JP2012232947A - Method of producing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a compound free of an ester borate residue and an organotin residue by allowing two or more species of heterocyclic compounds to react with each other.SOLUTION: The method of producing the compound includes allowing a compound represented by formula (1) (in the formula, Arrepresents a heteroarylene compound and H represents a hydrogen atom) and a compound represented by formula (2) (in the formula, Arrepresents a heteroarylene compound and X represents a chlorine atom, a bromine atom or an iodine atom, provided that two X may be the same or different) to react with each other in the presence of an alkaline compound or a phosphine compound.

Description

  The present invention relates to a method for producing a compound.

In recent years, electronic devices including an organic layer as a functional layer, such as an organic electroluminescence element (sometimes referred to as an organic EL element), an organic thin film solar cell, and an organic thin film transistor, have been actively developed. In particular, a high molecular compound is used as the functional material of the organic layer, and an electronic device can be produced by forming an organic layer by applying a film by a simple coating method. This is possible, and significant manufacturing cost reduction is expected.
As a method for producing a polymer compound, the structure of the polymer compound can be easily controlled, and a compound having a higher molecular weight can be synthesized under relatively mild conditions. Therefore, production of a polymer compound using Suzuki coupling or Stille coupling is possible. The method is widely adopted.

  As a method for producing a polymer compound using Suzuki coupling, a heterocyclic compound represented by the following formula (A) is reacted with a heterocyclic compound represented by the following formula (B), and the following formula: A method for producing a polyheteroarylene containing a heteroarylene group represented by (C) as a residue has been proposed (see Non-Patent Document 1).

Advanced Functional Materials (Adv. Funct. Mater.), 2009, Vol. 19, p. 3262-3270

  However, in the method for producing a polymer compound using Suzuki coupling, a monomer containing a borate ester residue is used, or in the method for producing a polymer compound using Stille coupling, a monomer containing an organotin residue is used. Since it is used, a structure derived from a boric acid ester residue or an organotin residue is included in the produced polymer compound, and these have been a cause of deterioration in characteristics of the electronic device.

  In view of this, the present invention provides a high-residue containing a heteroarylene group as a residue by reacting two or more kinds of heterocyclic compounds without using a monomer containing a borate ester residue and a monomer containing an organotin residue. It aims at providing the manufacturing method of the compound which can manufacture a molecular compound.

（式（１）中、Ａｒ^１は、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基で置換されていてもよいヘテロアリーレン基を表す。Ｈは、水素原子を表す。）
で表される化合物と、
下記式（２）：

（式（２）中、Ａｒ^２は、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基で置換されていてもよいヘテロアリーレン基を表す。Ｘは、塩素原子、臭素原子又はヨウ素原子を表す。２個あるＸは、同一でも相異なってもよい。）
で表される化合物とを反応させる、
下記式（３）：

（式（３）中、Ａｒ^１及びＡｒ^２は、前述と同じ意味を表す。ｎは、１以上の数を表す。）
で表される構造単位を含む化合物の製造方法。
［２］ 式（１）で表される化合物と式（２）で表される化合物とを、遷移金属化合物の存在下で反応させる、［１］に記載の化合物の製造方法。
［３］ 式（１）で表される化合物と式（２）で表される化合物とを、塩基性化合物の存在下で反応させる、［１］又は［２］に記載の化合物の製造方法。
［４］ 式（１）で表される化合物と式（２）で表される化合物とを、ホスフィン化合物の存在下で反応させる、［１］〜［３］のいずれか１つに記載の製造方法。
［５］ Ａｒ^１が、１個〜３個の電子吸引性の置換基を有しているヘテロアリーレン基である、［１］〜［４］のいずれか１つに記載の化合物の製造方法。
［６］ 電子吸引性の置換基が、フッ素原子である、［５］に記載の製造方法。
［７］ Ａｒ^２が、下記式（５）で表される基である、［１］〜［６］のいずれか１つに記載の製造方法。

［式（５）中、Ａｒ^１３及びＡｒ^１４は、それぞれ独立に、芳香族複素環式化合物又は芳香族炭素環化合物から水素原子を３個取り除いた基を表し、該芳香族複素環式化合物及び芳香族炭素環化合物のうちの少なくとも一方は、フッ素原子、シアノ基、ニトロ基、アミノ基若しくは１価の有機基で置換されていてもよい。ただし、Ａｒ^１３及びＡｒ^１４のうちの少なくとも一方は、フッ素原子、シアノ基、ニトロ基、アミノ基若しくは１価の有機基で置換されていてもよい芳香族複素環式化合物から水素原子を３個取り除いた基である。Ａは、下記式（４−１）〜式（４−１２）で表される２価の基を表す。

（式（４−１）〜式（４−１２）中、Ｒ^１〜Ｒ^１５は、それぞれ独立に、水素原子、フッ素原子、シアノ基、ニトロ基、アミノ基又は１価の有機基を表す。）］
［８］ Ａｒ^２が、チオフェン環構造を含むヘテロアリーレン基である、［１］〜［７］のいずれか１つに記載の化合物の製造方法。
［９］ ［１］〜［８］のいずれか１つに記載の化合物の製造方法により、得ることができる化合物。
［１０］ 質量分析法で求めた化合物中のスズの含有量と化合物中のホウ素の含有量との和が、１重量ｐｐｍ未満である、［９］に記載の化合物。 That is, the present invention provides the following [1] to [10].
[1] The following formula (1):

(In Formula (1), Ar ¹ represents a fluorine atom, a cyano group, a nitro group, an amino group, or a heteroarylene group optionally substituted with a monovalent organic group. H represents a hydrogen atom.)
A compound represented by
Following formula (2):

(In the formula (2), Ar ² represents a fluorine atom, a cyano group, a nitro group, an amino group or a heteroarylene group optionally substituted with a monovalent organic group. X represents a chlorine atom, a bromine atom or Represents an iodine atom, and two Xs may be the same or different.)
With a compound represented by
Following formula (3):

(In formula (3), Ar ¹ and Ar ² represent the same meaning as described above. N represents a number of 1 or more.)
The manufacturing method of the compound containing the structural unit represented by these.
[2] The method for producing a compound according to [1], wherein the compound represented by the formula (1) and the compound represented by the formula (2) are reacted in the presence of a transition metal compound.
[3] The process for producing a compound according to [1] or [2], wherein the compound represented by the formula (1) and the compound represented by the formula (2) are reacted in the presence of a basic compound.
[4] The production according to any one of [1] to [3], wherein the compound represented by the formula (1) and the compound represented by the formula (2) are reacted in the presence of a phosphine compound. Method.
[5] The method for producing a compound according to any one of [1] to [4], wherein Ar ¹ is a heteroarylene group having 1 to 3 electron-withdrawing substituents.
[6] The production method according to [5], wherein the electron-withdrawing substituent is a fluorine atom.
[7] The production method according to any one of [1] to [6], wherein Ar ² is a group represented by the following formula (5).

[In the formula (5), Ar ¹³ and Ar ¹⁴ each independently represent a group obtained by removing three hydrogen atoms from an aromatic heterocyclic compound or an aromatic carbocyclic compound, and the aromatic heterocyclic compound and At least one of the aromatic carbocyclic compounds may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. However, at least one of Ar ¹³ and Ar ¹⁴ contains three hydrogen atoms from an aromatic heterocyclic compound which may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. The removed group. A represents a divalent group represented by the following formula (4-1) to formula (4-12).

