WO2012176820A1

WO2012176820A1 - Fused heterocyclic compound and polymer thereof

Info

Publication number: WO2012176820A1
Application number: PCT/JP2012/065780
Authority: WO
Inventors: 菅　誠治; 耕一光藤; 泰輔鎌田; 美樹 ▲つる▼田; 純一吉本; 杉岡　尚
Original assignee: 国立大学法人岡山大学; 株式会社クラレ
Priority date: 2011-06-22
Filing date: 2012-06-20
Publication date: 2012-12-27
Also published as: JPWO2012176820A1

Abstract

The present invention provides a compound represented by formula (1) and a polymer thereof. [In the formula, R¹ and each R² group are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or -CO-R (in this formula, R is an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group), ring A, ring B and ring C are each independently an optionally substituted 5-membered or 6-membered aromatic heterocyclic ring, and n is an integer between 1 and 4.]

Description

Fused heterocyclic compounds and polymers thereof

The present invention relates to a condensed heterocyclic compound and a polymer thereof.

A polymer obtained by polymerizing a compound having a 5-membered ring structure or 6-membered ring structure in which a hetero atom exists inside or outside of the ring, such as pyrrole, thiophene, aniline, or the like, or a compound having a hydrocarbon aromatic ring structure, It has conductivity. Use of these polymers as semiconductor materials (semiconductors) for various organic electronic members such as solid electrolytic transistors, organic thin film transistors, and individual identification (RFID) devices using radio waves has been studied. In addition, these doped polymers have electrical conductivity, and the electrical characteristics and optical characteristics can be appropriately controlled by adjusting the amount of dopant to coexist. Therefore, these doped polymers have been studied for use in various applications such as various electrodes, electrochromic materials, various sensors, primary batteries, secondary batteries, solid electrolytic capacitors, antistatic agents and the like.

The fused heterocyclic compound of Patent Document 1 has been studied as a semiconducting material that can be applied and printed because it has excellent semiconductor properties and high solubility in organic solvents. Further, in Patent Document 2 and Non-Patent Document 1, polymers having a structural unit derived from dithienopyrrole have been reported, and their use as a conductive material or a semiconductive material has been studied. Non-Patent Document 2 reports a fused heterocyclic compound containing a pyrrole ring. However, no compound has been reported in which both ends are composed of an aromatic heterocyclic ring and five or more rings are condensed.

Japanese Patent No. 4581062 US Patent Application Publication No. 2008/0262183

An object of the present invention is to provide a condensed heterocyclic compound and a polymer thereof that can be suitably used as a conductive material or a semiconductive material.

[1] Formula (1):

[Wherein, R ¹ and each R ² independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a hetero that may have a substituent. An aryl group or —CO—R (wherein R represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a heteroaryl group which may have a substituent); .) And
Ring A, Ring B and Ring C are each independently a 5-membered or 6-membered aromatic heterocyclic ring which may have a substituent,
n is an integer of 1 to 4. ]
A compound represented by
[2] Formula (2):

[Wherein R ¹ , each R ² and n are as described in the above [1],
W ¹ to W ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, An aryl group that may have a substituent, a heteroaryl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent It may have an alkylamino group, a cyano group, a nitro group, an azido group, a hydroxy group, a sulfanyl group, an amino group, a carboxyl group or a salt thereof, a phosphono group or a salt thereof, a sulfo group or a salt thereof, or a substituent. A good carbamoyl group, a phosphinoyl group which may have a substituent, a phosphanyl group which may have a substituent, —CO—R, —SO—R (wherein R may have a substituent) Good alkyl group, substituent Have also represents a heteroaryl group which may have an aryl group or a substituent), -. MgCl, -MgBr, -MgI, -ZnCl, -ZnBr, -ZnI, -Sn (Ak) 3, - B (OH) ₂ , —B (OAk) ₂ , —B (—OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O—), —Si (Ak) ₃ , or —Si (OAk) ₃ In the formula, Ak represents an alkyl group. ]
The compound according to [1], which is represented by
[3] Formula (3):

[Wherein R ¹ , R ² and W ¹ to W ⁴ are as defined in the above [2]. ]
The compound according to [2], which is represented by
[4] The compound according to [2] or [3], wherein at least two of W ¹ to W ⁴ are each independently a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.
[5] R ¹ and each R ² are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent. The compound according to any one of the above [1] to [4].
[6] Any of [1] to [4] above, wherein R ¹ and each R ² are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or a phenyl group which may have a substituent. A compound according to any one of the above.
[7] A composition comprising the compound according to any one of [1] to [6] and a dopant.
[8] The composition according to [7], wherein the compound according to any one of [1] to [6] is a cation and the dopant is an anion.
[9] A polymer comprising a structural unit derived from the compound according to [4].
[10] R ¹ and each R ² are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent. The polymer according to [9].
[11] The polymer according to [9], wherein R ¹ and each R ² are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an optionally substituted phenyl group.
[12] A composition comprising the polymer according to any one of [9] to [11] and a dopant.
[13] The composition described in [12], wherein the polymer described in any one of [9] to [11] is a cation and the dopant is an anion.
[14] An organic electronic member comprising the compound according to any one of [1] to [6] or the composition according to [7] or [8].
[15] Electrode, solid electrolytic capacitor, thermoelectric element, piezoelectric element, actuator, sensor, organic thin film solar cell, dye-sensitized solar cell, organic thin film transistor, individual identification (RFID) device using radio waves, field effect transistor (FET), integration The organic electronics member according to [14], which is a circuit (IC), an organic electroluminescence element (OLED), or an organic semiconductor element.
[16] An organic electronic member comprising the polymer according to any one of [9] to [11] or the composition according to [12] or [13].
[17] Electrode, solid electrolytic capacitor, thermoelectric element, piezoelectric element, actuator, sensor, organic thin film solar cell, dye-sensitized solar cell, organic thin film transistor, individual identification (RFID) device using radio waves, field effect transistor (FET), integration The organic electronics member according to [16], which is a circuit (IC), an organic electroluminescence element (OLED), or an organic semiconductor element.
[18] Formula (4):

