JP2011168544A - Pyrrole compound and organic electroluminescent element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pyrrole compound necessary for providing an organic electroluminescent element having high efficiency and an organic electroluminescent element using the same. <P>SOLUTION: The pyrrole compound is represented by formula (1) (wherein R<SP>1</SP>is a group selected from group consisting of an alkyl group, an aralkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group which may be substituted, and an aromatic heterocyclic group which may be substituted; R<SP>2</SP>to R<SP>4</SP>is each a group selected from the group consisting of hydrogen, an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group which may be substituted, and an aromatic heterocyclic group which may be substituted; L is a group selected from the group consisting of a mono- to hexavalent-group of a substituted or nonsubstituted aromatic hydrocarbon and a mono- to hexavalent-group of a substituted or nonsubstituted aromatic heterocyclic compound; n is an integer selected from 1-6; and the valence of L and the number of n are the same). The organic electroluminessent element using the compound is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a pyrrole compound and an organic electroluminescence device using the same.

  Organic compounds that can have a variety of molecular structures compared to inorganic compounds can impart various functions to molecules. In addition, since the process temperature is low compared with conventional silicon-based electronics devices, the environmental impact can be suppressed. In recent years, organic electronics devices using functional organic compounds have been extensively researched. (Non-Patent Document 1).

  Examples of organic electronic devices using functional organic materials include organic solar cells, organic electroluminescence (hereinafter abbreviated as “organic EL”) elements, organic memories, and organic field effect transistors (FETs). Can be mentioned. These are devices utilizing the electrical properties and optical properties of organic compounds, and particularly organic EL elements are making remarkable progress.

Since organic EL elements are self-luminous elements, they have a wide viewing angle, fast response speed, driven by direct current, and contain no substances harmful to the environment such as mercury. It is attracting attention as a display light source for generations, and as an illumination light source that replaces fluorescent lamps. However, in order to replace existing displays and fluorescent lamps, reduction of power consumption and extension of the life of organic EL elements are listed as essential issues.
Therefore, in order to solve this problem, organic EL elements using phosphorescent materials have recently been studied.

  When phosphorescent materials are used, in addition to singlet excitons generated by charge recombination, triplet excitons generated at the same time contribute to light emission, which makes organic EL more efficient than fluorescent materials. An element can be created. That is, since excitons generated by recombination are related to 100% emission, the external quantum efficiency is 20% at the maximum even considering the extraction efficiency, and energy can be used efficiently.

  The first phosphorescent material was used for organic EL devices by Baldo et al. Of Princeton University, and it has been reported that highly efficient red light emission is possible by using a platinum complex (Non-patent Document 2). Thereafter, iridium complexes that emit green light at room temperature have been developed (Non-patent Documents 3 and 4), and phosphorescent materials have been actively developed. The organic EL device is characterized in that a mixture of a phosphorescent material that is a guest and a host material that gives energy to the phosphorescent material is used as a light emitting layer. The host material used at this time was 4,4'-N, N'-dicarbazole-biphenyl (CBP), an amine-based material. What is important for the host material is that it has the ability to give sufficient energy to the phosphorescent material. To estimate this ratio, the band gap value between the HOMO and LUMO of the host material is used as a guide. The

  According to this value, CBP functions adequately from green to red at relatively long wavelengths, but it does not have enough energy for blue phosphorescent materials with high energy levels to function. Since the wide band gap of the host material (hereinafter referred to as wide gap) was important, the external quantum efficiency of blue phosphorescent organic EL devices was improved by developing various wide gap host materials (non-patented Reference 5). Furthermore, the efficiency of the blue phosphorescent organic EL device was further improved by widening the material contained in the hole (hole) transport layer and the electron transport layer adjacent to the light emitting layer (Patent Documents 1 to 6).

  The efficiency of blue phosphorescent organic EL elements has been steadily improved by using a wide gap material, but it is still insufficient from the viewpoint of practical use, so the development of a new material is required.

  In Patent Document 7, a compound having a pyrrole ring is used as a host material or a hole blocking layer that prevents holes from passing through the electron transport layer. The hall transport capability is not fully utilized.

  In Patent Document 8, a compound having a pyrrole ring is used as a host material. However, this also does not make full use of the hole transport capability of a 6π-electron 5-membered ring, which is a feature of the pyrrole ring.

JP 2005-320227 A Japanese Patent Laid-Open No. 2005-220088 JP 2007-15993 A JP 2008-120696 A JP 2008-127326 A JP 2009-35524 A JP 2004-146368 A JP 2005-232159 A

Latest Trends in Organic Devices, Toray Research Center, February 2009 Nature, Vol. 395, p151 (1998) Appl. Phys. Lett. , Vol. 75, p4 (1999) Appl. Phys. Lett. , Vol. 77, p904 (2000) Appl. Phys. Lett. , Vol. 83, p569 (2003)

  An object of the present invention is to provide a pyrrole compound necessary for providing a highly efficient organic EL device and an organic EL device using the same.

（式中、Ｒ^１は、炭素数１〜６の直鎖または分岐のアルキル基、炭素数７〜１２の未置換、もしくは炭素数１〜４の直鎖もしくは分岐のアルキル基を有するアラルキル基、炭素数６〜２０の脂環式炭化水素基、未置換、もしくは炭素数１〜４の直鎖もしくは分岐のアルキル基、あるいは炭素数１〜４の直鎖もしくは分岐のアルコキシ基を有する芳香族炭化水素基および未置換、もしくは炭素数１〜４の直鎖もしくは分岐のアルキル基、あるいは炭素数１〜４の直鎖もしくは分岐のアルコキシ基を有する芳香族複素環基よりなる群から選ばれた基であり、Ｒ^２〜Ｒ^４は、水素原子、炭素数１〜６の直鎖または分岐のアルキル基、炭素数６〜２０の脂環式炭化水素基、未置換、もしくは炭素数１〜４の直鎖もしくは分岐のアルキル基、あるいは炭素数１〜４の直鎖もしくは分岐のアルコキシ基を有する芳香族炭化水素基および未置換、もしくは炭素数１〜４の直鎖もしくは分岐のアルキル基、あるいは炭素数１〜４の直鎖もしくは分岐のアルコキシ基を有する芳香族複素環基よりなる群から選ばれた基であるが、Ｒ^２〜Ｒ^４のうち少なくとも１つは未置換、もしくは炭素数１〜４の直鎖もしくは分岐のアルキル基、あるいは炭素数１〜４の直鎖もしくは分岐のアルコキシ基を有する芳香族炭化水素基であり、Ｌは、置換もしくは無置換の炭素数６〜４５の芳香族炭化水素の１〜６価基および置換もしくは無置換の炭素数４〜４０の芳香族複素環化合物の１〜６価基よりなる群から選ばれた基であり、ｎは１〜６から選ばれた整数であり、かつ、Ｌの価数とｎの数は同一である。）
で示されるピロール系化合物に関する。
本発明の第２は、前記一般式（１）においてｎが２であり、Ｌが、置換もしくは無置換の炭素数６〜４５の芳香族炭化水素の２価基、置換もしくは無置換の炭素数４〜４０の芳香族複素環化合物の２価基であることを特徴とする請求項１に記載のピロール系化合物に関する。
本発明の第３は、前記一般式（１）においてｎが２であり、Ｌが、置換もしくは無置換の炭素数６〜４５の芳香族炭化水素の２価基であることを特徴とする請求項１または２に記載のピロール系化合物に関する。
本発明の第４は、前記一般式（１）においてｎが２であり、Ｌが置換基を有しても良いビフェニレン基であることを特徴とする請求項１〜３に記載のピロール系化合物に関する。
本発明の第５は、請求項１〜４記載のピロール系化合物を用いた有機エレクトロニクスデバイスに関する。
本発明の第６は、請求項１〜４記載のピロール系化合物を用いた有機ＥＬ素子に関する。
本発明の第７は、請求項６記載の有機ＥＬ素子において、前記ピロール系化合物がホール輸送層に含有されることを特徴とする有機ＥＬ素子に関する。
本発明の第８は、請求項６記載の有機ＥＬ素子において、前記ピロール系化合物が発光層に含有されることを特徴とする有機ＥＬ素子に関する。 The first of the present invention is the following general formula (1)

(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, an unsubstituted aralkyl group having 7 to 12 carbon atoms, or an aralkyl group having a linear or branched alkyl group having 1 to 4 carbon atoms; Aromatic hydrocarbon having an alicyclic hydrocarbon group having 6 to 20 carbon atoms, unsubstituted, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms A group selected from the group consisting of an aromatic heterocyclic group having a hydrogen group and an unsubstituted or linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms R ^{2 to} R ⁴ are each a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 6 to 20 carbon atoms, unsubstituted, or having 1 to 4 carbon atoms. A linear or branched alkyl group, or Aromatic hydrocarbon group having a linear or branched alkoxy group having 1 to 4 carbon atoms and unsubstituted, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched group having 1 to 4 carbon atoms A group selected from the group consisting of an aromatic heterocyclic group having at least one alkoxy group, but at least one of R ^{2 to} R ⁴ is unsubstituted or a linear or branched alkyl group having 1 to 4 carbon atoms. Or an aromatic hydrocarbon group having a linear or branched alkoxy group having 1 to 4 carbon atoms, wherein L is a substituted or unsubstituted 1 to 6 valent group of an aromatic hydrocarbon having 6 to 45 carbon atoms and A group selected from the group consisting of 1 to 6 valent groups of substituted or unsubstituted aromatic heterocyclic compounds having 4 to 40 carbon atoms, n is an integer selected from 1 to 6 and L The valence and the number of n are the same.)
It relates to a pyrrole compound represented by the formula:
A second aspect of the present invention is that in the general formula (1), n is 2, and L is a substituted or unsubstituted divalent group of an aromatic hydrocarbon having 6 to 45 carbon atoms, a substituted or unsubstituted carbon number. The pyrrole compound according to claim 1, which is a divalent group of 4 to 40 aromatic heterocyclic compounds.
According to a third aspect of the present invention, in the general formula (1), n is 2, and L is a substituted or unsubstituted divalent group of an aromatic hydrocarbon having 6 to 45 carbon atoms. It relates to the pyrrole compound according to Item 1 or 2.
A fourth aspect of the present invention is the pyrrole compound according to any one of claims 1 to 3, wherein in the general formula (1), n is 2 and L is a biphenylene group which may have a substituent. About.
5th of this invention is related with the organic electronics device using the pyrrole type compound of Claims 1-4.
6th of this invention is related with the organic EL element using the pyrrole type compound of Claims 1-4.
A seventh aspect of the present invention relates to the organic EL element according to claim 6, wherein the pyrrole compound is contained in a hole transport layer.
An eighth aspect of the present invention relates to the organic EL element according to claim 6, wherein the pyrrole compound is contained in a light emitting layer.

According to the present invention, a novel pyrrole compound, a charge transport material comprising the same, and an organic EL device using the same can be provided.
The pyrrole compound of the present invention is useful as a charge transport material for blue phosphorescence and is known as a hole transport material for blue phosphorescence. N ³ , N ³ , N ³ ″ ″, N ³ ″ ″ -Tetra-p-tolyl -[1,1 ';2', 1 ";2", 1 '"] When used as an alternative to quarterphenyl-3,3'"-diamin (3DTAPBP), the organic EL device emits light with high luminous efficiency and long life. be able to. Therefore, by using the pyrrole compound of the present invention, an organic EL device with high luminous efficiency is provided. Therefore, the pyrrole compound of the present invention is extremely important industrially.

It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. It is sectional drawing which shows an example of the organic EL element in this invention. The ¹ H-NMR spectrum of Pyr1 (measurement solvent: C ₆ D ₆ ) is shown. The MS spectrum of Pyr1 is shown. ¹ shows a ¹ H-NMR spectrum of Pyr2 (measuring solvent: CDCl ₃ ). The MS spectrum of Pyr2 is shown. ¹ shows an ¹ H-NMR spectrum of Pyr3 (measurement solvent: CDCl ₃ ). The MS spectrum of Pyr3 is shown. ¹ shows a ¹ H-NMR spectrum of Pyr4 (measuring solvent: CDCl ₃ ). The MS spectrum of Pyr4 is shown. ¹ shows a ¹ H-NMR spectrum of Pyr5 (measuring solvent: CDCl ₃ ). The MS spectrum of Pyr5 is shown. ¹ shows a ¹ H-NMR spectrum of Pyr6 (measurement solvent: CDCl ₃ ). The MS spectrum of Pyr6 is shown. ¹ shows the ¹ H-NMR spectrum of Pyr7 (measurement solvent: CDCl ₃ ). The MS spectrum of Pyr7 is shown. ¹ shows a ¹ H-NMR spectrum (measuring solvent: CDCl ₃ ) of Pyr8. The MS spectrum of Pyr8 is shown. The EL spectrum of Examples 1-3 and the comparative example 1 is shown. The current density-voltage characteristics of Examples 1 to 3 and Comparative Example 1 are shown. The luminance-voltage characteristics of Examples 1 to 3 and Comparative Example 1 are shown. The current efficiency-current density characteristics of Examples 1 to 3 and Comparative Example 1 are shown. The luminance-current density characteristics of Examples 1 to 3 and Comparative Example 1 are shown. The element lifetime characteristics of Examples 1 to 3 and Comparative Example 1 are shown. The CIE chromaticity coordinate of Example 4 is shown. The current efficiency-current density characteristic of Example 4 is shown. The current density-voltage characteristic of Example 4 is shown. The luminance-voltage characteristic of Example 4 is shown.

