), 1.59 - 1.45 (m, 4H), 1.39 - 1.26 (m, 6H). (Synthesis of 4-Bromo-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-3-benzyloxy-N-methylaniline)

[0334]

Chem.

[0335] Under an argon atmosphere, imidazole (0.711 g, 10.4 mmol) and tert-butyldimethylchlorosilane (1.18 g, 7.83 mmol) were sequentially added to a solution of 4-bromo-N-(7-hydroxyheptyl)-3-benzyloxy-N-methylaniline (2.12 g, 5.22 mmol) in DMF (15 mL), and the mixture was stirred for 1 hour. Water (50 mL) was added to stop the reaction, and the mixture was extracted with a mixed solvent of hexane / ethyl acetate (volume ratio 4:1, 50 mL × 3). The obtained organic layer was washed with water (150 mL) and saturated brine (150 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 100:0 to 92:8) to obtain the title compound as a pale yellow oil (yield: 2.68 g, yield: 99%). 1 1H-NMR (400 MHz, CDCl3): δ 7.49 - 7.47 (m, 2H), 7.40 - 7.36 (m, 2H), 7.32 - 7.29 (m, 2H), 6.23 (d, J = 2.7 Hz, 1H), 6.17 (dd, J = 8.8, 2.7 Hz, 1H), 5.14 (s, 2H), 3.60 (t, J = 6.6 Hz, 2H), 3.20 (t, J = 7.7 Hz, 2H), 2.86 (s, 3H), 1.54 - 1.44 (m, 4H), 1.29 (brs, 6H), 0.892 (s, 9H), 0.0444 (s, 6H). (Synthesis of 1-[3-benzyloxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methylaniline)

[0336]

Chem.

[0337] Under an argon atmosphere, a solution of 4-bromo-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-3-benzyloxy-N-methylaniline (8.64 g, 16.6 mmol) in THF (70 mL) was cooled to -78 °C. To this was added dropwise a 1.6 M hexane solution of n-butyllithium (13.2 mL, 19.9 mmol), and the mixture was stirred for 1 hour. Then, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.7 mL, 23.2 mmol) was added dropwise, and after stirring for 30 minutes, the temperature was raised to room temperature and the mixture was stirred for 2 hours. After completion of the reaction, water (140 mL) was added under ice-cooling to stop the reaction, and the mixture was extracted with a mixed solvent of hexane / ethyl acetate (volume ratio 1:1, 140 mL × 3). The obtained organic layer was washed with saturated brine (500 mL), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 100:0 to 85:15) to obtain the title compound as a brown oily substance (yield: 7.87 g, yield: 84%). 1 1H-NMR (400 MHz, CDCl3): δ 7.65 (d, J = 7.4 Hz, 2H), 7.59 (d, J = 8.4 Hz, 1H), 7.36 (t, J = 7.4 Hz, 2H), 7.28 (d, J = 7.4 Hz, 1H), 6.28 (dd, J = 8.4, 2.2 Hz, 1H), 6.18 (d, J = 2.2 Hz, 1H), 5.12 (s, 2H), 3.59 (t, J = 6.6 Hz, 2H), 3.31 (t, J = 7.5 Hz, 2H), 2.95 (s, 3H), 1.55 - 1.48 (m, 4H), 1.32 (brs, 6H), 0.890 (s, 9H), 0.0431 (s, 6H). Synthesis of (5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]-3-benzyloxyphenyl]thieno[3,2-b]thiophene-2-carbaldehyde)

[0338]

