WO2024075537A1

WO2024075537A1 - Reactive compound, production method for polymer compound, and intermediate

Info

Publication number: WO2024075537A1
Application number: PCT/JP2023/034320
Authority: WO
Inventors: 柾律阿部; 優季横井; 貴史荒木
Original assignee: 住友化学株式会社
Priority date: 2022-10-06
Filing date: 2023-09-21
Publication date: 2024-04-11
Also published as: JP2024055217A

Abstract

The present invention addresses the problem of providing a reactive compound having excellent storage stability.　The present invention relates to a reactive compound represented by formula (1). (In formula (1), Ar₁ denotes an aromatic hydrocarbon cyclic group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings, Ar₂ denotes an aromatic hydrocarbon cyclic group, X denotes a group represented by -O- or a group represented by -NH-, Y denotes a group represented by -O-, a group represented by -NH-, a group represented by -O-CH₂-, a group represented by -CH₂-NH-, a group represented by -NH-C(=O)-, or a group represented by -C(=O)-O-, and n denotes an integer from 1 to 4.)

Description

Reactive compounds, methods for producing polymeric compounds, and intermediates

This disclosure relates to reactive compounds, methods for producing polymer compounds, and intermediates.

Non-Patent Document 1 discloses a reactive compound represented by the following formula (A). Patent Document 1 discloses that a polymer compound is obtained by reacting the reactive compound represented by the following formula (A) with a compound represented by the following formula (B).

The reactive compounds may undergo decomposition reactions over time and may have poor storage stability.
Therefore, a problem to be solved by one embodiment of the present disclosure is to provide a reactive compound having excellent storage stability.
Another problem to be solved by another embodiment of the present disclosure is to provide a method for producing a polymer compound using a reactive compound having excellent storage stability.
Furthermore, a problem to be solved by another embodiment of the present disclosure is to provide an intermediate from which a reactive compound having excellent storage stability can be obtained.

Means for solving the above problems include the following means.
<1> A reactive compound represented by the following formula (1):

In formula (1),
Ar ₁ represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings;
_Ar2 represents an aromatic hydrocarbon ring group;
X represents a group represented by -O- or a group represented by -NH-;
Y represents a group represented by -O-, a group represented by -NH-, a group represented by -O-CH ₂ -, a group represented by -CH ₂ -NH-, a group represented by -NH-C(=O)- or a group represented by -C(=O)-O-;
n represents an integer of 1 or more and 4 or less.
<2> The reactive compound according to <1>, represented by the following formula (2):

In formula (2),
Ar ₁ represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings;
_Ar2 represents an aromatic hydrocarbon ring group;
X represents a group represented by -O- or a group represented by -NH-;
Y represents a group represented by -O-, a group represented by -NH-, a group represented by -O-CH ₂ -, a group represented by -CH ₂ -NH-, a group represented by -NH-C(=O)- or a group represented by -C(=O)-O-;
In the formula (2), two Ar ₂ , two X and two Y may be the same or different.
<3> The reactive compound according to <2>, wherein Ar ₁ is a group represented by the following formula (3) or the following formula (4):

In formula (3) and formula (4),
_Ar3 represents a carbocyclic group or a heterocyclic group;
* represents a bond.
<4> The reactive compound according to <2> or <3>, wherein Ar ₁ is a group represented by the following formula (5):

In formula (5),
Z represents a group represented by the following formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), or (Z-7):
* represents a bond.

In formulas (Z-1) to (Z-7),
* represents a bond,
R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent group, and may be the same or different.
<5> The reactive compound according to any one of <2> to <4>, wherein Ar ₁ is a group represented by the following formula (6):

In formula (6),
* represents a bond,
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent group, and may be the same or different.
<6> The reactive compound according to <2>, wherein the compound represented by formula (2) is a compound represented by the following formula (7), the following formula (8), the following formula (9), or the following formula (10).

In formulae (7) to (10), R ₁₂ and R ₁₃ each independently represent a hydrogen atom or a monovalent group, and may be the same or different.
<7> A method for producing a polymer compound, comprising reacting the reactive compound according to any one of <1> to <6> with a compound represented by the following formula (11):

In formula (11),
_Ar4 represents a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group;
Each HX independently represents a halogen atom.
<8> An intermediate of the reactive compound according to any one of <1> to <6>, represented by the following formula (12):

In formula (12),
Ar ₁ represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings;
L represents a hydrogen atom or a halogen atom;
n represents an integer of 1 or more and 4 or less.

According to one embodiment of the present disclosure, a reactive compound having excellent storage stability is provided.
According to another embodiment of the present disclosure, there is provided a method for producing a polymer compound using a reactive compound having excellent storage stability.
According to another embodiment of the present disclosure, there is provided an intermediate which provides a reactive compound having excellent storage stability.

Below, a compound according to one embodiment of the present invention will be described, and a photoelectric conversion element in which the compound according to one embodiment is used will be described. The present invention is not limited to the following description, and each component can be modified as appropriate without departing from the gist of the present invention.

First, terms commonly used in the following description will be explained.
A reactive compound according to the present disclosure is a compound that contains a reactive group.
The "reactive group" is a group represented by the following formula (R):

In formula (R), X, Y and _Ar2 are defined the same as X, Y and _Ar2 in formula (1), respectively, and * represents a bond.

The term "aromatic hydrocarbon ring group" refers to the atomic group remaining after removing one or more hydrogen atoms directly bonded to carbon atoms constituting an aromatic hydrocarbon ring which may be unsubstituted or substituted and which may have two or more condensed rings. For example, it may be referred to as a "p-valent aromatic hydrocarbon ring group" (p is an integer of 1 or more), in which case it refers to the atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms constituting an aromatic hydrocarbon ring which may have a substituent.
In addition, it may be referred to as an "aromatic hydrocarbon ring group having q rings condensed therein" (q is an integer of 2 or more), and in this case, it means an aromatic hydrocarbon ring group having q rings condensed therein.

The term "aromatic heterocyclic group" refers to an atomic group remaining after removing one or more hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting an aromatic heterocyclic ring, which may be unsubstituted or substituted and may have two or more condensed rings. For example, it may be referred to as a "p-valent aromatic heterocyclic group" (p is an integer of 1 or more), in which case it refers to an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting an aromatic heterocyclic ring, which may have a substituent.
In addition, it may be referred to as an "aromatic heterocyclic group having q rings condensed therein" (q is an integer of 2 or more), and in this case, it means an aromatic heterocyclic group having q rings condensed therein.

Examples of "substituent A" include a halogen atom, an alkyl group (including a cycloalkyl group), an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. Note that, in this specification, when referring to the number of carbon atoms, the number of carbon atoms does not usually include the number of carbon atoms of the substituent A.

Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

The alkyl group preferably has 1 or more and 50 or less carbon atoms, more preferably has 1 or more and 30 or less carbon atoms, and further preferably has 1 or more and 20 or less carbon atoms.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, a 2-ethylbutyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a cyclohexylmethyl group, a cyclohexylethyl group, an n-octyl group, a 2-ethylhexyl group, a 3-n-propylheptyl group, an adamantyl group, an n-decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-n-hexyl-decyl group, an n-dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.

The alkenyl group preferably has 2 or more and 30 or less carbon atoms, and more preferably has 3 or more and 20 or less carbon atoms.
Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenyl group, and a 7-octenyl group.

The alkynyl group preferably has 2 or more and 20 or less carbon atoms, and more preferably has 3 or more and 20 or less carbon atoms.
Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, and a 5-hexynyl group.

The alkoxy group preferably has 1 or more and 40 or less carbon atoms, and more preferably has 1 or more and 10 or less carbon atoms.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group, an n-decyloxy group, a 3,7-dimethyloctyloxy group, a 3-heptyldodecyloxy group, and a lauryloxy group.

The alkylthio group preferably has 1 or more and 40 or less carbon atoms, and more preferably has 1 or more and 10 or less carbon atoms.
Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

An aryl group is a monovalent aromatic hydrocarbon ring group.
The aryl group preferably has 6 or more and 30 or less carbon atoms, and more preferably has 6 or more and 20 or less carbon atoms.
Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, and a 4-phenylphenyl group.

The aryloxy group preferably has 6 or more and 60 or less carbon atoms, and more preferably has 6 or more and 48 or less carbon atoms.
Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, and a 1-pyrenyloxy group.

The arylthio group preferably has 6 or more and 60 or less carbon atoms, and more preferably has 6 or more and 48 or less carbon atoms.
Examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group (C1-C12 indicates that the group immediately following it has 1 or more and 12 or less carbon atoms, and the same applies below), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a pentafluorophenylthio group, and the like.

The monovalent heterocyclic group preferably has 2 or more and 60 or less carbon atoms, and more preferably has 4 or more and 20 or less carbon atoms.
Examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group, and a triazinyl group.

The substituted amino group means an amino group having a substituent. Examples of the substituent of the amino group include an alkyl group, an aryl group, and a monovalent heterocyclic group, and an alkyl group, an aryl group, or a monovalent heterocyclic group is preferable.
The substituted amino group preferably has 2 or more and 30 or less carbon atoms.
Examples of the substituted amino group include dialkylamino groups such as a dimethylamino group and a diethylamino group; and diarylamino groups such as a diphenylamino group, a bis(4-methylphenyl)amino group, a bis(4-tert-butylphenyl)amino group, and a bis(3,5-di-tert-butylphenyl)amino group.

The acyl group preferably has 2 or more and 20 or less carbon atoms, and more preferably has 2 or more and 18 or less carbon atoms.
Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

The imine residue refers to the remaining atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon-nitrogen double bond from an imine compound. The "imine compound" refers to an organic compound having a carbon-nitrogen double bond in the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atom bonded to the nitrogen atom constituting the carbon-nitrogen double bond in an aldimine is substituted with an alkyl group or the like.
The imine residue preferably has 2 or more and 20 or less carbon atoms, and more preferably has 2 or more and 18 or less carbon atoms.
Examples of the imine residue include groups represented by the following structural formula: In the following structural formula, * represents a bond.

The amide group preferably has 1 or more and 20 or less carbon atoms, and more preferably has 1 or more and 18 or less carbon atoms.
Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

The acid imide group means an atomic group remaining after removing one hydrogen atom bonded to the nitrogen atom from an acid imide.
The acid imide group preferably has 4 or more and 20 or less carbon atoms.
Examples of the acid imide group include groups represented by the following structural formula: In the following structural formula, * represents a bond.

The substituted oxycarbonyl group means a group represented by R'-O-(C=O)-, where R' represents an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group.
The substituted oxycarbonyl group preferably has 2 or more and 60 or less carbon atoms, and more preferably has 2 or more and 48 or less carbon atoms.
Examples of the substituted oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl group, a dodecyloxycarbonyl group, and a trifluoromethoxycarbonyl group.
Examples of the alkyl group include a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.

The alkylsulfonyl group preferably has 1 or more and 30 or less carbon atoms.
Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

<Reactive Compounds>
The reactive compound according to the present disclosure is represented by the following formula (1).

In formula (1),
Ar ₁ represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings;
_Ar2 represents an aromatic hydrocarbon ring group;
X represents a group represented by -O- or a group represented by -NH-;
Y represents a group represented by -O-, a group represented by -NH-, a group represented by -O-CH ₂ -, a group represented by -CH ₂ -NH-, a group represented by -NH-C(=O)- or a group represented by -C(=O)-O-;
n represents an integer of 1 or more and 4 or less.

The reactive compound according to the present disclosure is a compound in which, when it reacts with another compound, a reactive group is eliminated and the atomic group bonded to the reactive group forms a bond with an atom in the other compound.
An example of the reaction is the Suzuki-Miyaura coupling reaction.

The reactive compound according to the present disclosure has excellent storage stability due to the above-mentioned constitution, and the reason for this is presumed to be as follows.
In formula (1), the reactive group has high structural stability, and therefore decomposition reactions occurring over time are easily suppressed, and therefore it is presumed that the reactive compound according to the present disclosure has excellent storage stability.

(Ar ₁ )
In formula (1), Ar ₁ represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings.
Ar ₁ is an aromatic hydrocarbon ring group having a valence of 1 to 4, or an aromatic heterocyclic group having a valence of 1 to 4.

From the viewpoint of storage stability, Ar ₁ is preferably a monovalent or greater and trivalent aromatic hydrocarbon ring group or a monovalent or greater and trivalent aromatic heterocyclic group.
From the viewpoint of storage stability and reactivity, Ar ₁ is more preferably a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group. That is, the reactive compound according to the present disclosure is preferably a compound represented by the following formula (2).

In formula (2), Ar ₁ , Ar ₂ , X and Y are respectively defined as Ar ₁ , Ar ₂ , X and Y in formula (1), and two Ar ₂ , two X and two Y in formula (2) may be the same or different.

Examples of the aromatic hydrocarbon ring group for Ar ₁ in formula (1) or formula (2) include groups represented by the following formulae Ar ₁ -(A1) to Ar ₁ -(A15).

In formulae Ar ₁ -(A1) to Ar ₁ -(A15), * represents a bond.
In Ar ₁ -(A1), m represents an integer of 0 or more.
In the formulae Ar ₁ -(A11) to Ar ₁ -(A15), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom or a monovalent group, and may be the same or different. Examples of the monovalent group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ include the same groups as the monovalent groups represented by R ₁ and R ₂ , and the preferred embodiments are also the same.

From the viewpoint of storage stability, the aromatic heterocyclic group for Ar ₁ is preferably a group represented by the following formula (3) or (4).

In formula (3) and formula (4), _Ar3 represents a carbocyclic group or a heterocyclic group, and * represents a bond.
The carbocyclic group and heterocyclic group represented by _Ar3 may each have a substituent. Examples of the substituent include the substituent A described above.
Moreover, the carbocyclic group and heterocyclic group represented by _Ar3 may each be a monocyclic ring or a condensed ring.
The carbocyclic and heterocyclic groups represented by _Ar3 are preferably 5- or 6-membered rings.

