JP6421474B2 - Cyclic azine compound, method for producing the same, and organic electroluminescent device using the same - Google Patents

Description

  The present invention relates to a cyclic azine compound having a specific heteroaromatic group consisting of only a carbon atom and a group 16 element, a method for producing the same, and an organic electroluminescent device using the same.

  An organic electroluminescent element is formed by sandwiching a light-emitting layer containing a light-emitting material between a hole transport layer and an electron transport layer, and further attaching an anode and a cathode to the outside, and recombination of holes and electrons injected into the light-emitting layer. It is an element that utilizes light emission (fluorescence or phosphorescence) when the excitons that are generated are deactivated, and is applied not only to small displays but also to large televisions and lighting. The hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron blocking layer, a light emitting layer and a hole blocking layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. May be configured. In some cases, a co-deposited film doped with a metal, an organometallic compound, or another organic compound may be used as the carrier transport layer (electron transport layer or hole transport layer) of the organic electroluminescence device.

  Conventional organic electroluminescent elements have higher driving voltage than inorganic light-emitting diodes, low luminance and luminous efficiency, and extremely low element lifetime, so that they have not been put to practical use in a wide range of fields. In addition, although recent organic electroluminescence devices have been improved gradually, excellent materials are required for the purpose of further improving luminous efficiency characteristics, driving voltage characteristics, and long life characteristics. Among them, improvement of element lifetime is an urgent need for widespread use in a wide range of fields, and material development for that is required.

  As an electron transport material excellent in long-life property for organic electroluminescent elements, the cyclic azine compound disclosed in Patent Document 1 can be mentioned. However, further improvements have been demanded in terms of improving the device life.

JP 2011-063584 A

  An object of the present invention is to provide a specific cyclic azine compound that significantly improves the lifetime of the organic electroluminescence device as compared with a conventionally known cyclic azine compound.

  Another object of the present invention is to provide an organic electroluminescent device having a long life using the specific cyclic azine compound.

  Another object of the present invention is to provide a method for producing the cyclic azine compound.

  Another object of the present invention is to provide a production intermediate necessary for producing the cyclic azine compound.

  As a result of intensive studies to solve the above problems, the present inventors have a specific heteroaromatic group consisting of only a carbon atom and a group 16 element represented by the following general formula (1). The organic electroluminescent device using the characteristic cyclic azine compound (hereinafter referred to as “cyclic azine compound (1)”) as an electron transport material has a significantly long life characteristic as compared with the case of using a conventionally known material. I found it to show. Furthermore, the present inventors have found that the organic electroluminescent device using the cyclic azine compound (1) is superior in driving voltage and power efficiency as compared with the case where a conventionally known material is used, and has completed the present invention.

  That is, the present invention relates to the general formula (1)

（一般式（１）中、
２つのＡｒ^１は同一の置換基を表す。Ａｒ^１は、炭素数６〜３０の芳香族炭化水素基（フッ素原子、炭素数１〜４のアルキル基、炭素数６〜１８の芳香族炭化水素基、フッ素原子で置換された炭素数６〜１８の芳香族炭化水素基、炭素数３〜１３の複素芳香族基、炭素数３〜１３の複素芳香族基で置換された炭素数６〜１８の芳香族炭化水素基、炭素数１〜４のアルキル基で置換された炭素数３〜１３の複素芳香族基、又は炭素数１〜４のアルキル基で置換された炭素数６〜１８の芳香族炭化水素基を置換基として有してもよい）、又はフェニル基若しくはメチル基で置換されていてもよいピリジル基を表す。
Ａｒ^２は、水素原子又は炭素数３〜１３の含窒素複素芳香族基（フッ素原子、炭素数１〜４のアルキル基、炭素数６〜１８の芳香族炭化水素基、フッ素原子で置換された炭素数６〜１８の芳香族炭化水素基、炭素数３〜１３の複素芳香族基、炭素数３〜１３の複素芳香族基で置換された炭素数６〜１８の芳香族炭化水素基、炭素数１〜４のアルキル基で置換された炭素数３〜１３の複素芳香族基、又は炭素数１〜４のアルキル基で置換された炭素数６〜１８の芳香族炭化水素基を置換基として有してもよい）を表す。
Ｘは、各々独立して、メチル基で置換されていてもよい炭素数６〜１８の二価の芳香族炭化水素基又はメチル基若しくはフェニル基で置換されていてもよい炭素数３〜１３の二価の含窒素複素芳香族基を表す。
ｐ及びｑは、各々独立して、０、１又２を表す。
Ｚは、窒素原子又は炭素原子を表す。
Ｔは、炭素原子及び１６族元素のみからなる炭素数４〜３０の複素芳香族基（フッ素原子、炭素数１〜４のアルキル基、炭素数６〜１８の芳香族炭化水素基、フッ素原子で置換された炭素数６〜１８の芳香族炭化水素基、炭素数３〜１３の複素芳香族基、炭素数３〜１３の複素芳香族基で置換された炭素数６〜１８の芳香族炭化水素基、炭素数１〜４のアルキル基で置換された炭素数３〜１３の複素芳香族基、又は炭素数１〜４のアルキル基で置換された炭素数６〜１８の芳香族炭化水素基を置換基として有してもよい）を表す。）
で示される環状アジン化合物、その製造方法、及びそれを用いた有機電界発光素子、好ましくは、下記一般式（１）

(In general formula (1),
Two Ar ¹ represent the same substituent. Ar ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 6 to 6 carbon atoms substituted with a fluorine atom). 18 aromatic hydrocarbon group, C3-C13 heteroaromatic group, C6-C18 aromatic hydrocarbon group substituted with C3-C13 heteroaromatic group, C1-C4 A C3-C13 heteroaromatic group substituted with an alkyl group, or a C6-C18 aromatic hydrocarbon group substituted with a C1-C4 alkyl group as a substituent. Or a pyridyl group optionally substituted with a phenyl group or a methyl group.
Ar ² is substituted with a hydrogen atom or a nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a fluorine atom). An aromatic hydrocarbon group having 6 to 18 carbon atoms, a heteroaromatic group having 3 to 13 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a heteroaromatic group having 3 to 13 carbon atoms, carbon A heteroaromatic group having 3 to 13 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent May be included).
X is each independently a C6-C18 divalent aromatic hydrocarbon group which may be substituted with a methyl group, or a C3-C13 group which may be substituted with a methyl group or a phenyl group. Represents a divalent nitrogen-containing heteroaromatic group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom or a carbon atom.
T is a heteroaromatic group having 4 to 30 carbon atoms consisting of only a carbon atom and a group 16 element (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a fluorine atom. C6-C18 aromatic hydrocarbon substituted, C3-C13 heteroaromatic group, C3-C13 heteroaromatic group substituted with C3-C13 aromatic hydrocarbon group A C3-C13 heteroaromatic group substituted with a C1-C4 alkyl group, or a C6-C18 aromatic hydrocarbon group substituted with a C1-C4 alkyl group Which may be present as a substituent. )
, A production method thereof, and an organic electroluminescence device using the same, preferably the following general formula (1)

（一般式（１）中、
２つのＡｒ^１は同一の置換基を表す。
Ａｒ^１は、炭素数６〜１０の芳香族炭化水素基（フッ素原子、メチル基、フェニル基又はピリジル基を置換基として有してもよい）、又はフェニル基若しくはメチル基で置換されていてもよいピリジル基を表す。
Ａｒ^２は、炭素数６〜１８の芳香族炭化水素基又は６員環のみで形成されるＣ、Ｈ、及びＮのみからなる炭素数３〜１３の複素芳香族基（これらの置換基はフッ素原子、メチル基又はフェニル基で置換されていてもよい）を表す。
Ｘは、各々独立して、メチル基で置換されていてもよい炭素数６〜１０の二価の芳香族炭化水素基又はメチル基で置換されていてもよい炭素数５〜９の二価の含窒素複素芳香族基を表す。
ｐ及びｑは、各々独立して、０、１又２を表す。
Ｚは、窒素原子を表す。
Ｔは、炭素原子、水素原子及び１６族元素のみからなる炭素数４〜２０の複素芳香族基（メチル基、フェニル基、又はメチル基を有してもよい炭素数３〜９の含窒素複素芳香族基を置換基として有してもよい）を表す。）
で示される環状アジン化合物、その製造方法、及びそれを用いた有機電界発光素子に関するものである。

(In general formula (1),
Two Ar ¹ represent the same substituent.
Ar ¹ may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms (which may have a fluorine atom, a methyl group, a phenyl group or a pyridyl group as a substituent), or a phenyl group or a methyl group. Represents a good pyridyl group.
Ar ² is an aromatic hydrocarbon group having 6 to 18 carbon atoms or a heteroaromatic group having 3 to 13 carbon atoms composed of only C, H, and N formed of a 6-membered ring (these substituents are fluorine atoms). And optionally substituted with an atom, methyl group or phenyl group.
X is each independently a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group or a divalent divalent hydrocarbon having 5 to 9 carbon atoms which may be substituted with a methyl group. Represents a nitrogen-containing heteroaromatic group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom.
T is a heteroaromatic group having 4 to 20 carbon atoms consisting of only a carbon atom, a hydrogen atom and a group 16 element (a nitrogen-containing complex having 3 to 9 carbon atoms which may have a methyl group, a phenyl group or a methyl group). An aromatic group as a substituent. )
And a method for producing the same, and an organic electroluminescent device using the same.

  By introducing a heteroaromatic group having 4 to 20 carbon atoms consisting of only carbon atoms, hydrogen atoms and group 16 elements, the electron donor property of the compound is enhanced, and the electron transport ability is improved without impairing the durability and device lifetime of the compound. It becomes possible to improve.

  The cyclic azine compound of the present invention is used as an electron transport material excellent in durability, driving voltage, and power efficiency. Furthermore, according to the present invention, an organic EL element with low power consumption and excellent element lifetime can be provided.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to the above cyclic azine compound (1), a method for producing the same, and an organic electroluminescent device containing the same.

  The substituents in the cyclic azine compound (1) of the present invention are defined as follows.

Ar ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 6 to 6 carbon atoms substituted with a fluorine atom). 18 aromatic hydrocarbon group, C3-C13 heteroaromatic group, C6-C18 aromatic hydrocarbon group substituted with C3-C13 heteroaromatic group, C1-C4 A C3-C13 heteroaromatic group substituted with an alkyl group, or a C6-C18 aromatic hydrocarbon group substituted with a C1-C4 alkyl group as a substituent. Or a pyridyl group optionally substituted with a phenyl group or a methyl group.

In formula (1), two Ar ¹ represent the same substituent.

The aromatic hydrocarbon group having 6 to 30 carbon atoms in Ar ¹ is not particularly limited, but is phenyl group, biphenyl group, naphthyl group, phenanthryl group, anthryl group, pyrenyl group, triphenylenyl group, chrysenyl group, Preferred examples include an olanthenyl group, an acenaphthylenyl group, a fluorenyl group, or a benzofluorenyl group.

The alkyl group having 1 to 4 carbon atoms in Ar ^1, is not particularly limited, and methyl group, an ethyl group, a propyl group, an isopropyl group, preferred examples n- butyl group, or t- butyl group and the like It is done.

The aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar ¹ is not particularly limited, but is phenyl group, biphenyl group, naphthyl group, phenanthryl group, anthryl group, pyrenyl group, triphenylenyl group, chrysenyl group, Preferred examples include an olanthenyl group, an acenaphthylenyl group, a fluorenyl group, or a benzofluorenyl group.

The aromatic hydrocarbon group having 6 to 18 carbon atoms which is substituted with a fluorine atom in Ar ^1, is not particularly limited, fluorophenyl group, difluorophenyl biphenyl group, fluoro naphthyl, difluoromethyl naphthyl group, fluoro phenanthryl Group, difluorophenanthryl group, fluoroanthryl group, difluoroanthryl group, fluoropyrenyl group, difluoropyrenyl group, fluorotriphenylenyl group, difluorotriphenylenyl group, fluorochrysenyl group, difluorochrenyl group, Preferred examples include a fluorofluoranthenyl group, a difluorofluoranthenyl group, a fluoroacenaphthylenyl group, or a difluoroacenaphthyl group.