(In Formula (4-1) to Formula (4-12), R ^{1 to} R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. ]]
[8] The method for producing a compound according to any one of [1] to [7], wherein Ar ² is a heteroarylene group containing a thiophene ring structure.
[9] A compound that can be obtained by the method for producing a compound according to any one of [1] to [8].
[10] The compound according to [9], wherein the sum of the tin content in the compound and the boron content in the compound determined by mass spectrometry is less than 1 ppm by weight.

The production method of the present invention can produce a polymer compound useful as a functional material of an electronic device such as a photoelectric conversion device without using a monomer containing a borate ester residue and a monomer containing an organic tin residue.
Since the compound of the present invention produced by the above production method can be produced without using a monomer containing a boric acid ester residue and a monomer containing an organotin residue, the content of tin in the compound and in the compound The boron content of can be made extremely small. Therefore, when the compound of the present invention is used as a functional material for an electronic device, further improvement in the electrical characteristics of the electronic device is expected.

Hereinafter, the present invention will be described in detail.
The present invention includes a compound represented by the following formula (1):

下記式（２）で表される化合物とを反応させる、

Reacting with a compound represented by the following formula (2):

下記式（３）で表される構造単位を含む化合物の製造方法に関するものである。

The present invention relates to a method for producing a compound containing a structural unit represented by the following formula (3).

In formula (1), Ar ¹ represents a heteroarylene group which may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group. H represents a hydrogen atom.
The heteroarylene group which may have a substituent is a group obtained by removing two hydrogen atoms from an aromatic heterocyclic compound which may have a substituent. Examples of the heteroarylene group which may have a substituent include a group obtained by removing two hydrogen atoms from a monocyclic aromatic heterocyclic compound which may have a substituent, and a substituent. A group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic heterocyclic compound in which two or more monocyclic aromatic heterocyclic compounds may be condensed with each other may have a substituent. Two or more monocyclic or polycyclic aromatic heterocyclic compounds are linked directly or via a divalent group such as a methylene group, an ethylene group, or a carbonyl group. In the aromatic heterocyclic compound which may have a substituent, a group obtained by removing one hydrogen atom from each of two different aromatic rings in the aromatic heterocyclic compound and a substituent. The monocyclic or polycyclic aromatic heterocyclic compounds which may be A bridge having a substituent which is bonded by a tangential bond and two or more bonds selected from the group consisting of a bond through a divalent group such as a methylene group, an ethylene group or a carbonyl group; And a group obtained by removing two hydrogen atoms from a polycyclic aromatic heterocyclic compound.
Examples of the monovalent organic group that is a substituent that the heteroarylene group may have include an alkyl group that may be substituted with a fluorine atom, an alkoxy group that may be substituted with a fluorine atom, and a fluorine atom. Alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, substituted amino group, substituted silyl group, Examples thereof include a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, a heterocyclic oxy group, a heterocyclic thio group, an arylalkenyl group, an arylalkynyl group, and a carboxyl group.

  The alkyl group that may be possessed by the heteroarylene group and may be further substituted with a fluorine atom may be linear or branched, or may be a cycloalkyl group. The number of carbon atoms of the alkyl group which may be substituted with a fluorine atom is usually 1-30, preferably 1-20. Specific examples of the alkyl group which may be substituted with a fluorine atom include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, n -Pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl Group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, eicosyl group and other chain alkyl groups, cyclopentyl group, cyclohexyl group And a cycloalkyl group such as an adamantyl group.

  The alkoxy group that may be possessed by the heteroarylene group and may be further substituted with a fluorine atom may be linear or branched, or may be a cycloalkoxy group. The number of carbon atoms of the alkoxy group is usually about 1 to 30, and preferably 1 to 20. Specific examples of the alkoxy group which may be substituted with a fluorine atom include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyl group. Oxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group Perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group, and 2-methoxyethyloxy group.

  The alkylthio group which may be substituted with a fluorine atom may be linear or branched, and may be a cycloalkylthio group. The number of carbon atoms of the alkylthio group is usually about 1 to 30, and preferably 1 to 20. Specific examples of the alkylthio group which may be substituted with a fluorine atom 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, and a cyclohexylthio group. Group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group.

The aryl group which is a substituent that the heteroarylene group may have is a group obtained by removing one hydrogen atom from an aromatic carbocyclic compound which may have a substituent. Examples of the aryl group include a group obtained by removing one hydrogen atom from a monocyclic aromatic carbocyclic compound which may have a substituent, and a monocyclic aromatic carbocycle which may have a substituent. A group obtained by removing one hydrogen atom from a condensed polycyclic aromatic carbocyclic compound in which two or more selected from the compounds are condensed with each other, or two or more aromatic carbocyclic compounds optionally having a substituent From a bridged polycyclic aromatic carbocyclic compound optionally having a substituent, having a structure in which a direct bond or a divalent group such as a methylene group, an ethylene group or a carbonyl group is bridged And a group in which one is removed.
Examples of the substituent that the aromatic carbocyclic compound may have include a fluorine atom, an alkyl group that may be substituted with a fluorine atom, an alkoxy group that may be substituted with a fluorine atom, and a substituent that is substituted with a fluorine atom. The alkylthio group which may be mentioned is mentioned. The number of carbon atoms and specific examples of the alkyl group optionally substituted with a fluorine atom, the alkoxy group optionally substituted with a fluorine atom, and the alkylthio group optionally substituted with a fluorine atom include the above heteroarylene group. The number of carbon atoms of the alkyl group which may be substituted with a fluorine atom, the alkoxy group which may be substituted with a fluorine atom, and the alkylthio group which may be substituted with a fluorine atom, which are exemplified as the substituents which may have Same as example.
The number of carbon atoms of the aryl group is usually about 6 to 60, preferably 6 to 20. Specific examples of the aryl group include a phenyl group, a C1-C12 alkyloxyphenyl group, a C1-C12 alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a pentafluorophenyl group.
Here, “C” represents a carbon atom, and the number attached represents the number of carbon atoms in the group described immediately after. That is, the “C1 to C12 alkyloxyphenyl group” means a group having an alkyl (oxy) group having 1 to 12 carbon atoms, and the same applies to the following. Specific examples of the C1-C12 alkyl group, the C1-C8 alkyl group, and the C1-C6 alkyl group are substituents that the heteroarylene group may have, and further an alkyl group that may be substituted with a fluorine atom. What has been described and illustrated.

  The aryloxy group, which is a substituent that the heteroarylene group may have, usually has about 6 to 60 carbon atoms, and preferably 6 to 20 carbon atoms. Specific examples of the aryloxy group include a phenoxy group, a C1-C12 alkyloxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group.

  The arylthio group, which is a substituent that the heteroarylene group may have, usually has about 6 to 60 carbon atoms, and preferably 6 to 20 carbon atoms. Specific examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

  The arylalkyl group, which is a substituent that the heteroarylene group may have, usually has about 7 to 60 carbon atoms, and preferably 7 to 20 carbon atoms. Specific examples of the arylalkyl group include a phenyl-C1-C12 alkyl group, a C1-C12 alkyloxyphenyl-C1-C12 alkyl group, a C1-C12 alkylphenyl-C1-C12 alkyl group, and a 1-naphthyl-C1-C12 alkyl group. Group, 2-naphthyl-C1-C12 alkyl group.