[Wherein, X ¹ to X ⁴ are each independently a chlorine atom, a bromine atom or an iodine atom,
W ¹ to W ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, An aryl group that may have a substituent, a heteroaryl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent It may have an alkylamino group, a cyano group, a nitro group, an azido group, a hydroxy group, a sulfanyl group, an amino group, a carboxyl group or a salt thereof, a phosphono group or a salt thereof, a sulfo group or a salt thereof, or a substituent. A good carbamoyl group, a phosphinoyl group which may have a substituent, a phosphanyl group which may have a substituent, —CO—R, —SO—R (wherein R may have a substituent) Good alkyl group, substituent Have also represents a heteroaryl group which may have an aryl group or a substituent), -. MgCl, -MgBr, -MgI, -ZnCl, -ZnBr, -ZnI, -Sn (Ak) 3, - B (OH) ₂ , —B (OAk) ₂ , —B (—OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O—), —Si (Ak) ₃ , or —Si (OAk) ₃ In the formula, Ak represents an alkyl group. ]
A compound of formula (5):
R ¹ —NH ₂ (5)
[Wherein R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —CO—R ( In the above formula, R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]
A compound of formula (6):
R ² —NH ₂ (6)
[Wherein R ² represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —CO—R ( In the above formula, R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]
Comprising reacting with a compound of formula (3):

[Wherein R ¹ , R ² and W ¹ to W ⁴ are as defined above. ]
The manufacturing method of the compound shown by these.
[19] R ¹ and R ² are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. The production method according to the above [18].
[20] The production method according to the above [18], wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an optionally substituted phenyl group.

The fused heterocyclic compound and polymer thereof of the present invention are suitably used as a conductive material or a semiconductive material.

Hereinafter, modes for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these modes. Hereinafter, the “compound represented by the formula (1)” or the like may be abbreviated as “compound (1)” or the like.

First, the compound (1) of the present invention will be described. R ¹ and each R ^{2 in} Formula (1) may each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. A good heteroaryl group or —CO—R (wherein R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent) Represents.).

In the present specification, the alkyl group may be linear or branched, and the carbon number thereof is preferably 1-20, more preferably 1-15, still more preferably 1-10. It is. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, and hexyl. Group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, etc. Can be mentioned. The alkyl group may have a substituent. Examples of the substituent of the alkyl group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), an aryl group which may have a substituent, and the like. .

In the present specification, the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of the aryl group include aryl groups derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyrene ring, perylene ring, tetracene ring, pentaphen ring, pentacene ring, rubicene ring and the like. The aryl group may have a substituent. Examples of the substituent of the aryl group include a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and 1 to 20 carbon atoms (preferably 1 to 10, more preferably Are alkoxy groups of 1 to 5).

In the present specification, a heteroaryl group is a group derived from an aromatic heterocycle containing 1 to 5 heteroatoms such as nitrogen, oxygen, sulfur, selenium, silicon, germanium in addition to carbon atoms. . The aromatic heterocyclic ring may be monocyclic or polycyclic (eg, bicyclic, tricyclic). The number of atoms of the heteroaryl group is preferably 5 to 30, more preferably 5 to 10. Examples of heteroaryl groups include thiophene ring, pyrrole ring, furan ring, selenophene ring, silole ring, gelmol ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole ring, tetrazole ring , Pyridine ring, pyrazine ring, pyrimidine ring, indole ring, isoindole ring, indazole ring, phthalazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, cinnoline ring, β-carboline ring, etc. It is done. The heteroaryl group may have a substituent. Examples of the substituent of the heteroaryl group include a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms). Preferred examples include alkoxy groups 1 to 5).

R ¹ and each R ² are each independently preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent, More preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and even more preferably an alkyl group which may have a substituent or a substituent A phenyl group, more preferably an alkyl group having 1 to 10 carbon atoms, a benzyl group or an optionally substituted phenyl group, still more preferably an alkyl group having 1 to 10 carbon atoms, a benzyl group, or A phenyl group which may have at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms; Group, a benzyl group or an alkyl group and a phenyl group which may have at least one member selected from the group consisting of an alkoxy group having 1 to 5 carbon atoms of 1 to 5 carbon atoms. When the phenyl group has a substituent, the number of the substituent is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
When n is 2 or more, the plurality of R ² may be the same as or different from each other, and are preferably the same. Further, it is preferable that all of R ¹ and each R ² is the same.

Ring A, ring B and ring C in the formula (1) are each independently a 5-membered or 6-membered aromatic heterocyclic ring which may have a substituent. Ring A, ring B and ring C are preferably the same.

In this specification, the 5-membered or 6-membered aromatic heterocycle contains a heteroatom such as nitrogen, oxygen, sulfur, selenium, silicon, germanium in addition to the carbon atom. The number of heteroatoms in the 5-membered or 6-membered aromatic heterocycle is preferably 1 to 3, more preferably 1. Examples of the 5- or 6-membered aromatic heterocycle include, for example, a thiophene ring, a pyrrole ring, a furan ring, a selenophene ring, a silole ring, a gelmol ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, and an isothiazole. And a ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring. The 5-membered or 6-membered aromatic heterocyclic ring may have a substituent. Examples of the substituent of the 5-membered or 6-membered aromatic heterocyclic ring include a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and 1 to 20 carbon atoms ( Preferred examples include alkoxy groups of 1 to 10, more preferably 1 to 5).

Ring A, Ring B and Ring C are each independently preferably a 5-membered aromatic heterocyclic ring which may have a substituent, more preferably a thiophene ring which may have a substituent, More preferably, it is a thiophene ring which may have a halogen atom, more preferably a thiophene ring which may have at least one selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom. An unsubstituted thiophene ring is preferred.

N in the formula (1) is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

As preferred compound (1),
R ¹ and each R ² are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent,
Examples include compounds in which Ring A, Ring B and Ring C are each independently a 5-membered or 6-membered aromatic heterocyclic ring which may have a substituent.

As a more preferred compound (1),
R ¹ and each R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent,
Examples thereof include compounds in which Ring A, Ring B and Ring C are each independently a 5-membered aromatic heterocyclic ring which may have a substituent.

As an even more preferred compound (1),
R ¹ and each R ² are each independently an alkyl group which may have a substituent or a phenyl group which may have a substituent,
Examples include a compound in which Ring A, Ring B and Ring C are each independently a thiophene ring which may have a substituent.