The heteroaromatic group having 3 to 13 carbon atoms in Ar ¹ is not particularly limited, but includes pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, triazyl group, quinolyl group, isoquinolyl group, phenanthridyl group, Preferred examples include a benzoquinolyl group or an acridyl group.

The aromatic hydrocarbon group having 6 to 18 carbon atoms which is substituted by a heteroaromatic group of 3 to 13 carbon atoms in Ar ^1, is not particularly limited, pyridyl phenyl group, pyridyl biphenyl, Pirijirunafuchiru group , Pyridylphenanthryl group, pyridylanthryl group, pyridylpyrenyl group, pyridyltriphenylenyl group, pyridylchlycenyl group, pyridylfluoranthenyl group, pyridylacenaphthylenyl group, pyrimidylphenyl group, pyrimidylbiphenyl Group, pyrimidyl naphthyl group, pyrimidyl phenanthryl group, pyrimidyl anthryl group, pyrimidyl pyrenyl group, pyrimidyl triphenylenyl group, pyrimidyl chrysenyl group, pyrimidyl fluoranthenyl group , Pyrimidyl acenaphthylenyl group, pyrazylphenyl group, pyrazylbiphenyl group, pyrazyl Naphtyl group, pyrazylphenanthryl group, pyrazylanthryl group, pyrazylpyrenyl group, pyrazyltriphenylenyl group, pyrazylcrisenyl group, pyrazylfluoranthenyl group, pyrazylacenaphthylenyl group, quinolylphenyl Group, quinolylbiphenyl group, quinolylnaphthyl group, quinolylphenanthryl group, quinolylanthryl group, quinolylpyrenyl group, quinolyltriphenylenyl group, quinolylchrycenyl group, quinolylfluoranthenyl group, quinolylacena group Futylenyl, isoquinolylphenyl, isoquinolylbiphenyl, isoquinolylnaphthyl, isoquinolylphenanthryl, isoquinolylanthryl, isoquinolylpyrenyl, isoquinolyltriphenylenyl Group, isoquinolyl chrysenyl group, isoquinolyl fluoranthenyl group, Is such isoquinolylmethyl Asena borderless les sulfonyl group are preferred examples.

Examples of the heterocyclic aromatic group having a carbon number of 3 to 13 substituted with an alkyl group having 1 to 4 carbon atoms in Ar ^1, is not particularly limited, methylpyridyl, Mechirupirajiru group, Mechirupirimijiru group, Mechirupiridajiru group, methyl Triazyl group, methylquinolyl group, methylisoquinolyl group, methylphenanthridyl group, methylbenzoquinolyl group, methylacridyl group, dimethylpyridyl group, dimethylpyrazyl group, dimethylpyrimidyl group, dimethylpyridazyl group Preferred examples include dimethyltriazyl group, dimethylquinolyl group, dimethylisoquinolyl group, dimethylphenanthridyl group, dimethylbenzoquinolyl group, and dimethylacridyl group.

The aromatic hydrocarbon group having 6 to 18 carbon atoms which is substituted with an alkyl group having 1 to 4 carbon atoms in Ar ^1, is not particularly limited, methylphenyl group, a methyl biphenyl group, methylnaphthyl group, methyl Phenanthryl group, anthryl group, methylpyrenyl group, methyltriphenylenyl group, methylchrycenyl group, methylfluoranthenyl group, methylacenaphthylenyl group, dimethylphenyl group, dimethylbiphenyl group, dimethylnaphthyl group, dimethylphenanthryl group Anthryl group, dimethylpyrenyl group, dimethyltriphenylenyl group, dimethylchrysenyl group, dimethylfluoranthenyl group, dimethylacenaphthylenyl group, didimethylfluorenyl group, dimethylbenzofluorenyl group, etc. A preferred example is given.

The pyridyl group optionally substituted with a phenyl group or a methyl group in Ar ¹ is not particularly limited, but includes a pyridyl group, a 3-phenylpyridin-2-yl group, and a 4-phenylpyridin-2-yl group. Preferred examples include 5-phenylpyridin-2-yl group, 3-methylpyridin-2-yl group, 4-methylpyridin-2-yl group, and 5-methylpyridin-2-yl group.

Ar ¹ is a phenyl group, a biphenyl group, or a naphthyl group (these groups are an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a nitrogen-containing heteroaromatic group having 1 to 13 carbon atoms) in terms of excellent electron transporting material characteristics. Group (which may have a group as a substituent) is preferable, and a phenyl group (which may have a phenyl group, a methyl group or a pyridyl group as a substituent) is more preferable.

Ar ¹ is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms (which may have a fluorine atom, a methyl group, a phenyl group or a pyridyl group as a substituent), or a phenyl group or a methyl group. It may preferably be a pyridyl group which may be a phenyl group, a biphenyl group or a naphthyl group (these groups may have a fluorine atom, a methyl group, a phenyl group or a pyridyl group as a substituent). More preferred.

The aromatic hydrocarbon group having 6 to 10 carbon atoms in Ar ^1, is not particularly limited, a phenyl group, a biphenyl group, a naphthyl group, etc. Preferred examples.

Specific examples of Ar ¹ include phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, and 2-ethylphenyl group. 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4 -Dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2 -Butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenol Nyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group Biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4 -Yl group, 2,2'-dimethylbiphenyl-4-yl group, 2 ', 4', 6'-trimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl-3 -Yl group, 2'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3-yl group, 6,2'-dimethylbiphenyl-3-yl group, 2 ', 4', 6'-trimethylbiphenyl -3- Group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl-2-yl group, 6,2'- Dimethylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-trimethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 4′-ethylbiphenyl-4-yl group, 2 ′, 4 ', 6'-triethylbiphenyl-4-yl group, 6-ethylbiphenyl-3-yl group, 4'-ethylbiphenyl-3-yl group, 5-ethylbiphenyl-2-yl group, 4'-ethylbiphenyl- 2-yl group, 2 ′, 4 ′, 6′-triethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group, 4′-propylbiphenyl-4-yl group, 2 ′, 4 ′, 6 '-Tripropylbiphenyl-4-yl group, 6-pro Rubiphenyl-3-yl group, 4′-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tri Propylbiphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group, 4′-isopropylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-triisopropylbiphenyl-4-yl group, 6-isopropyl Biphenyl-3-yl group, 4′-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 4′-isopropylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-triisopropyl Biphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 4′-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tributylbiphenyl-4-yl group, 6-butylbiphenyl Enyl-3-yl group, 4′-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 4′-butylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tributylbiphenyl 2-yl group, 3-tert-butylbiphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tritert-butylbiphenyl-4-yl group 6-tert-butylbiphenyl-3-yl group, 4′-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 4′-tert-butylbiphenyl-2-yl group 2 ′, 4 ′, 6′-tritert-butylbiphenyl-2-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine -4-yl group, -Methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5-yl group, 3 -Methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6-dimethylpyridin-4- Yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 2-phenylpyridin-6-yl group, 3 -Phenylpyridin-6-yl group, 4-phenylpyridin-6-yl group, 5-phenylpyridin-6-yl group, 2-phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3 -Phenylpyri N-5-yl group, 4-phenylpyridin-3-yl group, 3-phenylpyridin-4-yl group, 2-phenylpyridin-4-yl group, 2- (2-pyridyl) phenyl group, 3- ( 2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 2- (3-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 2- ( 4-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1-phenylnaphthalen-2-yl group, 1-phenyl Naphthalen-3-yl group, 1-phenylnaphthalen-4-yl group, 1-phenylnaphthalen-5-yl group, 1-phenylnaphthalen-6-yl group, 1-phenylnaphthalen-7-yl group, 1-phenyl Naphthalen-8-yl group, 2-phenylnaphthalen-1-yl group, 2-phenylnaphthalen-3-yl group, 2-phenylnaphthalen-4-yl group, 2-phenylnaphthalen-5-yl group, 2-phenyl Naphthalen-6-yl group, 2-phenylnaphthalen-7-yl group, 2-phenylnaphthalen-8-yl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalen-5-yl group, 1-methyl Naphthalen-6-yl group, 1-methylnaphthalen-7-yl group, 1-methylnaphthalen-8-yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphthalen-3-yl group, 2-methyl Naphthalen-4-yl group, 2-methylnaphthalen-5-yl group, 2-methylnaphthalen-6-yl group, 2-methylnaphthalen-7-yl group, 2-methylnaphtha N-8-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-phenylphenanthren-2-yl group, 1-phenylphenanthren-3-yl Group, 1-phenylphenanthren-4-yl group, 1-phenylphenanthren-5-yl group, 1-phenylphenanthrene-6-yl group, 1-phenylphenanthren-7-yl group, 1-phenylphenanthren-8-yl group Group, 1-phenylphenanthren-9-yl group, 1-phenylphenanthren-10-yl group, 2-phenylphenanthren-1-yl group, 2-phenylphenanthren-3-yl group, 2-phenylphenanthren-4-yl Group, 2-phenylphenanthren-5-yl group, 2-phenylphen N-Tren-6-yl group, 2-phenylphenanthren-7-yl group, 2-phenylphenanthren-8-yl group, 2-phenylphenanthren-9-yl group, 2-phenylphenanthren-10-yl group, 3-phenyl Phenanthren-1-yl group, 3-phenylphenanthren-2-yl group, 3-phenylphenanthren-4-yl group, 3-phenylphenanthren-5-yl group, 3-phenylphenanthren-6-yl group, 3-phenyl Phenanthren-7-yl group, 3-phenylphenanthren-8-yl group, 3-phenylphenanthren-9-yl group, 3-phenylphenanthren-10-yl group, 4-phenylphenanthren-1-yl group, 4-phenyl Phenanthren-2-yl group, 4-phenylphenanthren-3-yl group, 4-phenylphenanthren-5-yl group, 4-phenylphenanthren-6-yl group, 4-phenylphenanthren-7-yl group, 4-phenylphenanthren-8-yl group, 4-phenylphenanthren-9-yl group, 4-phenylphenanthren-10-yl group, 1-methylphenanthren-2-yl group, 1-methylphenanthren-3-yl group, 1-methylphenanthren-4-yl group, 1-methylphenanthren-5-yl group, 1-methylphenanthren-6-yl group, 1-methylphenanthren-7-yl group, 1-methylphenanthren-8-yl group, 1-methylphenanthren-9-yl group, 1-methylphenanthren-10-yl group, 2-methylphenanthren-1-yl group, 2-methylphenanthren-3-yl group, 2- Tylphenanthren-4-yl group, 2-methylphenanthren-5-yl group, 2-methylphenanthren-6-yl group, 2-methylphenanthren-7-yl group, 2-methylphenanthren-8-yl group, 2- Methylphenanthren-9-yl group, 2-methylphenanthren-10-yl group, 3-methylphenanthren-1-yl group, 3-methylphenanthren-2-yl group, 3-methylphenanthren-4-yl group, 3- Methylphenanthren-5-yl group, 3-methylphenanthren-6-yl group, 3-methylphenanthren-7-yl group, 3-methylphenanthren-8-yl group, 3-methylphenanthren-9-yl group, 3- Methylphenanthren-10-yl group, 4-methylphenanthren-1-yl group, 4-methylphenanthate N-2-yl group, 4-methylphenanthren-3-yl group, 4-methylphenanthren-5-yl group, 4-methylphenanthren-6-yl group, 4-methylphenanthren-7-yl group, 4-methyl Phenanthren-8-yl group, 4-methylphenanthren-9-yl group, 4-methylphenanthren-10-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenylanthracen-2-yl Group, 1-phenylanthracen-3-yl group, 1-phenylanthracen-4-yl group, 1-phenylanthracen-5-yl group, 1-phenylanthracen-6-yl group, 1-phenylanthracen-7-yl Group, 1-phenylanthracen-8-yl group, 1-phenylanthracen-9-yl group, 1-phenylanthracene -10-yl group, 2-phenylanthracen-1-yl group, 2-phenylanthracen-3-yl group, 2-phenylanthracen-4-yl group, 2-phenylanthracen-5-yl group, 2-phenylanthracene -6-yl group, 2-phenylanthracen-7-yl group, 2-phenylanthracen-8-yl group, 2-phenylanthracen-9-yl group, 2-phenylanthracen-10-yl group, 9-phenylanthracene -1-yl group, 9-phenylanthracen-2-yl group, 9-phenylanthracen-3-yl group, 9-phenylanthracen-4-yl group, 9-phenylanthracen-5-yl group, 1-pyrenyl group 2-pyrenyl group, 4-pyrenyl group, 1-phenylpyren-2-yl group, 1-phenylpyren-3-yl group, 1- Enylpyren-4-yl group, 1-phenylpyren-5-yl group, 1-phenylpyren-6-yl group, 1-phenylpyren-7-yl group, 1-phenylpyren-8-yl group, 1-phenyl Pyren-9-yl group, 1-phenylpyrene-10-yl group, 2-phenylpyren-1-yl group, 2-phenylpyren-3-yl group, 2-phenylpyren-4-yl group, 2-phenyl Pyren-5-yl group, 2-phenylpyren-6-yl group, 2-phenylpyren-7-yl group, 2-phenylpyren-8-yl group, 2-phenylpyren-9-yl group, 2-phenyl Pyrene-10-yl group, 9-phenylpyren-1-yl group, 9-phenylpyren-2-yl group, 9-phenylpyren-3-yl group, 9-phenylpyren-4-yl group, 9-phenyl Pyrene-5-i Group, 9-phenylpyren-6-yl group, 9-phenylpyren-7-yl group, 9-phenylpyren-8-yl group, 9-phenylpyren-10-yl group, 1-methylpyren-2-yl group 1-methylpyren-3-yl group, 1-methylpyren-4-yl group, 1-methylpyren-5-yl group, 1-methylpyren-6-yl group, 1-methylpyren-7-yl group, 1-methylpyrene- 8-yl group, 1-methylpyren-9-yl group, 1-methylpyren-10-yl group, 2-methylpyren-1-yl group, 2-methylpyren-3-yl group, 2-methylpyren-4-yl group, 2-methylpyren-5-yl group, 2-methylpyren-6-yl group, 2-methylpyren-7-yl group, 2-methylpyren-8-yl group, 2-methylpyren-9-yl group, 2-methylpyrene-1 0-yl group, 9-methylpyren-1-yl group, 9-methylpyren-2-yl group, 9-methylpyren-3-yl group, 9-methylpyren-4-yl group, 9-methylpyren-5-yl group, 9-methylpyren-6-yl group, 9-methylpyren-7-yl group, 9-methylpyren-8-yl group, 9-methylpyren-10-yl group, fluoranthen-1-yl group, fluoranthen-1-yl group, Fluoranthen-2-yl group, fluoranthen-3-yl group, fluoranthen-4-yl group, fluoranthen-5-yl group, fluoranthen-6-yl group, fluoranthen-7-yl group, fluoranthen-8-yl group, fluoranthene -9-yl group, fluoranthen-10-yl group, triphenylene-1-yl group, triphenylene-2-yl group, acenaphthylene- -Yl, acenaphthylene-3-yl, acenaphthylene-4-yl, acenaphthylene-5-yl, chrysen-1-yl, chrysen-2-yl, chrysen-5-yl, or chrysene-6 -A yl group etc. are mentioned as a preferable example.