Chemical formula

[0339] Under an argon atmosphere, 2M aqueous potassium carbonate solution (15.8 mL) was added to a solution of 1-[3-benzyloxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methylaniline (4.58 g, 8.06 mmol) in 1,4-dioxane (48 mL), and the mixture was stirred. This was added to 5-bromothieno[3,2-b]thiophene-2-carboxaldehyde (1.53 g, 6.20 mmol), and then argon gas was bubbled through the reaction solution for 15 minutes. Next, tetrakis(triphenylphosphine)palladium(0) (0.358 g, 0.310 mmol) was added, and argon gas was further bubbled through the reaction solution for 15 minutes. The reaction solution was heated to 90 °C and stirred for 29 hours, water (100 mL) was added, and the mixture was extracted with chloroform (100 mL × 3). The obtained organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The residue was dissolved in chloroform, filtered through silica gel (250 mL), and slowly eluted with chloroform (800 mL). The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate = 95:5 to 74:26) to obtain the title compound as a yellow solid (yield: 2.43 g, yield: 65%). 1 1H-NMR (400 MHz, CDCl3): δ 9.89 (s, 1H), 7.84 (d, J = 0.5 Hz, 1H), 7.58 (d, J = 0.5 Hz, 1H), 7.54 (d, J = 8.8 Hz, 1H), 7.50 - 7.48 (m, 2H), 7.42 - 7.38 (m, 2H), 7.37 - 7.34 (m, 1H), 6.34 (dd, J = 8.8, 2.4 Hz, 1H), 6.25 (d, J = 2.4 Hz, 1H), 5.24 (s, 2H), 3.60 (t, J = 6.5 Hz, 2H), 3.29 (t, J = 7.4 Hz, 2H), 2.95 (s, 3H), 1.51 (brs, 4H), 1.31 (brs, 6H), 0.893 (s, 9H), 0.0473 (s, 6H). (Synthesis of N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-3-benzyloxyphenyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0340] [Chem.]

[0341] Under an argon atmosphere, diethyl (2-methyl-4-nitrobenzyl)phosphonate (2.50 g, 8.71 mmol) was dissolved in tetrahydrofuran (31 mL) and cooled in ice. Sodium hydride (approx. 60% mineral oil dispersion, 0.97 g, 16.2 mmol) was added thereto, and the mixture was stirred for 30 minutes under ice-cooling. Then, a solution of 5-[4-[[7-[(tert-butyldimethylsilyl)oxy]heptyl](methyl)amino]-3-benzyloxyphenyl]thieno[3,2-b]thiophene-2-carbaldehyde (3.78 g, 6.22 mmol) in tetrahydrofuran (78 mL) was added, and after returning to room temperature and stirring for 1 hour, water (200 mL) was added to stop the reaction. The precipitated solid was collected by filtration, washed with water and hexane, and then reprecipitated with chloroform / methanol to obtain a brown solid (yield: 3.30 g, yield: 72%) of the title compound. 1 H-NMR (400 MHz, CDCl3): δ 8.05 - 8.03 (m, 2H), 7.68 (d, J = 9.4 Hz, 1H), 7.52 - 7.50 (m, 3H), 7.49 (s, 1H), 7.42 - 7.38 (m, 2H), 7.36 - 7.32 (m, 2H), 7.25 (s, 1H), 7.03 (d, J = 15.8 Hz, 1H), 6.34 (dd, J = 8.8, 2.3 Hz, 1H), 6.26 (d, J = 2.3 Hz, 1H), 5.23 (s, 2H), 3.60 (t, J = 6.6 Hz, 2H), 3.28 (t, J = 7.8 Hz, 2H), 2.94 (s, 3H), 2.51 (s, 3H), 1.52 (brs, 4H), 1.31 (brs, 6H), 0.896 (s, 9H), 0.0492 (s, 6H). (Synthesis of N-(7-hydroxyheptyl)-N-methyl-3-benzyloxyphenyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline)

[0342] [Chem.]