Examples of the linear or branched alkyl group having 1 to 6 carbon atoms as R ^{1 to} R ⁴ in the present invention include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec- Butyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,2-dimethylbutyl, 2,3 -Dimethylbutyl, 3,3-dimethylbutyl and the like can be mentioned. When the number of carbon atoms in the alkyl group exceeds 6, the thermal properties such as the melting point of the compound and the glass transition point may be reduced, and as a result, organic EL elements such as crystallization and changes in film shape may be observed. As a result, undesirable effects may occur.

Examples of the aralkyl group that may have a substituent having 7 to 12 carbon atoms as R ¹ include a benzyl group, a phenethyl group, a cumyl group, and a naphthylmethyl group.

^Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms as R 1 to R ^4, bicyclic, such as tricyclo ring, and, as specific examples, (1) adamantane and its derivatives, (2) norbornane And (3) perhydroanthracene and derivatives thereof, (4) perhydronaphthalene and derivatives thereof, and (5) cyclohexane and derivatives thereof.
The following is its specific structural formula.

Examples of the aromatic hydrocarbon group which may have a substituent as R ^{1 to} R ⁴ in the present invention include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-phenyl-1-naphthyl group, 4- Phenyl-2-naphthyl group, 5-phenyl-1-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 10-phenyl-9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 1-fluoranthenyl group, 2-fluoranthenyl group, 3 -Fluoranthenyl group, 8-fluoranthenyl group, 2-triphenylenyl group, 9,9-dimethylfluoren-2-yl group, 9,9-dibutylfluorene 2-yl group, 9,9-dihexylfluoren-2-yl group, 9,9-dioctylfluoren-2-yl group, 9,9-diphenylfluoren-2-yl group, 2-biphenylyl group, 3-biphenylyl group 4-biphenylyl group, p-terphenyl-3-yl group, p-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-4-yl group, o-terphenyl -3-yl group, o-terphenyl-4-yl group, 4- (1-naphthyl) -1-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, p-tert-butylphenyl Group, 4-methoxyphenyl group, 4-fluorophenyl group, 4-dimethylaminophenyl group, 4-cyanophenyl group, 4- (trifluoromethyl) phenyl group, 4-methyl-1-naphthyl group, 2-metho Ci-1-naphthyl group, 10-methyl-9-anthryl group, 10-methoxy-9-anthryl group, 4-phenyl-8-fluoranthenyl group, 7-dimethylamino-9,9-dimethylfluorene-2- Yl group, 3 ', 5'-diphenylbiphenyl-4-yl group, and the like.

Examples of the aromatic heterocyclic group which may have a substituent as R ^{1 to} R ⁴ in the present invention include a 2-furyl group, a 4-phenyl-2-furyl group, a 2-thienyl group, and 4-phenyl-2. -Thienyl group, 4- (2-thienyl) -2-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4-phenyl-2-pyridyl group, 6-phenyl-2-pyridyl group, 4- (dimethylamino) -2-pyridyl group, 2,2'-bipyridyl-6-yl group, 2,2'-bipyridyl-5-yl group, 2,3'-bipyridyl-6-yl group, 2- Pyrimidinyl group, 2-pyrazinyl group, 2-indolidinyl group, 2-isoindolyl group, 8-purinyl group, 1-isoquinolyl group, 3-isoquinolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 8- Quinolyl group, 8-methoxy 2-quinolyl group, 4-phenyl-2-quinolyl group, 2-quinoxalinyl group, 2-quinazolinyl group, 4-quinazolinyl group, 5-quinazolinyl group, 6-quinazolinyl group, 1,8-naphthyridin-2-yl group 2-pteridinyl group, 2-carbazolyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 8-phenanthridinyl group, 2-acridinyl group, 3- Acridinyl group, 9-acridinyl group, 1,10-phenanthrolin-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-4-yl group, 1,10-phenanthroline-5-yl Group, 3-phenyl-1,10-phenanthrolin-2-yl group, 3-phenyl-1,10-phenanthrolin-4-yl group, 1,10-phenanthroline-5-yl group, 4-phenyl-1,10-phenanthroline-2-yl group, 4-phenyl-1,10-phenanthroline-3-yl group, 4-phenyl-1,10 -Phenanthrolin-5-yl group, 4,7-diphenyl-1,10-phenanthroline-2-yl group, 4,7-diphenyl-1,10-phenanthroline-3-yl group, 1,8-phenanthroline-2- Yl group, 1,8-phenanthroline-3-yl group, 1,8-phenanthroline-4-yl group, 1,8-phenanthroline-5-yl group, 1,8-phenanthroline-6-yl group, 1,8 -Phenanthroline-7-yl group, 1,8-phenanthroline-9-yl group, 1,7-phenanthroline-2-yl group, 1-phenazinyl group, 2-phenazinyl group Group, benzo [b] furan-2-yl group, benzo [b] furan-3-yl group, benzo [b] furan-5-yl group, benzo [b] furan-6-yl group, benzo [b] Thiophen-2-yl group, benzo [b] thiophen-3-yl group, benzo [b] thiophen-5-yl group, benzo [b] thiophen-6-yl group, 1-methylindol-2-yl group, 1-methylindol-3-yl group, 1-methylindol-5-yl group, dibenzofuran-1-yl group, dibenzofuran-2-yl group, dibenzofuran-3-yl group, dibenzofuran-4-yl group, dibenzothiophene -1-yl group, dibenzothiophen-2-yl group, dibenzothiophen-3-yl group, dibenzothiophen-4-yl group, 9-phenylcarbazol-2-yl group, 9-pheny Carbazol-3-yl group, 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, benzo [b] [1,8] naphthyridin-2-yl group, pyrido [2,3-g Quinolin-2-yl group, pyrido [3,2-g] quinolin-2-yl group, 1,8,9-triazaanthracen-2-yl group and the like.

Examples of the 1- to 6-valent group of substituted or unsubstituted aromatic hydrocarbon having 6 to 45 carbon atoms as L in the present invention include an aromatic group that may have a substituent as R ^{1 to} R ^4. A monovalent group exemplified as a hydrocarbon group and a divalent to hexavalent group formed by replacing a hydrogen atom with a bond, a p-phenylene group, an m-phenylene group, a 1,4-naphthylene group, , 5-naphthylene group, 9,10-anthracenediyl group, 2,7-phenanthrylene group, biphenyl-4,4'-diyl group, biphenyl-3,5-diyl group, 1,1'-binaphthalene-4,4 '-Diyl group, 4,4'-isopropylidenediphenyl-1,1'-diyl group, 4,4'-hexafluoroisopropylidenediphenyl-1,1'-diyl group, benzene-1,3,5-triyl Group 4,4 ', ″ -Ethylidenetriphenyl-1,1 ′, 1 ″ -triyl group, biphenyl-3,5,3 ′, 5′-tetrayl group, 1,3,5-triazine-2,4,6-triyl group, A hexaphenylbenzene group can be exemplified.

  Examples of the 1- to 6-valent group of the substituted or unsubstituted aromatic heterocyclic compound having 4 to 40 carbon atoms as L in the present invention are listed as the aromatic heterocyclic group which may have the substituent. A monovalent group and a divalent to hexavalent group formed by replacing a hydrogen atom with a bond, pyridine-2,6-diyl group, quinoline-2,4-diyl group, 1,10-phenanthroline- Examples include 2,9-diyl group, 1,10-phenanthroline-4,7-diyl group, pyridine-2,4,6-triyl group.

A method for synthesizing the pyrrole compound of the present invention will be described. Here, as an example, a method for synthesizing a pyrrole compound represented by the following general formula (2) will be described.

The compound represented by the general formula (2) can be synthesized by the following reaction. In the following reaction formulas, R ^{1 to} R ⁴ are as described above. X represents a halogen element such as chlorine, bromine or iodine.

The first reaction of the compound represented by the general formula (2) is a reaction in which a ketone having α-hydrogen and a dihalogenated benzene are coupled using a palladium catalyst in the presence of a base. The palladium catalyst used in the reaction is zero-valent such as Pd ₂ (dba) ₃ (Pd = palladium, dba = dibenzylideneacetone), Pd (dba) ₂ , Pd (PPh ₃ ) ₄ (PPh ₃ = triphenylphosphine). And divalent palladium compounds such as palladium acetate [Pd (OAc) ₂ ], PdCl ₂ (PPh ₃ ) ₂ , and PdCl ₂ (dppf) ₂ can be used. The dppf refers to 1,1′-bis (diphenylphosphino) ferrocene. As ligands to be added thereto, BINAP [= 2,2′-bis (diphenylphosphino-1,1′-binaphthyl)], tri (tert-butylphosphine) [P (t-Bu) ₃ ], tri (Cyclohexylphosphine), 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,3-bis (diphenylphosphino) butane, dppf, and the like can be used.
As the base used in the reaction, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium phosphate, potassium carbonate, cesium carbonate, triethylamine and the like can be used.
Tetrahydrofuran, dioxane, dimethoxyethane, dimethyl sulfoxide and the like can be used as a solvent used in the reaction, and the reaction is performed at 0 to 200 ° C. over 1 to 60 hours.
The second reaction is a reaction in which the obtained coupling product and α-halogenated ketone are coupled in the presence of a base. In addition to α-halogenated ketones, α-halogenated ketone derivatives such as α-halogenated aldehydes, α-halogenated ketals, α-halogenated acetals, and the like can be used. As the base used in the reaction, basic substances such as sodium hydroxide, potassium hydroxide, sodium-tert-butoxide, potassium-tert-butoxide, sodium hydride, calcium hydride, cesium carbonate, triethylamine and the like can be used. As the solvent used in the reaction, N, N-dimethylformamide, N, N-dimethylacetamide, dimethoxyethane, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc. can be used, and it takes 1 to 48 hours at 0 to 100 ° C. Perform the reaction.
The third reaction is a reaction in which the obtained 1,4-diketone and primary amine are dehydrated and cyclized in the presence of an acid catalyst. As the acid catalyst used in the reaction, acidic substances such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and acetic acid can be used. As a solvent used for the reaction, toluene, xylene, methanol, ethanol, acetic acid, or the like can be used, and the reaction is performed at 50 to 150 ° C. for 1 to 48 hours.
The fourth reaction uses the Yamamoto coupling reaction (Bull. Chem. Soc. Jpn., Vol. 72, p621, 1999) to couple the halogen element sites of the pyrrole compound to obtain the target compound. It is. Specifically, in an inert gas such as nitrogen gas, bis (1,5-cyclooctadiene) which is 0 to 1.5 equivalents of zero-valent nickel with respect to the pyrrole compound obtained in the third reaction. ) Nickel [Ni (cod) ₂ ] is reacted with 1.0 to 1.5 equivalents of 2,2′-bipyridine (2,2′-bpy) using N, N-dimethylformamide as a solvent. As a compound used in the reaction, in addition to a combination of Ni (cod) ₂ and 2,2′-bpy, a combination of nickel chloride (NiCl ₂ ), zinc, triphenylphosphine, and 2,2′-bpy can be used. In addition to N, N-dimethylformamide, N, N-dimethylacetamide, toluene, N-methyl-2-pyrrolidone or the like can be used as a solvent, and the reaction is carried out at 0 to 100 ° C. over 1 to 48 hours.

In addition, the pyrrole compound of the present invention can be synthesized by a synthesis method as shown in [Chemical Formula 5]. In the structural formula, X represents a halide such as chlorine, bromine or iodine. That is, a target compound can be obtained by reacting a halide having X in the structural formula with an organometallic compound having B (OH) ₂ in the structural formula by a palladium coupling method. Palladium catalysts used for the reaction include zero-valent palladium catalysts such as Pd ₂ (dba) ₃ , Pd (dba) ₂ , Pd (PPh ₃ ) ₄ , PdCl ₂ , PdCl ₂ (PPh ₃ ) ₂ , PdCl ₂ (dppf ) it can be used a divalent palladium compound such as _2. As ligands to be added thereto, BINAP, tri (tert-butylphosphine), tri (cyclohexylphosphine), 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1 , 3-bis (diphenylphosphino) butane, dppf, etc. can be used.
As the base used in the reaction, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium phosphate, potassium carbonate, cesium carbonate, triethylamine and the like can be used.
As the solvent used in the reaction, tetrahydrofuran, dioxane, dimethoxyethane, dimethyl sulfoxide, xylene, toluene and the like can be used. The reaction temperature is 0 to 200 ° C., preferably 50 to 150 ° C., and the reaction time is 1 to 60 hours, preferably 5 The corresponding coupling compound can be synthesized by stirring for ˜48 hours.

Specific examples of the compound of the present invention are illustrated below. In the following exemplified compounds, the methyl group can be replaced with other alkyl groups such as an ethyl group and a propyl group.

  Next, although an organic EL element is demonstrated as an example of the organic electronics device of this invention, the organic electronics device using the pyrrole type compound shown by General formula (1) of this invention is not limited at all.

  The pyrrole compound of the present invention can be used as a hole transport material or a host material.

  The pyrrole compound of the present invention can be used as a single compound as well as in combination of two or more compounds.

  When using the pyrrole-type compound of this invention as a host material of an organic EL element, it can be used in combination with a suitable luminescent material.