  Among these groups, a phenyl group, a p-tolyl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a 3- (2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 2-pyridyl group, 3-pyridyl group, 2-phenylpyridin-6-yl group, 2- Phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenylpyridin-6-yl group, 1-naphthyl group, or 2-naphthyl group Preferably, a phenyl group, a p-tolyl group, a biphenyl-3-yl group, or a biphenyl-4-yl group is more preferable.

Ar ² is substituted with a hydrogen atom or a nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a fluorine atom). An aromatic hydrocarbon group having 6 to 18 carbon atoms, a heteroaromatic group having 3 to 13 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a heteroaromatic group having 3 to 13 carbon atoms, carbon A heteroaromatic group having 3 to 13 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent May be included).

Among these, Ar ² is a heteroaromatic group having 3 to 13 carbon atoms consisting of only C, H, and N formed by a 6-membered ring (these substituents are substituted with a fluorine atom, a methyl group or a phenyl group) It is preferable that it may be used.

With respect to the following groups represented by Ar ² , the same substituents as exemplified for Ar ¹ can be exemplified.
-C1-C4 alkyl group-C6-C18 aromatic hydrocarbon group-C6-C18 aromatic hydrocarbon group substituted with a fluorine atom-C3-C13 heteroaromatic group A C6-C18 aromatic hydrocarbon group substituted with a C3-C13 heteroaromatic group A C3-C13 heteroaromatic group substituted with a C1-C4 alkyl group Alternatively, the nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms in Ar ² substituted with an alkyl group having 1 to 4 carbon atoms is not particularly limited, Pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, triazyl group, quinolyl group, isoquinolyl group, naphthyridyl group, quinazolyl group, quinoxalyl group, benzoquinolyl group, acridyl group, phenanthridyl group, or phenanthroyl group It is mentioned as preferable examples.

Examples of the heterocyclic aromatic group having a carbon number of 3 to 13 C, consisting of H, and N only formed only at 6-membered ring in Ar ^2, not particularly limited, a pyridyl group, pyrazyl group, pyrimidyl group, Preferred examples include a pyridazyl group, a triazyl group, a quinolyl group, an isoquinolyl group, a naphthyridyl group, a quinazolyl group, a quinoxalyl group, a benzoquinolyl group, an acridyl group, a phenanthridyl group, and a phenanthroyl group.

Ar ² is preferably a hydrogen atom or a nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms which may be substituted with a phenyl group or a methyl group in terms of excellent electron transporting material properties, and a hydrogen atom Or an unsubstituted nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms.

Specific examples of Ar ² include, but are not limited to, hydrogen atom, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine-4. -Yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5 -Yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6- Dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, pyridin-6-yl group 5-phenylpyridine-6 -Yl group, 2-phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3-phenylpyridin-5-yl group, 4-phenylpyridin-3-yl group, 3-phenylpyridin-4 -Yl group, 2-phenylpyridin-4-yl group, 2,4-diphenylpyridin-2-yl group, 2,6-diphenylpyridin-4-yl group, 4- (1-naphthyl) -2-phenylpyridine -6-yl group, 4- (2-naphthyl) 2-phenylpyridin-6-yl group, 2- (1-naphthyl) -4-phenylpyridin-6-yl group, 2- (2-naphthyl) -4 -Phenylpyridin-6-yl group, 2,4-di (1-naphthyl) pyridin-2-yl group, 2,4-di (2-naphthyl) pyridin-2-yl group, 2,6-di (1 -Naphthyl) pyridin-4-yl group, 2,6 Di (2-naphthyl) pyridin-4-yl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 4,6-dimethylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl Group, 5-phenylpyrimidin-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7 -Yl group, quinolin-8-yl group, quinolin-9-yl group, 2-methylquinolin-3-yl group, 2-methylquinolin-4-yl group, 2-methylquinolin-5-yl group, 2- Methylquinolin-6-yl group, 2-methylquinolin-7-yl group, 2-methylquinolin-8-yl group, isoquinolin-1-yl group, isoquinolin-3-yl group, isoquinolin-4-yl group, Rin-5-yl group, isoquinolin-6-yl group, isoquinolin-7-yl group, isoquinolin-8-yl group, pyrazyl group, 2-phenylpyrazin-5-yl group, 2-phenylpyrazin-6-yl group 2-methylpyrazin-5-yl group, 2-methylpyrazin-6-yl group, pyridazin-3-yl group, pyridazin-4-yl group, 3-phenylpyridazin-4-yl group, 3-phenylpyridazine- 5-yl group, 3-phenylpyridazin-6-yl group, 4-phenylpyridazin-3-yl group, 4-phenylpyridazin-5-yl group, 4-phenylpyridazin-6-yl group, 5-phenylpyridazine- 3-yl group, 5-phenylpyridazin-3-yl group, 5-phenylpyridazin-4-yl group, 5-phenylpyridazin-6-yl group, 6-phenylpyrida Gin-3-yl group, 6-phenylpyridazin-4-yl group, 6-phenylpyridazin-5-yl group, 3-methylpyridazin-5-yl group, 3-methylpyridazin-6-yl group, 4-methyl Pyridazin-3-yl group, 4-methylpyridazin-5-yl group, 4-methylpyridazin-6-yl group, 5-methylpyridazin-3-yl group, 5-methylpyridazin-3-yl group, 5-methyl Pyridazin-4-yl group, 5-methylpyridazin-6-yl group, 6-methylpyridazin-3-yl group, 6-methylpyridazin-4-yl group, 6-methylpyridazin-5-yl group, triazyl group, 2,4-diphenyltriazin-6-yl group, 2,4-dimethyltriazin-6-yl group, naphthyridin-2-yl group, naphthyridin-3-yl group, naphthyridin-4-y Group, quinoxalin-2-yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, 2,3-dimethylquinoxalin-5-yl group, 2,3-dimethylquinoxalin-6-yl group, quinazoline-2 -Yl group, quinazolin-4-yl group, quinazolin-5-yl group, quinazolin-6-yl group, quinazolin-7-yl group, quinazolin-8-yl group, phenanthridin-1-yl group, phenant Lysine-2-yl group, phenanthridin-3-yl group, phenanthridin-4-yl group, phenanthridin-6-yl group, phenanthridin-7-yl group, phenanthridin-8-yl Group, phenanthridin-9-yl group, phenanthridin-10-yl 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, acridine-1-yl group, acridine-2-yl group, acridine-3-yl group, acridine-4-yl group, acridine- A 9-yl group, a phenazin-1-yl group, a phenazin-2-yl group, a benzo [h] quinolyl group, a benzo [f] quinolyl group, or the like can be given.

Among these, Ar ² is a hydrogen atom, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-methylpyridin-6-yl group, and a 3-methylpyridine in terms of excellent electron transporting material characteristics. -6-yl group, 4-methylpyridin-6-yl group, 2-methylpyridin-5-yl group 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group. 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-pyrimidyl group, 4,6-dimethylpyrimidyl group, or pyrazyl group are preferable, and 2-pyridyl group 3-pyridyl group, 2-quinolyl group, 3-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, or 4-isoquinolyl group are more preferable, and a hydrogen atom, 3-pyridyl group, 2- A pyridyl group, a 3-quinolyl group, or a 4-isoquinolyl group is more preferable.

In addition to the above, Ar ² is composed only of C, H, and N formed of only an aromatic hydrocarbon group having 6 to 18 carbon atoms or a 6-membered ring in that it has excellent electron transporting material characteristics. It is preferably a C3-C13 heteroaromatic group (these substituents may be substituted with a fluorine atom, a methyl group or a phenyl group), and more specifically, a phenyl group, a biphenyl group, and a naphthyl group. Group, phenanthryl group, anthryl group, fluoranthenyl group, chrysenyl group or triphenylenyl group (these substituents may be substituted with methyl group or phenyl group), or pyridyl group, pyrimidyl group, pyrazyl group, triazyl group A quinolyl group, an isoquinolyl group, or a phenanthridyl group (these substituents may be substituted with a methyl group or a phenyl group). More preferred.

  Among these, phenyl group, biphenyl group, naphthyl group, phenyl-naphthyl group, phenanthryl group, anthryl group, fluoranthenyl group, chrycenyl group, triphenylenyl group, pyridyl group, phenyl-pyridyl group, diphenyl-pyridyl group (for example, 4,6-diphenylpyridin-2-yl group, 2,6-diphenylpyridin-4-yl group, etc.), pyrimidyl group, phenyl-pyrimidyl group, diphenyl-pyrimidyl group (for example, 4,6-diphenylpyrimidin-2- Yl group, etc.), pyrazyl group, phenyl-pyrazyl group (eg, 5-phenylpyrazyl-2-yl group, 6-phenylpyrazyl-2-yl group, etc.), triazyl group, diphenyl-triazyl group (eg, 3 , 5-diphenyltriazyl group, etc.), quinolyl group, phenyl-quinolyl group, isoquinol group Lil group, phenyl - more preferably isoquinolyl group, or a phenanthridyl group.

  Among these, phenyl group, biphenyl group, naphthyl group, phenanthryl group, anthryl group, fluoranthenyl group, chrysenyl group, triphenylenyl group, pyridyl group, phenyl-pyridyl group, diphenyl-pyridyl group, pyrimidyl group, phenyl-pyrimidyl group Groups (for example, 4,6-diphenylpyridin-2-yl group, 2,6-diphenylpyridin-4-yl group), diphenyl-pyrimidyl groups (for example, 4,6-diphenylpyrimidin-2-yl group) , Pyrazyl group, triazyl group, diphenyl-triazyl group (for example, 3,5-diphenyltriazyl group, etc.), quinolyl group, isoquinolyl group, or phenanthridyl group.