From the viewpoint of storage stability, Ar ₁ is preferably a group represented by the following formula (5).

In formula (5), Z represents a group represented by formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6) or (Z-7), and * represents a bond.

In formulae (Z-1) to (Z-7), * represents a bond, and R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent group, and may be the same or different.
Examples of the monovalent group include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amido group, an acid imide group, an amino group, a heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, and a cyano group.
The monovalent group may have a substituent, and examples of the substituent include the substituent A described above.
From the viewpoint of storage stability, the monovalent group is preferably at least one type selected from the group consisting of an alkyl group and an aryl group.

The alkyl group may be linear or branched, or may be a cycloalkyl group.
The alkyl group preferably has 1 or more and 30 or less carbon atoms.
The alkyl group may have a substituent, and examples of the substituent include the above-mentioned substituent A.
Specific examples of the alkyl group include chain alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.

The aryl group has the same meaning as a monovalent aromatic hydrocarbon ring group, and preferably has 6 to 60 carbon atoms.
The aryl group may have a substituent, and examples of the substituent include the above-mentioned substituent A.
Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, and a 4-phenylphenyl group.

For specific examples of the monovalent groups represented by R ₁ and R ₂ other than an alkyl group and an aryl group, see paragraphs 0022 to 0048 of WO 2014/112656.

Examples of the aromatic heterocyclic group for Ar ₁ include groups represented by the following formulae Ar ₁ -(B1) to Ar ₁ -(B87).

In formulae Ar ₁ -(B1) to Ar ₁ -(B87), * represents a bond, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each independently represent a hydrogen atom or a monovalent group and may be the same or different.
The monovalent groups represented by _R11 , _R12 , _R13 , _R14 , _R15 , _R16 , _R17 , and _R18 include the same groups as the monovalent groups represented by _R1 and _R2 , and preferred embodiments are also the same.

From the viewpoint of storage stability, the formulae Ar ₁ -(B9), Ar ₁ -(B16), Ar ₁ -(B17), Ar ₁ -(B20), Ar ₁ -(B21), Ar ₁ -(B22), and Ar
Preferably, it is a group represented by formula Ar ₁ -(B23), formula Ar ₁ -(B25), formula Ar ₁ -(B26), formula Ar ₁ -(B27) (i.e., formula (6) below) or formula Ar ₁ -(B28), and more preferably a group represented by formula Ar ₁ -(B27) (i.e., formula (6) below).

In formula (6), * represents a bond, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent group, and may be the same or different.

(Reactive Group)
The reactive compound according to the present disclosure has a reactive group.
In the reactive group, Ar ₂ represents an aromatic hydrocarbon ring group, X represents a group represented by -O- or a group represented by -NH-, Y represents a group represented by -O-, a group represented by -NH-, a group represented by -O-CH ₂ -, a group represented by -CH ₂ -NH-, a group represented by -NH-C(=O)- or a group represented by -C(=O)-O-, and n represents an integer of 1 or more and 4 or less.

The aromatic hydrocarbon ring group represented by _Ar2 includes a divalent aromatic hydrocarbon ring group.
Specific examples of the divalent aromatic hydrocarbon ring group include a phenylene group, a naphthylene group, an anthrylene group, and a phenanthonylene group. From the viewpoint of storage stability, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.
The aromatic hydrocarbon ring group represented by _Ar2 may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned substituent A.

From the viewpoint of storage stability, Y is preferably a group represented by -O-, a group represented by -O-CH ₂ - or a group represented by -NH-C(=O)-, more preferably a group represented by -O-CH ₂ - or a group represented by -NH-C(=O)-, and even more preferably a group represented by -NH-C(=O)-.
From the viewpoint of storage stability, n is preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and even more preferably 2.
Examples of the reactive group include groups represented by the following formulae (R1) to (R4): In the following formulae (R1) to (R4), * represents a bond.

From the viewpoint of storage stability, the reactive compound according to the present disclosure is preferably a compound represented by the following formula (7), the following formula (8), the following formula (9) or the following formula (10).

In formulae (7) to (10), R ₁₂ and R ₁₃ have the same definitions as R ₁₂ and R ₁₃ in formulae Ar ₁ -(B1) to Ar ₁ -(B87), respectively.

Tables 1 to 18 show specific examples of reactive compounds, but the present invention is not limited thereto.
In addition, "R ₁₁ ", "R ₁₂ ", "R ₁₃ ", "R ₁₄ ", "R _{15 ", "R 16 ", "R 17 " and "R 18 " in the column under "Ar 1 " in Tables 1 to 18 mean R 11 , R 12 , R 13 , R 14 , R 15} _, _R ₁₆ _, _R ₁₇ _and _R ₁₈ in formulae Ar ₁ -(A1) to Ar ₁ -( _A15 ) and formulae Ar ₁ -( _B1 ) to Ar ₁ -( _B87 ).
In Tables 1 to 18, "Ar ₂ ", "X", "Y" and "n" described in the column under "Reactive Group" mean Ar ₂ , X, Y and n in formula (1).
In Tables 1 to 18, the "formula" described in the column under "reactive group" indicates the corresponding reactive group when it corresponds to any of the above formulas (R1) to (R4).
In Tables 1 to 18, the "substituent" shown in the column under "Ar ₂ " indicates the type of the substituent when the aromatic hydrocarbon ring group represented by Ar ₂ has a substituent.
The "substitution position" shown in the column under "Ar ₂ " in Tables 1 to 18 indicates which carbon atom among the carbon atoms forming the aromatic hydrocarbon ring group has a substituent, when the aromatic hydrocarbon ring group represented by Ar ₂ has a substituent. The carbon atom having a substituent is represented using the position number defined by the following method.
Method of Defining Position Numbers Among the carbon atoms forming the aromatic hydrocarbon ring group represented by _Ar2 , the carbon atom forming a bond with the group represented by X is designated as the carbon atom with position number 1. Then, clockwise from the carbon atom with position number 1, starting from the carbon atom adjacent to the carbon atom with position number 1, consecutive integers starting from 2 are assigned to each carbon atom, and these are designated as the position numbers of each carbon atom.
When the aromatic hydrocarbon ring group represented by _Ar2 is a condensed ring, the position numbers of the carbon atoms are set so that the position numbers of the carbon atoms shared by a plurality of rings do not have consecutive values.
Here, an example of the position number is shown in the following formula (EX1) and formula (EX2).

The numbers in formula (EX1) and formula (EX2) refer to the position numbers of the carbon atoms.