  Next, the organic EL element of the present invention will be described. The organic EL device of the present invention is a device in which a single layer or a multilayer organic compound is laminated between an anode and a cathode, and at least one layer of the organic compound layer contains the pyrrole compound of the present invention. When the organic EL element is a single layer, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material and may contain a hole injecting material or an electron injecting material for the purpose of transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. Examples of the configuration of the multilayer organic EL element include, for example, ITO (indium-tin oxide) / hole transport layer / light emitting layer / electron transport layer / cathode, ITO / hole injection layer / hole transport layer / light emitting layer / electron transport. Layer / cathode, ITO / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode, ITO / hole injection layer / hole transport Layer / light emitting layer / hole block layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection layer / cathode, ITO / hole injection layer / hole transport layer / light emitting layer And a multilayer structure such as / hole block layer / electron transport layer / electron injection layer / cathode. Moreover, you may have a sealing layer on a cathode as needed.

  Each of the hole (hole) transport layer, the electron transport layer, and the light emitting layer may have a single layer structure or a multilayer structure. In addition, the hole transport layer and the electron transport layer are divided into a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer). It can also be provided.

  The organic EL element of the present invention is not limited to the above configuration example, and can have various configurations. That is, if necessary, a layer in which a hole transport layer component and a light emitting layer component are mixed, a layer in which an electron transport layer component and a light emitting layer component are mixed, and a hole transporting light emitting layer and an electron transporting light emitting layer, respectively. be able to.

  Hereinafter, the constituent elements of the organic EL device of the present invention will be described in detail, taking as an example the device configuration comprising anode / hole transport layer / light emitting layer / electron transport layer / cathode.

  The organic EL element of the present invention is preferably supported on a substrate.

  The material of the substrate is not particularly limited, and any material commonly used in conventional organic EL elements can be used. For example, a material made of glass, quartz glass, transparent plastic, or the like can be used.

As an anode of the organic EL device of the present invention, it is preferable to use a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof as an electrode material. . Specific examples of such electrode materials include metals such as gold, silver, and copper, conductive transparent materials such as ITO, tin oxide (SnO ₂ ), and zinc oxide (ZnO), and conductive polymers such as polypyrrole and polythiophene. Materials. For the anode, these electrode materials can be formed on the substrate by a method such as vapor deposition, sputtering, or coating. The sheet electrical resistance of the anode is preferably 100Ω / □ or less, and more preferably 50Ω / □ or less. The thickness of the anode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm.

  As the cathode, an electrode material is preferably a single metal having a small work function (4 eV or less), an alloy of metals having a small work function (4 eV or less), a conductive substance, or a mixture thereof. Specific examples of such electrode materials include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy. Can be mentioned. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet electrical resistance of the cathode is preferably several hundred Ω / □ or less. The thickness of the cathode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm. In order to efficiently extract light emitted from the organic EL device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent.

The hole transport layer of the organic EL device of the present invention is made of a hole transport material and has a function of transporting holes injected from the anode to the light emitting layer. When a hole transport material is disposed between two electrodes to which an electric field is applied and holes are injected from the anode, at least 1.0 × 10 ⁻⁶ m ² / V · sec or more, more preferably 1.0 × A hole transport material having a hole mobility of 10 ⁻⁵ m ² / V · sec or more is preferable. The hole transport material used in the hole transport layer of the organic EL device of the present invention is preferably the pyrrole compound of the present invention, but is not particularly limited as long as it has the above-mentioned preferred properties, and has been conventionally used. Select any photoconductive material that is commonly used as a hole injection material or hole transport material, or a known material used for a hole injection layer or hole transport layer of an organic EL device. Can be used. The pyrrole compound of the present invention may be used alone or in combination with other compounds. In other words, examples thereof include a pyrrole compound alone, another hole transport material alone, and a pyrrole compound and another hole transport material mixed, laminated, and co-deposited for use.

  Examples of the known hole transport material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, and N, N′-di (m-tolyl). -N, N'-diphenyl-4,4'-diaminobiphenyl (TPD), N, N'-di (1-naphthyl) -N, N'-diphenyl-4,4'-diaminobiphenyl (α-NPD) Bis [4- (di-p-tolylamino) phenyl] diphenylsilane (DTASi), 1,3,5-tris [3- (di-p-tolylamino) phenyl] benzene (m-DTATPB), 1,1- And triarylamine derivatives such as bis [4-bis (4-tolyl) aminophenyl] cyclohexane (TAPC), polyphenylenediamine derivatives, and polythiophene derivatives. .

Examples of the hole injection material include PEDOT / PSS (polyethylenedioxathiophene-polystyrenesulfonic acid) and N, N′-bis [4- (di-m-tolylamino) phenyl] -N, N′-diphenylbiphenyl-4, 4'-diamine (DNTPD) and the like can be mentioned. Furthermore, known hole transport materials include organic oxidative dopants such as tetracyanoquinodimethane (TCNQ) and trinitrofluorenone (TNF), vanadium oxide, molybdenum oxide (MoO ₃ ), tungsten oxide, aluminum oxide and the like. A radical cation can be formed by the action of an inorganic oxidizing dopant and used as a hole injection layer. The oxidizing dopant concentration in the hole injection layer is not particularly limited, but is preferably about 0.1 to 99% by weight.

The electron transport layer of the organic EL device of the present invention is made of an electron transport material, and has a function of transmitting electrons injected from the cathode to the light emitting layer. When an electron transport material is disposed between two electrodes to which an electric field is applied and electrons are injected from the cathode, at least 1.0 × 10 ⁻⁸ m ² / V · sec or more, more preferably 1.0 × 10 10 An electron transport material having an electron mobility of ⁻⁷ m ² / V · sec or more is preferable. The electron transport material used for the electron transport layer of the organic EL device of the present invention is not particularly limited as long as it has the above-mentioned preferable performance. Select any one of the materials conventionally used as an electron injection material or an electron transport material in a photoconductive material, or a known material used for an electron injection layer or an electron transport layer of an organic EL element. Can be used.

Examples of the electron transporting material include quinoline complexes such as tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), 1-N-phenyl-2- (p-biphenylyl) -5- (p- Triazine derivatives such as tert-butylphenyl) -1,3,5-triazine (TAZ), phenanthroline derivatives such as 1,4-di (1,10-phenanthroline-2-yl) benzene (DPB), and the like. It is done. The electron transport layer may be composed of one or more of these other electron transport materials, and may be a stack of electron transport layers composed of a compound different from the electron transport material. .

In the organic EL device of the present invention, an electron injection layer may be further provided between the cathode and the electron transport layer for the purpose of further improving the electron injection property. As the electron injection layer used here, it is preferable to use at least one metal compound selected from alkali metal halides and alkaline earth metal halides. Examples of the alkali metal halide include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride. Examples of the alkaline earth metal halide include magnesium fluoride, calcium fluoride, barium fluoride, and strontium fluoride. Further, 8-hydroxyquinolinolatolithium complex (Liq), lithium complexes of phenanthroline derivatives (LiPB, LiPBPy) listed in JP-A-2008-106015, and lithium complexes of phenoxypyridine (LiPP) listed in JP-A-2008-195623 ) Can also be used.

  The light emitting material of the light emitting layer of the organic EL device of the present invention is not particularly limited, and any one of conventionally known compounds can be selected and used.

Examples of the light-emitting material include perylene derivatives, naphthacene derivatives, quinacridone derivatives, coumarin derivatives (eg, coumarin 1, coumarin 540, coumarin 545, etc.), pyran derivatives (eg, DCM-1, DCM-2, DCJTB, etc.), organometallic complexes [Tris Fluorescent materials such as (8-hydroxyquinolinolato) aluminum (Alq ₃ ) and tris (4-methyl-8-hydroxyquinolinolato) aluminum (Almq ₃ ) and bis [2- (4,6-difluorophenyl) pyridinate -N, ^{C 2} '] iridium (III) picolinate (FIrpic), tris {1- [4- (trifluoromethyl) phenyl] -1H- ^Pirazorato, N, ^C 2'} iridium (III) (Irtfmppz3), bis [2- (4 ′, 6′-difluorophenyl) pyridinato N, ^{C 2} '] iridium (III) tetrakis (1-pyrazolyl) borate (FIr6), fac-iridium (III) tris [2- (2,4-difluorophenyl) pyridine] [Ir _(FPPy) 3], tris (Phosphorescent material such as (2-phenylpyridinato) iridium (III) [Ir (ppy) ₃ ]).

The light emitting layer is formed of a host material and a light emitting material (dopant) [Appl. Phys. Lett. 65 3610 (1989)]. In particular, when a phosphorescent material is used for the light emitting layer, it is necessary to use a host material that can give energy to the phosphorescent material. it can. Other existing host materials such as 4,4'-di (N-carbazolyl) -1,1'-biphenyl (CBP), 1,4-di (N-carbazolyl) benzene-2,2'-di [4 " -(N-carbazolyl) phenyl] -1,1'-biphenyl (4CzPBP), tris- (4-carbazolyl-9-yl-phenyl) -amine (TCTA), 1,3-di (9H-carbazole-9- Yl) benzene (mCP) or the like may be used, or may be used in combination with the pyrrole compound of the present invention.

  The light emitting material is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight with respect to the host material.

  The formation method of the hole injection layer and the hole transport layer of the element containing the pyrrole compound of the present invention is not particularly limited. For example, a dry film forming method (for example, a vacuum vapor deposition method, an ionization vapor deposition method, or the like) or a wet film forming method (for example, a solution coating method such as a spin coating method, a casting method, or an ink jet method) can be used. As a method for forming the light emitting layer, the electron transport layer, the electron injection layer, and the like, a dry film forming method (for example, a vacuum deposition method or an ionization deposition method) is preferable. This is because if the wet film forming method is used, the lower layer may be eluted. Note that the above-described film formation method may be used in combination for manufacturing the element.

When forming each layer such as a hole transport layer, a light emitting layer, and an electron transport layer by a vacuum deposition method, the vacuum deposition conditions are not particularly limited. Usually, a boat temperature (deposition source temperature) of about 50 to 500 ° C. under a vacuum of about 10 ⁻⁴ Pa or less, a substrate temperature of about −50 to 300 ° C., and 0.01 to 50 nm / sec. Vapor deposition is preferred. When forming each layer of a positive hole transport layer, a light emitting layer, and an electron carrying layer using a some compound, it is preferable to co-evaporate each boat which put the compound, temperature-controlling each.

  When forming the hole injection layer and the hole transport layer by a solvent coating method, the components constituting each layer are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) ), Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like), aprotic solvents (for example, N, N'-dimethylacetamide, dimethyl sulfoxide and the like), water and the like. The solvent may be used alone, or a plurality of solvents may be used in combination.

  The thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited, but is usually 5 to 5,000 nm.

The organic EL device of the present invention can be protected by providing a protective layer (sealing layer) for the purpose of blocking contact with oxygen, moisture or the like, or by enclosing the device in an inert substance.
Examples of the inert substance include paraffin, silicon oil, and fluorocarbon.
Examples of the material used for the protective layer include fluorine resin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.

  The organic EL device of the present invention can be usually used as a direct-current drive device. When a DC voltage is applied, light emission is observed when a voltage of about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. The organic EL element of the present invention can also be used as an AC drive element. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state. The organic EL element of the present invention includes, for example, an electrophotographic photosensitive member, a flat panel display, a surface light emitter such as illumination, a copying machine, a printer, a backlight of a liquid crystal display, a light source such as an instrument, various light emitting elements, various display elements, and various types. It can be used for signs, various sensors, various accessories, and the like.

  The preferable example of the organic EL element of this invention is shown in FIGS.

  FIG. 1 is a cross-sectional view showing one example of the organic EL element of the present invention. FIG. 1 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, and a cathode 4 are sequentially provided on a substrate 1. In this case, the light emitting layer is useful when it has an electron transporting function.

  FIG. 2 is a cross-sectional view showing another example of the organic EL element of the present invention. FIG. 2 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. This is a separation of the functions of carrier transport and light emission, and the degree of freedom in material selection increases, so that the efficiency of light emission and the degree of freedom in light emission color increase.

  FIG. 3 is a cross-sectional view showing another example of the organic EL element of the present invention. FIG. 3 shows a structure in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, the provision of the hole injection layer 7 improves the adhesion between the anode 2 and the hole transport layer 5, improves the injection of holes from the anode, and is effective in lowering the voltage of the light emitting element.

  FIG. 4 is a cross-sectional view showing another example of the organic EL element of the present invention. FIG. 4 shows a structure in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. In this case, injection of electrons from the cathode 4 is improved, which is effective for lowering the voltage of the light emitting element.

  FIG. 5 is a cross-sectional view showing another example of the organic EL element of the present invention. FIG. 5 shows a configuration in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. In this case, hole injection from the anode 2 is improved and electron injection from the cathode 4 is improved, which is the most effective for driving at a low voltage.

  6 to 9 are sectional views of the device in which the hole block layer 9 is inserted. The hole blocking layer 9 has an effect of preventing holes injected from the anode or excitons generated by recombination in the light emitting layer 3 from escaping to the cathode 4, and is effective in improving the light emission efficiency of the organic EL element. is there. The hole blocking layer 9 can be inserted between the light emitting layer 3 and the cathode 4, between the light emitting layer 3 and the electron transport layer 6, or between the light emitting layer 3 and the electron injection layer 8. More preferred is between the light emitting layer 3 and the electron transport layer 6.