  The arylalkyloxy group which is a substituent that the heteroarylene group may have usually has about 7 to 60 carbon atoms, and preferably 7 to 20 carbon atoms. Specific examples of the arylalkyloxy group include phenyl-C1-C12 alkyloxy group, C1-C12 alkyloxyphenyl-C1-C12 alkyloxy group, C1-C12 alkylphenyl-C1-C12 alkyloxy group, 1-naphthyl- A C1-C12 alkyloxy group and a 2-naphthyl-C1-C12 alkyloxy group are mentioned.

  The arylalkylthio group, which is a substituent that the heteroarylene group may have, usually has about 7 to 60 carbon atoms, and preferably 7 to 20 carbon atoms. Specific examples of the arylalkylthio group include a phenyl-C1-C12 alkylthio group, a C1-C12 alkyloxyphenyl-C1-C12 alkylthio group, a C1-C12 alkylphenyl-C1-C12 alkylthio group, and a 1-naphthyl-C1-C12 alkylthio group. Group, 2-naphthyl-C1-C12 alkylthio group.

  The acyl group which is a substituent that the heteroarylene group may have means a group excluding the hydroxyl group in the carboxyl group (—COOH) of the carboxylic acid, and the number of carbon atoms is usually 2-20. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a trifluoroacetyl group, etc., and an alkylcarbonyl optionally substituted with a halogen atom having 2 to 20 carbon atoms. Group, a benzoyl group, a phenylcarbonyl group which may be substituted with a halogen such as a pentafluorobenzoyl group.

  The acyloxy group which is a substituent that the heteroarylene group may have means a group excluding a hydrogen atom in a carboxyl group (—COOH) of a carboxylic acid, and usually has 2 to 20 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

  The amide group, which is a substituent that the heteroarylene group may have, means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from the amide, and the number of carbon atoms is usually 2-20. Specific 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, and a dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.

  The acid imide group which is a substituent which the heteroarylene group may have refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid imide. Specific examples of the acid imide group include a succinimide group and a phthalimide group.

  The substituted amino group which is a substituent that the heteroarylene group may have is one in which one or two of the hydrogen atoms of the amino group are substituted with a substituent. Examples of the substituent include: An alkyl group and an aryl group are mentioned. Specific examples of the alkyl group and aryl group are the same as the number of carbon atoms and specific examples of the alkyl group and aryl group which may be substituted with the above-described fluorine atom. The number of carbon atoms of the substituted amino group is usually 1-40. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 alkyl Oxyphenylamino group, di (C1-C12 alkyloxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Dazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkyloxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 alkyl Amino group, di (C1-C12 alkyloxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group and 2-naphthyl -C1-C 2 alkylamino group.

  The substituted silyl group, which is a substituent that the heteroarylene group may have, is a group in which one, two, or three of the hydrogen atoms of the silyl group are substituted with a substituent. The substituted silyl group is generally one in which all three hydrogen atoms of the silyl group are substituted with a substituent, and the substituent is, for example, an alkyl group and an aryl group. The number of carbon atoms and specific examples of the alkyl group and aryl group are the same as the number of carbon atoms and specific examples of the alkyl group and aryl group described above. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

  The substituted silyloxy group that is a substituent that the heteroarylene group may have is a group in which an oxygen atom is bonded to a substituted silyl group that is a substituent that the heteroarylene group may have. Specific examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylyl group. Examples thereof include a silyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

  The substituted silylthio group, which is a substituent that the heteroarylene group may have, is a group in which a sulfur atom is bonded to the substituted silyl group. Specific examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, triisopropylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, and tri-p-xylyl. Examples thereof include a silylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

  The substituted silylamino group that is a substituent that the heteroarylene group may have is a group in which one or two of the hydrogen atoms of the amino group are substituted with a substituted silyl group, and the substituted silyl group is the above substituted silyl group. Is the same. Specific examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylyl. Silylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, bis (tripropylsilyl) ) Amino group, bis (triisopropylsilyl) amino group, bis (tert-butyldimethylsilyl) amino group, bis (triphenylsilyl) amino group, bis (tri-p-xylylsilyl) amino group, bis (tribe Jirushiriru) amino group, bis (diphenylmethylsilyl) amino group, bis (tert- butyldiphenylsilyl) amino group and bis (dimethylphenylsilyl) and amino group.

  As the monovalent heterocyclic group that is a substituent that the heteroarylene group may have, an optionally substituted furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, Imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, Benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quino Gin, benzimidazole, benzothiazole, indazole, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, And a group obtained by removing one hydrogen atom from a heterocyclic compound such as phenoxazine, phenothiazine, and phenazine. As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable.

  Examples of the heterocyclic oxy group that is a substituent that the heteroarylene group may have include a group represented by the following formula (11) in which an oxygen atom is bonded to the monovalent heterocyclic group. Examples of the heterocyclic thio group include a group represented by the following formula (12) in which a sulfur atom is bonded to the monovalent heterocyclic group.

式（１１）及び式（１２）中、Ａｒ^７は、１価の複素環基を表す。

In formula (11) and formula (12), Ar ⁷ represents a monovalent heterocyclic group.

The heterocyclic oxy group usually has about 4 to 60 carbon atoms. Specific examples of the heterocyclic oxy group include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.
The heterocyclic thio group, which is a substituent that the heteroarylene group may have, usually has about 4 to 60 carbon atoms. Specific examples of the heterocyclic thio group include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.

  The arylalkenyl group, which is a substituent that the heteroarylene group may have, usually has 8 to 20 carbon atoms, and a specific example of the arylalkenyl group includes a styryl group.

  The arylalkynyl group, which is a substituent that the heteroarylene group may have, usually has 8 to 20 carbon atoms, and specific examples of the arylalkynyl group include a phenylacetylenyl group.

In the formula (1), examples of the group represented by Ar ¹ include groups represented by the following formula 39 to formula 205.

  The groups represented by Formula 39 to Formula 205 and R each independently represent a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group.

  The definition and specific examples of the monovalent organic group represented by R are the same as the definition and specific examples of the monovalent organic group that the above-described heteroarylene group may have.

Of the groups represented by Formula 39 to Formula 205, the group represented by Ar ¹ is preferably a group represented by Formula 108 to Formula 127, or a group represented by Formula 131 to Formula 138. The group represented by Ar ¹ is more preferably a group represented by formula 108 to formula 113, a group represented by formula 116 to formula 119, or a group represented by formula 131 to formula 136, and more preferably Is a group represented by Formula 109, Formula 116, or Formula 131, and particularly preferably a group represented by Formula 116.

Ar ¹ is preferably a heteroarylene group substituted with 1 to 3 electron-withdrawing substituents. Examples of the electron-withdrawing substituent include a fluorine atom, a cyano group, a nitro group, an acyl group, and a carboxyl group, preferably a fluorine atom, a cyano group, and a nitro group, and particularly preferably a fluorine atom.