As a more preferred compound (1),
R ¹ and each R ² are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group or an optionally substituted phenyl group,
Examples thereof include compounds in which Ring A, Ring B and Ring C are each independently a thiophene ring which may have a halogen atom.

As an even more preferred compound (1),
R ¹ and each R ² are each independently at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. A phenyl group which may have one,
Examples thereof include compounds in which Ring A, Ring B and Ring C are each independently a thiophene ring which may have at least one selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom.

As particularly preferred compound (1),
R ¹ and each R ² are each independently at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. A phenyl group which may have one,
Examples include compounds in which Ring A, Ring B, and Ring C are unsubstituted thiophene rings.

In any of the above preferred compounds (1), it is preferred that R ¹ and each R ² are the same.

Next, the compound (2) of the present invention will be described. The description of R ¹ and each R ^{2 in} the formula (2) is the same as described above. W ¹ to W ^{4 in} formula (2) each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An alkynyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent An optionally substituted alkylamino group, cyano group, nitro group, azide group, dicyanomethyl group, hydroxy group, sulfanyl group, amino group, carboxyl group or salt thereof, phosphono group or salt thereof, sulfo group or Its salts, optionally substituted carbamoyl groups, optionally substituted phosphinoyl groups, optionally substituted phosphanyl groups, —CO—R, —SO—R, —SO ₂ — R (in the above formula R represents an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.), —MgCl, —MgBr, —MgI, —ZnCl, —ZnBr, —ZnI, —Sn (Ak) ₃ , —B (OH) ₂ , —B (OAk) ₂ , —B (—OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O—), —Si (Ak) ₃ or —Si (OAk) ₃ (In the formula, Ak represents an alkyl group). Note that the structure of —B (—OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O—) is as follows.

In the present specification, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom.

In the present specification, the alkenyl group may be linear or branched, and the carbon number thereof is preferably 2 to 20, more preferably 2 to 10. Examples of the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group and the like. The alkenyl group may have a substituent. Examples of the substituent of the alkenyl group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.

In the present specification, the alkynyl group may be linear or branched, and the alkynyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms. Examples include ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 1-hexynyl group, 1-heptynyl group, 1-octynyl group and the like. The alkynyl group may have a substituent. Examples of the substituent of the alkynyl group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.

In the present specification, the alkoxy group may be linear or branched, and the carbon number thereof is preferably 1-20, more preferably 1-10. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a neopentyloxy group, tert-pentyloxy group, hexyloxy group, isohexyloxy group, 2-ethylhexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, tetradecyloxy group, pentadecyloxy group, Hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, icosyloxy group and the like can be mentioned. The alkoxy group may have a substituent. Examples of the substituent of the alkoxy group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.

In the present specification, the alkylthio group may be linear or branched, and the carbon number thereof is preferably 1-20, more preferably 1-10. 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 sec-butylthio group, a tert-butylthio group, a pentylthio group, an isopentylthio group, a neopentylthio group, tert-pentylthio group, hexylthio group, isohexylthio group, 2-ethylhexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, An octadecylthio group, a nonadecylthio group, an icosylthio group, etc. are mentioned. The alkylthio group may have a substituent. Examples of the substituent for the alkylthio group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.

In the present specification, the alkylamino group may be linear or branched, and the carbon number thereof is preferably 1 to 10, more preferably 1 to 5, and the alkyl group. Is 1 or 2, preferably 1. Examples of the alkylamino group include a methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, A dimethylamino group, a diethylamino group, etc. are mentioned. The alkylamino group may have a substituent. Examples of the substituent of the alkylamino group include a halogen atom, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5), and the like.

In the present specification, any of the carboxyl group, phosphono group and sulfo group may be in a salt form. Examples of these salt forms include alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts, guanidinium salts, and the like.

In the present specification, the carbamoyl group which may have a substituent is represented by —CO—N (R ′) (R ″) (wherein R ′ and R ″ each independently represents a hydrogen atom) Or a substituent.) The substituent of the carbamoyl group is, for example, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.

In the present specification, the phosphinoyl group which may have a substituent is represented by —PO (R ′) (R ″) (wherein R ′ and R ″ each independently represents a hydrogen atom or a substituent). Group.) The substituent of the phosphinoyl group is, for example, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.

In the present specification, the phosphanyl group which may have a substituent is represented by —P (R ′) (R ″) (wherein R ′ and R ″ each independently represents a hydrogen atom or a substituent). Group.) The substituent of the phosphanyl group is, for example, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent.

In the present specification, Ak represents an alkyl group. Ak may be linear or branched, and the carbon number thereof is preferably 1 to 10, more preferably 1 to 5. Examples of Ak include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, and hexyl groups. , Isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

W ¹ to W ⁴ are preferably each independently a hydrogen atom, a halogen atom or an alkyl group which may have a substituent. W ¹ to W ⁴ are each independently more preferably a hydrogen atom or a halogen atom, still more preferably a hydrogen atom or a bromine atom, and still more preferably a hydrogen atom. It is preferable that W ¹ to W ⁴ are all the same.

In order for the compound (2) to polymerize, at least two of W ¹ to W ⁴ are each independently required to be a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom. At least two of W ¹ to W ⁴ are each independently preferably a hydrogen atom or a bromine atom, more preferably a hydrogen atom. The “at least two of W ¹ to W ⁴ ” is preferably W ¹ and W ² .

N in the formula (2) is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2. The compound (2) in which n is 1 is the compound (3). The explanation of R ¹ , R ² and W ¹ to W ^{4 in} the formula (3) is the same as described above.

As preferred compound (2) or compound (3),
R ¹ and each R ² are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent,
W ¹ to W ⁴ are each independently a hydrogen atom, a halogen atom or an alkyl group which may have a substituent,
Examples thereof include compounds in which at least two of W ¹ to W ⁴ are each independently a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.

As a more preferred compound (2) or compound (3),
R ¹ and each R ² are each independently an alkyl group which may have a substituent or an aryl group which may have a substituent,
W ¹ to W ⁴ are each independently a hydrogen atom or a halogen atom,
Examples include compounds in which at least two of W ¹ to W ⁴ are each independently a hydrogen atom or a bromine atom.

As an even more preferable compound (2) or compound (3),
R ¹ and each R ² are each independently an alkyl group which may have a substituent or a phenyl group which may have a substituent,
Examples thereof include compounds in which W ¹ to W ⁴ are hydrogen atoms.