In this case, specific examples of Ar ² are not particularly limited, but 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine-4 -Yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5 -Yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 4,6- Dimethylpyridin-2-yl group, pyridin-6-yl group, 5-phenylpyridin-6-yl group, 2-phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3-phenylpyridine- 5-yl group, 4 -Phenylpyridin-3-yl group, 3-phenylpyridin-4-yl group, 2-phenylpyridin-4-yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2- Yl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 4,6-dimethylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl group, 5-phenylpyrimidin-2-yl Group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group Quinolin-9-yl group, 2-methylquinolin-3-yl group, 2-methylquinolin-4-yl group, 2-methylquinolin-5-yl group, 2-methylquinolin-6-yl group, 2- Methyl Norin-7-yl group, 2-methylquinolin-8-yl group, isoquinolin-1-yl group, isoquinolin-3-yl group, isoquinolin-4-yl group, isoquinolin-5-yl group, isoquinolin-6-yl Group, isoquinolin-7-yl group, isoquinolin-8-yl group, pyrazyl group, 2-phenylpyrazin-5-yl group, 2-phenylpyrazin-6-yl group, 2-methylpyrazin-5-yl group, 2 -Methylpyrazin-6-yl group, pyridazin-3-yl group, pyridazin-4-yl group, 3-phenylpyridazin-4-yl group, 3-phenylpyridazin-5-yl group, 3-phenylpyridazine-6- Yl group, 4-phenylpyridazin-3-yl group, 4-phenylpyridazin-5-yl group, 4-phenylpyridazin-6-yl group, 5-phenylpyridazine 3-yl group, 5-phenylpyridazin-3-yl group, 5-phenylpyridazin-4-yl group, 5-phenylpyridazin-6-yl group, 6-phenylpyridazin-3-yl group, 6-phenylpyridazine- 4-yl group, 6-phenylpyridazin-5-yl group, 3-methylpyridazin-5-yl group, 3-methylpyridazin-6-yl group, 4-methylpyridazin-3-yl group, 4-methylpyridazine- 5-yl group, 4-methylpyridazin-6-yl group, 5-methylpyridazin-3-yl group, 5-methylpyridazin-3-yl group, 5-methylpyridazin-4-yl group, 5-methylpyridazine- 6-yl group, 6-methylpyridazin-3-yl group, 6-methylpyridazin-4-yl group, 6-methylpyridazin-5-yl group, triazyl group, 2,4-dipheni Lutriazin-6-yl group, 2,4-dimethyltriazin-6-yl group, naphthyridin-2-yl group, naphthyridin-3-yl group, naphthyridin-4-yl group, quinoxalin-2-yl group, quinoxaline- 5-yl group, quinoxalin-6-yl group, 2,3-dimethylquinoxalin-5-yl group, 2,3-dimethylquinoxalin-6-yl group, quinazolin-2-yl group, quinazolin-4-yl group, Quinazolin-5-yl group, quinazolin-6-yl group, quinazolin-7-yl group, quinazolin-8-yl group, phenanthridin-1-yl group, phenanthridin-2-yl group, phenanthridine- 3-yl group, phenanthridin-4-yl group, phenanthridin-6-yl group, phenanthridin-7-yl group, phenanthridin-8-yl group, phena Trizin-9-yl group, phenanthridin-10-yl group, 1,10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-4-yl group, 1 , 10-phenanthroline-5-yl group, acridine-1-yl group, acridine-2-yl group, acridine-3-yl group, acridine-4-yl group, acridine-9-yl group, phenazin-1-yl Group, phenazin-2-yl group, benzo [h] quinolyl group, benzo [f] quinolyl group, 1-naphthyl group, 2-naphthyl group, 1-phenylnaphthalen-2-yl group, 1-phenylnaphthalene-3- Yl group, 1-phenylnaphthalen-4-yl group, 1-phenylnaphthalen-5-yl group, 1-phenylnaphthalen-6-yl group, 1-phenylnaphthalene 7-yl group, 1-phenylnaphthalen-8-yl group, 2-phenylnaphthalen-1-yl group, 2-phenylnaphthalen-3-yl group, 2-phenylnaphthalen-4-yl group, 2-phenylnaphthalene- 5-yl group, 2-phenylnaphthalen-6-yl group, 2-phenylnaphthalen-7-yl group, 2-phenylnaphthalen-8-yl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalene- 5-yl group, 1-methylnaphthalen-6-yl group, 1-methylnaphthalen-7-yl group, 1-methylnaphthalen-8-yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphthalene- 3-yl group, 2-methylnaphthalen-4-yl group, 2-methylnaphthalen-5-yl group, 2-methylnaphthalen-6-yl group, 2-methylnaphthalene-7- Yl group, 2-methylnaphthalen-8-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-phenylphenanthren-2-yl group, 1- Phenylphenanthren-3-yl group, 1-phenylphenanthren-4-yl group, 1-phenylphenanthren-5-yl group, 1-phenylphenanthren-6-yl group, 1-phenylphenanthren-7-yl group, 1- Phenylphenanthren-8-yl group, 1-phenylphenanthren-9-yl group, 1-phenylphenanthrene-10-yl group, 2-phenylphenanthren-1-yl group, 2-phenylphenanthren-3-yl group, 2- Phenylphenanthren-4-yl group, 2-phenylphenanthrene-5- Group, 2-phenylphenanthren-6-yl group, 2-phenylphenanthrene-7-yl group, 2-phenylphenanthrene-8-yl group, 2-phenylphenanthren-9-yl group, 2-phenylphenanthrene-10- Yl group, 3-phenylphenanthren-1-yl group, 3-phenylphenanthren-2-yl group, 3-phenylphenanthren-4-yl group, 3-phenylphenanthren-5-yl group, 3-phenylphenanthrene-6- Yl group, 3-phenylphenanthrene-7-yl group, 3-phenylphenanthrene-8-yl group, 3-phenylphenanthrene-9-yl group, 3-phenylphenanthren-10-yl group, 4-phenylphenanthrene-1- Yl group, 4-phenylphenanthren-2-yl group, 4-phenyl group Nanthren-3-yl group, 4-phenylphenanthren-5-yl group, 4-phenylphenanthren-6-yl group, 4-phenylphenanthren-7-yl group, 4-phenylphenanthren-8-yl group, 4-phenyl Phenanthren-9-yl group, 4-phenylphenanthren-10-yl group, 1-methylphenanthren-2-yl group, 1-methylphenanthren-3-yl group, 1-methylphenanthren-4-yl group, 1-methyl Phenanthren-5-yl group, 1-methylphenanthrene-6-yl group, 1-methylphenanthrene-7-yl group, 1-methylphenanthren-8-yl group, 1-methylphenanthren-9-yl group, 1-methyl Phenanthren-10-yl group, 2-methylphenanthren-1-yl group, 2-methylphenane Tren-3-yl group, 2-methylphenanthren-4-yl group, 2-methylphenanthren-5-yl group, 2-methylphenanthren-6-yl group, 2-methylphenanthren-7-yl group, 2-methyl Phenanthren-8-yl group, 2-methylphenanthren-9-yl group, 2-methylphenanthren-10-yl group, 3-methylphenanthren-1-yl group, 3-methylphenanthren-2-yl group, 3-methyl Phenanthren-4-yl group, 3-methylphenanthren-5-yl group, 3-methylphenanthrene-6-yl group, 3-methylphenanthren-7-yl group, 3-methylphenanthren-8-yl group, 3-methyl Phenanthren-9-yl group, 3-methylphenanthren-10-yl group, 4-methylphenanthren-1-yl 4-methylphenanthren-2-yl group, 4-methylphenanthren-3-yl group, 4-methylphenanthren-5-yl group, 4-methylphenanthren-6-yl group, 4-methylphenanthren-7-yl group 4-methylphenanthren-8-yl group, 4-methylphenanthrene-9-yl group, 4-methylphenanthrene-10-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenylanthracene 2-yl group, 1-phenylanthracen-3-yl group, 1-phenylanthracen-4-yl group, 1-phenylanthracen-5-yl group, 1-phenylanthracen-6-yl group, 1-phenylanthracene -7-yl group, 1-phenylanthracen-8-yl group, 1-phenylanthracen-9-yl group 1-phenylanthracen-10-yl group, 2-phenylanthracen-1-yl group, 2-phenylanthracen-3-yl group, 2-phenylanthracen-4-yl group, 2-phenylanthracen-5-yl group, 2-phenylanthracen-6-yl group, 2-phenylanthracen-7-yl group, 2-phenylanthracen-8-yl group, 2-phenylanthracen-9-yl group, 2-phenylanthracen-10-yl group, 9-phenylanthracen-1-yl group, 9-phenylanthracen-2-yl group, 9-phenylanthracen-3-yl group, 9-phenylanthracen-4-yl group, 9-phenylanthracen-5-yl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1-phenylpyren-2-yl group, 1-phenyl Pyren-3-yl group, 1-phenylpyren-4-yl group, 1-phenylpyren-5-yl group, 1-phenylpyren-6-yl group, 1-phenylpyren-7-yl group, 1-phenyl Pyren-8-yl group, 1-phenylpyren-9-yl group, 1-phenylpyren-10-yl group, 2-phenylpyren-1-yl group, 2-phenylpyren-3-yl group, 2-phenyl Pyren-4-yl group, 2-phenylpyren-5-yl group, 2-phenylpyren-6-yl group, 2-phenylpyren-7-yl group, 2-phenylpyren-8-yl group, 2-phenyl Pyren-9-yl group, 2-phenylpyrene-10-yl group, 9-phenylpyren-1-yl group, 9-phenylpyren-2-yl group, 9-phenylpyren-3-yl group, 9-phenyl Pyren-4-yl group, 9 Phenylpyren-5-yl group, 9-phenylpyren-6-yl group, 9-phenylpyren-7-yl group, 9-phenylpyren-8-yl group, 9-phenylpyren-10-yl group, 1- Methylpyren-2-yl group, 1-methylpyren-3-yl group, 1-methylpyren-4-yl group, 1-methylpyren-5-yl group, 1-methylpyren-6-yl group, 1-methylpyren-7-yl Group, 1-methylpyren-8-yl group, 1-methylpyren-9-yl group, 1-methylpyren-10-yl group, 2-methylpyren-1-yl group, 2-methylpyren-3-yl group, 2-methylpyrene -4-yl group, 2-methylpyren-5-yl group, 2-methylpyren-6-yl group, 2-methylpyren-7-yl group, 2-methylpyren-8-yl group, 2-methylpyrene-9-i Group, 2-methylpyren-10-yl group, 9-methylpyren-1-yl group, 9-methylpyren-2-yl group, 9-methylpyren-3-yl group, 9-methylpyren-4-yl group, 9-methylpyrene -5-yl group, 9-methylpyren-6-yl group, 9-methylpyren-7-yl group, 9-methylpyren-8-yl group, 9-methylpyren-10-yl group, fluoranthen-1-yl group, fluoranthene -1-yl group, fluoranthen-2-yl group, fluoranthen-3-yl group, fluoranthen-4-yl group, fluoranthen-5-yl group, fluoranthen-6-yl group, fluoranthen-7-yl group, fluoranthene- 8-yl group, fluoranthen-9-yl group, fluoranthen-10-yl group, triphenylene-1-yl group, triphenylene-2- Yl group, acenaphthylene-1-yl group, acenaphthylene-3-yl group, acenaphthylene-4-yl group, acenaphthylene-5-yl group, chrysen-1-yl group, chrysen-2-yl group, chrysen-5-yl Group, chrysen-6-yl group, and the like.

Among these, Ar ² is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-phenanthryl group, a 9-phenanthryl group, a 9-anthryl group, and a 1-pyrenyl group in terms of excellent electron transporting material characteristics. Fluoranthen-3-yl group, triphenylene-1-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-6-yl group, 3-methylpyridin-6-yl group, 2-methylpyridin-5-yl group, 2,6-dimethylpyridin-4-yl group, 4,6-dimethylpyridin-2-yl group, 2,6-diphenylpyridin-4-yl group, 4,6- Diphenylpyridin-2-yl group, 4,6-dimethylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl group, 2,4-diphenyltriazin-6-yl group, 2-quino Ryl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group. 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-pyrimidyl group, 4,6-dimethylpyrimidyl group or pyrazyl group are preferred.