In Formula (2), Ar ² represents a heteroarylene group which may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. X represents a chlorine atom, a bromine atom or an iodine atom. Two Xs may be the same or different.
The definition and specific examples of the heteroarylene group and the monovalent organic group are the definition and specific examples of the heteroarylene group represented by the aforementioned Ar ¹ and the monovalent organic group that the heteroarylene group may have. The same.

Specific examples of the heteroarylene group which may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group represented by Ar ² are represented by the above formulas 39 to 205. Group. Among the groups represented by Formula 39 to Formula 205, preferably a group represented by Formula 94, a group represented by Formula 128 to Formula 139, a group represented by Formula 142, a group represented by Formula 147, A group represented by Formula 152, a group represented by Formula 157, a group represented by Formula 162, a group represented by Formula 167 to Formula 172, and more preferably a group represented by Formula 128 and a formula A group represented by Formula 142, a group represented by Formula 162, and particularly preferably a group represented by Formula 162.

Since the reactivity can be further increased, Ar ² is preferably a group represented by the following formula (5).

In formula (5), Ar ¹³ and Ar ¹⁴ each independently represents a hydrogen atom from an aromatic carbocyclic compound optionally substituted with a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group. A group obtained by removing three hydrogen atoms from a group obtained by removing three or an aromatic heterocyclic compound which may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group or a monovalent organic group. However, at least one of Ar ¹³ and Ar ¹⁴ contains three hydrogen atoms from an aromatic heterocyclic compound which may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. The removed group.

The number of carbon atoms of the aromatic carbocyclic compound that can be Ar ¹³ and Ar ¹⁴ is usually 6 to 60, preferably 6 to 20. The aromatic carbocyclic compound may have a substituent, and examples of the substituent include a fluorine atom, a cyano group, a nitro group, an amino group, and a monovalent organic group. The definition and specific examples of the monovalent organic group are the same as the definition and specific examples of the monovalent organic group that the heteroarylene group represented by Ar ¹ may have.

  Examples of the group obtained by removing three hydrogen atoms from the aromatic carbocyclic compound include the following groups.

The number of carbon atoms of the aromatic heterocyclic compound that can be Ar ¹³ and Ar ¹⁴ is usually 2 to 60, preferably 4 to 20. The aromatic heterocyclic compound may have a substituent, and examples of the substituent include a fluorine atom, a cyano group, a nitro group, an amino group, and a monovalent organic group. The definition and specific examples of the monovalent organic group are the same as the definition and specific examples of the monovalent organic group that the heteroarylene group represented by Ar ¹ may have.

  Examples of the group obtained by removing three hydrogen atoms from this aromatic heterocyclic compound include groups represented by the following formulas (206) to (289).

In the groups represented by formula (206) to formula (289), R ′ each independently represents a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aryl. An alkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group or cyano group is represented.
R ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group or a monovalent heterocyclic group.

  An alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide group, aryl represented by R ′ The definition and specific examples of the alkenyl group, arylalkynyl group, and monovalent heterocyclic group include the halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aryl represented by the aforementioned R. The definition and specific examples of the alkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide group, arylalkenyl group, arylalkynyl group and monovalent heterocyclic group are the same.

  The definition and specific examples of the alkyl group, aryl group, arylalkyl group, substituted silyl group, and monovalent heterocyclic group represented by R ″ are the alkyl group, aryl group, and arylalkyl represented by R described above. The definition and specific examples of the group, substituted silyl group and monovalent heterocyclic group are the same.

  In formula (5), A represents a divalent group represented by the following formula (4-1) to formula (4-12).

In formulas (4-1) to (4-12), R ^{1 to} R ¹⁵ each independently represent any of a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. . The definition and specific examples of the monovalent organic group are the same as the definition and specific examples of the monovalent organic group that the heteroarylene group represented by Ar ¹ may have.

  In the present invention, a compound containing a structural unit represented by the following formula (3) is produced by reacting a compound represented by the formula (1) with a compound represented by the formula (2).

In formula (3), Ar ¹ and Ar ² represent the same meaning as described above. n represents an integer of 1 or more.
n is preferably an integer of 2 or more, more preferably an integer of 3 or more, and particularly preferably an integer of 5 or more.

  The molecular weight of the compound containing the structural unit represented by the formula (3) is preferably 500 or more, more preferably 1000 or more, and particularly preferably 3000 or more. When the compound containing the structural unit represented by formula (3) has a molecular weight distribution, the number average molecular weight of the compound containing the structural unit represented by formula (3) is preferably 500 or more, more preferably 1000 or more. Especially preferably, it is 3000 or more.

In the method for producing a compound of the present invention, the compound represented by the formula (1) and the compound represented by the formula (2) are preferably reacted in the presence of a transition metal compound as a catalyst. Examples of the transition metal compound include a palladium compound, a ruthenium compound, a rhodium compound, a nickel compound, an iron compound, and a copper compound, preferably a palladium compound and a rhodium compound, and particularly preferably a palladium compound.
Examples of the palladium compound include a Pd (0) compound and a Pd (II) compound. Specific examples include palladium [tetrakis (triphenylphosphine)], dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, and reaction (polymerization). From the viewpoint of ease of operation and reaction (polymerization) rate, palladium acetate is preferred.

  The addition amount of a catalyst is not specifically limited, What is necessary is just an effective amount as a catalyst. For example, the addition amount of the palladium compound is usually 0.0001 mol to 0.5 mol, preferably 0.0003 mol to 0.2 mol, relative to 1 mol of the compound represented by the formula (1).

  In the manufacturing method of the compound of this invention, it is preferable to make the compound represented by Formula (1), and the compound represented by Formula (2) react in presence of a basic compound.

Examples of basic compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, phosphoric acid Examples include potassium hydrogen, sodium hydrogen phosphate, and tert-butoxy potassium. Among basic compounds, preferably sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, more preferably sodium carbonate, Potassium carbonate, cesium carbonate, lithium carbonate, potassium phosphate, sodium phosphate, and cesium phosphate are preferable, and sodium carbonate, potassium carbonate, cesium carbonate, and lithium carbonate are particularly preferable.
The addition amount of the basic compound is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the compound represented by the formula (1). Is a mole.

In the method for producing a compound of the present invention, the compound represented by the formula (1) and the compound represented by the formula (2) may be reacted in the presence of a ligand. Examples of the ligand include phosphine compounds, amine compounds, pyridines and the like.
Examples of the phosphine compound include triarylphosphine, trialkylphosphine, diarylmonoalkylphosphine, monoaryldialkylphosphine, and the like. Examples of triarylphosphine include triphenylphosphine, tri (o-tolyl) phosphine, and tri (o-methoxyphenyl) phosphine. Examples of the trialkylphosphine include tricyclohexylphosphine, tri (tert-butyl) phosphine, and bis (tert-butyl) methylphosphine. Examples of the monoaryldialkylphosphine include bis (cyclohexyl) biphenylphosphine and bis (tert-butyl) biphenylphosphine.
Examples of the amine compound include triarylamine, trialkylamine, diarylmonoalkylamine, monoaryldialkylamine and the like. Examples of pyridines include pyridine and bipyridine. Among the ligands, a phosphine compound is preferable, trialkylphosphine is more preferable, and tricyclohexylphosphine is still more preferable.