The abbreviations in Tables 1 to 18 are as follows.
"H": hydrogen; "Me": methyl group; "F": fluorine group; "S1": a group represented by the following formula (S1).
"S2": represents a group represented by the following formula (S2).
"S3": represents a group represented by the following formula (S3).
"S4": represents a group represented by the following formula (S4).
"S5": represents a group represented by the following formula (S5).
"S6": represents a group represented by the following formula (S6).
"S7": represents a group represented by the following formula (S7).
"S8": represents a group represented by the following formula (S8).
"S9": represents a group represented by the following formula (S9).
"S10": represents a group represented by the following formula (S10).
"S11": represents a group represented by the following formula (S11).
"S12": represents a group represented by the following formula (S12).
"S13": represents a group represented by the following formula (S13).
"S14": represents a group represented by the following formula (S14).

Here, when a polymer compound is obtained by reacting a compound containing a group represented by formula (S1) as a reactive compound according to the present disclosure with a compound represented by formula (11) described below, the heat resistance of the polymer compound is likely to be improved. Therefore, the reactive compound containing a group represented by formula (S1) can be suitably used as a heat resistance improver for polymer compounds.
In addition, when a polymer compound is obtained by reacting a compound containing a group represented by formula (S1) as a reactive compound according to the present disclosure with a compound represented by formula (11) described below, the solubility of the polymer compound in a solvent is likely to be improved. Therefore, the reactive compound containing a group represented by formula (S1) can be suitably used as a solubility enhancer for polymer compounds.

When the reactive compound containing a group represented by formula (S1) is used as a heat resistance improver and a solubility improver, it is preferably compound 477, compound 478, compound 479, or compound 480.

(Method for producing reactive compounds)
The reactive compound according to the present disclosure can be suitably synthesized by using an intermediate represented by the following formula (12) as a raw material.

In formula (12), Ar ₁ and n are defined as Ar ₁ and n in formula (1), and L represents a hydrogen atom or a halogen atom.
In the formula (12), the preferred embodiments of Ar ₁ and n are the same as those of Ar ₁ and n in the formula (1).
The halogen atom in L includes chlorine, bromine and iodine.

In formula (12), Ar ₁ is preferably a group represented by formula (3) or formula (4), more preferably a group represented by formula (5), and further preferably a group represented by formula (6).
In formula (12), L is preferably a hydrogen atom, bromine or iodine, and more preferably a hydrogen atom.

As the intermediate, for example, a compound in which Ar ₁ is the same as Ar ₁ described in Tables 1 to 18 and n is 2 can be mentioned.

Specific examples of intermediates are shown in Tables 19 and 20, but the invention is not limited thereto.
"R ₁₁ ", "R ₁₂ ", "R ₁₃ ", "R ₁₄ ", "R 15 ", "R ₁₆ ", "R 17 " and "R ₁₈ " in the column under "Ar ₁ " in Tables 19 and ₂₀ mean R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ in Formulae Ar ₁ -(B1) to Ar ₁ _- (B87).
In Tables 19 and 20, "L" and "n" refer to L and n in formula (12).
The meanings of "H", "S1", "S2", "S3", "S4", "S5", "S6", "S7", "S8", "S9", "S10", "S11", "S12", "S13" and "S14" in Tables 19 and 20 are the same as those in Tables 1 to 18.

From the viewpoint of reactivity, the intermediate is preferably a compound represented by compound 12-1, compound 12-2, compound 12-5, compound 12-6, compound 12-9, compound 12-10, compound 12-13, compound 12-14, compound 12-39, or compound 12-40, more preferably a compound represented by compound 12-13 or compound 12-14, and even more preferably a compound represented by compound 12-13.

As a method for converting the intermediate represented by formula (12) into the reactive compound according to the present disclosure, for example, in a diethyl ether solvent, the intermediate represented by formula (12) is subjected to dilithiation using a base such as n-butyl lithium, and then the corresponding boronic acid is synthesized by reacting it with a polar group-containing aromatic compound such as 2-hydroxybenzyl alcohol, 4-methylcatechol, 2,3-naphthalenediol, or 2-aminobenzamide.

The reactive compounds disclosed herein can be easily purified by recrystallization. Examples of solvents used for recrystallization include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclohexane, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, ethyl acetate, etc., and may be a single solvent or a mixed solvent. Preferred examples include a single solvent of toluene or ethyl acetate, a mixed solvent of n-heptane and toluene, and a mixed solvent of n-heptane and ethyl acetate.

<Method of Producing Polymer Compound>
The method for producing a polymer compound according to the present disclosure comprises reacting a reactive compound according to the present disclosure with a compound represented by the following formula (11).

In formula (11), Ar ₄ represents a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group, and each HX independently represents a halogen atom.

(Compound represented by formula (11))
As the divalent aromatic hydrocarbon ring group or divalent aromatic heterocyclic group represented by _Ar4 , from the viewpoint of increasing the open circuit voltage when the polymer compound according to the present disclosure is used as an active layer of an organic thin-film solar cell, or from the viewpoint of suppressing the dark current when the polymer compound is used as an active layer of an organic light-detecting element, a group represented by any of formulas (Cy-1) to (Cy-5) is preferable.

In formula (Cy-1) to formula (Cy-5), R ₁ and R ₂ are the same as R ₁ and R ₂ in formula (Z-1) to formula (Z-7). R ₂₁ and R ₂₂ each independently represent a hydrogen atom, a halogen atom, or a monovalent group. R ₂₁ and R ₂₂ may be linked to form a cyclic structure. Ring Cy is the same or different and represents an aromatic ring which may have a substituent, and examples of the substituent include the above-mentioned substituent A. R ₂₃ represents a divalent group. Also, * represents a bond.

In formula (Cy-1), specific examples of the halogen atom and monovalent group represented by R ₂₁ and R ₂₂ are the same as the specific examples of the halogen atom and monovalent group represented by R ₁ and R ₂ .

R ₂₁ and R ₂₂ may be linked to each other to form a cyclic structure. Specific examples of the cyclic structure include structures represented by formulae (D-1) to (D-5). In formulae (D-1) to (D-5), R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in formulae (Z-1) to (Z-7), respectively, and * represents a bond.

In formulas (Cy-1) to (Cy-5), the aromatic ring represented by the ring Cy may be a monocyclic ring or a condensed ring. Examples of monocyclic aromatic rings include a benzene ring, a pyrrole ring, a furan ring, a thiophene ring, an oxazole ring, a thiazole ring, a thiadiazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, an imidazole ring, a triazole ring, an isoxazole ring, an isothiazole ring, a pyrimidine ring, a pyridazine ring, and a triazine ring.

　Aromatic rings that are fused rings include aromatic rings in which any ring is fused to the above-mentioned monocyclic ring. Examples of rings fused to a monocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a pyrazole ring, a pyrazoline ring, a prazolidine ring, a furazan ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a tetrazole ring, a pyran ring, a pyridine ring, a piperidine ring, a thiopyran ring, a ridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring, a morpholine ring, a triazine ring, a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, and an indole ring. , isoindole ring, indolizine ring, indoline ring, isoindoline ring, chromene ring, chroman ring, isochroman ring, benzopyran ring, quinoline ring, isoquinoline ring, quinolizine ring, benzimidazole ring, benzothiazole ring, indazole ring, naphthyridine ring, quinoxaline ring, quinazoline ring, quinazolidine ring, cinnoline ring, phthalazine ring, purine ring, pteridine ring, carbazole ring, xanthene ring, phenanthridine ring, acridine ring, β-carboline ring, perimidine ring, phenanthroline ring, thianthrene ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring, and phenazine ring.