  1 to 9, each of the hole transport layer 5, the hole injection layer 7, the electron transport layer 6, the electron injection layer 8, the light emitting layer 3, and the hole blocking layer 9 has a single layer structure or a multilayer structure. May be.

  1 to 9 are basic device configurations to the last, and the configuration of the organic EL device using the compound of the present invention is not limited thereto.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

（ａ）３方コックを装着した３００ミリリットルの４口フラスコにナトリウムｔｅｒｔ−ブトキシド（ＮａＯ−ｔＢｕ）２５．４ｇ（２６４ｍｍｏｌ）、酢酸パラジウム０．２７ｇ（１．２ｍｍｏｌ）を加え、脱気、窒素置換を３回繰り返した。つづいて脱水テトラヒドロフラン（ＴＨＦ）１２０ミリリットル、Ｐ（ｔ−Ｂｕ）_３０．３２ミリリットル（１．２ｍｍｏｌ）を加え、５分間攪拌した。その後、３−ブロモクロロベンゼン２３．０ｇ（１２０ｍｍｏｌ）、アセトフェノン１４．４ｇ（１２０ｍｍｏｌ）を順次加え反応を開始した。系内はオレンジ色から赤褐色へと変化していった。２０時間後反応を停止した。溶液を酢酸溶液（酢酸１４ミリリットル、水１００ミリリットル）に滴下し中和した後、トルエン１６０ミリリットルを加え飽和ＮａＣｌ水溶液で分液を行った。有機層を硫酸ナトリウムで乾燥させエバポレーターで濃縮することにより茶色のオイルを得た。この粗製生物をシリカゲルカラムクロマトグラフィーで精製を行い２−（３−クロロフェニル）−１−フェニルエタノン１８．０ｇ（７８．２ｍｍｏｌ、６５．１％）を得た。
（ｂ）次に、５００ミリリットルの４口フラスコに脱水Ｎ、Ｎ−ジメチルホルムアミド（ＤＭＦ）２５０ミリリットル、上記で得られた２−（３−クロロフェニル）−１−フェニルエタノン１８．０ｇ（７８．２ｍｍｏｌ）、ＮａＯ−ｔＢｕ（ナトリウムｔｅｒｔブトキシド）９．０１ｇ（９３．８ｍｍｏｌ）を加え、室温で攪拌している所へブロモアセトアルデヒドジエチルアセタール１８．５ｇ（９３．８ｍｍｏｌ）を滴下した。滴下後、昇温した（６５〜７０℃）。２４時間後、エバポレーターでＤＭＦを留去し、クロロホルム２００ミリリットル、塩化アンモニウム水溶液１００ミリリットル×２、水１００ミリリットル×１で分液洗浄を行い、有機層を硫酸ナトリウムで乾燥させ濃縮することにより油状物をえた。これをシリカゲルカラムクロマトグラフィーで精製を行い２−（３−クロロフェニル）−４,４−ジエトキシ−１−フェニル−ブタン−１−オン１２．８ｇ（３６．８ｍｍｏｌ、４７．１％）を得た。
（ｃ）続いて、１００ミリリットルの２口フラスコに前記で得られた２−（３−クロロフェニル）−４,４−ジエトキシ−１−フェニル−ブタン−１−オン３．８３ｇ（１２．０ｍｍｏｌ）、アニリン１．１２ｇ（１２．０ｍｍｏｌ）、ｐ−トルエンスルホン酸（ＰＴＳＡ）１水和物０．１１ｇ（０．６ｍｍｏｌ）、トルエン５０ミリリットルを加え還流温度まで昇温した。１８時間後反応を停止し、反応溶液をエバポレータで濃縮した。残渣をシリカゲルカラムクロマトグラフィーにより精製を行い、３−（３−クロロフェニル）−１,２−ジフェニル−１Ｈ−ピロール２．９１ｇ（８．８２ｍｍｏｌ、７３．５％）を得た。
（ｄ）次に５０ミリリットルの２口フラスコに上記で得られた３−（３−クロロフェニル）−１，２−ジフェニル−１Ｈ−ピロール１．２ｇ（３．６３ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２１．５２ｇ（５．２４ｍｍｏｌ）、２,２′−ビピリジン０．８２ｇ（５．２４ｍｍｏｌ）、脱水ＤＭＦ２０ミリリットルを加え５５〜６０℃で窒素気流下、加熱攪拌した。１９時間後、原料が完全に消失したため、反応を停止した。
反応溶液にクロロホルム２００ミリリットルを加え溶解させたところへ１Ｍ−ＨＣｌａｑ１００ミリリットル、水１００ミリリットル×３で分液洗浄した。有機層を硫酸マグネシウムで乾燥させ、ろ過した。シリカゲルを７５ｇ敷きつめたキリヤマロートでろ過を行いクロロホルム５０ミリリットルでシリカゲルを洗浄した。ろ液を濃縮した後、ｎ−ヘキサン５０ミリリットルで攪拌洗浄した。不溶物をろ過、乾燥させることにより３，３′−ビス（１，２−ジフェニル−１Ｈ−ピロール−３−イル）ビフェニル（Ｐｙｒ１）０．９９ｇ（１．６８ｍｍｏｌ,９２．６％）を微黄色固体で得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図１０に^１Ｈ−ＮＭＲスペクトル、図１１にＭＳスペクトルを記す。 Synthesis example 1
Synthesis of 3,3′-bis (1,2-diphenyl-1H-pyrrol-3-yl) biphenyl (Pyr1)

(A) Sodium tert-butoxide (NaO-tBu) 25.4 g (264 mmol) and palladium acetate 0.27 g (1.2 mmol) were added to a 300 ml four-necked flask equipped with a three-way cock, and deaerated and purged with nitrogen Was repeated three times. Subsequently, 120 ml of dehydrated tetrahydrofuran (THF) and 0.32 ml (1.2 mmol) of P (t-Bu) ₃ were added and stirred for 5 minutes. Thereafter, 23.0 g (120 mmol) of 3-bromochlorobenzene and 14.4 g (120 mmol) of acetophenone were sequentially added to start the reaction. The system changed from orange to reddish brown. The reaction was stopped after 20 hours. The solution was dropped into an acetic acid solution (14 ml of acetic acid, 100 ml of water) for neutralization, and 160 ml of toluene was added, followed by separation with a saturated NaCl aqueous solution. The organic layer was dried over sodium sulfate and concentrated with an evaporator to obtain a brown oil. The crude product was purified by silica gel column chromatography to obtain 18.0 g (78.2 mmol, 65.1%) of 2- (3-chlorophenyl) -1-phenylethanone.
(B) Next, 250 ml of dehydrated N, N-dimethylformamide (DMF) was added to a 500 ml four-necked flask, and 18.0 g of 2- (3-chlorophenyl) -1-phenylethanone obtained above (78. 2 mmol), 9.01 g (93.8 mmol) of NaO-tBu (sodium tert-butoxide) was added, and 18.5 g (93.8 mmol) of bromoacetaldehyde diethyl acetal was added dropwise to the stirring at room temperature. After dropping, the temperature was raised (65 to 70 ° C.). After 24 hours, DMF was distilled off with an evaporator, and liquid separation washing was performed with 200 ml of chloroform, 100 ml of ammonium chloride aqueous solution x 2, 100 ml of water x 1, and the organic layer was dried over sodium sulfate and concentrated to give an oily substance. I gave This was purified by silica gel column chromatography to obtain 12.8 g (36.8 mmol, 47.1%) of 2- (3-chlorophenyl) -4,4-diethoxy-1-phenyl-butan-1-one.
(C) Subsequently, 3.83 g (12.0 mmol) of 2- (3-chlorophenyl) -4,4-diethoxy-1-phenyl-butan-1-one obtained above in a 100 ml two-necked flask, 1.12 g (12.0 mmol) of aniline, 0.11 g (0.6 mmol) of p-toluenesulfonic acid (PTSA) monohydrate and 50 ml of toluene were added, and the temperature was raised to reflux temperature. After 18 hours, the reaction was stopped, and the reaction solution was concentrated with an evaporator. The residue was purified by silica gel column chromatography to obtain 2.91 g (8.82 mmol, 73.5%) of 3- (3-chlorophenyl) -1,2-diphenyl-1H-pyrrole.
(D) Next, 1.2 g (3.63 mmol) of 3- (3-chlorophenyl) -1,2-diphenyl-1H-pyrrole obtained above in a 50 ml two-necked flask, Ni (cod) ₂ . 52 g (5.24 mmol), 2,2′-bipyridine 0.82 g (5.24 mmol) and 20 ml of dehydrated DMF were added, and the mixture was heated and stirred at 55-60 ° C. in a nitrogen stream. After 19 hours, the reaction was stopped because the raw materials had completely disappeared.
To the reaction solution, 200 ml of chloroform was added and dissolved, followed by separation and washing with 100 ml of 1M HClaq and 100 ml of water × 3. The organic layer was dried over magnesium sulfate and filtered. The mixture was filtered through a Kyriamalot with 75 g of silica gel and washed with 50 ml of chloroform. The filtrate was concentrated and washed with stirring with 50 ml of n-hexane. Insoluble matter was filtered and dried, and 0.99 g (1.68 mmol, 92.6%) of 3,3′-bis (1,2-diphenyl-1H-pyrrol-3-yl) biphenyl (Pyr1) was slightly yellow. Obtained as a solid.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 10 shows the ¹ H-NMR spectrum, and FIG. 11 shows the MS spectrum.

１００ミリリットルの２口フラスコに合成例１で得られた２−（３−クロロフェニル）−４，４−ジエトキシ−１−フェニル−ブタン−１−オン５．０５ｇ（１５．８４ｍｍｏｌ）、ｐ−トルイジン１．７０ｇ（１５．８４ｍｍｏｌ）、ｐ−トルエンスルホン酸１水和物０．１５ｇ（０．８ｍｍｏｌ）、トルエン７０ミリリットルを加え還流温度まで昇温した。１６時間後反応を停止し、反応溶液をエバポレータで濃縮した。残渣をシリカゲルカラムクロマトグラフィーにより精製を行い、３−（３−クロロフェニル）−２−フェニル−１−（４−トリル）−１Ｈ−ピロール４．４ｇ（１２．８０ｍｍｏｌ，８０．８％）を得た。
続いて、５０ミリリットルの２口フラスコに上記で得られた３−（３−クロロフェニル）−２−フェニル−１−（４−トリル）−１Ｈ−ピロール１．２ｇ（３．４８ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２１．５２ｇ（５．２４ｍｍｏｌ）、２，２′−ビピリジン０．８２ｇ（５．２４ｍｍｏｌ）、脱水ＤＭＦ
２０ミリリットルを加え、５５〜６０℃で窒素気流下、加熱攪拌した。１９時間後、原料が完全に消失したため、反応を停止した。
反応溶液にクロロホルム２００ミリリットルを加え溶解させたところへ１Ｍ−ＨＣｌ ａｑ１００ミリリットル、水１００ミリリットル×３で分液洗浄した。有機層を硫酸マグネシウムで乾燥させ、ろ過した。シリカゲルを７５ｇ敷きつめたキリヤマロートでろ過を行い、クロロホルム５０ミリリットルでシリカゲルを洗浄した。ろ液を濃縮した後、ｎ−ヘキサン５０ミリリットルで攪拌洗浄した。不溶物をろ過、乾燥させることにより３，３′−ビス〔２−フェニル−１−（４−トリル）−１Ｈ−ピロール−３−イル〕ビフェニル（Ｐｙｒ２）０．９９ｇ（１．６１ｍｍｏｌ，９２．５％）を微黄色固体で得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図１２に^１Ｈ−ＮＭＲスペクトル、図１３にＭＳスペクトルを記す。 Synthesis example 2
Synthesis of 3,3'-bis [2-phenyl-1- (4-tolyl) -1H-pyrrol-3-yl] biphenyl (Pyr2)

In a 100 ml two-necked flask, 5.05 g (15.84 mmol) of 2- (3-chlorophenyl) -4,4-diethoxy-1-phenyl-butan-1-one obtained in Synthesis Example 1 and p-toluidine 1 .70 g (15.84 mmol), p-toluenesulfonic acid monohydrate 0.15 g (0.8 mmol) and 70 ml of toluene were added and the temperature was raised to reflux temperature. After 16 hours, the reaction was stopped, and the reaction solution was concentrated with an evaporator. The residue was purified by silica gel column chromatography to obtain 4.4 g (12.80 mmol, 80.8%) of 3- (3-chlorophenyl) -2-phenyl-1- (4-tolyl) -1H-pyrrole. .
Subsequently, 1.2 g (3.48 mmol) of 3- (3-chlorophenyl) -2-phenyl-1- (4-tolyl) -1H-pyrrole obtained above in a 50 ml two-necked flask, Ni (cod ) ₂ 1.52 g (5.24 mmol), 2,2′-bipyridine 0.82 g (5.24 mmol), dehydrated DMF
20 ml was added, and the mixture was heated and stirred at 55 to 60 ° C. under a nitrogen stream. After 19 hours, the reaction was stopped because the raw materials had completely disappeared.
To the reaction solution, 200 ml of chloroform was added and dissolved, followed by separation and washing with 100 ml of 1M HCl aq and 100 ml of water × 3. The organic layer was dried over magnesium sulfate and filtered. The mixture was filtered through a Kyriamalot with 75 g of silica gel, and the silica gel was washed with 50 ml of chloroform. The filtrate was concentrated and washed with stirring with 50 ml of n-hexane. Insoluble matter was filtered and dried to obtain 0.99 g (1.61 mmol, 92.3) of 3,3′-bis [2-phenyl-1- (4-tolyl) -1H-pyrrol-3-yl] biphenyl (Pyr2). 5%) was obtained as a slightly yellow solid.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 12 shows the ¹ H-NMR spectrum, and FIG. 13 shows the MS spectrum.