As more preferred compound (2) or compound (3),
R ¹ and each R ² are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group or an optionally substituted phenyl group,
Examples thereof include compounds in which W ¹ to W ⁴ are hydrogen atoms.

As still more preferred compound (2) or compound (3),
R ¹ and each R ² are each independently at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. A phenyl group which may have one,
Examples thereof include compounds in which W ¹ to W ⁴ are hydrogen atoms.

In any of the above-mentioned preferred compound (2) or compound (3), it is preferred that R ¹ and each R ² are the same.

In order to improve conductivity, a dopant may be added to the compound of the present invention. In the composition containing the dopant and the compound of the present invention, the compound of the present invention is preferably a cation and the dopant is preferably an anion. The addition amount of the dopant can be arbitrarily adjusted depending on the dopant to be used, but is preferably 1 to 1000 parts by weight, more preferably 1 to 200 parts by weight with respect to 100 parts by weight of the compound. The method of doping the compound and the description of the dopant used therefor are the same as those of the polymer described later.

Next, a method for producing the fused heterocyclic compound of the present invention (that is, compound (1) to compound (3)) will be described. A manufacturing method is first demonstrated from the manufacturing method of a compound (3). Compound (3) can be produced by reacting compound (4), compound (5) and compound (6) as shown in the following formula (hereinafter abbreviated as “reaction A”). It is preferable that a compound (5) and a compound (6) are the same compounds.

W ¹ to W ^{4 in the} formula (4) and R ¹ and R ² in the formulas (5) and (6) are as defined above. X ¹ to X ⁴ are each independently a chlorine atom, bromine atom or iodine atom, preferably a bromine atom.

Although it does not specifically limit as a solvent used for Reaction A, For example, saturated aliphatic hydrocarbons or alicyclic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane; benzene, toluene, ethylbenzene, propyl Aromatic hydrocarbons such as benzene, xylene, ethyl toluene, chlorobenzene, o-dichlorobenzene; dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, butyl methyl ether, tert-butyl methyl ether, dibutyl ether, tetrahydrofuran, 1, And ethers such as 4-dioxane; aprotic polar solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide; Only 1 type may be used for a solvent and it may use 2 or more types together. The temperature of reaction A is not particularly limited, but is preferably −50 ° C. to 200 ° C. The time for reaction A is not particularly limited, but is preferably 1 minute to 48 hours.

Reaction A is performed in the presence of a catalyst and a base. Examples of the catalyst used in the reaction A include metal catalysts such as a palladium catalyst and a nickel catalyst. The amount of the catalyst is preferably 0.001 to 1 mol with respect to 1 mol of the compound (4). Examples of the base used in the reaction A include n-butyllithium, tert-butyllithium, methyllithium and the like. The amount of the base is preferably 0.8 to 1.2 mol with respect to 1 mol of the compound (4). After completion of the reaction A, the crude product is preferably purified by a known method (for example, extraction, chromatography).

The compound (4) used in the reaction A is produced by reacting the compound (7), the compound (8) and the compound (9) as shown in the following formula (hereinafter abbreviated as “reaction B”). be able to.

In the formulas (4) and (7) to (9), X ¹ to X ⁴ and W ¹ to W ⁴ are as defined above. X ⁵ to X ⁸ in the formulas (7) to (9) are each independently a chlorine atom, a bromine atom or an iodine atom, preferably a bromine atom.

As the method and conditions for reaction B, the methods and conditions of Kumada-Tamao coupling and Negishi coupling are preferred, and the methods and conditions of Negishi coupling are more preferred. Both Kumada-Tamao coupling and Negishi coupling are well known in the field of synthetic organic chemistry. For example, the Kumada-Tamao coupling is described in Pure and Applied Chemistry, 1980, Vol. 52, p. 669, Negishi Coupling is described in Accounts of Chemical Research, 1982, Vol. 15, p. 340.

Although it does not specifically limit as a solvent used for reaction B, For example, saturated aliphatic hydrocarbons or alicyclic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane; benzene, toluene, ethylbenzene, propyl Aromatic hydrocarbons such as benzene, xylene, ethyl toluene, chlorobenzene, o-dichlorobenzene; dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, butyl methyl ether, tert-butyl methyl ether, dibutyl ether, tetrahydrofuran, 1, And ethers such as 4-dioxane; aprotic polar solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide; Only 1 type may be used for a solvent and it may use 2 or more types together. Examples of the catalyst used in the reaction B include metal catalysts such as a palladium catalyst and a nickel catalyst. The temperature of reaction B is not particularly limited, but is preferably −50 ° C. to 200 ° C. The time for reaction B is not particularly limited, but is preferably 1 minute to 48 hours. After completion of the reaction B, the crude product is preferably purified by a known method (for example, extraction, chromatography).

Next, a method for producing compound (2) will be described. In the compound (2) in which n is 2 to 4, in the reaction A, instead of the compound (4) (a compound having three thiophene rings), a compound having four thiophene rings, It can be produced by using a compound having five or a compound having six thiophene rings as a starting material. The starting material used in the method for producing compound (2) can be produced by a method well known in the field of synthetic organic chemistry.

Next, a method for producing compound (1) will be described. a compound in which n is 1, and a part or all of ring A, ring B and ring C is a 5-membered or 6-membered aromatic heterocycle other than the thiophene ring (hereinafter abbreviated as “other ring”) ( 1) can be produced by using, as a starting material, a compound in which part or all of the thiophene ring is replaced with another ring in the above reaction A instead of the compound (4). Examples of other rings include pyrrole ring, furan ring, selenophene ring, silole ring, gelmol ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, pyridine ring, pyrazine ring, pyrimidine ring. Etc. In addition, compound (1) wherein n is 2 to 4 can be produced in the same manner as in the production method of compound (2). The starting material used in the method for producing compound (1) can be produced by a method well known in the field of synthetic organic chemistry.

Next, the polymer of the present invention will be described. The polymer of the present invention has a constitution derived from the compound (2) (preferably the compound (3)) in which at least two of W ¹ to W ⁴ are each independently a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom. The unit is included.