The reaction of the compound represented by the formula (1) and the compound represented by the formula (2) is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide (hereinafter sometimes referred to as DMF), N, N-dimethylacetamide (hereinafter sometimes referred to as DMAc), toluene, dimethoxyethane, and tetrahydrofuran.
From the viewpoint of the solubility of the compound containing the structural unit represented by the formula (3), the solvent is preferably toluene or tetrahydrofuran.
Further, an aqueous solution of a basic compound may be further added, and the reaction may be carried out in a solvent composed of two phases of an aqueous phase and an organic phase. When an inorganic salt is used as the basic compound, it is usually added as an aqueous solution of the inorganic salt and reacted from the viewpoint of solubility of the inorganic salt.
In addition, when making it react in the solvent which consists of two phases, an aqueous phase and an organic phase, adding as aqueous solution of a basic compound, you may add phase transfer catalysts, such as a quaternary ammonium salt, as needed.

  The temperature of the reaction between the compound represented by the formula (1) and the compound represented by the formula (2) is usually about 50 ° C. to 160 ° C., depending on the solvent, and is represented by the formula (3). From the viewpoint of increasing the molecular weight of the compound containing the structural unit, 60 ° C. to 120 ° C. is preferable. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may end when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 hour to 30 hours is efficient and preferable.

  When the reaction between the compound represented by formula (1) and the compound represented by formula (2) is performed in the presence of a catalyst, the reaction in which the catalyst is not deactivated, such as in an inert atmosphere such as argon gas or nitrogen gas Perform in the system. For example, the reaction is performed in a system sufficiently deaerated with argon gas, nitrogen gas, or the like. Specifically, the gas in the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas, and the compound represented by the formula (1), the compound represented by the formula (2), and the palladium compound are added to the polymerization vessel. In addition, the gas in the polymerization vessel is sufficiently replaced with nitrogen gas and bubbled with nitrogen gas in advance to add a degassed solvent, for example, DMAc, and then bubbled with nitrogen gas in advance to the resulting solution. After adding a basic compound degassed by this, for example, potassium carbonate, the mixture is heated and heated, and reacted, for example, at 100 ° C. for 24 hours while maintaining an inert atmosphere.

When a compound containing the structural unit represented by the formula (3), which is produced by the method for producing a compound of the present invention, is used as a functional material for an electronic device, from the viewpoint of enhancing the properties of the electronic device, It is preferable that the amount of metal element and boron element contained is small. Especially, it is preferable that there are few amounts of the transition metal element, typical metal element, and boron element which are contained in the compound containing the structural unit represented by Formula (3). Examples of the transition metal element include palladium, iron, tin, nickel, and copper. Among them, it is preferable that the amount of palladium, iron, and tin is small, and it is particularly preferable that the amount of tin is small. The amount of the impurity element contained in the compound containing the structural unit represented by the formula (3) produced by the production method of the present invention is measured by elemental analysis, but the total of the tin content and the boron content The amount is preferably 50 ppm or less, more preferably 10 ppm or less, still more preferably 1 ppm or less, and particularly preferably 0.5 ppm or less.
Examples of elemental analysis methods include atomic absorption spectrometry, emission spectroscopy, plasma emission analysis, fluorescent X-ray analysis, plasma mass spectrometry, glow discharge mass spectrometry, ion chromatography analysis, and the like. .

  Since the compound containing the structural unit represented by the formula (3) produced by the production method of the present invention can exhibit high electron and / or hole transportability, an organic thin film containing the compound is used. When used in an element, electrons, holes, or charges generated by light absorption injected from the electrode can be transported. Taking advantage of these characteristics, it can be suitably used for various devices such as a photoelectric conversion device, an organic thin film transistor, and an organic EL device. Hereinafter, these elements will be described individually.

<Photoelectric conversion element>
The photoelectric conversion element containing the compound containing the structural unit represented by the formula (3), which is produced by the method for producing a compound of the present invention, as a functional material is between the first electrode and the second electrode, It has 1 or more active layers containing the compound containing the structural unit represented by Formula (3) manufactured with the manufacturing method of the compound of this invention.
As a preferable form of the photoelectric conversion element, an organic composition containing a pair of electrodes (first electrode and second electrode) at least one of which is transparent or translucent, an electron donating compound, and an electron accepting compound is used. It has an active layer to be formed. The compound containing the structural unit represented by the formula (3) produced by the production method of the present invention is preferably used as an electron donating compound.

  The photoelectric conversion element is usually formed on a substrate. This substrate should just be what does not change chemically, when forming an electrode and forming the layer of an organic composition. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the side opposite to the substrate (that is, the electrode far from the substrate) is transparent or translucent.

  The other aspect of the photoelectric conversion element which has a compound containing the structural unit represented by Formula (3) manufactured by the manufacturing method of the compound of the present invention is between a pair of electrodes, at least one of which is transparent or translucent. A first active layer containing a compound containing the structural unit represented by the formula (3), which is produced by the method for producing a compound of the present invention, and a fullerene derivative or the like adjacent to the first active layer. It is a photoelectric conversion element containing the 2nd active layer containing an electron-accepting compound.

  It is preferable that the compound represented by Formula (3) used for said photoelectric conversion element is a high molecular compound.

Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium tin oxide (ITO), indium zinc oxide (IZO), or the like, which is a composite of indium oxide, zinc oxide, tin oxide, NESA, Gold, platinum, silver, copper films and the like are used, and ITO, IZO, and tin oxide are preferable. Examples of the electrode forming method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

  When one electrode is transparent or translucent, the other electrode may not be transparent, and as an electrode material of the opaque electrode, a metal, a conductive polymer, or the like can be used. Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin. Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  In order to improve the photoelectric conversion efficiency, an additional intermediate layer other than the active layer may be used. Examples of the material for the intermediate layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene).

<Active layer>
The active layer may contain one type of compound containing the structural unit represented by formula (3), which is produced by the method for producing a compound of the present invention, or may contain two or more types in combination. Moreover, in order to improve the hole transport property of an active layer, it represents with Formula (3) manufactured with the manufacturing method of the compound of this invention as an electron-donating compound and / or an electron-accepting compound in an active layer. A compound other than the compound containing a structural unit can also be used as a mixture. The electron donating compound and the electron accepting compound are relatively determined from the energy levels of these compounds.

  Examples of the electron donating compound include compounds containing the structural unit represented by the formula (3) produced by the method for producing a compound of the present invention, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine. Derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amine residues in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof , Polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

Examples of the electron-accepting compound include compounds containing a structural unit represented by the formula (3) produced by the method for producing a compound of the present invention, as well as, for example, carbon materials, metal oxides such as titanium oxide, oxadi Azole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8 -Metal complexes of hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, phenanthates such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocproline) Phosphorus derivatives, fullerenes, include fullerene derivative, preferably, titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.
Fullerenes include C ₆₀ fullerene, C ₇₀ fullerene, C ₇₆ fullerene, C ₇₈ fullerene, C ₈₄ fullerene, C ₈₄ fullerene derivatives, C ₆₀ fullerene derivatives, C ₇₀ fullerene derivatives, C ₇₆ fullerene derivatives, C ₇₈ fullerene derivatives, Derivatives and derivatives of C ₈₄ fullerene. Here, “C” represents a carbon atom, and the number attached to the subscript represents the number of carbon atoms.
The fullerene derivative represents a compound in which at least a part of fullerene is modified.