２００ミリリットルの２口フラスコに合成例１で得られた２−（３−クロロフェニル）−４，４−ジエトキシ−１−フェニル−ブタン−１−オン５．０２ｇ（１４．４７ｍｍｏｌ）、４−ｔｅｒｔ−ブチルアニリン２．１６ｇ（１４．４７ｍｍｏｌ）、ｐ−トルエンスルホン酸１水和物０．１４ｇ（０．７２ｍｍｏｌ）、トルエン７０ミリリットルを加え還流温度まで昇温した（１０８〜１０９℃）。１９時間後反応を停止し、反応溶液をエバポレータで濃縮した。残渣をシリカゲルカラムクロマトグラフィーにより精製を行い、１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−２−フェニル−１Ｈ−ピロール５．１ｇ（１３．２１ｍｍｏｌ，９１．３％）を得た。
続いて、１００ミリリットルの２口フラスコに上記で得られた１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−２−フェニル−１Ｈ−ピロール２．０ｇ（５．１８ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２２．２５ｇ（７．７７ｍｍｏｌ）、２，２′−ビピリジン１．２１ｇ（７．７７ｍｍｏｌ）、脱水ＤＭＦ３０ミリリットルを加え５５〜６０℃で窒素気流下、加熱攪拌した。２．５時間後、原料が完全に消失したため、反応を停止した。
反応溶液にクロロホルム２００ミリリットルを加え溶解させたところへ１Ｍ−ＨＣｌａｑ１００ミリリットル、重曹水１００ミリリットル、水１００ミリリットルで分液洗浄した。有機層を硫酸マグネシウムで乾燥させろ過した。シリカゲルを７５ｇ敷きつめたキリヤマロートでろ過を行いクロロホルム４００ミリリットルでシリカゲルを洗浄した。ろ液を濃縮した後、ｎ−ヘキサン５０ミリリットルで攪拌洗浄した。不溶物をろ過、乾燥させることにより３，３′−ビス〔１−（４−ｔｅｒｔ−ブチルフェニル）−２−フェニル−１Ｈ−ピロール−３−イル〕ビフェニル（Ｐｙｒ３）１．４０ｇ（２．０ｍｍｏｌ，７７．２％）を微黄色固体で得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図１４に^１Ｈ−ＮＭＲスペクトル、図１５にＭＳスペクトルを記す。 Synthesis example 3
Synthesis of 3,3′-bis [1- (4-tert-butylphenyl) -2-phenyl-1H-pyrrol-3-yl] biphenyl (Pyr3)

In a 200 ml two-necked flask, 5.02 g (14.47 mmol) of 2- (3-chlorophenyl) -4,4-diethoxy-1-phenyl-butan-1-one obtained in Synthesis Example 1, 4-tert- 2.16 g (14.47 mmol) of butylaniline, 0.14 g (0.72 mmol) of p-toluenesulfonic acid monohydrate and 70 ml of toluene were added, and the temperature was raised to the reflux temperature (108 to 109 ° C.). After 19 hours, the reaction was stopped, and the reaction solution was concentrated with an evaporator. The residue was purified by silica gel column chromatography, and 5.1 g (13.21 mmol, 91.3%) of 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -2-phenyl-1H-pyrrole was obtained. Got.
Subsequently, 2.0 g (5.18 mmol) of 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -2-phenyl-1H-pyrrole obtained above in a 100 ml two-necked flask, Ni (cod) ₂ 2.25 g (7.77 mmol), 2,2′-bipyridine 1.21 g (7.77 mmol) and 30 ml of dehydrated DMF were added, and the mixture was heated and stirred at 55 to 60 ° C. in a nitrogen stream. After 2.5 hours, the reaction was stopped because the raw materials had completely disappeared.
To the reaction solution, 200 ml of chloroform was added and dissolved, followed by separation and washing with 100 ml of 1M HClaq, 100 ml of sodium bicarbonate water, and 100 ml of water. The organic layer was dried over magnesium sulfate and filtered. The mixture was filtered through a Kyriamalot with 75 g of silica gel and washed with 400 ml of chloroform. The filtrate was concentrated and washed with stirring with 50 ml of n-hexane. Insoluble matter was filtered and dried to obtain 1.40 g (2.0 mmol) of 3,3′-bis [1- (4-tert-butylphenyl) -2-phenyl-1H-pyrrol-3-yl] biphenyl (Pyr3). , 77.2%) was obtained as a slightly yellow solid.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 14 shows the ¹ H-NMR spectrum, and FIG. 15 shows the MS spectrum.

（ａ）３方コックを装着した３００ミリリットルの４口フラスコにＮａＯ−ｔＢｕ２１．５ｇ（２２３．７ｍｍｏｌ）、酢酸パラジウム０．２１ｇ（０．９ｍｍｏｌ）を加え、脱気、窒素置換を３回繰り返した。つづいて脱水ＴＨＦ１００ミリリットル、Ｐ（ｔ−Ｂｕ）_３０．２５ミリリットル（０．９ｍｍｏｌ）を加え、５分間攪拌した。その後、３−ブロモクロロベンゼン１７．８ｇ（９３．２ｍｍｏｌ）、４−トリルエタノン１２．５ｇ（９３．２ｍｍｏｌ）を順次加え反応を開始した。系内はオレンジ色から赤褐色へと変化していった。４０時間後反応を停止した。溶液を酢酸溶液（酢酸１４．６ミリリットル、水２００ミリリットル）に滴下し中和した後、トルエン１００ミリリットルを加え飽和ＮａＣｌ水溶液で分液を行った。有機層を硫酸ナトリウムで乾燥させエバポレーターで濃縮することにより２−（３−クロロフェニル）−１−（４−トリル）エタノンを茶色のオイルで得た。
（ｂ）続いて、５００ミリリットルの４口フラスコに脱水ＤＭＦ２００ミリリットル、前記で得られた未精製の２−（３−クロロフェニル）−１−（４−トリル）エタノン２２．８ｇ（９３．２ｍｍｏｌ）、ＮａＯ−ｔＢｕ１０．７ｇ（１１１．８ｍｍｏｌ）を加え、６０℃付近まで昇温した。５６℃の時点でブロモアセトアルデヒドジエチルアセタール２２．０ｇ（１１１．８ｍｍｏｌ）を滴下した。滴下後、８０〜８５℃で２３時間反応を行った〔ＴＬＣ（薄層クロマトグラフィー）（ヘキサン／クロロホルム＝１／３）で反応の終了を確認〕。エバポレーターでＤＭＦを留去し、クロロホルム３００ミリリットル、水１００ミリリットル×４で分液洗浄を行い、有機層を硫酸ナトリウムで乾燥させ濃縮することにより油状物をえた。これをシリカゲルカラムクロマトグラフィーで精製することにより２−（３−クロロフェニル）−４，４−ジエトキシ−１−（４−トリル）−ブタン−１−オン９．０１ｇ（２５．０ｍｍｏｌ，２６．８％）を褐色油状物で得た。
（ｃ）次に、１００ミリリットルの２口フラスコに上記で得られた２−（３−クロロフェニル）−４，４−ジエトキシ−１−（４−トリル）−ブタン−１−オン３．０ｇ（８．３１ｍｍｏｌ）、４−ｔｅｒｔ−ブチルアニリン１．２４ｇ（８．３１ｍｍｏｌ）、ｐ−トルエンスルホン酸１水和物０．０８ｇ（０．４２ｍｍｏｌ）、トルエン５０ミリリットルを加え還流温度まで昇温した。４時間後ＴＬＣで反応をチェックしたところ原料が消失していたため反応を停止した。反応溶液をエバポレータで濃縮し、残渣をシリカゲルカラムクロマトグラフィーにより精製を行い、１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−２−（４−トリル）−１Ｈ−ピロール２．４７ｇ（６．１８ｍｍｏｌ，７４．４％）を得た。
（ｄ）続いて、１００ミリリットルの２口フラスコに前記で得られた１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−２−（４−トリル）−１Ｈ−ピロール２．４７ｇ（６．１８ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２２．５５ｇ（９．２７ｍｍｏｌ）、２，２′−ビピリジン１．４５ｇ（９．２７ｍｍｏｌ）、脱水ＤＭＦ３０ミリリットルを加え５５〜６０℃で窒素気流下、加熱攪拌した。１８時間後、反応を停止しクロロホルム２００ミリリットルに溶解させ、１Ｍ−ＨＣｌａｑ１００ミリリットル、重曹水１００ミリリットル、水１００ミリリットルの順に分液洗浄した。クロロホルム層を硫酸マグネシウムで乾燥させエバポレータで濃縮することにより粗生成物を得た。これをシリカゲルカラムクロマトグラフィーで精製した。得られた目的物をヘキサン２００ミリリットルで洗浄し、６０℃で減圧乾燥することで３，３′−ビス〔１−（４−ｔｅｒｔ−ブチルフェニル）−２−（４−トルイル）−１Ｈ−ピロール−３−イル〕ビフェニル（Ｐｙｒ４）１．５５ｇ（２．１３ｍｍｏｌ，６８．９％）を得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図１６に^１Ｈ−ＮＭＲスペクトル、図１７にＭＳスペクトルを記す。 Synthesis example 4
Synthesis of 3,3′-bis [1- (4-tert-butylphenyl) -2- (4-tolyl) -1H-pyrrol-3-yl] biphenyl (Pyr4)

(A) NaO-tBu 21.5 g (223.7 mmol) and palladium acetate 0.21 g (0.9 mmol) were added to a 300 ml four-necked flask equipped with a three-way cock, and degassing and nitrogen substitution were repeated three times. . Subsequently, 100 ml of dehydrated THF and 0.25 ml (0.9 mmol) of P (t-Bu) ₃ were added and stirred for 5 minutes. Thereafter, 17.8 g (93.2 mmol) of 3-bromochlorobenzene and 12.5 g (93.2 mmol) of 4-tolylethanone were sequentially added to start the reaction. The system changed from orange to reddish brown. The reaction was stopped after 40 hours. The solution was added dropwise to an acetic acid solution (14.6 ml of acetic acid, 200 ml of water) for neutralization, and then 100 ml of toluene was added, followed by separation with a saturated NaCl aqueous solution. The organic layer was dried over sodium sulfate and concentrated with an evaporator to give 2- (3-chlorophenyl) -1- (4-tolyl) ethanone as a brown oil.
(B) Subsequently, 200 ml of dehydrated DMF was added to a 500 ml four-necked flask, 22.8 g (93.2 mmol) of the crude 2- (3-chlorophenyl) -1- (4-tolyl) ethanone obtained above, NaO-tBu10.7g (111.8mmol) was added, and it heated up to 60 degreeC vicinity. At 56 ° C., 22.0 g (111.8 mmol) of bromoacetaldehyde diethyl acetal was added dropwise. After the dropping, the reaction was carried out at 80 to 85 ° C. for 23 hours [TLC (thin layer chromatography) (hexane / chloroform = 1/3) confirming the completion of the reaction]. DMF was distilled off with an evaporator, and liquid separation washing was performed with 300 ml of chloroform and 100 ml of water × 4, and the organic layer was dried over sodium sulfate and concentrated to obtain an oily substance. This was purified by silica gel column chromatography to give 9.01 g (25.0 mmol, 26.8%) of 2- (3-chlorophenyl) -4,4-diethoxy-1- (4-tolyl) -butan-1-one. ) Was obtained as a brown oil.
(C) Next, 3.0 g (8) of 2- (3-chlorophenyl) -4,4-diethoxy-1- (4-tolyl) -butan-1-one obtained above was added to a 100 ml two-necked flask. .31 mmol), 1.24 g (8.31 mmol) of 4-tert-butylaniline, 0.08 g (0.42 mmol) of p-toluenesulfonic acid monohydrate and 50 ml of toluene were added, and the temperature was raised to reflux temperature. After 4 hours, when the reaction was checked by TLC, the reaction was stopped because the raw materials had disappeared. The reaction solution is concentrated by an evaporator, the residue is purified by silica gel column chromatography, and 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -2- (4-tolyl) -1H-pyrrole 2 is obtained. Obtained .47 g (6.18 mmol, 74.4%).
(D) Subsequently, 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -2- (4-tolyl) -1H-pyrrole obtained in the above was placed in a 100 ml two-necked flask. 47 g (6.18 mmol), 2.55 g (9.27 mmol) of Ni (cod) ₂ , 1.45 g (9.27 mmol) of 2,2′-bipyridine, and 30 ml of dehydrated DMF were added under nitrogen stream at 55-60 ° C. Stir with heating. After 18 hours, the reaction was stopped, dissolved in 200 ml of chloroform, and separated and washed in the order of 100 ml of 1M HClaq, 100 ml of sodium bicarbonate water, and 100 ml of water. The chloroform layer was dried with magnesium sulfate and concentrated with an evaporator to obtain a crude product. This was purified by silica gel column chromatography. The obtained target product was washed with 200 ml of hexane and dried under reduced pressure at 60 ° C., whereby 3,3′-bis [1- (4-tert-butylphenyl) -2- (4-toluyl) -1H-pyrrole was obtained. -3-yl] biphenyl (Pyr4) (1.55 g, 2.13 mmol, 68.9%) was obtained.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 16 shows the ¹ H-NMR spectrum, and FIG. 17 shows the MS spectrum.