In the present invention, the average molecular weight of the polymer is not particularly limited. In addition, since the polymer of the present invention has a rigid structural unit in which five or more aromatic heterocycles derived from the compound (2) (preferably the compound (3)) are condensed, many of the polymers of the present invention Does not dissolve in the solvent, and the average molecular weight cannot be measured by GPC or the like. The weight average molecular weight of a general polymer is in the range of 1000 to 1,000,000.

In order to improve conductivity, a dopant may be added to the polymer of the present invention. In the composition containing the polymer of the present invention and the dopant, the polymer of the present invention is preferably a cation and the dopant is preferably an anion. In this case, the dopant which is an anion functions as a counter anion with respect to the polymer of the present invention which is a cation. Examples of the dopant include a halogenated anion of a Group 5B element such as PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ ; a halogenated anion of a Group 3B element such as BF ₄ ⁻ ; I ⁻ (I ₃ ⁻ ), Br ^−. Halogen anions such as Cl 2 ⁻ ; Halogen anions such as ClO ₄ ⁻ ; Metal halide anions such as AlCl ₄ ⁻ , FeCl ₄ ⁻ , SnCl ₅ ⁻ ; Nitrate anions (NO ₃ ⁻ ); Sulfate anions (SO ₄ ²⁻ ); Organic sulfonate anions such as p-toluenesulfonate anion, naphthalenesulfonate anion, CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ^— ; carboxylate anions such as CF ₃ COO ⁻ , C ₆ H ₅ COO ⁻ ; and And modified polymers having the above anionic species in the main chain or side chain. These dopants may be used independently and may use 2 or more types together.

The method for adding the dopant is not particularly limited. For example, a desired dopant may be appropriately added to the obtained polymer after polymerizing the monomer. When the monomer is chemically oxidatively polymerized or when the polymer is subjected to chemical oxidative doping, an anion derived from an oxidant used for polymerization or doping can be used as a dopant. Further, when the monomer is electrochemically polymerized or when the polymer is subjected to electrochemical doping, an anion derived from an electrolyte used for polymerization or doping can be used as a dopant.

The addition amount of the dopant can be arbitrarily adjusted depending on the dopant to be used, but is preferably 1 to 1000 parts by weight, more preferably 1 to 200 parts by weight with respect to 100 parts by weight of the polymer.

The polymer of the present invention is produced by chemical oxidative polymerization or electrochemical polymerization of the polymerizable compound (2) (preferably compound (3)) of the present invention and, if necessary, other monomers. It is preferable. Hereinafter, polymerization will be described together with doping.

The solvent used in the chemical oxidative polymerization or chemical oxidative doping is not particularly limited. For example, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, acetonitrile, benzonitrile, propylene carbonate, nitromethane, tetrohydrofuran, methanol, Water etc. are mentioned.

The oxidizing agent used in chemical oxidative polymerization or chemical oxidative doping is not particularly limited, but is preferably a halogen or a transition metal salt. Examples of the oxidizing agent include halogens such as I ₂ , Br ₂ , and Cl ₂ ; ferric chloride (FeCl ₃ ), ferric perchlorate (Fe (ClO ₄ ) ₃ ), and ferric sulfate (Fe _2). (SO ₄ ) ₃ ), C 1-16 iron alkoxybenzene sulfonate, C 1-16 alkyl benzene sulfonic acid iron, phenol sulfonic acid iron, sulfoisophthalic acid iron dialkyl ester, alkyl sulfonic acid iron, naphthalene sulfonic acid And ferric salts of iron, iron alkoxynaphthalene sulfonate, iron tetralin sulfonate, and the like. Further, instead of the ferric salt (that is, iron (III) salt), a salt in which iron (III) is replaced with cerium (IV), copper (II), manganese (VII), ruthenium (III), It can be used as an oxidizing agent.

Only one type of oxidizing agent may be used, or two or more types may be used in combination. Examples of the combination of oxidizing agents used in combination include, for example, a combination of oxidizing agents having a dopant action; a combination of oxidizing agents having no dopant action; an oxidizing agent having a dopant action (for example, one or more kinds having a dopant action) A combination of a ferric salt) and an oxidizing agent having no dopant action (for example, one or more ferric salts having no dopant action).

In chemical oxidative polymerization or chemical oxidative doping, the amount of oxidant in the solvent (ie, “molar amount of oxidant / volume of solvent”) is preferably 0.001 to 10 mol / L.

In the chemical oxidative polymerization, the amount of monomer in the solvent (that is, “molar amount of monomer / volume of solvent”) can be appropriately set depending on the polymerization conditions and the like to be employed. 001 to 10 mol / L.

The reaction temperature in chemical oxidative polymerization or chemical oxidative doping is not particularly limited, but is preferably −50 ° C. to 200 ° C. The reaction time in chemical oxidative polymerization or chemical oxidative doping is not particularly limited, but is preferably 1 minute to 48 hours.

In chemical oxidative polymerization or chemical oxidative doping, a supporting salt may be used as an additive. The supporting salt is not particularly limited. For example, perchlorate ion, boron tetrafluoride ion, phosphorus hexafluoride ion, halide ion, arsenic hexafluoride ion, antimony hexafluoride ion, sulfate ion, hydrogen sulfate ion, Examples thereof include support salts containing anions such as alkyl sulfonate ions, benzene sulfonate ions, alkyl benzene sulfonate ions, naphthalene sulfonate ions, alkyl naphthalene sulfonate ions, polystyrene sulfonate ions, and polyvinyl sulfonate ions.

Examples of the solvent used in electrochemical polymerization or electrochemical doping include nitromethane, acetonitrile, propylene carbonate, nitrobenzene, cyanobenzene, o-dichlorobenzene, dimethyl sulfoxide, and γ-butyrolactone.

Examples of the supporting electrolyte used in electrochemical polymerization or electrochemical doping include (a) alkali metal ions such as lithium ion, potassium ion and sodium ion, cations such as quaternary ammonium ion, and (b) perchlorine. Examples thereof include support electrolytes composed of a combination with anions such as acid ions, boron tetrafluoride ions, phosphorus hexafluoride ions, halide ions, arsenic hexafluoride ions, antimony hexafluoride ions, sulfate ions and hydrogen sulfate ions. The supporting electrolyte may be used alone or in combination of two or more.

Examples of the electrolytic solution used in electrochemical polymerization or electrochemical doping include an electrolytic solution composed of the solvent and the supporting electrolyte. Moreover, ionic liquids, such as an alkyl imidazolium salt and an alkyl pyridinium salt, can also be used as an electrolytic solution.