In the ring Cy, the aromatic ring may have a substituent. Examples of the substituent that the aromatic ring may have include a halogen atom and a monovalent group. Specific examples of the halogen atom and the monovalent group are the same as those represented by _R1 and _R2 .

In formula (Cy-5), examples of the divalent group represented by R ₂₃ include groups represented by formulae (b-1) to (b-7).

In formulae (b-1) to (b-7), R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in formulae (Z-1) to (Z-7), respectively, and * represents a bond.

When the polymer compound according to the present disclosure is used as an organic light-detecting element material, the groups represented by formulas (Cy-1) to (Cy-5) are preferably groups represented by formula (Cy-2) or formula (Cy-3) from the viewpoint of suppressing dark current, and more preferably groups represented by formula (Cy-3).

Examples of groups represented by formulas (Cy-1) to (Cy-5) include groups represented by formulas (C-1) to (C-31) shown below.

In formulae (C-1) to (C-29), R ₃₁ to R ₃₈ represent a hydrogen atom or a monovalent group, and in formulae (C-1) to (C-31), * represents a bond.
The monovalent groups represented by R ₃₁ to R ₃₈ include the same groups as the monovalent groups represented by R ₁ and R ₂ , and preferred embodiments are also the same.

When the polymer compound according to the present disclosure is used as an organic light-detecting element material, the group represented by formula (C-15) is preferably a group represented by formula (C-32) or a group represented by formula (C-33) from the viewpoint of suppressing dark current. In formulas (C-32) and (C-33), * represents a bond.

When the polymer compound according to the present disclosure is used as an organic light-detecting element material, the groups represented by formulas (Cy-1) to (Cy-5) are preferably groups represented by formula (C-30) or formula (C-31), and from the viewpoint of suppressing dark current, the groups represented by formula (C-31) are more preferable.

In formula (11), examples of the halogen atom represented by HX include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of synthesis of the polymer compound, it is preferable that the halogen atom is at least one selected from a bromine atom and an iodine atom, and it is more preferable that the halogen atom is a bromine atom.

(Reaction of reactive compound with compound represented by formula (11))
In the method for producing a polymer compound according to the present disclosure, the method for reacting a reactive compound with a compound represented by formula (11) is not particularly limited. From the viewpoint of ease of synthesis of the polymer compound, a method using the Suzuki-Miyaura coupling reaction is preferred.

The Suzuki-Miyaura coupling reaction can be carried out in any solvent using a palladium catalyst in the presence of a base.

Palladium catalysts used in the Suzuki-Miyaura coupling reaction include, for example, Pd(0) catalysts and Pd(II) catalysts. Specific examples include palladium [tetrakis(triphenylphosphine)], palladium acetates, dichlorobis(triphenylphosphine)palladium, palladium acetate, tris(dibenzylideneacetone)dipalladium, and bis(dibenzylideneacetone)palladium. From the standpoint of ease of reaction (polymerization) operations and reaction (polymerization) speed, however, dichlorobis(triphenylphosphine)palladium, palladium acetate, and tris(dibenzylideneacetone)dipalladium are preferred.

The amount of palladium catalyst added is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 moles or more and 0.5 moles or less, and preferably 0.0003 moles or more and 0.1 moles or less, per mole of the reactive compound represented by formula (1) (i.e., the reactive compound according to the present disclosure).

When palladium acetates are used as the palladium catalyst in the Suzuki-Miyaura coupling reaction, phosphorus compounds such as triphenylphosphine, tri(o-tolyl)phosphine, and tri(o-methoxyphenyl)phosphine can be added as ligands. In this case, the amount of ligand added is usually 0.5 to 100 moles, preferably 0.9 to 20 moles, and more preferably 1 to 10 moles, per mole of palladium catalyst.

Examples of the base used in the Suzuki-Miyaura coupling reaction include inorganic bases, organic bases, and inorganic salts. Examples of the inorganic base include potassium carbonate, sodium carbonate, barium hydroxide, and potassium phosphate. Examples of the organic base include triethylamine and tributylamine. Examples of the inorganic salt include cesium fluoride.

The amount of base added is usually 0.5 moles or more and 100 moles or less, preferably 0.9 moles or more and 20 moles or less, and more preferably 1 mole or more and 10 moles or less, per mole of the reactive compound represented by formula (1) (i.e., the reactive compound according to the present disclosure).

The Suzuki-Miyaura coupling reaction is usually carried out in a solvent. Examples of the solvent include N,N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran, methylene chloride, etc. From the viewpoint of the solubility of the polymer compound according to the present disclosure, toluene or tetrahydrofuran is preferable.

Alternatively, the base may be added by adding an aqueous solution containing the base to the reaction solution and reacting in a two-phase system of an aqueous phase and an organic phase. When an inorganic salt is used as the base, the aqueous solution containing the base is usually added to the reaction solution to react, from the viewpoint of the solubility of the inorganic salt.
When the reaction is carried out in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added, if necessary.

The temperature at which the Suzuki-Miyaura coupling reaction is carried out depends on the solvent, but is usually 40°C or higher and 160°C or lower. From the viewpoint of increasing the molecular weight of the polymer compound, 60°C or higher and 120°C or lower are preferable. The temperature may also be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the desired degree of polymerization is reached, but is usually 0.1 hours or higher and 200 hours or lower. A reaction time of 0.5 hours or higher and 30 hours or lower is efficient and preferable.

(Polymer Compound)
The polymer compound according to the present disclosure contains, as a structural unit, one or more aromatic hydrocarbon ring groups or aromatic heterocyclic groups represented by Ar ₁ in formula (1) and one or more aromatic hydrocarbon ring groups or aromatic heterocyclic groups represented by Ar ₄ in formula (11).
The polymer compound according to the present disclosure preferably contains two or more, and more preferably three or more, aromatic hydrocarbon ring groups or aromatic heterocyclic groups represented by Ar ₁ in formula (1) as structural units.

When the polymer compound according to the present disclosure is used in an element, it is desirable for the polymer compound to have high solubility in a solvent from the viewpoint of ease of element fabrication. Specifically, it is preferable for the polymer compound according to the present disclosure to have a solubility that allows a solution containing 0.01 weight (wt) % or more of the polymer compound to be prepared, more preferably a solubility that allows a solution containing 0.1 wt % or more of the polymer compound to be prepared, and even more preferably a solubility that allows a solution containing 0.2 wt % or more to be prepared.