（ａ）３方コックを装着した３００ミリリットルの４口フラスコにＮａＯ−ｔＢｕ２１．５ｇ（２２３．７ｍｍｏｌ）、酢酸パラジウム０．２１ｇ（０．９ｍｍｏｌ）を加え、脱気、窒素置換を３回繰り返した。つづいて脱水ＴＨＦ１００ミリリットル、Ｐ（ｔ−Ｂｕ）_３０．２５ミリリットル（０．９ｍｍｏｌ）を加え、５分間攪拌した。その後、３−ブロモクロロベンゼン１７．８ｇ（９３．２ｍｍｏｌ）、３−トリルエタノン１２．５ｇ（９３．２ｍｍｏｌ）を順次加え反応を開始した。系内はオレンジ色から赤褐色へと変化していった。１６時間後、ＴＬＣをチェックしたところ、原料がほぼ消失したため反応を停止した。溶液を酢酸溶液（酢酸１３．４ミリリットル、水２００ミリリットル）に滴下し中和した後、トルエン１００ミリリットルを加え飽和ＮａＣｌ水溶液で分液を行った。有機層を硫酸ナトリウムで乾燥させエバポレーターで濃縮することにより２−（３−クロロフェニル）−１−（３−トリル）エタノンを茶色のオイルで得た。
（ｂ）続いて、５００ミリリットルの４口フラスコに脱水ＤＭＦ２００ミリリットル、上記で得られた未精製の２−（３−クロロフェニル）−１−（３−トリル）エタノン２１．９ｇ（８９．３ｍｍｏｌ）、ＮａＯ−ｔＢｕ１０．３ｇ（１０７．２ｍｍｏｌ）を加え、６０℃付近まで昇温した。６０℃の時点でブロモアセトアルデヒドジエチルアセタール２１．１ｇ（１０７．２ｍｍｏｌ）を滴下した。滴下後、６０〜６５℃で１８時間反応を行った。エバポレーターでＤＭＦを留去し、クロロホルム３００ミリリットル、水１００ミリリットル×４で分液洗浄を行い、有機層を硫酸ナトリウムで乾燥させ濃縮することにより油状物をえた。これをシリカゲルカラムクロマトグラフィーで精製することにより２−（３−クロロフェニル）−４，４−ジエトキシ-１−（３-トリル）−ブタン−１−オン５．３１ｇ（１４．７ｍｍｏｌ，１６．５％）を褐色油状物で得た。
（ｃ）次に、１００ミリリットルの２口フラスコに前記で得られた２−（３−クロロフェニル）−４，４−ジエトキシ−１−（３−トリル）−ブタン−１−オン３．０ｇ（８．３１ｍｍｏｌ）、４−ｔｅｒｔ−ブチルアニリン１．２４ｇ（８．３１ｍｍｏｌ）、ｐ−トルエンスルホン酸１水和物０．０８ｇ（０．４２ｍｍｏｌ）、トルエン５０ミリリットルを加え還流温度まで昇温した。２０時間後ＴＬＣで反応をチェックしたところ原料が消失していたため反応を停止した。反応溶液をエバポレータで濃縮し、残渣をシリカゲルカラムクロマトグラフィーで２回精製することにより１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−２−（３−トリル）−１Ｈ−ピロール２．５ｇ（６．２５ｍｍｏｌ，７５．２％）を得た。
（ｄ）続いて、１００ミリリットルの２口フラスコに１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−２−（３−トリル）−１Ｈ−ピロール２．５０ｇ（６．２５ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２１．９０ｇ（６．９ｍｍｏｌ）、２，２′−ビピリジン１．０８ｇ（６．９ｍｍｏｌ）、脱水ＤＭＦ３０ミリリットルを加え５５〜６０℃で窒素気流下、加熱攪拌した。１９時間後、反応を停止しクロロホルム３００ミリリットルに溶解させ、１Ｍ−ＨＣｌａｑ１００ミリリットル、重曹水１００ミリリットル、水１００ミリリットルで分液洗浄した。クロロホルム層を硫酸マグネシウムで乾燥させエバポレータで濃縮することにより粗生成物を得た。これをシリカゲルカラムクロマトグラフィーで精製し３，３′−ビス〔１−（４−ｔｅｒｔ−ブチルフェニル）−２−（３−トリル）−１Ｈ−ピロール−３−イル〕ビフェニル（Ｐｙｒ５）１．８１ｇ（２．４８ｍｍｏｌ，７９．４％）を得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図１８に^１Ｈ−ＮＭＲスペクトル、図１９にＭＳスペクトルを記す。 Synthesis example 5
Synthesis of 3,3′-bis [1- (4-tert-butylphenyl) -2- (3-tolyl) -1H-pyrrol-3-yl] biphenyl (Pyr5)

(A) NaO-tBu 21.5 g (223.7 mmol) and palladium acetate 0.21 g (0.9 mmol) were added to a 300 ml four-necked flask equipped with a three-way cock, and degassing and nitrogen substitution were repeated three times. . Subsequently, 100 ml of dehydrated THF and 0.25 ml (0.9 mmol) of P (t-Bu) ₃ were added and stirred for 5 minutes. Thereafter, 17.8 g (93.2 mmol) of 3-bromochlorobenzene and 12.5 g (93.2 mmol) of 3-tolylethanone were sequentially added to start the reaction. The system changed from orange to reddish brown. After 16 hours, TLC was checked, and the reaction was stopped because the raw materials almost disappeared. The solution was added dropwise to an acetic acid solution (13.4 ml of acetic acid, 200 ml of water) for neutralization, and then 100 ml of toluene was added, followed by separation with a saturated NaCl aqueous solution. The organic layer was dried over sodium sulfate and concentrated with an evaporator to give 2- (3-chlorophenyl) -1- (3-tolyl) ethanone as a brown oil.
(B) Subsequently, 200 ml of dehydrated DMF was added to a 500 ml four-necked flask, and 21.9 g (89.3 mmol) of the unpurified 2- (3-chlorophenyl) -1- (3-tolyl) ethanone obtained above, NaO-tBu10.3g (107.2mmol) was added and it heated up to 60 degreeC vicinity. At 60 ° C., 21.1 g (107.2 mmol) of bromoacetaldehyde diethyl acetal was added dropwise. After dropping, the reaction was performed at 60 to 65 ° C. for 18 hours. DMF was distilled off with an evaporator, and liquid separation washing was performed with 300 ml of chloroform and 100 ml of water × 4, and the organic layer was dried over sodium sulfate and concentrated to obtain an oily substance. This was purified by silica gel column chromatography to give 5.31 g (14.7 mmol, 16.5%) of 2- (3-chlorophenyl) -4,4-diethoxy-1- (3-tolyl) -butan-1-one. ) Was obtained as a brown oil.
(C) Next, 3.0 g of 2- (3-chlorophenyl) -4,4-diethoxy-1- (3-tolyl) -butan-1-one obtained above was added to a 100 ml two-necked flask (8). .31 mmol), 1.24 g (8.31 mmol) of 4-tert-butylaniline, 0.08 g (0.42 mmol) of p-toluenesulfonic acid monohydrate and 50 ml of toluene were added, and the temperature was raised to reflux temperature. After 20 hours, when the reaction was checked by TLC, the reaction was stopped because the raw materials had disappeared. The reaction solution is concentrated by an evaporator, and the residue is purified twice by silica gel column chromatography to give 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -2- (3-tolyl) -1H- 2.5 g (6.25 mmol, 75.2%) of pyrrole was obtained.
(D) Subsequently, 2.50 g (6.25 mmol) of 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -2- (3-tolyl) -1H-pyrrole was added to a 100 ml two-necked flask. ), 1.90 g (6.9 mmol) of Ni (cod) ₂ , 1.08 g (6.9 mmol) of 2,2′-bipyridine and 30 ml of dehydrated DMF were added, and the mixture was heated and stirred at 55 to 60 ° C. in a nitrogen stream. After 19 hours, the reaction was stopped, dissolved in 300 ml of chloroform, and separated and washed with 100 ml of 1M HClaq, 100 ml of sodium bicarbonate water, and 100 ml of water. The chloroform layer was dried with magnesium sulfate and concentrated with an evaporator to obtain a crude product. This was purified by silica gel column chromatography to obtain 1.81 g of 3,3′-bis [1- (4-tert-butylphenyl) -2- (3-tolyl) -1H-pyrrol-3-yl] biphenyl (Pyr5). (2.48 mmol, 79.4%) was obtained.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 18 shows the ¹ H-NMR spectrum, and FIG. 19 shows the MS spectrum.

１００ミリリットルの４口フラスコに合成例１で得られた２−（３−クロロフェニル）−４，４−ジエトキシ−１−フェニル−ブタン−１−オン５．１ｇ（１６．０ｍｍｏｌ）、シクロヘキシルアミン４．７５ｇ（４７．９ｍｍｏｌ）、１２Ｍ−ＨＣｌａｑ２ミリリットル（２３．９ｍｍｏｌ）、トルエン８０ミリリットル、酢酸５．８ｇ（９５．８ｍｍｏｌ）を加え、還流温度まで昇温した。３２時間後ＴＬＣで反応をチェックしたところ目的物と思われるスポットが出現していたため反応を停止した。反応溶液にトルエン２００ミリリットルを追加し、水１００ミリリットル、重曹水１００ミリリットル、水１００ミリリットルの順に分液水洗を行った。有機層を硫酸ナトリウムで乾燥させ、ろ過濃縮することにより粗生成物を得た。これをシリカゲルカラムクロマトグラフィーにより精製を行い、３−（３−クロロフェニル）−１−シクロヘキシル−２−フェニル−１Ｈ−ピロール１．２１ｇ（３．６０ｍｍｏｌ，２２．５％）を得た。
続いて、１００ミリリットルの２口フラスコに上記で得られた３−（３−クロロフェニル）−１−シクロヘキシル−２−フェニル−１Ｈ−ピロール１．５２ｇ（４．５３ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２１．３７ｇ（４．９８ｍｍｏｌ）、２，２′−ビピリジン０．７８ｇ（４．９８ｍｍｏｌ）、脱水ＤＭＦ２０ミリリットルを加え５５〜６０℃で窒素気流下、加熱攪拌した。２１時間後、反応を停止しクロロホルム２００ミリリットルに溶解させ、１Ｍ−ＨＣｌａｑ１００ミリリットル、重曹水１００ミリリットル、水１００ミリリットルの順に分液洗浄した。クロロホルム層を硫酸マグネシウムで乾燥させ、エバポレータで濃縮することにより粗生成物を得た。これをシリカゲルカラムクロマトグラフィーで精製し、３，３′−ビス（１−シクロヘキシル−２−フェニル−１Ｈ−ピロール−３−イル）ビフェニル（Ｐｙｒ６）１．２６ｇ（２．１０ｍｍｏｌ，９２．８％）を得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図２０に^１Ｈ−ＮＭＲスペクトル、図２１にＭＳスペクトルを記す。 Synthesis Example 6
Synthesis of 3,3′-bis (1-cyclohexyl-2-phenyl-1H-pyrrol-3-yl) biphenyl (Pyr6)

In a 100 ml four-necked flask, 5.1 g (16.0 mmol) of 2- (3-chlorophenyl) -4,4-diethoxy-1-phenyl-butan-1-one obtained in Synthesis Example 1 and cyclohexylamine; 75 g (47.9 mmol), 12 M HClaq 2 ml (23.9 mmol), toluene 80 ml, acetic acid 5.8 g (95.8 mmol) were added, and the temperature was raised to reflux temperature. After 32 hours, the reaction was checked by TLC. As a result, a spot that appeared to be the target substance appeared and the reaction was stopped. 200 ml of toluene was added to the reaction solution, followed by separation and washing in the order of 100 ml of water, 100 ml of sodium bicarbonate water, and 100 ml of water. The organic layer was dried over sodium sulfate and concentrated by filtration to obtain a crude product. This was purified by silica gel column chromatography to obtain 1.21 g (3.60 mmol, 22.5%) of 3- (3-chlorophenyl) -1-cyclohexyl-2-phenyl-1H-pyrrole.
Subsequently, 1.52 g (4.53 mmol) of 3- (3-chlorophenyl) -1-cyclohexyl-2-phenyl-1H-pyrrole obtained above in a 100 ml two-necked flask, Ni (cod) ₂ . 37 g (4.98 mmol), 2,2′-bipyridine 0.78 g (4.98 mmol) and 20 ml of dehydrated DMF were added, and the mixture was heated and stirred at 55 to 60 ° C. in a nitrogen stream. After 21 hours, the reaction was stopped, dissolved in 200 ml of chloroform, and separated and washed in the order of 100 ml of 1M-HClaq, 100 ml of sodium bicarbonate water, and 100 ml of water. The chloroform layer was dried with magnesium sulfate and concentrated with an evaporator to obtain a crude product. This was purified by silica gel column chromatography, and 1.26 g (2.10 mmol, 92.8%) of 3,3′-bis (1-cyclohexyl-2-phenyl-1H-pyrrol-3-yl) biphenyl (Pyr6) was obtained. Got.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 20 shows the ¹ H-NMR spectrum, and FIG. 21 shows the MS spectrum.