[0343] N-[7-[(tert-butyldimethylsilyl)oxy]heptyl]-N-methyl-3-benzyloxyphenyl-4-[5-[(E)-2-methyl-4-nitrostyryl]thieno[3,2-b]thiophen-2-yl]aniline (2.97 g, 4.01 mmol) was suspended in a mixed solvent of dichloromethane / methanol (volume ratio 3:1, 176 mL), 4 M hydrogen chloride in 1,4-dioxane solution (42 mL) was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure, 1 M aqueous sodium hydroxide solution (30 mL) was added to the residue, and the precipitated solid was collected by filtration. The obtained solid was washed with water and hexane and dried under reduced pressure. The obtained solid was washed with hexane and dried to obtain a brown solid of the title compound (yield: 2.42 g, yield: 96%). 1 1H-NMR (400 MHz, CDCl3): δ 8.05 - 8.03 (m, 2H), 7.68 (d, J = 9.4 Hz, 1H), 7.52 - 7.50 (m, 3H), 7.49 (s, 1H), 7.42 - 7.38 (m, 2H), 7.36 - 7.31 (m, 2H), 7.25 (s, 1H), 7.03 (d, J = 15.8 Hz, 1H), 6.34 (dd, J = 8.8, 2.4 Hz, 1H), 6.27 (d, J = 2.4 Hz, 1H), 5.23 (s, 2H), 3.65 (dt, J = 5.4, 6.6 Hz, 2H), 3.29 (t, J = 7.5 Hz, 2H), 2.95 (s, 3H), 2.51 (s, 3H), 1.61 - 1.50 (m, 4H), 1.39 - 1.29 (m, 6H), 1.21 (t, J = 5.4 Hz, 1H). As a result of measuring the TG-DTA of the obtained compound (compound 6, 5.63 mg), the 5% weight loss temperature was 279 °C. (Comparative Example - 1) Evaluation of Compound NEO-823

[0344] [Chemical Structure Diagram]

[0345] Using NEO-823 (manufactured by Tokyo Chemical Industry Co., Ltd.), a commercially available organic electro-optical material, TG-DTA was measured. As a result, the 5% weight loss temperature was 237 °C.

[0346] From the above results, Compound (1) of the present invention has a higher decomposition temperature and excellent heat resistance compared to the conventionally known organic electro-optical material shown in Comparative Example-1. [Polymer Example 1]

[0347] [Chemical Formula]

[0348] A mixture of methyl methacrylate (10.0 g, 100 mmol), 2-isocyanatoethyl methacrylate (2.37 g, 15.3 mmol), azobisisobutyronitrile (568 mg, 3.46 mmol), and toluene (20 mL) was freeze-degassed and then reacted at 60 °C for 2 hours under a nitrogen atmosphere. With stirring, the reaction mixture was added to diisopropyl ether (500 mL), and the resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and vacuum-dried at 40 °C for 5 hours to obtain 6 g of a base polymer (1P).

[0349] Under a nitrogen atmosphere, a mixture of the base polymer (1P) (1.5 g) obtained above, methanol (4.5 mL), dibutyltin dilaurate (50 μL), and tetrahydrofuran (52.5 mL) was reacted at 60 °C for 2 hours. With stirring, the reaction mixture was added to diisopropyl ether (500 mL). The resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and vacuum-dried at 60 °C for 5 hours to obtain 1.5 g of a methyl carbamate-containing polymer (1P-Me). The molecular weight of (1P-Me) is shown in Table 1.

[0350] In a nitrogen atmosphere, a mixture of the base polymer (1P) (500 mg) obtained above, compound 1 (214 mg), dibutyltin dilaurate (20 μL), and tetrahydrofuran (18.7 mL) was reacted at 60 °C for 3 hours. Then, methanol (1 mL) and dibutyltin dilaurate (10 μL) were added and the reaction was continued for another 45 minutes. With stirring, the reaction mixture was added to diisopropyl ether (300 mL). The resulting solid was filtered off using a Kiriyama funnel. The obtained solid was washed with a diisopropyl ether-tetrahydrofuran mixed solvent (9:1) (100 mL) and diisopropyl ether (200 mL), and dried under vacuum at 60 °C for 5 hours to obtain 0.7 g of the polymer containing compound 1 (1P-compound 1). [Polymer Example 2]

[0351] [Chemical Structure]

[0352] A mixture of methyl methacrylate (10.0 g, 100 mmol), 2-isocyanatoethyl methacrylate (1.96 g, 12.6 mmol), azobisisobutyronitrile (554 mg, 3.40 mmol), and toluene (19.5 mL) was freeze-degassed and then reacted at 60 °C for 2 hours under a nitrogen atmosphere. With stirring, the reaction mixture was added to diisopropyl ether (500 mL). The resulting solid was filtered off using a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and dried under vacuum at 40 °C for 5 hours to obtain 6 g of the base polymer (2P).