In the electrochemical polymerization, the amount of the monomer in the electrolytic solution (that is, “molar amount of monomer / volume of the electrolytic solution”) can be appropriately set depending on the polymerization conditions to be employed, etc. 0.001 to 10 mol / L.

In the electrochemical polymerization or electrochemical doping, the amount of the supporting electrolyte in the electrolytic solution (that is, “the molar amount of the supporting electrolyte / the volume of the electrolytic solution”) is preferably 0.001 to 10 mol / L.

Examples of electrode materials used in electrochemical polymerization or electrochemical doping include platinum, gold, nickel, ITO, and the like.

The voltage at the time of application in electrochemical polymerization or electrochemical doping can be appropriately set depending on the conditions employed, etc., but is preferably 0.1 to 1.5 V (vs Ag / Ag ⁺ ), more The voltage is preferably 0.3 to 1.2 V (vs Ag / Ag ⁺ ). The temperature at which the voltage is applied is preferably −50 to 50 ° C., more preferably −30 to 30 ° C.

The reaction temperature in electrochemical polymerization or electrochemical doping is not particularly limited, but is preferably −50 ° C. to 200 ° C. The reaction time in electrochemical polymerization or electrochemical doping is not particularly limited, but is preferably 1 minute to 48 hours.

The compounds and polymers of the present invention are useful for organic electronics members as semiconductive materials or conductive materials. Accordingly, the present invention also relates to an organic electronic member comprising the compound of the present invention; the composition comprising the compound of the present invention and a dopant; the polymer of the present invention; the composition comprising the polymer and the dopant of the present invention; or a mixture thereof. provide. Examples of organic electronics members include electrodes, solid electrolytic capacitors, thermoelectric elements, piezoelectric elements, actuators, sensors, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors, individual identification (RFID) devices using radio waves, field effect transistors (FET), integrated circuit (IC), organic electroluminescence element (OLED), organic semiconductor element and the like.

Hereinafter, the present invention will be described more specifically using examples.

Production Example 1
To a 100 mL three-necked flask equipped with a thermometer and a Dimroth condenser, 15 mL of diethyl ether and 3.60 g (14.9 mmol) of 2,3-dibromothiophene were added. After cooling the reaction vessel to −78 ° C., 28.1 mL of 1.6 M n-butyllithium (hexane solution) was added dropwise over 30 minutes. A diluted solution of ZnCl ₂ (15.0 mmol, 20.4 g) in 29 mL of tetrahydrofuran was cooled to −78 ° C. and transferred into the reaction vessel by cannulation. The temperature of the reaction vessel was raised to 0 ° C. and stirred for 1 hour. Thereafter, 2,3,4,5-tetrabromothiophene (2.0 g, 5.0 mmol) was added, and [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (PdCl ₂ (dppf)) ) 220 mg (300 mmol) was added. The temperature of the reaction vessel was raised to 50 ° C. and stirred for 24 hours. After completion of the reaction, it was quenched with an aqueous ammonium chloride solution, and then extracted three times with 40 mL of methylene chloride. The obtained organic layer was dehydrated with MgSO ₄ , concentrated and dried under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain a compound represented by the formula (10) (3,4,3 ′, 3 ″ -tetrabromo-2,2 ′: 5 ′, 2 ″ -ter Thiophene) was obtained in 2.39 mg (4.24 mmol, 85%).

Physical property data of compound (10) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.11 (d, J = 7.2 Hz, 2H), 7.46 (d, J = 7.2 Hz, 2H)
¹³ C-NMR (400 MHz, CDCl ₃ ) δ: 113.1, 116.5, 128.2, 128.3, 130.9

Example 1
To a Schlenk dried under reduced pressure and substituted with argon, 0.052 g (0.05 mmol) of tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, 0.111 g of 1,1-bis (diphenylphosphino) ferrocene ( 0.20 mmol), sodium tert-butoxide 0.770 g (8.0 mmol), compound (10) 0.282 g (0.50 mmol), and toluene 3.0 mL were added. The mixture was stirred at room temperature for 20 minutes. Then, 0.128 g (1.2 mmol) of p-toluidine and 0.5 mL of toluene were added to make Schlenk sealed, and the reaction mixture was stirred at 110 ° C. for 12 hours. After completion of the reaction, the solution obtained by passing through a neutral alumina column (developing solvent: toluene) while diluting by adding toluene to the reaction mixture is concentrated and dried under reduced pressure to obtain a crude product as a brown solid. Obtained (196 mg). The obtained crude product was purified by silica gel column chromatography to obtain 110.1 mg (0.242 mmol, 48%) of the compound represented by the formula (11).

Physical property data of compound (11) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.06 (d, J = 8.3 Hz, 4H), 7.05 (d, J = 5.3 Hz, 2H), 6 .93 (d, J = 5.3 Hz, 2H), 6.78 (d, J = 8.3 Hz, 4H), 2.26 (s, 6H)

Example 2
The Schlenk dried under reduced pressure and substituted with argon was charged with 0.029 g (0.05 mmol) of bis (dibenzylideneacetone) dipalladium, 0.111 g (0.20 mmol) of 1,1-bis (diphenylphosphino) ferrocene, sodium Tert-butoxide 0.770 g (8.0 mmol), 0.282 g (0.50 mmol) of compound (10) and 3.5 mL of toluene were added. The mixture was stirred at room temperature for 20 minutes. Thereafter, 0.180 g (1.2 mmol) of 4-butylaniline was added to make Schlenk sealed, and the reaction mixture was stirred at 110 ° C. for 6 hours. After completion of the reaction, the reaction mixture was poured into distilled water and extracted with methylene chloride. The obtained organic layer was dried over anhydrous magnesium sulfate and purified by silica gel column chromatography to obtain 164 mg (0.305 mmol, 61%) of the compound represented by the formula (12).

Physical property data of compound (12) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.08 (d, J = 8.6 Hz, 2H), 7.06 (d, J = 5.4 Hz, 4H), 6 .96 (d, J = 5.4 Hz, 2H), 6.78 (d, J = 8.6 Hz, 4H), 2.46 (t, J = 7.6 Hz, 4H), 1.51 (q, J = 7.6 Hz, 4H), 1.37 (sextet, J = 7.6 Hz, 4H), 0.95 (t, J = 7.6 Hz, 6H)

Example 3
In the same manner as in Example 2 except that 0.148 g (1.2 mmol) of p-anisidine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline, 181 mg ( 0.371 mmol, 74%).