  Among these substituents, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-phenanthryl group, 9-phenanthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyridyl group, 3-pyridyl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 4,6-dimethylpyrimidin-2-yl group, 2-quinolyl group, 3-quinolyl group, 8-quinolyl group 1-isoquinolyl group, 3-isoquinolyl group, or 4-isoquinolyl group is more preferable.

  Among these, phenyl group, 9-phenanthryl group, 1-naphthyl group, 2-naphthyl group, 3-pyridyl group, 2-pyridyl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenyl A pyridin-2-yl group, a 4,6-dimethylpyrimidin-2-yl group, a 1-pyrenyl group, a 2-quinolyl group, or a 3-quinolyl group is more preferable.

  X is each independently a C6-C18 divalent aromatic hydrocarbon group which may be substituted with a methyl group, or a C3-C13 group which may be substituted with a methyl group or a phenyl group. Represents a divalent nitrogen-containing heteroaromatic group.

  Among these, X is each independently substituted with a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a methyl group, which may be substituted with a methyl group, in terms of excellent electron transport material properties. A divalent nitrogen-containing heteroaromatic group having 5 to 9 carbon atoms which may be present is preferable.

  Although it does not specifically limit as a C6-C18 bivalent aromatic hydrocarbon group which may be substituted by the methyl group in X, For example, a phenylene group, a biphenylene group, a naphthylene group, a phenanthrylene group, Anthrylene group, pyrenylene group, triphenylenylene group, chrysenylene group, fluoranthenylene group, acenaphthyleneylene group, fluorenylene group, benzofluorenylene group, dimethylfluorenylene group, or dimethylbenzofluorenylene group are preferable. Take as an example.

  Although it does not specifically limit as a C3-C13 bivalent nitrogen-containing heteroaromatic group which may be substituted by the methyl group or phenyl group in X, For example, a pyridylene group, a methyl pyridylene group, a dimethyl pyridene group, for example. Diylene group, phenylpyridylene group, pyrazylene group, methylpyrazylene group, dimethylpyrazylene group, phenylpyrazylene group, pyrimidylene group, dipyrimidylene group, methylpyrimidylene group, phenylpyrimidylene group, pyridazylene group, methylpyridazilene group , Phenyl pyridazylene group, triadylene group, methyl triadylene group, phenyl triadylene group, quinolylene group, methyl quinolylene group, phenyl quinolylene group, isoquinolylene group, methyl isoquinolylene group, phenyl isoquinolylene group, naphthyridylene group, methyl Naphthyridylene Phenylnaphthylidylene group, quinazolylene group, methylquinazolylene group, phenylquinazolylene group, quinoxarylene group, methylquinoxarylene group, phenylquinoxarylene group, benzoquinolylene group, methylbenzoquinolylene group, phenylbenzoquinolylene group Group, acridylene group, methylacridylene group, phenylacridylene group, phenanthridylene group, methylphenanthridylene group, phenylphenanthridylene group, phenanthrolylene group, methylphenanthrolylene group, or phenyl A preferred example is a phenanthroylene group.

  Although it does not specifically limit as a C6-C10 bivalent aromatic hydrocarbon group which may be substituted by the methyl group in X, For example, a phenylene group, a tolylene group, or a naphthylene group etc. are preferable. Take as an example.

  The divalent nitrogen-containing heteroaromatic group having 5 to 9 carbon atoms which may be substituted with a methyl group or a phenyl group in X is not particularly limited, and examples thereof include a pyridylene group, a methylpyridylene group, and dimethylpyrylene group. Dilene group, pyrazylene group, methylpyrazylene group, dimethylpyrazylene group, pyrimidylene group, dipyrimidylene group, methylpyrimidylene group, phenylpyrimidylene group, pyridazylene group, methylpyridazilene group, triadylene group, methyltriazilene group, phenyl Preferred examples include triadylene group, quinolylene group, methylquinolylene group, isoquinolylene group, methylisoquinolylene group, naphthyridylene group, methylnaphthylidylene group, quinazolylene group, methylquinazolylene group, quinoxalylene group, or methylquinoxalylene group. As mentioned.

  X is independently a phenylene group or a biphenylene group (for example, 4,4′-biphenylene group, 4,3′-biphenylene group, 3,3′-biphenylene group, etc.) in that it has excellent electron transporting material characteristics. ), Naphthylene group, phenanthrylene group, anthrylene group, pyrenylene group, pyridylene group (for example, 2,5-pyridylene group, 3,6-pyridylene group, etc.), methylpyridylene group (for example, 6-methyl-2,5-pyridylene group) , 2-methyl-3,6-pyridylene group, etc.), dimethylpyridylene group, pyrazylene group, methylpyrazylene group, dimethylpyrazylene group, pyrimidylene group, methylpyrimidylene group, or dimethylpyrimidylene group (for example, 4, 6-dimethyl-2,4-pyrimidylene group).

  Of these substituents, each X is independently a phenylene group (1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, etc.) or pyridylene group (for example, 2,5-phenylene group). More preferred are pyridylene group, 3,6-pyridylene group and the like.

  p represents 0, 1 or 2. In view of excellent sublimation purification operability, p is preferably 0 or 1.

Incidentally, -X _p - represents that the group represented by -X- is p pieces connected. That is, in the case of _p = 2, -X p - denotes a -X-X-. In this case, two Xs may be the same or different.

  q represents 0, 1 or 2. Q is preferably 0 or 1 in terms of excellent sublimation purification operability.

Incidentally, -X _q - represents that the group represented by -X- is q pieces connected. That is, in the case of _q = 2, -X q - means -X-X-. In this case, two Xs may be the same or different.

  Z represents a nitrogen atom or a carbon atom. Z is preferably a nitrogen atom from the viewpoint of excellent characteristics of the electron transporting material.

  T represents a heteroaromatic group having 4 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, consisting of only a carbon atom, a hydrogen atom and a group 16 element; C6-C18 aromatic hydrocarbon group substituted with fluorine atom, C3-C13 heteroaromatic group, C6-C18 aromatic substituted with C3-C13 heteroaromatic group Aromatic hydrocarbon group substituted with an aromatic hydrocarbon group, a C3-C13 heteroaromatic group substituted with a C1-C4 alkyl group, or a C1-C4 alkyl group Which may have a hydrogen group as a substituent.

  Among these, T is a heteroaromatic group having 4 to 20 carbon atoms (methyl group, phenyl group, or methyl group consisting only of carbon atoms, hydrogen atoms, and group 16 elements in terms of excellent characteristics of the electron transporting material. It may preferably have a nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms as a substituent.

With respect to the following substituents represented by T, the same substituents as those exemplified for Ar ¹ can be exemplified.
-C1-C4 alkyl group-C6-C18 aromatic hydrocarbon group-C6-C18 aromatic hydrocarbon group substituted with a fluorine atom-C3-C13 heteroaromatic group A C6-C18 aromatic hydrocarbon group substituted with a C3-C13 heteroaromatic group A C3-C13 heteroaromatic group substituted with a C1-C4 alkyl group Or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, and a heteroaromatic group having 4 to 30 carbon atoms (fluorine) consisting only of carbon atoms, hydrogen atoms and group 16 elements in T Atom, alkyl group having 1 to 4 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom, heteroaromatic group having 3 to 13 carbon atoms Group, C6-C18 aromatic charcoal substituted with C3-C13 heteroaromatic group A hydrocarbon group, a C3-C13 heteroaromatic group substituted with a C1-C4 alkyl group, or a C6-C18 aromatic hydrocarbon substituted with a C1-C4 alkyl group Group (which may have a group as a substituent) is not particularly limited, but consists of only carbon atoms, hydrogen atoms and oxygen atoms, only carbon atoms, hydrogen atoms and sulfur atoms, or carbon atoms, Heteroaromatic group having 4 to 30 carbon atoms consisting of only hydrogen atom, oxygen atom and sulfur atom (these groups are fluorine atom, alkyl group having 1 to 4 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms) , An aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom, a heteroaromatic group having 3 to 13 carbon atoms, and a 6 to 18 carbon atom substituted with a heteroaromatic group having 3 to 13 carbon atoms Substituted by aromatic hydrocarbon group, alkyl group having 1 to 4 carbon atoms As a preferred example, a heteroaromatic group having 3 to 13 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be used as a substituent. Can be mentioned.

  More specific examples include a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group, a benzofuranyl group, a thiophenyl group, or a furanyl group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, carbon An aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom, a heteroaromatic group having 3 to 13 carbon atoms, and a heteroaromatic group having 3 to 13 carbon atoms Substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heteroaromatic group having 3 to 13 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms And may have an aromatic hydrocarbon group having 6 to 18 carbon atoms as a substituent).

  Among these, T is a heteroaromatic group having 4 to 30 carbon atoms (only carbon atoms, hydrogen atoms and oxygen atoms, or only carbon atoms, hydrogen atoms and sulfur atoms) in terms of excellent electron transporting material characteristics. These groups include a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom, and 3 carbon atoms. -13 heteroaromatic group, C6-C18 aromatic hydrocarbon group substituted with a C3-C13 heteroaromatic group, C3-C3 substituted with a C1-C4 alkyl group 13 heteroaromatic groups, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be more preferable.

  In addition, a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group, or a benzofuranyl group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and an aromatic group having 6 to 18 carbon atoms). Group hydrocarbon group, aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with fluorine atom, heteroaromatic group having 3 to 13 carbon atoms, carbon number substituted with heteroaromatic group having 3 to 13 carbon atoms 6-18 aromatic hydrocarbon group, C3-C13 heteroaromatic group substituted with a C1-C4 alkyl group, or C6-C4 substituted with a C1-C4 alkyl group 18 aromatic hydrocarbon groups (which may have 18 substituents as substituents) are more preferred, and dibenzothiophenyl group, dibenzofuranyl group, benzothiophenyl group or benzofuranyl group (these groups are methyl group, pyridyl group or Feni May be substituted with a group) is more preferred.

  Although it does not specifically limit as a C3-C9 nitrogen-containing heteroaromatic group which may have the methyl group represented in T, For example, an imidazolyl group, a pyridyl group, a methyl pyridyl group, a dimethyl pyridyl group Preferred examples include a pyrazyl group, a pyrimidyl group, a dimethylpyrimidyl group, a pyridazyl group, a triazyl group, a quinolyl group, a methylquinolyl group, an isoquinolyl group, a methylisoquinolyl group, a naphthyridyl group, a quinazolyl group, and a quinoxalyl group. . Of these, imidazolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, pyrimidyl group, dimethylpyrimidyl group, quinolyl group, methylquinolyl group, isoquinolyl group, methyl group are preferred because of their excellent electron transport properties. An isoquinolyl group, a quinazolyl group, or a quinoxalyl group is more preferable.

  Heteroaromatic group having 4 to 20 carbon atoms consisting of only carbon atom, hydrogen atom and group 16 element in T (nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms which may have a methyl group, a phenyl group or a methyl group) The group may have a group as a substituent), but is not particularly limited, but consists of carbon atoms, hydrogen atoms and oxygen atoms only, carbon atoms, hydrogen atoms and sulfur atoms only, or carbon atoms , A heteroaromatic group having 4 to 20 carbon atoms consisting of only a hydrogen atom, an oxygen atom and a sulfur atom (a nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms which may have a methyl group, a phenyl group or a methyl group) As a substituent, and more specific examples include dibenzothiophenyl group, dibenzofuranyl group, benzothiophenyl group, benzofuranyl group, and thiophenyl. Or furanyl group (methyl group, a phenyl group, or a nitrogen-containing heterocyclic aromatic group having carbon atoms of 3 to 9 may have a methyl group which may have a substituent group).

  Among these, T is a heteroaromatic group having 4 to 20 carbon atoms (only a carbon atom, a hydrogen atom, and an oxygen atom, or only a carbon atom, a hydrogen atom, and a sulfur atom) in that the electron transporting material characteristics are excellent. A methyl group, a phenyl group, or a nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms which may have a methyl group may be used as a substituent.