[0353] In a nitrogen atmosphere, a mixture of the base polymer (2P) (1.5 g) obtained above, methanol (4.5 mL), dibutyltin dilaurate (50 μL), and tetrahydrofuran (52.5 mL) was reacted at 60 °C for 2 hours. With stirring, the reaction mixture was added to diisopropyl ether (500 mL). The resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and dried under vacuum at 60 °C for 5 hours to obtain 1.5 g of a methylcarbamate-containing polymer (2P-Me). The molecular weight of (2P-Me) is shown in Table 1.

[0354] In a nitrogen atmosphere, a mixture of the base polymer (2P) (541 mg) obtained above, compound 3 (200 mg), dibutyltin dilaurate (20 μL), and tetrahydrofuran (20.2 mL) was reacted at 60 °C for 3 hours. Then, methanol (1 mL) and dibutyltin dilaurate (10 μL) were added and the reaction was continued for another 45 minutes. With stirring, the reaction mixture was added to diisopropyl ether (300 mL). The resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with a diisopropyl ether-tetrahydrofuran mixed solvent (9:1) (100 mL) and diisopropyl ether (200 mL), and dried under vacuum at 60 °C for 5 hours to obtain 0.5 g of a compound 3-containing polymer (2P-compound 3). The glass transition temperature of (2P-compound 3) measured by DSC was 109 °C. [Polymer Example 3]

[0355] [Chemical formula]

[0356] A mixture of methyl methacrylate (10.0 g, 100 mmol), 2-isocyanatoethyl methacrylate (1.03 g, 6.62 mmol), azobisisobutyronitrile (525 mg, 3.19 mmol), and toluene (18.5 mL) was freeze-degassed and then reacted at 60 °C for 2 hours under a nitrogen atmosphere. With stirring, the reaction mixture was added to diisopropyl ether (500 mL), and the resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and dried under vacuum at 40 °C for 5 hours to obtain 5 g of a base polymer (3P).

[0357] Under a nitrogen atmosphere, a mixture of the base polymer (3P) (2.00 g) obtained above, methanol (4.5 mL), dibutyltin dilaurate (50 μL), and tetrahydrofuran (52.5 mL) was reacted at 60 °C for 2 hours. With stirring, the reaction mixture was added to diisopropyl ether (500 mL). The resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and dried under vacuum at 60 °C for 5 hours to obtain 970 mg of a methyl carbamate-containing polymer (3P-Me). The molecular weight of (3P-Me) is shown in Table 1.

[0358] Under a nitrogen atmosphere, a mixture of the base polymer (3P) (2.00 g) obtained above, compound 4 (500 mg), dibutyltin dilaurate (67 μL), and tetrahydrofuran (18.7 mL) was reacted at 60 °C for 3 hours, then methanol (4 mL) and dibutyltin dilaurate (33 μL) were added and the reaction was continued for an additional 45 minutes. With stirring, the reaction mixture was added to diisopropyl ether (300 mL). The resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with a diisopropyl ether-tetrahydrofuran mixed solvent (9:1) (100 mL) and diisopropyl ether (200 mL), and dried under vacuum at 60 °C for 5 hours to obtain 2.2 g of a compound 4-containing polymer (3P-compound 4). [Polymer Example 4]

[0359] [Chemical Formula]

[0360] A mixture of methyl methacrylate (10.0 g, 100 mmol), 2-isocyanatoethyl methacrylate (1.15 g, 7.41 mmol), azobisisobutyronitrile (529 mg, 3.22 mmol), and toluene (18.6 mL) was freeze-degassed and then reacted at 60 °C for 2 hours under a nitrogen atmosphere. With stirring, the reaction mixture was added to diisopropyl ether (500 mL), and the resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and vacuum dried at 40 °C for 5 hours to obtain 5 g of a base polymer (4P).