  Examples of the fullerene derivative include a compound represented by the following formula (I), a compound represented by the following formula (II), a compound represented by the following formula (III), and a compound represented by the formula (IV). Can be mentioned.

In formulas (I) to (IV), R ^a is an alkyl group, an aryl group, a heteroaryl group or a group having an ester structure which may be substituted with a fluorine atom. A plurality of ^Ra may be the same or different. R ^b represents an alkyl group or an aryl group which may be substituted with a fluorine atom. A plurality of R ^b may be the same or different.

The number of carbon atoms and specific examples of the alkyl group, aryl group, and heteroaryl group that may be substituted with a fluorine atom represented by ^Ra include the heteroarylene group represented by Ar ¹ described above. This is the same as the number of carbon atoms and specific examples of the alkyl group, aryl group and heteroaryl group which may be substituted with a good fluorine atom.
The number of carbon atoms and specific examples of the alkyl group and aryl group that may be substituted with a fluorine atom represented by R ^b are the fluorine atoms that the heteroarylene group represented by Ar ¹ may have. The number of carbon atoms and the specific examples of the alkyl group and aryl group which may be substituted with atoms are the same.

Examples of the group having an ester structure represented by ^Ra include a group represented by the following formula (V).

In formula (V), u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R ^c represents an alkyl group, aryl group or heteroaryl group optionally substituted with a fluorine atom. Represents. )

The number of carbon atoms and specific examples of the alkyl group, aryl group, and heteroaryl group that may be substituted with a fluorine atom represented by R ^c may be the same as the heteroarylene group represented by Ar ¹ described above. The number of carbon atoms of the alkyl group, aryl group and heteroaryl group which may be substituted with a fluorine atom and the specific examples are the same.

Specific examples of the C ₆₀ fullerene derivative include the following compounds.

Specific examples of the C ₇₀ fullerene derivative include the following compounds.

Examples of fullerene derivatives include [6,6] phenyl-C ₆₁ butyric acid methyl ester (C ₆₀ PCBM, [6,6] -Phenyl C ₆₁ butyric acid methyl ester), [6,6] phenyl-C _71. Butyric acid methyl ester (C ₇₀ PCBM, [6,6] -Phenyl C ₇₁ butyric acid methyl ester), [6,6] Phenyl-C ₈₅ butyric acid methyl ester (C ₈₄ PCBM, [6,6] -Phenyl C ₈₅ butyric acid methyl ester), [6,6] thienyl _{-C 61} butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester) and the like.

  When the active layer contains a compound containing the structural unit represented by the formula (3) obtained by the method for producing the compound of the present invention and a fullerene derivative, the ratio of the fullerene derivative is obtained by the method for producing the compound of the present invention. It is preferable that it is 10-1000 weight part with respect to 100 weight part of compounds containing the structural unit represented by Formula (3) obtained, and it is more preferable that it is 20 weight part-500 weight part.

  The thickness of the active layer is usually preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.

  The active layer may be manufactured by any method, and examples thereof include a film forming method using a solution containing a polymer compound and a solvent, and a film forming method using a vacuum deposition method.

<Method for producing photoelectric conversion element>
A preferred method for producing a photoelectric conversion element is a method for producing an element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode, A coating film is formed by a coating method in which a solution (ink) containing a compound containing a structural unit represented by the formula (3) and a solvent obtained by the method for producing a compound of the present invention is applied onto the first electrode. A method of manufacturing an element having a step of forming an active layer and a step of forming a second electrode on the active layer.

  The solvent used in the coating method using a solution may be any solvent that dissolves the compound containing the structural unit represented by the formula (3) obtained by the method for producing a compound of the present invention. Examples of the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene, carbon tetrachloride, chloroform, and dichloromethane. Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, and halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene Examples of the solvent include ether solvents such as tetrahydrofuran and tetrahydropyran. The compound containing the structural unit represented by the formula (3) obtained by the method for producing a compound of the present invention can be usually dissolved in the solvent in an amount of 0.1% by weight or more.

When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Application methods such as spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, capillary coating, slit coating, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an ink jet coating method, and a spin coating method are preferable.
From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.

<Organic thin film transistor>
The compound containing the structural unit represented by Formula (3) obtained by the method for producing a compound of the present invention can also be used for an organic thin film transistor. As an organic thin film transistor, a source electrode and a drain electrode, an organic semiconductor layer (active layer) formed as an organic thin film serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path are provided. What has the structure provided is mentioned. Examples of such organic thin film transistors include field effect organic thin film transistors and electrostatic induction type organic thin film transistors.

A field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an organic semiconductor layer and a gate electrode It is preferable to provide an insulating layer disposed between the two.
In particular, the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer (active layer) and further have a structure in which a gate electrode is provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween. In the field effect organic thin film transistor, the organic semiconductor layer is constituted by an organic thin film containing a compound containing a structural unit represented by the formula (3), which is obtained by the method for producing a compound of the present invention.

  An electrostatic induction organic thin film transistor has a source electrode and a drain electrode, an organic semiconductor layer (active layer) formed as an organic thin film serving as a current path between them, and a gate electrode for controlling the amount of current passing through the current path. The gate electrode is preferably provided in the organic semiconductor layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer. Here, the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned. Also in the static induction organic thin film transistor, the organic semiconductor layer is constituted by an organic thin film containing a compound containing a structural unit represented by the formula (3), which is obtained by the method for producing a compound of the present invention.

  The compound containing the structural unit represented by the formula (3) used for the organic thin film transistor is preferably a polymer compound.

<Application of device>
The photoelectric conversion element using the compound containing the structural unit represented by the formula (3) obtained by the method of the present invention makes light such as sunlight enter from the transparent or semi-transparent electrode side, thereby allowing the light to enter between the electrodes. Photovoltaic power can be generated and operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

In addition, in a state where a voltage is applied between the electrodes or in a state where no voltage is applied, light is incident from the transparent or translucent electrode side, a photocurrent flows, and the organic light sensor can be operated. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
The organic thin film transistor described above can be used as a pixel driving element used for controlling pixels of an electrophoretic display, a liquid crystal display, an organic EL display, etc., screen brightness uniformity, and screen rewriting speed.

<Solar cell module>
The organic thin film solar cell can have a module structure basically similar to that of a conventional solar cell module. In general, a solar cell module has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin, protective glass, etc., and light is incident from the side opposite to the support substrate side. However, a transparent material such as tempered glass can be used for the support substrate, and a cell can be formed thereon so that light can enter from the transparent support substrate side. Specific examples of the module structure of the solar cell module include a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like. The organic thin-film solar cell produced using the compound containing the structural unit represented by the formula (3) obtained by the method for producing a compound of the present invention can also have these module structures appropriately depending on the purpose of use, place of use and environment. You can choose.

  In a typical super straight type or substrate type solar cell module, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are metal leads or flexible wiring. The current collecting electrodes are arranged on the outer edge portion, and the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filled resin depending on the purpose in order to improve the cell protection and current collection efficiency. . In addition, when the solar cell module is used in a place where it is not necessary to cover the surface with a hard material such as a place where there is little impact from the outside, the surface protective layer is made of a transparent plastic film or the above filling resin is cured. A protective function may be imparted and the support substrate on one side may be eliminated.

  The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. In addition, when a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.