  In addition, a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group, or a benzofuranyl group (these groups may have a methyl group, a phenyl group, or a methyl group having 3 to 3 carbon atoms in terms of easy synthesis). 9 may optionally have a nitrogen-containing heteroaromatic group as a substituent. A dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group, or a benzofuranyl group (these groups are a methyl group, a pyridyl group). , A quinolyl group, a methylpyridyl group, a dimethylpyridyl group, or a phenyl group, which may be substituted).

  Specific examples of T include, but are not limited to, thiophen-2-yl group, thiophen-3-yl group, furan-2-yl group, furan-3-yl group, and benzothiophen-2-yl group. Benzothiophen-3-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group, benzofuran-2-yl group, benzofuran- 3-yl group, benzofuran-4-yl group, benzofuran-5-yl group, benzofuran-6-yl group, benzofuran-7-yl group, dibenzothiophen-1-yl group, dibenzothiophen-2-yl group, dibenzo Thiophen-3-yl group, dibenzothiophen-4-yl group, dibenzofuran-1-yl group, dibenzofuran-2-yl group, dibenzoph N-3-yl group, dibenzofuran-4-yl group, 2-phenylthiophen-3-yl group, 2-phenylthiophen-4-yl group, 2-phenylthiophen-5-yl group, 3-phenylthiophene-2 -Yl group, 3-phenylthiophen-4-yl group, 3-phenylthiophen-5-yl group, 2-phenylfuran-3-yl group, 2-phenylfuran-4-yl group, 2-phenylfuran-5 -Yl group, 3-phenylfuran-2-yl group, 3-phenylfuran-4-yl group, 3-phenylfuran-5-yl group, 2- (2-pyridyl) thiophen-3-yl group, 2- (2-pyridyl) thiophen-4-yl group, 2- (2-pyridyl) thiophen-5-yl group, 3- (2-pyridyl) thiophen-2-yl group, 3- (2-pyridyl) thiophene-4 − Group, 3- (2-pyridyl) thiophen-5-yl group, 2- (2-pyridyl) furan-3-yl group, 2- (2-pyridyl) furan-4-yl group, 2- (2- Pyridyl) furan-5-yl group, 3- (2-pyridyl) furan-2-yl group, 3- (2-pyridyl) furan-4-yl group, 3- (2-pyridyl) furan-5-yl group 2- (3-pyridyl) thiophen-3-yl group, 2- (3-pyridyl) thiophen-4-yl group, 2- (3-pyridyl) thiophen-5-yl group, 3- (3-pyridyl) Thiophen-2-yl group, 3- (3-pyridyl) thiophen-4-yl group, 3- (3-pyridyl) thiophen-5-yl group, 2- (3-pyridyl) furan-3-yl group, 2 -(3-pyridyl) furan-4-yl group, 2- (3-pyridyl) furan-5 Yl group, 3- (3-pyridyl) furan-2-yl group, 3- (3-pyridyl) furan-4-yl group, 3- (3-pyridyl) furan-5-yl group 2- (4-pyridyl) ) Thiophen-3-yl group, 2- (4-pyridyl) thiophen-4-yl group, 2- (4-pyridyl) thiophen-5-yl group, 3- (4-pyridyl) thiophen-2-yl group, 3- (4-pyridyl) thiophen-4-yl group, 3- (4-pyridyl) thiophen-5-yl group, 2- (4-pyridyl) furan-3-yl group, 2- (4-pyridyl) furan -4-yl group, 2- (4-pyridyl) furan-5-yl group, 3- (4-pyridyl) furan-2-yl group, 3- (4-pyridyl) furan-4-yl group, 3- (4-Pyridyl) furan-5-yl group, 1-phenyldibenzofuran-2-yl 1-phenyldibenzofuran-3-yl group, 1-phenyldibenzofuran-4-yl group, 1-phenyldibenzofuran-5-yl group, 1-phenyldibenzofuran-6-yl group, 1-phenyldibenzofuran-7-yl group 1-phenyldibenzofuran-8-yl group, 1-phenyldibenzofuran-9-yl group, 2-phenyldibenzofuran-1-yl group, 2-phenyldibenzofuran-3-yl group, 2-phenyldibenzofuran-4-yl group 2-phenyldibenzofuran-5-yl group, 2-phenyldibenzofuran-7-yl group, 2-phenyldibenzofuran-8-yl group, 2-phenyldibenzofuran-9-yl group, 3-phenyldibenzofuran-1-yl group 3-phenyldibenzofuran-2-yl group, 3-phenyldibenzof N-4-yl group, 3-phenyldibenzofuran-6-yl group, 3-phenyldibenzofuran-7-yl group, 3-phenyldibenzofuran-8-yl group, 3-phenyldibenzofuran-9-yl group, 4-phenyl Dibenzofuran-1-yl group, 4-phenyldibenzofuran-2-yl group, 4-phenyldibenzofuran-3-yl group, 4-phenyldibenzofuran-6-yl group, 4-phenyldibenzofuran-7-yl group, 4-phenyl Dibenzofuran-8-yl group, 4-phenyldibenzofuran-9-yl group, 1- (2-pyridyl) dibenzofuran-2-yl group, 1- (2-pyridyl) dibenzofuran-3-yl group, 1- (2- Pyridyl) dibenzofuran-4-yl group, 1- (2-pyridyl) dibenzofuran-5-yl group, 1- (2-pyridyl) ) Dibenzofuran-6-yl group, 1- (2-pyridyl) dibenzofuran-7-yl group, 1- (2-pyridyl) dibenzofuran-8-yl group, 1- (2-pyridyl) dibenzofuran-9-yl group, 2- (2-pyridyl) dibenzofuran-1-yl group, 2- (2-pyridyl) dibenzofuran-3-yl group, 2- (2-pyridyl) dibenzofuran-4-yl group, 2- (2-pyridyl) dibenzofuran -5-yl group, 2- (2-pyridyl) dibenzofuran-7-yl group, 2- (2-pyridyl) dibenzofuran-8-yl group, 2- (2-pyridyl) dibenzofuran-9-yl group, 3- (2-pyridyl) dibenzofuran-1-yl group, 3- (2-pyridyl) dibenzofuran-2-yl group, 3- (2-pyridyl) dibenzofuran-4-yl group, 3- (2-pi Diyl) dibenzofuran-6-yl group, 3- (2-pyridyl) dibenzofuran-7-yl group, 3- (2-pyridyl) dibenzofuran-8-yl group, 3- (2-pyridyl) dibenzofuran-9-yl group 4- (2-pyridyl) dibenzofuran-1-yl group, 4- (2-pyridyl) dibenzofuran-2-yl group, 4- (2-pyridyl) dibenzofuran-3-yl group, 4- (2-pyridyl) Dibenzofuran-6-yl group, 4- (2-pyridyl) dibenzofuran-7-yl group, 4- (2-pyridyl) dibenzofuran-8-yl group, 4- (2-pyridyl) dibenzofuran-9-yl group, 1 -(3-pyridyl) dibenzofuran-2-yl group, 1- (3-pyridyl) dibenzofuran-3-yl group, 1- (3-pyridyl) dibenzofuran-4-yl group, 1- ( -Pyridyl) dibenzofuran-5-yl group, 1- (3-pyridyl) dibenzofuran-6-yl group, 1- (3-pyridyl) dibenzofuran-7-yl group, 1- (3-pyridyl) dibenzofuran-8-yl group Group, 1- (3-pyridyl) dibenzofuran-9-yl group, 2- (3-pyridyl) dibenzofuran-1-yl group, 2- (3-pyridyl) dibenzofuran-3-yl group, 2- (3-pyridyl) ) Dibenzofuran-4-yl group, 2- (3-pyridyl) dibenzofuran-5-yl group, 2- (3-pyridyl) dibenzofuran-7-yl group, 2- (3-pyridyl) dibenzofuran-8-yl group, 2- (3-pyridyl) dibenzofuran-9-yl group, 3- (3-pyridyl) dibenzofuran-1-yl group, 3- (3-pyridyl) dibenzofuran-2-yl group, 3 -(3-pyridyl) dibenzofuran-4-yl group, 3- (3-pyridyl) dibenzofuran-6-yl group, 3- (3-pyridyl) dibenzofuran-7-yl group, 3- (3-pyridyl) dibenzofuran- 8-yl group, 3- (3-pyridyl) dibenzofuran-9-yl group, 4- (3-pyridyl) dibenzofuran-1-yl group, 4- (3-pyridyl) dibenzofuran-2-yl group, 4- ( 3-pyridyl) dibenzofuran-3-yl group, 4- (3-pyridyl) dibenzofuran-6-yl group, 4- (3-pyridyl) dibenzofuran-7-yl group, 4- (3-pyridyl) dibenzofuran-8- Yl group, 4- (3-pyridyl) dibenzofuran-9-yl group, 1- (4-pyridyl) dibenzofuran-2-yl group, 1- (4-pyridyl) dibenzofuran-3-yl 1- (4-pyridyl) dibenzofuran-4-yl group, 1- (4-pyridyl) dibenzofuran-5-yl group, 1- (4-pyridyl) dibenzofuran-6-yl group, 1- (4-pyridyl) Dibenzofuran-7-yl group, 1- (4-pyridyl) dibenzofuran-8-yl group, 1- (4-pyridyl) dibenzofuran-9-yl group, 2- (4-pyridyl) dibenzofuran-1-yl group, 2 -(4-pyridyl) dibenzofuran-3-yl group, 2- (4-pyridyl) dibenzofuran-4-yl group, 2- (4-pyridyl) dibenzofuran-5-yl group, 2- (4-pyridyl) dibenzofuran- 7-yl group, 2- (4-pyridyl) dibenzofuran-8-yl group, 2- (4-pyridyl) dibenzofuran-9-yl group, 3- (4-pyridyl) dibenzofuran-1 Yl group, 3- (4-pyridyl) dibenzofuran-2-yl group, 3- (4-pyridyl) dibenzofuran-4-yl group, 3- (4-pyridyl) dibenzofuran-6-yl group, 3- (4- Pyridyl) dibenzofuran-7-yl group, 3- (4-pyridyl) dibenzofuran-8-yl group, 3- (4-pyridyl) dibenzofuran-9-yl group, 4- (4-pyridyl) dibenzofuran-1-yl group 4- (4-pyridyl) dibenzofuran-2-yl group, 4- (4-pyridyl) dibenzofuran-3-yl group, 4- (4-pyridyl) dibenzofuran-6-yl group, 4- (4-pyridyl) Preferred examples include a dibenzofuran-7-yl group, a 4- (4-pyridyl) dibenzofuran-8-yl group, or a 4- (4-pyridyl) dibenzofuran-9-yl group.

  Among these, T is benzothiophen-2-yl, benzothiophen-3-yl, benzothiophen-4-yl, benzothiophen-5-yl, benzothiophen-2-yl, benzothiophen-4-yl, Thiophen-6-yl group, benzothiophen-7-yl group, benzofuran-2-yl group, benzofuran-3-yl group, benzofuran-4-yl group, benzofuran-5-yl group, benzofuran-6-yl group, Benzofuran-7-yl group, dibenzothiophen-1-yl group, dibenzothiophen-2-yl group, dibenzothiophen-3-yl group, dibenzothiophen-4-yl group, dibenzofuran-1-yl group, dibenzofuran-2- Yl group, dibenzofuran-3-yl group, dibenzofuran-4-yl group, 2-phenyldibenzothiophene-8-i Group, 2-phenyldibenzofuran-8-yl group, 2- (3-pyridyl) dibenzothiophen-8-yl group or 2- (3-pyridyl) dibenzofuran-8-yl group is preferred, and the reaction for synthesizing the compound In terms of good yield, benzothiophen-2-yl group, benzofuran-2-yl group, dibenzothiophen-2-yl group, dibenzothiophen-4-yl group, dibenzofuran-2-yl group, dibenzofuran-4-yl Group, 2-phenyldibenzothiophen-8-yl group, 2-phenyldibenzofuran-8-yl group, 2- (3-pyridyl) dibenzothiophen-8-yl group, or 2- (3-pyridyl) dibenzofuran-8- An yl group is more preferable.

  That is, T is preferably a substituent represented by the following general formula (T-1) or (T-2).