[0361] Under a nitrogen atmosphere, a mixture of the base polymer (4P) (1.5 g) obtained above, methanol (4.5 mL), dibutyltin dilaurate (50 μL), and tetrahydrofuran (52.5 mL) was reacted at 60 °C for 2 hours. With stirring, the reaction mixture was added to diisopropyl ether (500 mL). The resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with diisopropyl ether (300 mL) and vacuum dried at 60 °C for 5 hours to obtain 1.5 g of a methyl carbamate-containing polymer (4P-Me). The molecular weight of (4P-Me) is shown in Table 1.

[0362] Under a nitrogen atmosphere, a mixture of the base polymer (4P) (1.50 g) obtained above, compound 6 (500 mg), dibutyltin dilaurate (50 μL), and tetrahydrofuran (56 mL) was reacted at 60 °C for 3 hours, and then methanol (3 mL) and dibutyltin dilaurate (25 μL) were added and the reaction was continued for an additional 45 minutes. With stirring, the reaction mixture was added to diisopropyl ether (300 mL). The resulting solid was filtered off through a Kiriyama funnel. The obtained solid was washed with a diisopropyl ether-tetrahydrofuran mixed solvent (9:1) (100 mL) and diisopropyl ether (200 mL), and vacuum dried at 60 °C for 5 hours to obtain 1.7 g of a compound 6-containing polymer (4P-compound 6).

[0363]

Table 1

[0364] [Calculation of Hyperpolarizability of Compounds] The hyperpolarizability β, which is an index of electro-optical properties, was calculated for compounds compound 1 to compound 6 and compound NEO-823. The hyperpolarizability β by calculation was calculated by Gaussian16, a quantum chemical calculation program manufactured by Gaussian. First, a structure optimization calculation was performed under the B3LYP / 6-31G(d,p) condition. Further, for the optimized structure, frequency calculation and polarizability calculation were performed under the LC-ωHPBE / 6-311++G** condition to calculate the hyperpolarizability β. In addition, for reducing the calculation load, the calculation was performed using as a model a structure in which two alkyl side chains bonded to the amino group were replaced with butyl groups. The results are shown in Table 2.

[0365]

Table 2

Industrial Applicability

[0366] By using the heterocyclic compound excellent in heat resistance of the present invention, an organic EO material and a device excellent in heat resistance can be produced. Therefore, the present invention has high industrial applicability.

Claims

1. A heterocyclic compound represented by the following formula (1). 【Chemical 1】 [In formula (1), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent. R １ and R ２ are each independently an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R ２１ -OH (where R ２１ represents a divalent hydrocarbon group), -R ２２ -NH ２ (where R ２２ represents a divalent hydrocarbon group), -R ２３ -SH (where R ２３ represents a divalent hydrocarbon group), or -R ２４ -NCO (where R ２４ represents a divalent hydrocarbon group). These groups may have a crosslinkable group. R １ and R ２ may be bonded to each other to form a ring together with the atoms to which each is attached. R ３ and R ４ each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R ３１ -OH (where R ３１ represents a divalent hydrocarbon group.), -O-R ３２ -OH (where R ３２ represents a divalent hydrocarbon group.), -R ３３ -NH ２ (where R ３３ represents a divalent hydrocarbon group.), -R ３４ -SH (where R ３４ represents a divalent hydrocarbon group.), -R ３５ -NCO (where R ３５ represents a divalent hydrocarbon group.), or -OC(=O)R ５ (where R ５ represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. When there are a plurality of R ３ and R ４ , they may be the same or different. R ３ may be bonded to R １ or R ２ to form a ring together with the atoms to which they are attached, respectively. k and m each independently represent an integer of 0 to 4. ]

2. The heterocyclic compound according to Claim 1, wherein Q is represented by the following formulas (a1) to (a10). [Chemical Formula 2] [R ６ , R ７ and R ８ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a cyano group, an aryl group, or a haloaryl group. * indicates the bonding position to other structural units.]