The weight average molecular weight of the polymer compound according to the present disclosure is preferably 3,000 or more and 10,000,000 or less.
When the weight average molecular weight of the polymer compound according to the present disclosure is 3,000 or more, defects are unlikely to occur in the film formed during device fabrication. Also, when the weight average molecular weight of the polymer compound according to the present disclosure is 10,000,000 or less, the solubility in a solvent and the coatability during device fabrication are likely to be improved.
The weight average molecular weight of the polymer compound according to the present disclosure is more preferably 4,000 or more and 5,000,000 or less, and further preferably 5,000 or more and 1,000,000 or less.

The weight average molecular weight of the polymer compound according to this disclosure refers to the weight average molecular weight calculated in terms of polystyrene using gel permeation chromatography (GPC) and a polystyrene standard sample.

The terminal groups of the polymer compounds according to the present disclosure may be protected with stable groups, since if the reactive groups remain as they are, the characteristics and lifespan of the resulting element may be reduced when used in the fabrication of an element. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferred, and they may also have a structure in which they are bonded to an aryl group or a heterocyclic group via a vinylene group, for example.

(Applications of polymer compounds)
Since the polymer compound according to the present disclosure can exhibit high electron and hole transport properties, when an organic thin film containing the polymer compound is used in an element, it can transport electrons and holes injected from an electrode, or charges generated by light absorption. By utilizing these properties, the polymer compound can be suitably used in various electronic elements such as photoelectric conversion elements, organic thin film transistors, and organic electroluminescence elements.

For example, in a photoelectric conversion element, the polymer compound according to the present disclosure is used as a material for the active layer. In an organic thin-film transistor, the polymer compound according to the present disclosure is used in the organic semiconductor layer (active layer) that serves as the current path between the source electrode and the drain electrode. In an organic electroluminescence element, the polymer compound according to the present disclosure is used in the light-emitting layer.

The following examples are provided, but the present invention is not limited to these examples.

<NMR Measurement>
Proton NMR measurement (hereinafter referred to as ¹ H-NMR measurement) for confirming the production of the compound was performed by dissolving the compound in deuterated chloroform and using a nuclear magnetic resonance (NMR) device (manufactured by JEOL Ltd., proton resonance frequency 400 MHz).

<Synthesis of intermediates>
(Synthesis of Compound 1)

In a flask purged with nitrogen, 65.2 g of magnesium (2.68 mol in molar terms), 275 mL of tetrahydrofuran (hereinafter simply referred to as THF), and two grains of iodine were added and stirred. After the purple color of the iodine disappeared, a solution containing 612.9 g of 1-bromo-3-hexylbenzene (2.54 mol in molar terms) and 4730 mL of THF was added dropwise to generate a Grignard reagent.
In a separate flask, add 550 g of 1,3-Dibromobenzene (2.3 moles).
3 mol), 2783 mL of THF, and 7.62 g (9.33 mmol in molar terms) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (in other words, PdCl ₂ (dppf)-CH ₂ Cl ₂ ) were added, stirred, and cooled to 10°C.
The prepared Grignard reagent was added dropwise so that the internal temperature did not exceed 10° C. After stirring for 1 hour, water was poured into the reaction solution to stop the reaction and the liquids were separated. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate was then totally concentrated with a rotary evaporator to obtain a concentrated liquid.
The concentrate was purified by silica gel column chromatography (hexane as a developing solvent) to obtain 532.2 g of Compound 1 (1.68 mol in molar terms, yield 67%).

The ¹ H-NMR measurement results of compound 1 are as follows.
δ(ppm): 7.73(t,1H), 7.52-7.50(dt,1H), 7.48-7.45(dq,1H), 7.38-7.28(m,4H), 7.21-7.18(m,1H), 2.67(t,2H), 1.69-1.58(m,2H), 1.40-1.28(m,6H), 0.89(t,3H)

(Synthesis of compound 3)

In a 1 L four-neck flask purged with nitrogen, 1.61 g of magnesium (0.066 mol in molar terms), 53 mL of THF, and 32 mg of iodine were added and stirred. After the purple color of iodine disappeared, a solution containing 19.8 g of compound 1 (0.063 mmol in molar terms) and 40 mL of THF was added dropwise to generate a Grignard reagent.
A solution containing 5.21 g (0.025 mol in terms of moles) of compound 2 synthesized by the method described in International Publication No. 2011/136311 and 120 mL of THF was dropped into the flask containing the Grignard reagent so that the internal temperature did not exceed 40° C. The mixture was then stirred for 1 hour, and an aqueous solution of ammonium chloride was poured into the reaction solution to stop the reaction and separate the liquids. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration, after which the filtrate was totally concentrated with a rotary evaporator to obtain a concentrated liquid.

The concentrated solution was purified by silica gel column chromatography (eluent: hexane and ethyl acetate) to obtain 14.21 g of compound 3 (20.7 mmol in molar terms, yield 83%).

The ¹ H-NMR measurement results of compound 3 are as follows.
δ(ppm): 7.82-7.76(m,1H), 7.64(s,2H), 7.43(m,2H), 7.31(m,10H), 7.25(m,2H), 7.21(m,1H), 7.13(m,2H), 6.91(d,1H), 6.64(d,1H), 6.43(d,1H), 3.72-3.64(m,1H), 2.63(t,4H), 1.61(m,4H), 1.22-1.34(m,12H), 0.86(t,6H)

(Synthesis of intermediate compound 4)

A 500 mL four-neck flask was charged with 14.21 g (0.0208 mmol in terms of moles) of compound 3 and 130 g of heptane. The atmosphere inside the reaction vessel was replaced with nitrogen, and then 0.409 g (0.0036 mmol in terms of moles) of trifluoroacetic acid was added. The mixture was heated to 60° C., stirred for 30 minutes, and then cooled to room temperature.
The reaction solution was washed twice with water, and then the organic layer was dehydrated with magnesium sulfate and passed through a Kiriyama funnel filled with silica gel. The filtrate was totally concentrated using a rotary evaporator, thereby obtaining 13.37 g (yield 96.6%) of an intermediate compound 4 (corresponding to compound 12-13 in Table 19).

The ¹ H-NMR measurement results of compound 4 are as follows.
δ(ppm): 7.73(s,2H), 7.64(s,2H), 7.45-7.43(m,7H), 7.33-7.31(m,2H), 7.26(s,2H), 7.22(s,1H), 7.16-7.13(m,1H), 6.93(d,1H), 6.65(d,1H), 6.44(d,1H), 2.64(t,4H), 1.67-1.58(m,4H), 1.34-1.26(m,12H), 0.86(t,6H)

In a 300 mL four-neck flask purged with nitrogen, 5.01 g (7.51 mmol in molar terms) of the intermediate compound 4, 0.873 g (7.51 mmol in molar terms) of tetraethylethylenediamine, and 75 mL of dehydrated THF were placed and stirred to dissolve. The solution was then cooled to -78°C in a cooling bath containing dry ice and acetone, after which 12.0 mL of n-butyllithium solution (concentration 1.57 mol/L, hexane solution) was added dropwise as a base and stirred at -78°C for 2 hours. While maintaining the temperature at -78°C, a solution of 3.96 g (21.0 mmol in molar terms) of triisopropoxyborane in 8 mL of THF was added dropwise, and the mixture was stirred at -78°C for another hour, after which it was warmed to room temperature. Next, 65 g of 10% aqueous acetic acid was added to the reaction solution, and the liquids were separated. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. 2.05 g (16.5 mmol in molar terms) of 2-hydroxybenzyl alcohol was added to the filtrate as a polar group-containing aromatic compound, and the mixture was stirred for 60 minutes. The solvent was then removed under reduced pressure, and recrystallization was carried out with ethyl acetate and hexane to obtain 5.13 g (5.51 mol in molar terms, yield 73.3%) of the reactive compound Compound 5 (corresponding to Compound 107 in Table 11).