Physical property data of compound (13) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.07 (d, J = 8.6 Hz, 4H), 7.05 (d, J = 5.1 Hz, 2H), 6 .86 (d, J = 5.1 Hz, 2H), 6.51 (d, J = 8.6 Hz, 4H), 3.78 (s, 6H)

Example 4
In the same manner as in Example 2, except that 0.130 g (1.22 mmol) of benzylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline and the reaction mixture was stirred at 90 ° C. for 4 hours. 14) The compound shown by 175 mg (0.385 mmol, 77%) was obtained.

Physical property data of compound (14) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.22 (m, 6H), 7.03 (d, J = 7.0 Hz, 2H), 6.94 (d, J = 7.7 Hz, 4H), 6.77 (d, J = 7.0 Hz, 2H), 5.27 (s, 4H)

Example 5
In the same manner as in Example 2 except that 0.081 g (1.20 mmol) of methylamine hydrochloride was added instead of 0.180 g (1.2 mmol) of 4-butylaniline and the reaction mixture was stirred at 90 ° C. for 2 hours. 78 mg (0.257 mmol, 51%) of the compound represented by the formula (15) was obtained.

Physical property data of compound (15) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.10 (d, J = 5.3 Hz, 2H), 7.01 (d, J = 5.3 Hz, 2H), 4 .14 (s, 6H)

Example 6
In the same manner as in Example 2 except that 0.098 g (1.34 mmol) of butylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline, and the reaction mixture was stirred at 90 ° C. for 6 hours. ) Was obtained in 139 mg (0.374 mmol, 74%).

Physical property data of compound (16) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.08 (d, J = 5.2 Hz, 2H), 7.00 (d = J = 5.2 Hz, 2H), 4 .38 (t, J = 7.5 Hz, 4H), 1,88 (q, J = 7.5 Hz, 4H), 1.36 (sextet, J = 7.5 Hz, 4H), 0.94 (t, J = 7.5Hz, 6H)

Example 7
85 mg of the compound represented by the formula (17) was obtained in the same manner as in Example 2 except that 0.121 g (1.20 mmol) of n-hexylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline. (0.193 mmol, 39%).

Physical property data of compound (17) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.08 (d, J = 5.2 Hz, 2H), 7.00 (d, J = 5.2 Hz, 2H), 4 .36 (t, J = 7.6 Hz, 4H), 1.89 (q, J = 7.5 Hz, 4H), 1.22-1.40 (m, 12H), 0.86 (t, J = 7.0Hz, 6H)

Example 8
In the same manner as in Example 2 except that 0.157 g (1.20 mmol) of n-octylamine was added instead of 0.180 g (1.2 mmol) of 4-butylaniline, and the reaction mixture was stirred at 110 ° C. for 4 hours. 109 mg (0.218 mmol, 44%) of the compound represented by formula (18) was obtained.

Physical property data of compound (18) ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.04 (d, J = 4.9 Hz, 2H), 7.00 (d, J = 4.9 Hz, 2H), 4 .36 (t, J = 7.6 Hz, 4H), 1.89 (q, J = 6.9 Hz, 4H), 1.20-1.40 (m, 20H), 0.86 (t, J = (6.8Hz, 6H)

Example 9
Using the compound (11), an organic thin film transistor was produced by the following procedure. A silicon wafer having a resistivity of 0.01 to 0.03 Ω · cm formed by forming a silicon oxide (SiO ₂ ) insulating layer having a thickness of 400 nm by a thermal oxidation method was used as a substrate. Here, the substrate (silicon wafer) itself becomes the gate electrode, and the SiO ₂ insulating layer becomes the gate insulating layer. This substrate was ultrasonically washed with acetone, methanol and ultrapure water for 5 minutes each, immersed in a mixed solution of concentrated sulfuric acid-hydrogen peroxide solution for 1 minute, and then washed with running water. Next, the surface treatment of the substrate was performed in a hexamethyldisilazane (HMDS) atmosphere. On top of this, the compound (11) was vacuum-deposited under vacuum (10 ⁻⁶ torr) at a deposition rate of 0.2 to form an organic semiconductor layer having a thickness of 23 nm. Further, on the organic semiconductor layer, using a mask, gold having a thickness of 48 nm was vacuum deposited to form a source electrode and a drain electrode, thereby obtaining an organic thin film transistor. The channel width was 2058 μm and the channel length was 30 μm. A gate voltage of −150 V was applied to the gate electrode of the obtained organic thin film transistor, a voltage was further applied between the source electrode and the drain electrode, and a current was passed to evaluate the transistor characteristics. The results are shown in Table 1.

Example 10
In the same manner as in Example 9, an organic thin film transistor was produced using the compound (15). The obtained organic thin film transistor had a channel width of 1470 μm and a channel length of 30 μm. A gate voltage of −100 V was applied to the gate electrode of the obtained organic thin film transistor, a voltage was further applied between the source electrode and the drain electrode, and a current was passed to evaluate the transistor characteristics. The results are shown in Table 1.

Example 11
Using the compound (11), an organic thin film transistor was produced by the following procedure. First, the same substrate as that used in Example 9 was ultrasonically cleaned with acetone, methanol, and ultrapure water for 5 minutes each. Next, a 0.5 wt% solution of the compound (11) in chloroform was applied onto the substrate using a spin coater (Kyowa Riken: K359S-1), and the film was removed by removing the solvent. A 3 nm organic semiconductor layer was formed. Further, using a mask, gold having a thickness of 43 nm was deposited on the organic semiconductor layer to form a source electrode and a drain electrode, thereby obtaining an organic thin film transistor. The channel width was 1220 μm and the channel length was 30 μm. A gate voltage of −150 V was applied to the gate electrode of the obtained organic thin film transistor, a voltage was further applied between the source electrode and the drain electrode, and a current was passed to evaluate the transistor characteristics. The results are shown in Table 1.