  In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material. Thus, the battery body can be produced. A module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 can also be used. Furthermore, a flexible solar cell using a flexible support can be used by being bonded and fixed to curved glass or the like.

<Organic EL device>
The compound containing the structural unit represented by Formula (3) obtained by the method for producing a compound of the present invention can also be used for an organic EL device. The organic EL element has a light emitting layer between the first electrode and the second electrode. The organic EL element may include a hole transport layer and an electron transport layer as other functional layers of the light emitting layer. The functional material that can be contained in any of the light emitting layer, the hole transport layer, and the electron transport layer includes the structural unit represented by the formula (3) obtained by the method for producing the compound of the present invention. Compounds can be used. In the light emitting layer, in addition to the compound containing the structural unit represented by the formula (3) obtained by the method of the present invention, an electron transport material and a hole transport material (these are collectively referred to as a charge transport material). May be included). Examples of the configuration of the organic EL element include an element having an anode, a light emitting layer, and a cathode, and an anode having an electron transport layer containing an electron transport material adjacent to the light emitting layer between the cathode and the light emitting layer. A structure having a light-emitting layer, an electron transport layer, and a cathode, and having a hole transport layer containing a hole transport material adjacent to the light-emitting layer between the anode and the light-emitting layer, and emitting light with the anode, the hole transport layer, and the light-emitting layer Examples include a structure having a layer and a cathode, and a structure having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode. At least one of the first electrode and the second electrode is preferably transparent or translucent.

  It is preferable that the compound containing the structural unit represented by Formula (3) used for said organic EL element is a high molecular compound.

  Examples are given below to illustrate the present invention in more detail. The present invention is not limited to the following examples.

(NMR measurement)
The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (Varian, INOVA300).

(Measurement of number average molecular weight and weight average molecular weight)
Regarding the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). The polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 30 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

Reference example 1
(Synthesis of Compound 1)
Compound 1 was synthesized according to the following scheme.

  Into a 1000 mL four-necked flask whose internal atmosphere was replaced with argon, 13.0 g (80.0 mmol) of 3-bromothiophene and 80 mL of diethyl ether were added to obtain a uniform solution. While maintaining the solution at −78 ° C., 31 mL (80.6 mmol) of a 2.6M n-butyllithium (n-BuLi) hexane solution was added dropwise. After reacting at −78 ° C. for 2 hours, a solution dissolved in 8.96 g (80.0 mmol) of 3-thiophenaldehyde and 20 mL of diethyl ether was added dropwise to the reaction solution. After the dropping, the reaction solution was stirred at −78 ° C. for 30 minutes, and further stirred at room temperature (25 ° C.) for 30 minutes. The reaction solution was again cooled to −78 ° C., and 62 mL (161 mmol) of 2.6 M n-BuLi in hexane was added dropwise over 15 minutes. After dropping, the reaction solution was stirred at −25 ° C. for 2 hours, and further stirred at room temperature (25 ° C.) for 1 hour. Thereafter, the reaction solution was cooled to −25 ° C., and a solution in which 60 g (236 mmol) of iodine was dissolved in 1000 mL of diethyl ether was added dropwise over 30 minutes. After dropping, the mixture was stirred at room temperature (25 ° C.) for 2 hours, and 50 mL of 1N aqueous sodium thiosulfate solution was added to stop the reaction. After extracting the reaction product with diethyl ether, the reaction product was dried with magnesium sulfate, and after filtration, the filtrate was concentrated to obtain 35 g of a crude product. The crude product was purified by recrystallization using chloroform to obtain 28 g of Compound 1.

Reference example 2
(Synthesis of Compound 2)
Compound 2 was synthesized from compound 1 according to the following scheme.

  10.5 g (23.4 mmol) of the compound 1: bisiodothienylmethanol synthesized in Reference Example 1 and 150 mL of methylene chloride were added to a four-necked flask with a volume of 300 mL to obtain a uniform solution. To the solution, 7.50 g (34.8 mmol) of pyridinium chlorochromate was added and stirred at room temperature (25 ° C.) for 10 hours. The reaction solution was filtered to remove insoluble matters, and then the filtrate was concentrated to obtain 10.0 g (22.4 mmol) of Compound 2.

Reference example 3
(Synthesis of Compound 3)
Compound 3 was synthesized from compound 2 according to the following scheme.

  In a flask with a capacity of 300 mL whose atmosphere was replaced with argon, 10.0 g (22.4 mmol) of Compound 2 synthesized in Reference Example 2, 6.0 g (94.5 mmol) of copper powder, and 120 mL of dehydrated DMF And stirred at 120 ° C. for 4 hours. After the reaction, the flask was cooled to room temperature (25 ° C.), and the reaction solution was passed through a silica gel column to remove insoluble components. Thereafter, 500 mL of water was added to the reaction solution, and the reaction product was extracted with chloroform. The oil layer, which is a chloroform solution, was dried over magnesium sulfate, the oil layer was filtered, and the filtrate was concentrated to obtain a crude product. The obtained crude product was purified with a silica gel column (developing solution: chloroform) to obtain 3.26 g of compound 3. The operation until obtaining compound 3 from compound 2 was repeated a plurality of times.

Reference example 4
(Synthesis of Compound 4)
Compound 4 was synthesized from compound 3 according to the following scheme.

  A 300 mL four-neck flask equipped with a mechanical stirrer and substituted with argon in the flask was uniformly charged with 3.85 g (20.0 mmol) of Compound 3 synthesized in Reference Example 3, 50 mL of chloroform, and 50 mL of trifluoroacetic acid. Solution. To the solution, 5.99 g (60 mmol) of sodium perborate monohydrate was added and stirred at room temperature (25 ° C.) for 45 minutes. Thereafter, 200 mL of water was added to the reaction solution, chloroform was further added, and the organic layer containing the reaction product was extracted. The organic layer, which is a chloroform solution, was passed through a silica gel column, and the solvent of the filtrate was distilled off with an evaporator. The residue was recrystallized using methanol to obtain 534 mg of compound 4.

¹ H NMR in CDCl ₃ (ppm): 7.64 (d, 1H), 7.43 (d, 1H), 7.27 (d, 1H), 7.10 (d, 1H)

Reference Example 5
(Synthesis of Compound 5)
Compound 5 was synthesized from compound 4 according to the following scheme.

  1.00 g (4.80 mmol) of compound 4 and 30 mL of dehydrated THF were placed in a four-necked flask with a capacity of 100 mL in which the atmosphere in the flask was replaced with argon to obtain a uniform solution. While maintaining the solution at −20 ° C., 12.7 mL of 1M 3,7-dimethyloctylmagnesium bromide ether solution was added. Thereafter, the temperature was raised to −5 ° C. over 30 minutes, and the mixture was stirred for 30 minutes. Thereafter, the temperature was raised to 0 ° C. over 10 minutes, and the mixture was stirred for 1.5 hours. Thereafter, water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer, which is an ethyl acetate solution, was dried over sodium sulfate and filtered, and then the ethyl acetate solution was passed through a silica gel column. The filtrate was evaporated to obtain 1.50 g of compound 5.