（一般式（Ｔ−１）及び（Ｔ−２）中、Ｗ^１及びＷ^２は、各々独立して、酸素原子又は硫黄原子を表す。Ａｒ^３は水素原子、メチル基、ピリジル基、メチルピリジル基、ジメチルピリジル基又はフェニル基を表す。）
また、Ｔとしては、下記一般式（Ｔ−３）又は（Ｔ−４）で表される置換基（（Ｔ−１）及び（Ｔ−２）における結合位置を限定した）であることがより好ましい。

(In General Formulas (T-1) and (T-2), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ represents a hydrogen atom, a methyl group, a pyridyl group, or a methylpyridyl group. Represents a group, a dimethylpyridyl group or a phenyl group.)
Moreover, as T, it is a substituent represented by the following general formula (T-3) or (T-4) (the bonding position in (T-1) and (T-2) is limited). preferable.

（一般式（Ｔ−３）及び（Ｔ−４）中、Ｗ^１及びＷ^２は、各々独立して、酸素原子又は硫黄原子を表す。Ａｒ^３は水素原子、メチル基、ピリジル基、キノリル基、メチルピリジル基、ジメチルピリジル基又はフェニル基を表す。＊は結合位置を表す。）
一般式（１）又は（１）で示される化合物の特に好ましい化合物の具体例としては、次の（Ａ−１）から（Ａ−５６１）を例示できるが、本発明はこれらに限定されるものではない。

(In General Formulas (T-3) and (T-4), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ represents a hydrogen atom, a methyl group, a pyridyl group, or a quinolyl group. And represents a methylpyridyl group, a dimethylpyridyl group, or a phenyl group. * Represents a bonding position.)
Specific examples of particularly preferable compounds of the compound represented by the general formula (1) or (1) include the following (A-1) to (A-561), but the present invention is limited to these. is not.

次に、本発明の製造方法について説明する。

Next, the manufacturing method of this invention is demonstrated.

  The cyclic azine compound (1) of the present invention may be reacted with the following reaction formula (1) in the presence of a base and optionally in the presence of a palladium catalyst.

（反応式（１）中、Ａｒ^１、Ａｒ^２、Ｔ、Ｚ、Ｘ、ｐ、及びｑは、前記と同じ置換基を表す。Ｙ^１、Ｙ^２は、各々独立して、後述する脱離基を表す。Ｍ^１及びＭ^２は、各々独立して、後述する置換基を表す。）
、反応式（２）

(In the reaction formula (1), Ar ¹ , Ar ² , T, Z, X, p, and q represent the same substituents as described above. Y ¹ and Y ² are each independently a desorption described later. M ¹ and M ² each independently represent a substituent described later.)
Reaction formula (2)

（反応式（２）中、Ａｒ^１、Ａｒ^２、Ｔ、Ｚ、Ｘ、ｐ、及びｑは前記と同じ置換基を表す。Ｙ^１、Ｙ^２は、各々独立して、後述する脱離基を表す。Ｍ^１及びＭ^２は、各々独立して、後述する置換基を表す。）
、反応式（３）

(In the reaction formula (2), Ar ¹ , Ar ² , T, Z, X, p, and q represent the same substituents as described above. Y ¹ and Y ² are each independently a leaving group described later. M ¹ and M ² each independently represent a substituent described later.)
Reaction formula (3)

（反応式（３）中、Ａｒ^１、Ａｒ^２、Ｔ、Ｚ、Ｘ、ｐ、及びｑは前記と同じ置換基を示す。Ｙ^３は後述する脱離基を表す。Ｍ^３は後述する置換基を表す。）
、又は反応式（４）

(In Reaction Formula (3), Ar ¹ , Ar ² , T, Z, X, p, and q represent the same substituents as described above. Y ³ represents a leaving group described later. M ³ represents a substituent described later. Represents a group.)
Or reaction formula (4)

（反応式（３）中、Ａｒ^１、Ａｒ^２、Ｔ、Ｚ、Ｘ、ｐ、及びｑは前記と同じ置換基を示す。Ｙ^４は後述する脱離基を表す。Ｍ^４は後述する置換基を表す。）
で示される方法により製造することができる。

(In the reaction formula (3), Ar ¹ , Ar ² , T, Z, X, p, and q represent the same substituents as described above. Y ⁴ represents a leaving group described later. M ⁴ represents a substituent described later. Represents a group.)
It can manufacture by the method shown by these.

  Hereinafter, the compound represented by the general formula (2) is referred to as a compound (2). In addition, it is synonymous also about a compound (3)-a compound (10).

  The compound (3) used in the reaction formula (1) or the reaction formula (2) is manufactured using, for example, a method disclosed in JP 2008-280330 A or JP 2001-335516 A. Can do. Examples of the compound (3) include the following (B-1) to (B-26), but the present invention is not limited to these.

Ｍ^１で表されるＺｎＲ^１、及びＭｇＲ^２としては、ＺｎＣｌ、ＺｎＢｒ、ＺｎＩ、ＭｇＣｌ、ＭｇＢｒ、ＭｇＩ等が例示できる。Ｍ^１で表されるＳｎ（Ｒ^３）_３としては、Ｓｎ（Ｍｅ）_３、Ｓｎ（Ｂｕ）_３等が例示できる。

Examples of ZnR ¹ and MgR ² represented by M ¹ include ZnCl, ZnBr, ZnI, MgCl, MgBr, and MgI. Examples of Sn (R ³ ) ₃ represented by M ¹ include Sn (Me) ₃ and Sn (Bu) ₃ .

Examples of B (OR ⁴ ) ₂ represented by M ¹ include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , and B (OBu) ₂ . Examples of B (OR ⁴ ) ₂ in the case where two R ⁴ are united to form a ring containing an oxygen atom and a boron atom include the following (C-1) to (C-6): The group shown can be illustrated, and the group shown by (C-2) is desirable in that the yield is good.

反応式（１）又は反応式（２）で用いられる、化合物（４）は、例えば、特開２００８−２８０３３０号公報に開示されている方法又は特開２００１−３３５５１６号公報に開示されている方法を用いて製造することができる。化合物（４）中のＭ^２は前記Ｍ^１と同様の置換基を例示する事ができる。化合物（４）としては、次の（Ｄ−１）から（Ｄ−３０）を例示できるが、本発明はこれらに限定されるものではない。

The compound (4) used in the reaction formula (1) or the reaction formula (2) is, for example, a method disclosed in JP 2008-280330 A or a method disclosed in JP 2001-335516 A. Can be used. M ² in the compound (4) can exemplify the same substituent as M ¹ described above. Examples of the compound (4) include the following (D-1) to (D-30), but the present invention is not limited to these.

反応式（３）で用いられる、化合物（６）は、前記化合物（４）のＭ^２をＹ^３に置き換えた化合物を例示することができる。

The compound (6) used in the reaction formula (3) can be exemplified by a compound in which M ² in the compound (4) is replaced with Y ³ .

The compound (8) used in the reaction formula (4) can be exemplified by a compound in which M ¹ of the compound (3) is replaced with Y ⁴ .

Compound represents a leaving group Y ⁴ are each independently of the Y ³ and compounds (6) (8) is not particularly limited, for example, a chlorine atom, a bromine atom, and an iodine atom or a triflate and the like. Among these, a bromine atom or a chlorine atom is preferable in terms of a good reaction yield. However, it may be preferable to use triflate because of the availability of raw materials.

Compounds (2) Y ¹ and Y ² each independently represent a leaving group and are not particularly limited, and examples thereof include a chlorine atom, a bromine atom, an iodine atom, and a triflate. Among these, a bromine atom or a chlorine atom is preferable in terms of a good reaction yield. In order to improve the selectivity of the reaction, it is more preferable that Y ¹ and Y ² have different leaving groups.

  Then, Reaction formula (1) is demonstrated. “Step 1” is a method in which compound (2) is reacted with compound (3) in the presence of a palladium catalyst, optionally in the presence of a base, to obtain compound (9) as a synthetic intermediate. -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield.

  Examples of the palladium catalyst that can be used in “Step 1” include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. In addition, π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro (1,1′-bis (diphenylphosphine). Examples include complex compounds such as fino) ferrocene) palladium. Among these, a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is preferable in terms of a good reaction yield. Particularly preferred.

  A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. The tertiary phosphine that can be used at this time is triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5. -Bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) Biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 ′ -Bis (diphenylphosphino) Erocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl And 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl or triphenylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio between the tertiary phosphine and the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

  Bases that can be used in “Step 1” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, fluorine. Examples thereof include cesium chloride, and potassium carbonate is preferable in terms of a good yield. The molar ratio of base to compound (3) is preferably from 1: 2 to 10: 1, and more preferably from 1: 1 to 3: 1 in terms of good yield.

  The molar ratio of the compound (2) and the compound (3) used in “Step 1” is preferably 1: 2 to 5: 1, and more preferably 1: 2 to 2: 1 in terms of a good yield.

  Examples of the solvent that can be used in “Step 1” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene. You may use it combining suitably. It is desirable to use dioxane or a mixed solvent of THF and water in terms of good yield.

  “Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 50 ° C. to 100 ° C. in terms of a good yield.

  Compound (9) can be obtained by carrying out a usual treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

  “Step 2” is a method in which the compound (9) is reacted with the compound (4) in the presence of a palladium catalyst in the presence of a palladium catalyst to obtain the cyclic azine compound (1) of the present invention. -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield. In “Step 2”, the same reaction conditions as those mentioned in “Step 1” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 1”. Alternatively, compound (4) can be added to the reaction system of “Step 1” and reacted without isolating compound (9), which is a synthetic intermediate, to synthesize cyclic azine compound (1). After completion of “Step 2”, the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  In addition, the compound (9) is excellent for industrially supplying a compound such as the compound (1) that remarkably improves the low driving voltage property, the high light emission efficiency, and the long life property of the organic electroluminescence device. It is an intermediate material for production and is very valuable industrially.

  Then, Reaction formula (2) is demonstrated. “Step 3” is a method in which compound (2) is reacted with compound (4) in the presence of a palladium catalyst, optionally in the presence of a base, to obtain compound (10) as a synthetic intermediate. -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield. In “Step 3”, the same reaction conditions as those mentioned in “Step 1” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 1”. After completion of “Step 3”, the obtained compound (10) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  “Step 4” is a method in which the compound (10) is reacted with the compound (3) in the presence of a palladium catalyst in the presence of a base in some cases to obtain the cyclic azine compound (1) of the present invention. -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield. In “Step 4”, reaction conditions similar to those mentioned in “Step 1” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 1”. Alternatively, compound (3) can be added to the reaction system of “Step 3” and reacted without isolating compound (10), which is a synthetic intermediate, to synthesize cyclic azine compound (1). After completion of “Step 4”, the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  Then, Reaction formula (3) is demonstrated. The compound (5) used in “Step 5” is prepared by using a reaction for synthesizing a general organometallic compound from the compound (9) (for example, Angew. Chem. Int. Ed. 2007, 46, 5359-5363). Can be synthesized. “Step 5” is a method in which the compound (5) is reacted with the compound (6) in the presence of a palladium catalyst in the presence of a base in some cases to obtain the cyclic azine compound (1) of the present invention. -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield.

  Examples of the palladium catalyst that can be used in “Step 5” include the same palladium catalysts as those mentioned in “Step 1”. Among these, a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is preferable in terms of a good reaction yield. Particularly preferred.

  A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. Examples of the tertiary phosphine that can be used in this case include the same tertiary phosphine as that described in “Step 1”. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl or triphenylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio between the tertiary phosphine and the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

  Examples of the base that can be used in “Step 5” include the same bases as those mentioned in “Step 1”. The molar ratio of base to compound (5) is preferably from 1: 2 to 10: 1, and more preferably from 1: 1 to 3: 1 in terms of good yield. The molar ratio of the compound (5) and the compound (6) used in “Step 5” is preferably 1: 5 to 2: 1, and more preferably 1: 1 to 1: 3 in terms of a good yield.