3. R ６ , R ７ and R ８ is a hydrogen atom or a methyl group, the heterocyclic compound according to claim 2.

4. R ３ The heterocyclic compound according to claim 1, wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

5. R ４ The heterocyclic compound according to claim 1, wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

6. R ３ 、 and R ４ is a hydrogen atom, the heterocyclic compound according to claim 1.

7. R １ is an optionally branched alkyl group having 1 to 12 carbon atoms, an optionally branched haloalkyl group having 1 to 12 carbon atoms, an optionally branched acyloxyalkyl group having 1 to 12 carbon atoms, -R ２１ -OH (R ２１ represents a divalent hydrocarbon group.), -R ２２ -NH ２ (R ２２ represents a divalent hydrocarbon group.), -R ２３ -SH (R ２３ represents a divalent hydrocarbon group.), or -R ２４ -NCO (R ２４ represents a divalent hydrocarbon group.), the heterocyclic compound according to claim 1.

8. R １ is -R ２１ -OH (wherein R ２１ represents a divalent hydrocarbon group.), the heterocyclic compound according to claim 1.

9. A heterocyclic compound represented by the following formulas (1A) to (1C). [Chemical Formula 3] [In formulas (1A) to (1C), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent. R １ is an alkyl group, haloalkyl group, acyloxyalkyl group, trialkylsilyloxyalkyl group, aryldialkylsilyloxyalkyl group, alkyldiarylsilyloxyalkyl group, aryl group, aralkyl group, -R ２１ -OH (where R ２１ represents a divalent hydrocarbon group.), -R ２２ -NH ２ (where R ２２ represents a divalent hydrocarbon group.), -R ２３ -SH (where R ２３ represents a divalent hydrocarbon group.), or -R ２４ -NCO (where R ２４ represents a divalent hydrocarbon group.). These groups may have a crosslinkable group. R ３ and R ４ each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R ３１ -OH (where R ３１ represents a divalent hydrocarbon group.), -O-R ３２ -OH (where R ３２ represents a divalent hydrocarbon group.), -R ３３ -NH ２ (where R ３３ represents a divalent hydrocarbon group.), -R ３４ -SH (where R ３４ represents a divalent hydrocarbon group.), -R ３５ -NCO (where R ３５ represents a divalent hydrocarbon group.), or -OC(=O)R ５ (where R ５ represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. When there are a plurality of R ３ and R ４ , they may be the same or different. R ３ may be bonded to R １ to form a ring together with the atoms to which they are attached, respectively. k and m each independently represent an integer of 0 to 4. Sp １ 、Sp ２ 、and Sp ３ each independently represents a single bond or an alkylene group which may be branched and has 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR ｂ２ or a halogen atom, and -CH ２ - in the alkylene group may each independently be substituted with -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR ｆ -C(=O)-, and the methine groups contained in the alkylene group may be substituted with a nitrogen atom. R ｂ and R ｆ may be the same as or different from each other and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. A, B, and C each independently represent a monocyclic aromatic ring, polycyclic aromatic ring, condensed aromatic ring, aliphatic hydrocarbon ring, or trivalent hydrocarbon group having constituent atoms selected from the group consisting of a carbon atom, nitrogen atom, oxygen atom, and sulfur atom. These monocyclic aromatic rings, polycyclic aromatic rings, condensed aromatic rings, aliphatic hydrocarbon rings, and trivalent hydrocarbon groups may have substituents, and the hydrogen atoms contained in the trivalent hydrocarbon group may be substituted with -OR ｂ or a halogen atom, and -CH ２ - in the hydrocarbon group may each independently be substituted with -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR ｆ -C(=O)-, and the methine group contained in the hydrocarbon group may be substituted with a nitrogen atom.]

10. A composition containing the heterocyclic compound according to any one of Claims 1 to 9 and a polymer.

11. The composition according to Claim 10, wherein the polymer is at least one selected from the group consisting of poly(meth)acrylate, polyester, polyamide, polyimide, polycarbonate, polystyrene, polysulfone, polyethersulfone, polymaleimide, silicone resin, and epoxy resin.