The ¹ H-NMR measurement results of compound 5 are as follows.
δ (ppm): 7.65 (t, _J = 1.8 Hz, 2H), 7.54 (dt, _J = 7.8, 1.5 Hz, 2H), 7.20-7.42 (m, 14H), 7.13 (dt, _J = 7.0, 1.6 Hz, 2H), 6.96-7.06 (m, 6H), 5.18 (d, _J = 3.2 Hz, 4H), 2.62 (t, _J = 7.8 Hz, 4H), 1.57-1.65 (m, 4H), 1.25-1.34 (m, 12H), 0.86 (t, _J = 6.9 Hz, 6H)
In addition, _JHH represents a coupling constant.

In a 300 mL four-neck flask substituted with nitrogen, 3.2 g (0.005 mol in molar terms) of compound 4, which is an intermediate, 0.56 g (0.005 mol in molar terms), and 50 mL of dehydrated THF were placed and stirred to dissolve. The solution was then cooled to -78°C in a cooling bath containing dry ice and acetone, and 7.7 mL of n-butyllithium solution (concentration 1.57 mol/L, hexane solution) was added dropwise as a base, and the mixture was stirred at -78°C for 2 hours. While maintaining the temperature at -78°C, a solution in which 2.53 g (0.013 mmol in molar terms) of triisopropoxyborane was dissolved in 5 mL of THF was added dropwise, and the mixture was stirred at -78°C for another hour, and then the mixture was warmed to room temperature. Next, 43 g of a 10% aqueous acetic acid solution was added to the reaction solution, and the mixture was separated. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. To the filtrate, 1.96 g (0.014 mmol in terms of moles) of 2-aminobenzamide was added as a polar group-containing aromatic compound, and the mixture was stirred for 60 minutes. The solvent was then removed under reduced pressure, and recrystallization was carried out with ethyl acetate and hexane to obtain Compound 6 (Table 11), which is a reactive compound.
Of these, 3.98 g (corresponding to compound 108) was obtained (4.17 mmol in molar terms, yield 87%).

The ¹ H-NMR measurement results of compound 6 are as follows.
δ(ppm): 8.19(t,2H), 7.66(s,2H), 7.58-7.22(m,13H), 7.15-7.10(m,5H), 7.04(dd,2H), 7.00(s,1H), 6.69(d,2H), 2.61(t,4H), 1.73(br,1H)1.63-1.55(m,4H), 1.34-1.24(m,12H), 0.86(t,6H)

In a 300mL four-neck flask purged with nitrogen, 4.95g (0.007mol in molar terms) of intermediate compound 4, 0.86g (0.007mol in molar terms) of tetraethylethylenediamine, and 87mL of dehydrated THF were placed and stirred to dissolve. The solution was then cooled to -78°C in a cooling bath containing dry ice and acetone, after which 11.7mL of n-butyllithium solution (concentration 1.57mol/L, hexane solution) was added dropwise as a base and stirred at -78°C for 2 hours. While maintaining the temperature at -78°C, a solution of 3.91g (0.021mmol in molar terms) of triisopropoxyborane in 8mL of THF was added dropwise, and the mixture was stirred at -78°C for another hour, after which it was warmed to room temperature. Next, 65g of 10% aqueous acetic acid was added to the reaction solution, and the liquids were separated. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. 2.02 g (0.016 mmol in molar terms) of 4-methylcatechol was added to the filtrate as a polar group-containing aromatic compound, and the mixture was stirred for 60 minutes. The solvent was then removed under reduced pressure, and the mixture was recrystallized from ethyl acetate and hexane to obtain 4.09 g (4.39 mmol in molar terms, 59% yield) of the reactive compound Compound 7 (corresponding to Compound 105 in Table 11).

The ¹ H-NMR measurement results of compound 7 are as follows.
δ(ppm): 7.65(t,2H), 7.57(s,1H), 7.55(t,1H), 7.54(t,1H), 7.40-7.36(m,3H), 7.32-7.26(m,8H), 7.13-7.02(m,6H), 6.96-6.87(m,2H), 2.61(t,4H), 2.37(d,6H), 1.63-1.53(m,4H), 1.32-1.25(m,12H), 0.86(t,6H)

In a 300mL four-neck flask purged with nitrogen, 5.3g (0.008mol in molar terms) of intermediate compound 4, 0.93g (0.008mol in molar terms) of tetraethylethylenediamine, and 83mL of dehydrated THF were placed and stirred to dissolve. The solution was then cooled to -78°C in a cooling bath containing dry ice and acetone, after which 12.7mL of n-butyllithium solution (concentration 1.57mol/L, hexane solution) was added dropwise as a base and stirred at -78°C for 2 hours. While maintaining the temperature at -78°C, a solution of 4.19g (0.022mmol in molar terms) of triisopropoxyborane in 8.3mL of THF was added dropwise, and the mixture was stirred at -78°C for another hour, after which it was warmed to room temperature. Next, 71g of 10% aqueous acetic acid was added to the reaction solution and the liquids were separated. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. 3.83 g (0.024 mmol in molar terms) of 2,3-naphthalenediol was added to the filtrate as a polar group-containing aromatic compound, and the mixture was stirred for 60 minutes. The solvent was then removed under reduced pressure, and the mixture was recrystallized from ethyl acetate and hexane to obtain 4.37 g (4.36 mmol in molar terms, 54% yield) of the reactive compound Compound 8 (corresponding to Compound 106 in Table 11).