１００ミリリットルの４口フラスコに脱水ＤＭＦ４０ミリリットル、合成例１で得られた２−（３−クロロフェニル）−１−フェニルエタノン２．０ｇ（８．６７ｍｍｏｌ）、ＮａＯ−ｔＢｕ０．８５ｇ（８．６７ｍｍｏｌ）を加えた。ついでブロモアセトン１．４６ｇ（９．５４ｍｍｏｌ，９０％）のＤＭＦ（２０ミリリットル）溶液を５分で滴下した。３時間後にＴＬＣで反応をチェックしたところ、原料は消失していたため反応を停止した。反応系内に水２００ミリリットル、クロロホルム５０ミリリットル加え分液抽出を行った。有機層を硫酸マグネシウムで乾燥させ、エバポレータで濃縮することにより、粗生成物を得た。これをシリカゲルカラムクロマトで精製することにより、２−（３−クロロフェニル）−１−フェニル−ペンタン−１，４−ジオン２．１４ｇ（７．４６ｍｍｏｌ，８６．０％）を得た。
続いて、ディーンスターク管を装着した３００ミリリットルのナスフラスコに上記で得られた２−（３−クロロフェニル）−１−フェニル−ペンタン−１，４−ジオン２．１４ｇ（７．４６ｍｍｏｌ）、４−ｔｅｒｔ−ブチルアニリン１．１１ｇ（７．４６ｍｍｏｌ）、ｐ−トルエンスルホン酸１水和物０．０７ｇ（０．３７ｍｍｏｌ）、トルエン３５ミリリットルを加え還流温度まで昇温した。１８時間後、ＴＬＣをチェックしたところ、ほぼ原料が消失していたため反応溶液をエバポレータで濃縮し、残渣をシリカゲルカラムクロマトにより精製を行い、１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−５−メチル−２−フェニル−１Ｈ−ピロール２．７４ｇ（６．８５ｍｍｏｌ，９１．８％）を得た。
次に、１００ミリリットルの２口フラスコに前記で得られた１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−５−メチル−２−フェニル−１Ｈ−ピロール２．７４ｇ（６．８５ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２２．４５ｇ（８．９１ｍｍｏｌ）、２，２′−ビピリジン１．３９ｇ（８．９１ｍｍｏｌ）、脱水ＤＭＦ３０ミリリットルを加え、５５〜６０℃で窒素気流下、加熱攪拌した。１６時間後、ＴＬＣで原料が消失したのを確認した後、反応を停止し、エバポレータで溶媒を回収した。残渣へクロロホルム１００ミリリットルを加えて溶解させ、１Ｍ−ＨＣｌａｑ１００ミリリットル、重曹水１００ミリリットル、水１００ミリリットルの順に分液洗浄した。クロロホルム層を硫酸マグネシウムで乾燥させ、エバポレータで濃縮することにより粗生成物を得た。これにトルエン７０ミリリットルを加え、６０℃まで加熱して溶解させ、シリカゲル２５ｇを加えて分散攪拌を３０分、６０℃で行った。その後、シリカゲルをろ過し、熱（５０〜６０℃）トルエン７０ミリリットルで濾滓を洗浄した。トルエン溶液をエバポレータで濃縮し、得られた残渣をトルエンで再結晶することにより３，３′−ビス〔１−（４−ｔｅｒｔ−ブチルフェニル）−５−メチル−２−フェニル−１Ｈ−ピロール−３−イル〕ビフェニル（Ｐｙｒ７）１．６４ｇ（２．２６ｍｍｏｌ，６５．９％）を白色微結晶で得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図２２に^１Ｈ−ＮＭＲスペクトル、図２３にＭＳスペクトルを記す。 Synthesis example 7
Synthesis of 3,3′-bis [1- (4-tert-butylphenyl) -5-methyl-2-phenyl-1H-pyrrol-3-yl] biphenyl (Pyr7)

In a 100 ml four-necked flask, 40 ml of dehydrated DMF, 2.0 g (8.67 mmol) of 2- (3-chlorophenyl) -1-phenylethanone obtained in Synthesis Example 1, and 0.85 g (8.67 mmol) of NaO-tBu Was added. Then, a solution of 1.46 g (9.54 mmol, 90%) of bromoacetone in DMF (20 ml) was added dropwise over 5 minutes. When the reaction was checked by TLC after 3 hours, the reaction was stopped because the raw material had disappeared. Liquid separation extraction was performed by adding 200 ml of water and 50 ml of chloroform into the reaction system. The organic layer was dried over magnesium sulfate and concentrated with an evaporator to obtain a crude product. This was purified by silica gel column chromatography to obtain 2.14 g (7.46 mmol, 86.0%) of 2- (3-chlorophenyl) -1-phenyl-pentane-1,4-dione.
Then, 2.14 g (7.46 mmol) of 2- (3-chlorophenyl) -1-phenyl-pentane-1,4-dione obtained above in a 300 ml eggplant flask equipped with a Dean-Stark tube, 4- 1.11 g (7.46 mmol) of tert-butylaniline, 0.07 g (0.37 mmol) of p-toluenesulfonic acid monohydrate and 35 ml of toluene were added, and the temperature was raised to reflux temperature. After 18 hours, when TLC was checked, the raw material was almost disappeared. Therefore, the reaction solution was concentrated with an evaporator, and the residue was purified by silica gel column chromatography. 1- (4-tert-butylphenyl) -3- (3 -Chlorophenyl) -5-methyl-2-phenyl-1H-pyrrole 2.74 g (6.85 mmol, 91.8%) was obtained.
Next, 2.74 g (6) of 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -5-methyl-2-phenyl-1H-pyrrole obtained above was placed in a 100 ml two-necked flask. .85 mmol), 2.45 g (8.91 mmol) of Ni (cod) ₂ , 1.39 g (8.91 mmol) of 2,2′-bipyridine, and 30 ml of dehydrated DMF were added and heated and stirred at 55-60 ° C. in a nitrogen stream. did. After 16 hours, after confirming disappearance of the raw material by TLC, the reaction was stopped, and the solvent was recovered by an evaporator. 100 ml of chloroform was added to the residue for dissolution, and separation and washing were carried out in the order of 100 ml of 1M HClaq, 100 ml of sodium bicarbonate water, and 100 ml of water. The chloroform layer was dried with magnesium sulfate and concentrated with an evaporator to obtain a crude product. To this was added 70 ml of toluene, and the mixture was heated to 60 ° C. to dissolve, 25 g of silica gel was added, and dispersion stirring was performed at 60 ° C. for 30 minutes. Thereafter, the silica gel was filtered, and the filter cake was washed with 70 ml of hot (50-60 ° C.) toluene. The toluene solution was concentrated with an evaporator, and the resulting residue was recrystallized with toluene to give 3,3′-bis [1- (4-tert-butylphenyl) -5-methyl-2-phenyl-1H-pyrrole- 1.64 g (2.26 mmol, 65.9%) of 3-yl] biphenyl (Pyr7) were obtained as white microcrystals.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 22 shows the ¹ H-NMR spectrum, and FIG. 23 shows the MS spectrum.

（ａ）３方コックを装着した３００ミリリットルの４口フラスコにＮａＯ−ｔＢｕ１７．９ｇ（１７８．８ｍｍｏｌ）、酢酸パラジウム０．１７ｇ（０．７４５ｍｍｏｌ）を加え、脱気、窒素置換を３回繰り返した。つづいて脱水ＴＨＦ８５ミリリットル、３−ブロモクロロベンゼン１４．３ｇ（７４．５ｍｍｏｌ）、４−トリルエタノン１０ｇ（７４．５ｍｍｏｌ）を加え、５分間攪拌した。その後Ｐ（ｔ−Ｂｕ）_３０．２ミリリットル（０．７４５ｍｍｏｌ）を加え、反応を開始した。系内はオレンジ色から赤褐色へと変化していった。１時間後、系内を５０℃まで昇温した。反応開始３時間後にＴＬＣで反応を確認したところ、アセトフェノンがほぼ消失したため反応を停止した。溶液を酢酸溶液〔酢酸１０．３ミリリットル（１８０ｍｍｏｌ）、水３５０ミリリットル〕に滴下し、中和した後、トルエン２００ミリリットルを加え、分液水洗を行った。続いて重曹水２００ミリリットル、水２００ミリリットルで分液を行った。有機層を硫酸ナトリウムで乾燥させ、エバポレーターで濃縮することにより、茶色のオイルを得た。これをシリカゲルカラムクロマトグラフィーで精製することにより２−（３−クロロフェニル）−１−（４−トリル）エタノン１０．０ｇ（４０．９ｍｍｏｌ、５４．９％）をロウ状の白色固体で得た。
（ｂ）続いて、１００ミリリットルの４口フラスコに脱水ＤＭＦ３０ミリリットル、前記で得られた２−（３−クロロフェニル）−１−（４−トリル）エタノン２．５ｇ（１０．２ｍｍｏｌ）、ＮａＯ−ｔＢｕ１．０ｇ（１０．２ｍｍｏｌ）を加えた。ついでブロモアセトン１．７ｇ（１１．２ｍｍｏｌ，９０％）のＤＭＦ（２０ミリリットル）溶液を５分で滴下した。１８時間後にＴＬＣで反応をチェックしたところ、原料は消失していたので反応を停止した。反応系内に水１００ミリリットル、クロロホルム５０ミリリットル加え、分液抽出を行った。有機層を硫酸マグネシウムで乾燥させ、エバポレータで濃縮することにより、粗生成物を得た。これをシリカゲルカラムクロマトグラフィーで精製することにより、２−（３−クロロフェニル）−１−（４−トリル）−ペンタン−１，４−ジオン２．３３ｇ（７．７５ｍｍｏｌ，７６．０％）を無色油状物で得た。
（ｃ）次に、ディーンスターク管を装着した３００ミリリットルナスフラスコに上記で得られた２−（３−クロロフェニル）−１−（４−トリル）−ペンタン−１，４−ジオン２．３３ｇ（７．７５ｍｍｏｌ）、４−ｔｅｒｔ−ブチルアニリン１．１６ｇ（７．７５ｍｍｏｌ）、ｐ−トルエンスルホン酸１水和物０．０８ｇ（０．４ｍｍｏｌ）、トルエン３５ミリリットルを加え、還流温度まで昇温した。２４時間後、ＴＬＣをチェックしたところ、ほぼ原料が消失していたため、反応溶液をエバポレータで濃縮し、残渣をシリカゲルカラムクロマトグラフィーで精製を行い、１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−５−メチル−２−（４−トリル）−１Ｈ−ピロール２．９０ｇ（７．０１ｍｍｏｌ，９０．５％）を得た。
（ｄ）続いて、１００ミリリットルの２口フラスコに前記で得られた１−（４−ｔｅｒｔ−ブチルフェニル）−３−（３−クロロフェニル）−５−メチル−２−（４−トリル）−１Ｈ−ピロール２．９０ｇ（７．０１ｍｍｏｌ）、Ｎｉ（ｃｏｄ）_２２．５０ｇ（９．１０ｍｍｏｌ）、２，２′−ビピリジン１．４２ｇ（９．１０ｍｍｏｌ）、脱水ＤＭＦ３０ミリリットルを加え、５５〜６０℃で窒素気流下、加熱攪拌した。１６時間後、ＴＬＣで原料が消失したのを確認した後、反応を停止した。反応溶液をクロロホルム１５０ミリリットルで希釈し、１Ｍ−ＨＣｌａｑ５０ミリリットル、重曹水５０ミリリットル、水５０ミリリットルの順に分液洗浄した。クロロホルム層を硫酸マグネシウムで乾燥させ、エバポレータで濃縮することにより、粗生成物を得た。これにトルエン１５０ミリリットルを加え６０℃まで加熱して溶解させ、シリカゲル５０ｇを加えて分散攪拌を３０分、６０℃で行った。その後、シリカゲルをろ過し、熱トルエン７０ミリリットルで濾滓を洗浄した。トルエン溶液をエバポレータで濃縮し、得られた残渣をトルエンで再結晶することにより３，３′−ビス〔１−（４−ｔｅｒｔ−ブチルフェニル）−５−メチル−２−（４−トリル）−１Ｈ−ピロール−３−イル〕ビフェニル（Ｐｙｒ８）１．９８ｇ（２．６２ｍｍｏｌ，７４．６％）を白色微結晶で得た。
構造確認は^１Ｈ−ＮＭＲ、ＭＳスペクトルにより行った。図２４に^１Ｈ−ＮＭＲスペクトル、図２５にＭＳスペクトルを記す。 Synthesis Example 8
Synthesis of 3,3′-bis [1- (4-tert-butylphenyl) -5-methyl-2- (4-tolyl) -1H-pyrrol-3-yl] biphenyl (Pyr8)