12. A polymer having a structure represented by the following formula (1‘). 【Chemical Formula 4】 [In formula (1‘), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent. R １ represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, an aryl group, an aralkyl group, -R ２１ -OH (where R ２１ represents a divalent hydrocarbon group.), -R ２２ -NH ２ (where R ２２ represents a divalent hydrocarbon group.), -R ２３ -SH (where R ２３ represents a divalent hydrocarbon group.), or -R ２４ -NCO (where R ２４ represents a divalent hydrocarbon group.). These groups may have a crosslinkable group. R ３ and R ４ each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R ３１ -OH (where R ３１ represents a divalent hydrocarbon group), -O-R ３２ -OH (where R ３２ represents a divalent hydrocarbon group), -R ３３ -NH ２ (where R ３３ represents a divalent hydrocarbon group), -R ３４ -SH (where R ３４ represents a divalent hydrocarbon group), -R ３５ -NCO (where R ３５ represents a divalent hydrocarbon group), or -OC(=O)R ５ (where R ５ represents a monovalent hydrocarbon group). These groups may have a crosslinkable group. When there are a plurality of R ３ and R ４ , they may be the same or different. R ３ may be bonded to R １ to form a ring together with the atoms to which they are respectively bonded. k and m each independently represent an integer of 0 to 4. Sp １ represents a single bond or an alkylene group which may be branched and has 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR ｂ２ or a halogen atom, and -CH ２ - in the alkylene group may each independently be substituted with -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR ｆ -C(=O)-, and the methine group contained in the alkylene group may be substituted with a nitrogen atom. R ｂ and R ｆ may be the same as or different from each other and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. PM represents a polymer. ]

13. The polymer according to Claim 12, wherein Q is represented by the following formulas (a1) to (a10). 【Chemical Formula 5】 [R ６ , R ７ and R ８ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a cyano group, an aryl group, or a haloaryl group. * indicates the bonding position to other structural units.]

14. The polymer according to Claim 12, wherein PM is any one of poly(meth)acrylate, polyester, polyimide, and polymaleimide.

15. A method for producing a heterocyclic compound represented by the following formula (1-1), which comprises a step of subjecting a heterocyclic compound represented by the following formula (2) to a deprotection reaction. ​ [In formulas (2) and (1-1), Q represents a divalent monocyclic or condensed heterocyclic ring which may have a substituent. R ８ represents an alkyl group, a haloalkyl group, an acyloxyalkyl group, a trialkylsilyloxyalkyl group, an aryldialkylsilyloxyalkyl group, an alkyldiarylsilyloxyalkyl group, or an aryl group. These groups may have a crosslinkable group. R ３ and R ４ each independently represents a hydrogen atom, an alkyl group, an alkyloxy 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 isocyanato group, -R ３１ -OH (where R ３１ represents a divalent hydrocarbon group.), -O-R ３２ -OH (where R ３２ represents a divalent hydrocarbon group.), -R ３３ -NH ２ (where R ３３ represents a divalent hydrocarbon group.), -R ３４ -SH (where R ３４ represents a divalent hydrocarbon group.), -R ３５ -NCO (where R ３５ represents a divalent hydrocarbon group.), or -OC(=O)R ５ (where R ５ represents a monovalent hydrocarbon group.). These groups may have a crosslinkable group. R ３ and R ４ When there are a plurality of them, they may be the same or different. R ３ may be bonded to R ８ to form a ring together with the atoms to which they are respectively bonded. k and m each independently represent an integer of 0 to 4. Sp ４ represents a single bond or an alkylene group which may be branched and has 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted with -OR ｂ or a halogen atom, and -CH ２ - in the alkylene group may each independently be substituted with -O-, -S-, -C(=O)O-, -C(=O)-, -NHC(=O)O-, -OC(=O)O-, or -NR ｆ -C(=O)-, and the methine group contained in the alkylene group may be substituted with a nitrogen atom. R ｂ 、 and R ｆ may be the same as or different from each other, and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. X represents -NH-, -O-, or -NHC(=O)-. PG represents a protecting group. Y represents a hydroxy group, an amino group, or an isocyanato group. ]

16. The production method according to Claim 15, wherein PG is a group represented by the following chemical formulas (Pg-1) to (Pg-19). 【Chemical Formula 7】

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