The ¹ H-NMR measurement results of compound 8 are as follows.
δ(ppm): 7.85-7.82(m,4H), 7.69(t,2H), 7.67(s,1H), 7.61(s,2H), 7.59(t,1H), 7.58(m,3H), 7.47(s,1H), 7.46-7.40(m,6H), 7.36-7.27(m,8H), 7.15(t,1H), 7.13(t,1H), 2.63(t,4H), 1.65-1.55(m,4H), 1.34-1.24(m,12H), 0.86(t,6H)

In a 300mL four-neck flask substituted with nitrogen, 0.67g of compound 4 (0.001mol in molar terms), 0.12g of tetraethylethylenediamine (0.001mol in molar terms), and 10.6mL of dehydrated THF were added and stirred to dissolve. The solution was then cooled to -78°C in a cooling bath containing dry ice and acetone, and 1.6mL of n-butyllithium solution (concentration 1.57mol/L, hexane solution) was added dropwise, and the mixture was stirred at -78°C for 2 hours. While maintaining the temperature at -78°C, a solution in which 0.53g of triisopropoxyborane (0.003mmol in molar terms) was dissolved in 1.1mL of THF was added dropwise, and the mixture was stirred at -78°C for another hour, and then the mixture was heated to room temperature. Next, 9g of a 10% aqueous acetic acid solution was added to the reaction solution, and the mixture was separated. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. To the filtrate, 0.35 g (0.003 mmol in terms of moles) of pinacol was added, and the mixture was stirred for 60 minutes. The solvent was then removed under reduced pressure, and recrystallization was carried out using ethyl acetate and hexane to obtain 0.83 g (0.9 mmol in terms of moles, yield 90%) of Compound 9, which is a reactive compound for comparison.

The ¹ H-NMR measurement results of compound 9 are as follows.
δ(ppm): 7.61(t,2H), 7.51(dt,2H), 7.36-7.26(m,7H), 7.18(dt,2H), 7.13(dt,2H), 7.05(s,1H), 2.62(t,4H), 1.66-1.58(m,4H), 1.38-1.25(m,36H), 0.86(t,6H)

<Storage stability evaluation>
The reactive compounds obtained in each example were used to evaluate storage stability according to the following procedure.
The storage stability was evaluated by calculating the initial purity and the purity after the storage test, and then calculating the purity maintenance rate from the calculated initial purity and the purity after the storage test. Here, a higher purity maintenance rate indicates higher storage stability.

(Calculation of initial purity)
The purity of the reactive compound obtained in each example was calculated by the internal standard method of ¹ H-NMR measurement.
The procedure for calculating the purity by the internal standard method in ¹ H-NMR measurement will be described later.

(Purity after storage test)
The reactive compound obtained in each example was added to a vial, and the vial was purged with nitrogen. The vial containing the reactive compound was then stored at 40° C. for one week. The purity of the reactive compound after storage was calculated by the internal standard method of ¹ H-NMR measurement.

(Calculation of Purity Maintenance Rate)
The purity maintenance rate was calculated according to the following formula (I) using the initial purity and the purity after the storage test calculated by the above procedure.
Formula (I): Purity maintenance rate (%) = (purity after storage test ÷ initial purity) × 100

(Procedure for calculating purity by the internal standard method in ¹ H-NMR measurement)
A measurement sample for ¹ H-NMR measurement is prepared with the following composition.
- Composition of measurement data -
Deuterated chloroform (Tokyo Chemical Industry Co., Ltd., 99.8 atom% D, does not contain tetramethylsilane): 0.6 mL
・Standard substance: 1,4-bis(trimethylsilyl)benzene-d4 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 1.0 mg
Reactive compound: 6.0 mg
Next, the measurement sample is subjected to ¹ H-NMR measurement. From the obtained NMR spectrum, the purity (P _sample ) of the reactive compound is calculated according to the following formula (II).

The symbols in formula (II) are explained below.
P _sample : Purity of reactive compound (%)
I _sample : integral value of peaks derived from reactive compounds in the NMR spectrum (compound 5: peak at 5.18 ppm, compound 6: peak at 8.19 ppm, compound 7: peak at 7.65 ppm, compound 8: peak at 7.67 ppm, compound 9: peak at 7.05 ppm) H _sample : number of protons of peaks derived from reactive compounds in the NMR spectrum (peak positions referenced for each compound are the same as those in I _sample ) M _sample : molecular weight of reactive compound W _sample : mass of reactive compound in the measurement sample (i.e., 6.0 mg)
P _std : Purity of standard material (%)
I _std : integral value of the peak (peak at 0.27 ppm) derived from the standard substance in the NMR spectrum H _std : number of protons of the peak (referenced peak position is the same as that in I _std ) derived from the standard substance in the NMR spectrum M _std : molecular weight of the standard substance W _std : mass of the standard substance in the measurement sample (i.e., 1.0 mg)

Table 21 shows the results of calculating the initial purity, purity after storage test, and purity maintenance rate of the reactive compounds obtained in each example.

The above results show that the reactive compound of this example has excellent storage stability.

Claims

A reactive compound represented by the following formula (1):

(In formula (1),
Ar 1 represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings;
Ar2 represents an aromatic hydrocarbon ring group;
X represents a group represented by -O- or a group represented by -NH-;
Y represents a group represented by -O-, a group represented by -NH-, a group represented by -O-CH 2 -, a group represented by -CH 2 -NH-, a group represented by -NH-C(=O)- or a group represented by -C(=O)-O-;
n represents an integer of 1 to 4.
The reactive compound according to claim 1, represented by the following formula (2):

(In formula (2),
Ar 1 represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings;
Ar2 represents an aromatic hydrocarbon ring group;
X represents a group represented by -O- or a group represented by -NH-;
Y represents a group represented by -O-, a group represented by -NH-, a group represented by -O-CH 2 -, a group represented by -CH 2 -NH-, a group represented by -NH-C(=O)- or a group represented by -C(=O)-O-;
In the formula (2), the two Ar 2 s, the two Xs, and the two Ys may be the same or different.
The reactive compound according to claim 2 , wherein Ar 1 is a group represented by the following formula (3) or the following formula (4):

(In formula (3) and formula (4),
Ar3 represents a carbocyclic group or a heterocyclic group;
* represents a bond.)
The reactive compound according to claim 2 , wherein Ar 1 is a group represented by the following formula (5):

(In formula (5),
Z represents a group represented by the following formula (Z-1), (Z-2), (Z-3), (Z-4), (Z-5), (Z-6), or (Z-7):
* represents a bond.)

(In formulas (Z-1) to (Z-7),
* represents a bond,
R1 and R2 each independently represent a hydrogen atom or a monovalent group, and may be the same or different.
The reactive compound according to claim 2 , wherein Ar 1 is a group represented by the following formula (6):

(In formula (6),
* represents a bond,
R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom or a monovalent group, and may be the same or different.
The reactive compound according to claim 2, wherein the compound represented by formula (2) is a compound represented by the following formula (7), the following formula (8), the following formula (9), or the following formula (10):

(In formulas (7) to (10), R 12 and R 13 each independently represent a hydrogen atom or a monovalent group, and may be the same or different.)
A method for producing a polymer compound, comprising reacting the reactive compound according to any one of claims 1 to 6 with a compound represented by the following formula (11):

(In formula (11),
Ar4 represents a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group;
Each HX independently represents a halogen atom.
An intermediate of the reactive compound according to claim 1, represented by the following formula (12):

(In formula (12),
Ar 1 represents an aromatic hydrocarbon ring group having two or more condensed rings or an aromatic heterocyclic group having two or more condensed rings;
L represents a hydrogen atom or a halogen atom;
n represents an integer of 1 to 4.