(A) To a 300 ml four-necked flask equipped with a three-way cock, 17.9 g (178.8 mmol) of NaO-tBu and 0.17 g (0.745 mmol) of palladium acetate were added, and deaeration and nitrogen substitution were repeated three times. . Subsequently, 85 ml of dehydrated THF, 14.3 g (74.5 mmol) of 3-bromochlorobenzene and 10 g (74.5 mmol) of 4-tolylethanone were added and stirred for 5 minutes. Thereafter, 0.2 ml (0.745 mmol) of P (t-Bu) ₃ was added to start the reaction. The system changed from orange to reddish brown. After 1 hour, the temperature in the system was raised to 50 ° C. When the reaction was confirmed by TLC 3 hours after the start of the reaction, the reaction was stopped because acetophenone almost disappeared. The solution was added dropwise to an acetic acid solution [10.3 ml (180 mmol) of acetic acid, 350 ml of water] and neutralized, and then 200 ml of toluene was added, followed by separation and washing with water. Subsequently, liquid separation was performed with 200 ml of sodium bicarbonate water and 200 ml of water. The organic layer was dried over sodium sulfate and concentrated with an evaporator to obtain a brown oil. This was purified by silica gel column chromatography to obtain 10.0 g (40.9 mmol, 54.9%) of 2- (3-chlorophenyl) -1- (4-tolyl) ethanone as a waxy white solid.
(B) Subsequently, 30 ml of dehydrated DMF was added to a 100 ml four-necked flask, 2.5 g (10.2 mmol) of 2- (3-chlorophenyl) -1- (4-tolyl) ethanone obtained above, NaO-tBu1. 0.0 g (10.2 mmol) was added. Then, a solution of 1.7 g (11.2 mmol, 90%) of bromoacetone in DMF (20 ml) was added dropwise over 5 minutes. When the reaction was checked by TLC 18 hours later, the reaction was stopped because the raw material had disappeared. Separation extraction was performed by adding 100 ml of water and 50 ml of chloroform into the reaction system. The organic layer was dried over magnesium sulfate and concentrated with an evaporator to obtain a crude product. By purifying this by silica gel column chromatography, 2.33 g (7.75 mmol, 76.0%) of 2- (3-chlorophenyl) -1- (4-tolyl) -pentane-1,4-dione was colorless. Obtained as an oil.
(C) Next, 2.33 g of 2- (3-chlorophenyl) -1- (4-tolyl) -pentane-1,4-dione obtained above in a 300 ml eggplant flask equipped with a Dean-Stark tube (7 .75 mmol), 1.16 g (7.75 mmol) of 4-tert-butylaniline, 0.08 g (0.4 mmol) of p-toluenesulfonic acid monohydrate, and 35 ml of toluene were added, and the temperature was raised to reflux temperature. After 24 hours, TLC was checked, and almost all of the starting materials had disappeared. Therefore, the reaction solution was concentrated with an evaporator, and the residue was purified by silica gel column chromatography. 1- (4-tert-butylphenyl) -3- 2.90 g (7.01 mmol, 90.5%) of (3-chlorophenyl) -5-methyl-2- (4-tolyl) -1H-pyrrole was obtained.
(D) Subsequently, 1- (4-tert-butylphenyl) -3- (3-chlorophenyl) -5-methyl-2- (4-tolyl) -1H obtained above was added to a 100 ml two-necked flask. -Add 2.90 g (7.01 mmol) of pyrrole, 2.50 g (9.10 mmol) of Ni (cod) ₂ , 1.42 g (9.10 mmol) of 2,2′-bipyridine, and 30 ml of dehydrated DMF to 55-60 ° C. And stirred under heating in a nitrogen stream. After 16 hours, the reaction was stopped after confirming the disappearance of the raw material by TLC. The reaction solution was diluted with 150 ml of chloroform, and separated and washed in the order of 50 ml of 1M HClaq, 50 ml of sodium bicarbonate water, and 50 ml of water. The chloroform layer was dried with magnesium sulfate and concentrated with an evaporator to obtain a crude product. To this, 150 ml of toluene was added and heated to 60 ° C. to dissolve, 50 g of silica gel was added, and dispersion stirring was performed at 60 ° C. for 30 minutes. Thereafter, the silica gel was filtered, and the filter cake was washed with 70 ml of hot toluene. The toluene solution was concentrated with an evaporator, and the resulting residue was recrystallized with toluene to give 3,3′-bis [1- (4-tert-butylphenyl) -5-methyl-2- (4-tolyl)- 1H-pyrrol-3-yl] biphenyl (Pyr8) 1.98 g (2.62 mmol, 74.6%) was obtained as white fine crystals.
The structure was confirmed by ¹ H-NMR and MS spectrum. FIG. 24 shows the ¹ H-NMR spectrum, and FIG. 25 shows the MS spectrum.

  By appropriately selecting the starting compounds, other pyrrole compounds of the present invention can be synthesized by a method according to the above synthesis example.

The organic EL elements according to Examples 1 to 3 and Comparative Example 1 were prepared, and the external quantum efficiency (%), luminous efficiency (lm / W), and energy conversion efficiency at 1 A / m ² and 25 A / m ² , respectively. (%) Was measured. Hereinafter, Examples 1 to 3 and Comparative Example 1 will be described in detail.

Table 1 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 1 to 3 and Comparative Example 1.

In Table 1, KLET-03 is an electron transport material manufactured by Chemipro Kasei Co., Ltd., and 3DTAPBP is N ³ , N ³ , N ^{3 ′ ″} , N ^{3 ′ ″} -tetra-p-tolyl- [1,1 ′. 2 ′, 1 ″; 2 ″, 1 ′ ″] quarterphenyl-3,3 ′ ″-diamine, FIrpic is bis [2- (4,6-difluorophenyl) pyridinate-N, C ² ′] iridium (III ) Picolinate, TCTA is tris- (4-carbazolyl-9-yl-phenyl) -amine, Liq is 8-hydroxyquinolinolatolithium.

Example 1
A blue phosphorescent element using Pyr4 (see Synthesis Example 4) as a hole transport material was evaluated. The hole injection material is Pyr4 doped with 20 wt% MoO ₃ , the host material is TCTA (see [Chemical Formula 89]), the electron transport material is KLET-03, and the electron injection material is Liq (Chemical Formula 87). Reference) was used. The specific element creation procedure is as follows.

  First, patterned ITO (indium tin oxide) glass substrate (ITO film thickness 110 nm) is subjected to ultrasonic cleaning with pure water and a surfactant, flowing water cleaning with pure water, and a 1: 1 mixed solution of pure water and isopropyl alcohol. Washing was carried out in the order of ultrasonic washing with, followed by boiling washing with isopropyl alcohol. The substrate was slowly pulled up from the boiling isopropyl alcohol, dried in isopropyl alcohol vapor, and finally UV ozone cleaned.

The cleaned substrate is placed in a vacuum chamber, evacuated to 1 × 10 ⁻⁶ Torr, each molybdenum boat filled with a deposition material in the vacuum chamber, and a film for forming a film in a predetermined pattern A vapor deposition mask was installed, and each organic layer was formed by energizing and heating the boat to sequentially evaporate a predetermined vapor deposition material.

  Finally, while maintaining the vacuum chamber in a vacuum, the mask was replaced and a cathode vapor deposition mask was installed to form an aluminum layer. Then, the vacuum chamber was returned to atmospheric pressure, the substrate on which each layer was deposited as described above was taken out, transferred to a nitrogen-substituted glove box, and sealed with a glass plate using a UV curable resin to obtain an organic EL element. .

The structure of the created element is described below.
Glass substrate / ITO (110 nm, anode) / MoO ₃ : Pyr4 (20 nm, 20:80, hole injection layer) / Pyr4 (20 nm, hole transport layer) / TCTA: FIrpic (10 nm, 84:16, light emitting layer) / KLET -03 (70 nm, electron transport layer) / Liq (0.5 nm, electron injection layer) / Al (100 nm, cathode)

Example 2
Evaluation of a blue phosphor element using Pyr5 as a hole transport material instead of Pyr4 used as a hole transport material in Example 1 was performed.

Example 3
Evaluation of a blue phosphor element using Pyr6 as a hole transport material instead of Pyr4 used as a hole transport material in Example 1 was performed.

Comparative Example 1
In Example 1, instead of Pyr4 used as the hole transport material, a blue phosphor element using 3DTAPBP as the hole transport material was evaluated.

26 shows the EL spectra of Examples 1 to 3 and Comparative Example 1, FIG. 27 shows the current density-voltage characteristics of Examples 1 to 3 and Comparative Example 1, and FIG. 28 shows the luminance of Examples 1 to 3 and Comparative Example 1. FIG. 29 shows the current efficiency-current density characteristics of Examples 1 to 3 and Comparative Example 1, and FIG. 30 shows the luminance-current density characteristics of Examples 1 to 3 and Comparative Example 1. In addition, since the emission color of Firepic is blue and the EL spectrum of the same shape as the comparative example 1 which is the EL spectrum is obtained in Examples 1-3, the elements of Examples 1-3 obtain blue light emission. ing. Table 2 below summarizes the element evaluation results.

In 1 A / m ² and 25 A / m ² of Example 3, the external quantum efficiency, luminous efficiency, and energy conversion efficiency of Comparative Example 1 could be exceeded. On the other hand, in Examples 1 and 2, the external quantum efficiency, luminous efficiency, and energy conversion efficiency of Comparative Example 1 were slightly lower, but since FIrpic-derived blue light emission could be obtained, the compound of the present invention was a hole transport material. It is clear that it worked as

The time (half life) until the light emission luminance at 25 A / m ² of the organic EL elements of Examples 1 to 3 was halved was measured and compared with the half life of Comparative Example 1. FIG. 31 shows element lifetime characteristics of Examples 1 to 3 and Comparative Example 1. As a result, each of Examples 1 to 3 exceeded the half life of the comparative example. Therefore, it is clear that the compound of the present invention has an effect of improving the device life.

Example 4
The white phosphorescent element using Pyr1 which is a pyrrole compound of the present invention as a host material was evaluated. The specific device configuration is ITO (110 nm, anode) / MoO ₃ : α-NPD (20 nm, 20:80, hole injection layer) / KLHT-03 (15 nm, hole transport layer) / Pyr1: FIrpic (4.5 nm, 80:20, light emitting layer) / Pyr1: PQ2Ir (dpm) (1 nm, 95: 5, light emitting layer) / Pyr1: FIrpic (4.5 nm, 80:20, light emitting layer) / KLET-03 (70 nm, electron transport layer) ) / Liq (1 nm, electron injection layer) / Al (100 nm, cathode).

KLHT-03 is a hole transport material manufactured by Chemipro Kasei Co., Ltd., and PQ2Ir (dpm) is iridium (III) bis- (2-phenylquinolinolato-N, C ^{2 ′} ) dipivaloylmethane.

FIG. 32 is a Commission Internationale d'Eclairage (CIE) chromaticity coordinate of the organic EL device prepared in Example 4, FIG. 33 is a current efficiency-current density characteristic of Example 4, and FIG. 34 is a current density-voltage of Example 4. Characteristics, FIG. 35 shows the luminance-voltage characteristics of Example 4. Table 3 below summarizes the element evaluation results.

  In Example 4, as is clear from the CIE chromaticity coordinates, white light emission with two wavelengths of blue and orange could be obtained. That is, it is clear that the compound of the present invention functions as a host of blue phosphorescent dopant and orange phosphorescent dopant.

1 Substrate 2 Anode (ITO)
DESCRIPTION OF SYMBOLS 3 Light emitting layer 4 Cathode 5 Hole transport layer 6 Electron transport layer 7 Hole injection layer 8 Electron injection layer 9 Hole block layer

Claims (8)

The following general formula (1)

(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, an unsubstituted aralkyl group having 7 to 12 carbon atoms, or an aralkyl group having a linear or branched alkyl group having 1 to 4 carbon atoms; Aromatic hydrocarbon having an alicyclic hydrocarbon group having 6 to 20 carbon atoms, unsubstituted, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms A group selected from the group consisting of an aromatic heterocyclic group having a hydrogen group and an unsubstituted or linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms R ^{2 to} R ⁴ are each a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 6 to 20 carbon atoms, unsubstituted, or having 1 to 4 carbon atoms. A linear or branched alkyl group, or Aromatic hydrocarbon group having a linear or branched alkoxy group having 1 to 4 carbon atoms and unsubstituted, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched group having 1 to 4 carbon atoms A group selected from the group consisting of an aromatic heterocyclic group having at least one alkoxy group, but at least one of R ^{2 to} R ⁴ is unsubstituted or a linear or branched alkyl group having 1 to 4 carbon atoms. Or an aromatic hydrocarbon group having a linear or branched alkoxy group having 1 to 4 carbon atoms, wherein L is a substituted or unsubstituted 1 to 6 valent group of an aromatic hydrocarbon having 6 to 45 carbon atoms and A group selected from the group consisting of 1 to 6 valent groups of substituted or unsubstituted aromatic heterocyclic compounds having 4 to 40 carbon atoms, n is an integer selected from 1 to 6 and L The valence and the number of n are the same.)
A pyrrole compound represented by:   In the general formula (1), n is 2, and L is a substituted or unsubstituted aromatic hydrocarbon divalent group having 6 to 45 carbon atoms, a substituted or unsubstituted aromatic heterocyclic ring having 4 to 40 carbon atoms. The pyrrole compound according to claim 1, which is a divalent group of the compound.   The pyrrole according to claim 1 or 2, wherein in the general formula (1), n is 2, and L is a substituted or unsubstituted divalent group of an aromatic hydrocarbon having 6 to 45 carbon atoms. Compounds.   The pyrrole compound according to any one of claims 1 to 3, wherein in the general formula (1), n is 2 and L is a biphenylene group which may have a substituent.   The organic electronics device using the pyrrole type compound of Claims 1-4.   The organic electroluminescent element using the pyrrole type compound of Claims 1-4.   The organic electroluminescence device according to claim 6, wherein the pyrrole compound is contained in a hole transport layer.   The organic electroluminescence device according to claim 6, wherein the pyrrole compound is contained in a light emitting layer.

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