¹ H NMR in CDCl ₃ (ppm): 8.42 (b, 1H), 7.25 (d, 1H), 7.20 (d, 1H), 6.99 (d, 1H), 6.76 ( d, 1H), 2.73 (b, 1H), 1.90 (m, 4H), 1.58-1.02 (b, 20H), 0.92 (s, 6H), 0.88 (s) , 12H)

Reference Example 6
(Synthesis of Compound 6)
Compound 6 was synthesized from compound 5 according to the following scheme.

  1. A 50 mL flask in which the atmosphere in the flask was replaced with argon was charged with 1.50 g of compound 5 and 30 mL of toluene to obtain a uniform solution. 100 mg of sodium p-toluenesulfonate monohydrate was added to the solution, and the mixture was stirred at 100 ° C. for 1.5 hours. After cooling the reaction solution to room temperature (25 ° C.), 50 mL of water was added, toluene was further added, and the organic layer containing the reaction product was extracted. The organic layer, which is a toluene solution, was dried over sodium sulfate and filtered, and then the solvent was distilled off. The obtained crude product was purified with a silica gel column having a solvent of hexane to obtain 1.33 g of Compound 6. The operation until obtaining Compound 6 from Compound 5 was repeated a plurality of times.

¹ H NMR in CDCl ₃ (ppm): 6.98 (d, 1H), 6.93 (d, 1H), 6.68 (d, 1H), 6.59 (d, 1H), 1.89 ( m, 4H), 1.58-1.00 (b, 20H), 0.87 (s, 6H), 0.86 (s, 12H)

Reference Example 7
(Synthesis of Compound 7)
Compound 7 was synthesized from compound 6 according to the following scheme.

  A uniform solution was prepared by adding 1.33 g (2.80 mmol) of compound 6 and 20 mL of dehydrated DMF to a 200 mL flask whose atmosphere in the flask was replaced with argon. The solution was kept at −30 ° C., 1040 mg (5.84 mmol) of succinimide (NBS) was added, and the temperature was raised from −30 ° C. to −10 ° C. over 30 minutes. After confirming the disappearance of compound 6 by liquid chromatography (LC), 50 ml of 1M sodium thiosulfate aqueous solution was added to the reaction solution to stop the reaction. Ether was added to the reaction solution, and the organic layer containing the reaction product was extracted. The organic layer, which is an ether solution, was washed with a saturated aqueous sodium chloride solution. Then, it was made to dry with magnesium sulfate, and after filtration, the solvent was distilled off to obtain a crude product. The obtained crude product was purified by a silica gel column having a solvent of hexane to obtain 1.65 g (93%) of Compound 7.

¹ H NMR in CDCl ₃ (ppm): 6.66 (1H), 6.63 (1H), 1.90 (m, 4H), 1.56-1.02 (b, 20H), 0.87 ( s, 6H), 0.85 (s, 12H)

Example 1

  In a four-necked flask whose atmosphere in the flask was replaced with argon, 434 mg (0.686 mmol) of Compound 7 synthesized in Reference Example 7, 105 mg (0.673 mmol) of Compound 8 (manufactured by CHEMSTEP), and 10 mL of DMF And the resulting DMF solution was bubbled with argon for 30 minutes. Thereafter, trans-bis (acetate) bis [o- (di-o-toluylphosphino) benzyl] dipalladium (II) (trans-Bis (acetato) bis [o- (di-o-tolylphosphino) benzyl) was added to the toluene solution. Dipalladium (II)) 9.66 mg, Tris (2-methoxyphenyl) phosphine (Tris (2-methoxyphenyl) phosphine) 12.5 mg, and cesium carbonate 512 mg were added and stirred at 100 ° C. for 16 hours. went. After the reaction, the reaction solution was analyzed by high performance liquid chromatography. As a result, it was confirmed that all raw materials were consumed. After the reaction, the reaction solution was cooled to 25 ° C., and 50 mL of water was added. Chloroform 20mL was added to the obtained liquid mixture, and the chloroform layer was extracted. This extraction operation of the chloroform layer was repeated twice. Thereafter, the chloroform layer was dried over sodium sulfate and filtered. Thereafter, the filtrate was concentrated, and the resulting crude product was purified with a silica gel column (eluent was hexane: chloroform = 2: 1 (vol / vol)) to obtain 320 mg of a reaction product. As the eluent of the silica gel column, a mixed solution in which hexane and chloroform were mixed so that the volume ratio of hexane to the volume of chloroform was 2 was used. When the obtained reaction product was measured by GPC, the number average molecular weight in terms of polystyrene was 2240, and the weight average molecular weight in terms of polystyrene was 3290.

¹⁹ F NMR in CDCl ₃ (ppm): −117.5
¹ H NMR in CDCl ₃ (ppm): 7.53 (b), 7.02 (b), 2.27 (b), 1.57 (b), 1.23 (b), 0.872 (b )

  From the NMR measurement results, it was found that the obtained reaction product had the following structure in the molecule.

Claims (10)

Following formula (1):

(In Formula (1), Ar ¹ represents a fluorine atom, a cyano group, a nitro group, an amino group, or a heteroarylene group optionally substituted with a monovalent organic group. H represents a hydrogen atom.)
A compound represented by
Following formula (2):

(In the formula (2), Ar ² represents a fluorine atom, a cyano group, a nitro group, an amino group or a heteroarylene group optionally substituted with a monovalent organic group. X represents a chlorine atom, a bromine atom or Represents an iodine atom, and two Xs may be the same or different.)
With a compound represented by
Following formula (3):

(In formula (3), Ar ¹ and Ar ² represent the same meaning as described above. N represents a number of 1 or more.)
The manufacturing method of the compound containing the structural unit represented by these.   The method for producing a compound according to claim 1, wherein the compound represented by the formula (1) and the compound represented by the formula (2) are reacted in the presence of a transition metal compound.   The method for producing a compound according to claim 1 or 2, wherein the compound represented by the formula (1) and the compound represented by the formula (2) are reacted in the presence of a basic compound.   The manufacturing method as described in any one of Claims 1-3 with which the compound represented by Formula (1) and the compound represented by Formula (2) are made to react in presence of a phosphine compound. The method for producing a compound according to claim 1, wherein Ar ¹ is a heteroarylene group having 1 to 3 electron-withdrawing substituents.   The production method according to claim 5, wherein the electron-withdrawing substituent is a fluorine atom. The manufacturing method as described in any one of Claims 1-6 whose Ar < ² > is group represented by following formula (5).

[In the formula (5), Ar ¹³ and Ar ¹⁴ each independently represent a group obtained by removing three hydrogen atoms from an aromatic heterocyclic compound or an aromatic carbocyclic compound, and the aromatic heterocyclic compound and At least one of the aromatic carbocyclic compounds may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. However, at least one of Ar ¹³ and Ar ¹⁴ contains three hydrogen atoms from an aromatic heterocyclic compound which may be substituted with a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. The removed group. A represents a divalent group represented by the following formula (4-1) to formula (4-12).

(In Formula (4-1) to Formula (4-12), R ^{1 to} R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, a cyano group, a nitro group, an amino group, or a monovalent organic group. ]] The method for producing a compound according to claim 1, wherein Ar ² is a heteroarylene group containing a thiophene ring structure.   The compound which can be obtained with the manufacturing method of the compound as described in any one of Claims 1-8.   The compound according to claim 9, wherein the sum of the tin content in the compound and the boron content in the compound determined by mass spectrometry is less than 1 ppm by weight.