Example 12
In a 50 mL three-necked flask equipped with a thermometer, compound (11) 20 mg (0.044 mmol), ferric perchlorate / n hydrate (anhydride content of 70 wt% or more), 78 mg, 10 mL of benzonitrile was added and the reaction mixture was stirred at 25 ° C. for 24 hours. After completion of the reaction, the reaction mixture was filtered to obtain 13.6 mg of a polymer. The obtained polymer was dried and then compression molded on a glass substrate to produce an electrode. The conductivity of the electrode (polymer) was measured by a four-probe method and found to be 4.27 × 10 ⁻² S / cm.

The obtained polymer was immersed in an aqueous solution of 10% by weight of hydrazine monohydrate for 10 minutes to prepare a dedoping polymer. The obtained dedoping polymer was dried and its conductivity was measured by a four-probe method. As a result, no conductivity was confirmed. This is a phenomenon peculiar to a conductive polymer whose conductivity is changed by doping and dedoping.

The condensed heterocyclic compound and the polymer thereof according to the present invention are, for example, inks, antistatic agents, organic electronics members (for example, electrodes, solid electrolytic capacitors, thermoelectric elements, piezoelectric elements, actuators) as semiconductive materials or conductive materials. , Sensors, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors, radio wave identification (RFID) devices, field effect transistors (FETs), integrated circuits (ICs), organic electroluminescence devices (OLEDs), organic semiconductor devices Etc.).

Claims

Formula (1):

[Wherein, R 1 and each R 2 independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a hetero that may have a substituent. An aryl group or —CO—R (wherein R represents an alkyl group which may have a substituent, an aryl group which may have a substituent or a heteroaryl group which may have a substituent); .) And
Ring A, Ring B and Ring C are each independently a 5-membered or 6-membered aromatic heterocyclic ring which may have a substituent,
n is an integer of 1 to 4. ]
A compound represented by
Formula (2):

[Wherein R 1 , each R 2 and n are as defined in claim 1;
W 1 to W 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, An aryl group that may have a substituent, a heteroaryl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent It may have an alkylamino group, a cyano group, a nitro group, an azido group, a hydroxy group, a sulfanyl group, an amino group, a carboxyl group or a salt thereof, a phosphono group or a salt thereof, a sulfo group or a salt thereof, or a substituent. A good carbamoyl group, a phosphinoyl group which may have a substituent, a phosphanyl group which may have a substituent, —CO—R, —SO—R (wherein R may have a substituent) Good alkyl group, substituent Have also represents a heteroaryl group which may have an aryl group or a substituent), -. MgCl, -MgBr, -MgI, -ZnCl, -ZnBr, -ZnI, -Sn (Ak) 3, - B (OH) 2 , —B (OAk) 2 , —B (—OC (CH 3 ) 2 C (CH 3 ) 2 O—), —Si (Ak) 3 , or —Si (OAk) 3 In the formula, Ak represents an alkyl group. ]
The compound of Claim 1 which is shown by these.
Formula (3):

[Wherein R 1 , R 2 and W 1 to W 4 are as defined in claim 2. ]
The compound of Claim 2 shown by these.
The compound according to claim 2 or 3, wherein at least two of W 1 to W 4 are each independently a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.
R 1 and each R 2 are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. The compound according to any one of 1 to 4.
The R 1 and each R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or a phenyl group which may have a substituent, according to any one of claims 1 to 4. Compound.
A composition comprising the compound according to any one of claims 1 to 6 and a dopant.
The composition according to claim 7, wherein the compound according to any one of claims 1 to 6 is a cation and the dopant is an anion.
A polymer containing a structural unit derived from the compound according to claim 4.
R 1 and each R 2 are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. 9. The polymer according to 9.
The polymer according to claim 9, wherein R 1 and each R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an optionally substituted phenyl group.
A composition comprising the polymer according to any one of claims 9 to 11 and a dopant.
The composition according to claim 12, wherein the polymer according to any one of claims 9 to 11 is a cation and the dopant is an anion.
An organic electronic member comprising the compound according to any one of claims 1 to 6 or the composition according to claim 7 or 8.
Electrodes, solid electrolytic capacitors, thermoelectric elements, piezoelectric elements, actuators, sensors, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors, individual identification (RFID) devices using radio waves, field effect transistors (FETs), integrated circuits (ICs) The organic electronics member according to claim 14, which is an organic electroluminescence element (OLED) or an organic semiconductor element.
An organic electronics member comprising the polymer according to any one of claims 9 to 11 or the composition according to claim 12 or 13.
Electrodes, solid electrolytic capacitors, thermoelectric elements, piezoelectric elements, actuators, sensors, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors, individual identification (RFID) devices using radio waves, field effect transistors (FETs), integrated circuits (ICs) The organic electronics member according to claim 16, which is an organic electroluminescence element (OLED) or an organic semiconductor element.
Formula (4):

[Wherein, X 1 to X 4 are each independently a chlorine atom, a bromine atom or an iodine atom,
W 1 to W 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, An aryl group that may have a substituent, a heteroaryl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent It may have an alkylamino group, a cyano group, a nitro group, an azido group, a hydroxy group, a sulfanyl group, an amino group, a carboxyl group or a salt thereof, a phosphono group or a salt thereof, a sulfo group or a salt thereof, or a substituent. A good carbamoyl group, a phosphinoyl group which may have a substituent, a phosphanyl group which may have a substituent, —CO—R, —SO—R (wherein R may have a substituent) Good alkyl group, substituent Have also represents a heteroaryl group which may have an aryl group or a substituent), -. MgCl, -MgBr, -MgI, -ZnCl, -ZnBr, -ZnI, -Sn (Ak) 3, - B (OH) 2 , —B (OAk) 2 , —B (—OC (CH 3 ) 2 C (CH 3 ) 2 O—), —Si (Ak) 3 , or —Si (OAk) 3 In the formula, Ak represents an alkyl group. ]
A compound of formula (5):
R 1 —NH 2 (5)
[Wherein R 1 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —CO—R ( In the above formula, R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]
A compound of formula (6):
R 2 —NH 2 (6)
[Wherein R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —CO—R ( In the above formula, R represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]
Comprising reacting with a compound of formula (3):

[Wherein R 1 , R 2 and W 1 to W 4 are as defined above. ]
The manufacturing method of the compound shown by these.
19. R 1 and R 2 are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent. The manufacturing method as described in.
The production method according to claim 18, wherein R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a benzyl group, or an optionally substituted phenyl group.