  Examples of the solvent that can be used in “Step 5” include the same solvents as those mentioned in “Step 1”. It is desirable to use dioxane or a mixed solvent of THF and water in terms of good yield. “Step 5” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 50 ° C. to 100 ° C. in terms of a good yield. After completion of “Step 5”, the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  Then, Reaction formula (4) is demonstrated. The compound (7) used in “Step 6” is obtained by using a reaction for synthesizing a general organometallic compound from the compound (10) (for example, Angew. Chem. Int. Ed. 2007, 46, 5359-5363). Can be synthesized. “Step 6” is a method in which the compound (7) is reacted with the compound (8) in the presence of a palladium catalyst in the presence of a palladium catalyst to obtain the cyclic azine compound (1) of the present invention. -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield. In “Step 6”, the same reaction conditions as those described in “Step 5” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 5”. After completion of “Step 6”, the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  In addition, the compound (7) is excellent for industrially supplying a compound such as the compound (1) that remarkably improves the low driving voltage property, the high light emission efficiency, and the long life property of the organic electroluminescence device. It is an intermediate material for production and is very valuable industrially.

  The cyclic azine compound (1) of the present invention is preferably used as a part of the components of the organic electroluminescence device. In particular, when used as an electron transport layer, effects such as longer life, higher efficiency, and lower voltage can be obtained than conventional devices. Moreover, when using the cyclic azine compound (1) of this invention as an organic electroluminescent element material, it is also possible to use it as a co-deposition film | membrane with arbitrary organometallic seeds, an organic compound, or an inorganic compound.

  The cyclic azine compound (1) of the present invention is preferable as a material for an organic thin film layer having an electron transporting property such as a light emitting layer, an electron transporting layer, and an electron injecting layer in an organic electroluminescence device because it exhibits good electron transporting properties. Can be used.

Although there is no restriction | limiting in particular in the manufacturing method of the thin film for organic electroluminescent elements containing the cyclic azine compound (1) of this invention, The film-forming by a vacuum evaporation method is possible. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is determined by taking into account the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device, and commonly used diffusion pumps, turbo molecular pumps, cryopumps, etc. 1 × 10 ⁻² to 1 × 10 ⁻⁶ Pa is preferable, and 1 × 10 ⁻⁴ to 1 × 10 ⁻⁶ Pa is more desirable.

  The deposition rate depends on the thickness of the film to be formed, but is more preferably 0.01 to 0.3 nm / second, but more desirably.

  In addition, since the cyclic azine compound (1) of the present invention has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran or the like, a spin coating method using a general-purpose apparatus, Film formation by an inkjet method, a cast method, a dip method, or the like is also possible.

  A typical structure of the organic electroluminescent element that can obtain the effects of the present invention includes a substrate, an anode, a hole injection layer, a hole transport layer light emitting layer, an electron transport layer, and a cathode.

  The anode and cathode of the organic electroluminescent element are connected to a power source through an electrical conductor. The organic electroluminescent device operates by applying a potential between the anode and the cathode. Holes are injected into the organic electroluminescent device from the anode, and electrons are injected into the organic electroluminescent device at the cathode.

  The organic electroluminescent device is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic electroluminescence device of the present invention is not limited to such a form. The substrate may be light transmissive or opaque, depending on the intended emission direction. Light transmission properties are desirable for viewing electroluminescent emission through a substrate. Transparent glass or plastic is generally employed as such a substrate. The substrate may be a composite structure including multiple material layers.

  If electroluminescent emission is viewed through the anode, the anode should pass or substantially pass the emission. Common transparent anode (anode) materials used in the present invention are indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide, but other metal oxides such as Aluminum or indium doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide are also useful. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode. The anode can be modified with plasma deposited fluorocarbon. For applications where electroluminescent emission is only seen through the cathode, the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium and platinum.

  A hole injection layer can be provided between the anode and the hole transport layer. The hole injection material can serve to improve the film forming properties of the subsequent organic layer and to facilitate injection of holes into the hole transport layer. Examples of materials suitable for use in the hole injection layer include porphyrin compounds, plasma deposited fluorocarbon polymers, and amines having aromatic rings such as biphenyl groups, carbazole groups, such as m-MTDATA (4,4 ' , 4 ″ -tris [(3-methylphenyl) phenylamino] triphenylamine), 2T-NATA (4,4 ′, 4 ″ -tris [(N-naphthalen-2-yl) -N-phenylamino ] Triphenylamine), triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N, N′N′-tetrakis (4-methylphenyl) -1,1′-biphenyl-4,4′-diamine, MeO-TPD N, N, N′N′-tetrakis (4-methoxyphenyl) -1,1′-biphenyl-4,4′-diamine), N, N′-diphenyl-N, N′-dinaphthyl-1,1 ′ -Biphenyl-4,4'-diamine, N, N'-bis (methylphenyl) -N, N'-bis (4-normalbutylphenyl) phenanthrene-9,10-diamine, or N, N'-diphenyl- N, N′-bis (9-phenylcarbazol-3-yl) -1,1′-biphenyl-4,4′-diamine and the like can be mentioned.

  The hole transport layer of the organic electroluminescent device preferably contains one or more hole transport compounds such as aromatic tertiary amines. Aromatic tertiary amine means that the compound contains one or more trivalent nitrogen atoms, the trivalent nitrogen atoms being bonded only to carbon atoms, one or more of these carbon atoms being An aromatic ring is formed. Specifically, the aromatic tertiary amine can be an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine.

  An aromatic tertiary amine having one or more amine groups can be used as the hole transport material. Furthermore, a polymeric hole transport material can be used. For example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, or the like can be used. For example, NPD (N, N′-bis (naphthalen-1-yl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), α-NPD (N, N′-di) (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), TPBi (1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) ) Benzene) or TPD (N, N′-bis (3-methylphenyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine).

  Dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile as a charge generation layer between the hole injection layer and the hole transport layer A layer containing (HAT-CN) may be provided.

  The light emitting layer of the organic electroluminescent element contains a phosphorescent material or a fluorescent material, and in this case, light emission occurs as a result of recombination of electron-hole pairs in this region. The emissive layer may consist of a single material including both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, in which case the emission is mainly from the dopant. Occurs and can have any color.

  Examples of the host material for the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. For example, DPVBi (4,4′-bis (2,2-diphenylvinyl) -1,1′-biphenyl), BCzVBi (4,4′-bis (9-ethyl-3-carbazovinylene) 1,1′-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

  The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, or another material that supports hole-electron recombination, or a combination of these materials.

  Examples of useful fluorescent dopants include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium or thiapyrylium compounds, fluorene derivatives, perifanthene derivatives, indeno Examples include perylene derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

  An example of a useful phosphorescent dopant is an organometallic complex of a transition metal of iridium, platinum, palladium, or osmium.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples include tris (2-phenylpyridine) iridium (III), FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)), and the like.

  The thin film forming material used for forming the electron transport layer of the organic electroluminescence device of the present invention is the cyclic azine compound (1) of the present invention. Note that the electron transporting layer may contain another electron transporting material, and examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Desirable alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolate) gallium, bis (2-methyl-8-quinolina) G) -1-naphthoquinone Trad aluminum or bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance. Preferred compounds for the hole blocking layer include BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 -Methyl-8-quinolinolato) -4- (phenylphenolate) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).

  In the organic electroluminescent device of the present invention, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, low voltage driving, or high durability).

Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, or anthrone. Etc. In addition, the above-described metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO _x , AlO _x , SiN _x , SiON, _{AlON, GeO X, LiO X,} LiON, TiO X, TiON, TaO X, TaON, TaN X, C and various oxides, may be used an inorganic compound such as a nitride, and oxynitride.

If light emission is seen only through the anode, the cathode used in the present invention can be formed from almost any conductive material. Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

It is sectional drawing of the organic electroluminescent element produced by embodiment (element evaluation).

  EXAMPLES Hereinafter, although a synthesis example, a synthesis example, a device example, a reference example, etc. are given and this invention is demonstrated further in detail, this invention is limited to these and is not interpreted.

  Synthesis Example-1

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（１．００ｇ，２．３７ｍｍｏｌ）、１−ジベンゾチオフェンボロン酸（０．５９３ｇ，２．６０ｍｍｏｌ）及びテトラキストリフェニルホスフィンパラジウム（８２．０ｍｇ，０．０７１０ｍｍｏｌ）をトルエン（３０ｍＬ）及びエタノール（３ｍＬ）の混合溶媒に懸濁し、６０℃に加熱した。これに３Ｍ−Ｋ_２ＣＯ_３水溶液（２．３７ｍＬ，７．１０ｍｍｏｌ）をゆっくりと滴下した後、１９時間撹拌した。室温まで放冷後、反応混合物に水（３０ｍＬ）及びメタノール（３０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−クロロ−３−（ジベンゾチオフェン−４−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジンの白色固体（収量０．９１１ｇ，収率７３．２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４７−７．５０（ｍ，２Ｈ），７．５４−７．６５（ｍ，８Ｈ），７．８４−７．８８（ｍ，１Ｈ），７．９４（ｔ，ｄ＝１．９Ｈｚ，１Ｈ），８．２１−８．２５（ｍ，２Ｈ），８．７７（ｄｄ，Ｊ＝８．３Ｈｚ，１．７Ｈｚ，４Ｈ），８．８０（ｄｄ，Ｊ＝２．０Ｈｚ，１．５Ｈｚ，１Ｈ），９．０６（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ）．
合成例−２

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (1.00 g, 2.37 mmol), 1-dibenzothiopheneboronic acid (0.593 g, 2.60 mmol) and tetrakistriphenylphosphine palladium (82.0 mg, 0.0710 mmol) were suspended in a mixed solvent of toluene (30 mL) and ethanol (3 mL), and heated to 60 ° C. A 3M-K ₂ CO ₃ aqueous solution (2.37 mL, 7.10 mmol) was slowly added dropwise thereto, followed by stirring for 19 hours. After cooling to room temperature, water (30 mL) and methanol (30 mL) were added to the reaction mixture, and the precipitate was collected by filtration. The resulting precipitate was purified by recrystallization from toluene, and the target product, 2- [5-chloro-3- (dibenzothiophen-4-yl) phenyl] -4,6-diphenyl-1,3,5- A white solid of triazine (yield 0.911 g, yield 73.2%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.47-7.50 (m, 2H), 7.54-7.65 (m, 8H), 7.84-7.88 (m, 1H) ), 7.94 (t, d = 1.9 Hz, 1H), 8.21-8.25 (m, 2H), 8.77 (dd, J = 8.3 Hz, 1.7 Hz, 4H), 8 .80 (dd, J = 2.0 Hz, 1.5 Hz, 1H), 9.06 (t, J = 1.6 Hz, 1H).
Synthesis Example-2

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（２．１６ｇ，５．１０ｍｍｏｌ）、２−ジベンゾチオフェンボロン酸（１．２８ｇ，５．６１ｍｍｏｌ）及びテトラキストリフェニルホスフィンパラジウム（１７６ｍｇ，０．１５３ｍｍｏｌ）をテトラヒドロフラン（１５０ｍＬ）に懸濁し、これに１Ｍ−Ｋ_２ＣＯ_３水溶液（１５．３ｍＬ，１５．３ｍｍｏｌ）をゆっくりと滴下した。懸濁液を６０℃まで加熱し、１８時間撹拌させて反応させた。反応混合物を室温まで冷却させた後、水を２００ｍＬ加え、得られた析出物をろ取した。得られた析出物をｏ−キシレンによる再結晶によって精製し、目的物である２−［５−クロロ−３−（ジベンゾチオフェン−２−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジンの灰白色固体（収量１．７９ｇ，収率６６．７％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４９−７．５１（ｍ，２Ｈ），７．５６−７．６４（ｍ，６Ｈ），７．８０（ｄｄ，Ｊ＝８．５Ｈｚ，１．８Ｈｚ，１Ｈ），７．８８−７．９１（ｍ，２Ｈ），７．９９（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．２７−８．２９（ｍ，１Ｈ）８．４３（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ），８．７４（ｄｄ，Ｊ＝２．１Ｈｚ，１．４Ｈｚ，１Ｈ）８．７８（ｄｄ，Ｊ＝８．３Ｈｚ，１．８Ｈｚ，４Ｈ）．８．９４（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ）．
合成例−３

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (2.16 g, 5.10 mmol), 2-dibenzothiopheneboronic acid (1.28 g, (5.61 mmol) and tetrakistriphenylphosphine palladium (176 mg, 0.153 mmol) were suspended in tetrahydrofuran (150 mL), and 1M-K ₂ CO ₃ aqueous solution (15.3 mL, 15.3 mmol) was slowly added dropwise thereto. The suspension was heated to 60 ° C. and allowed to react with stirring for 18 hours. After the reaction mixture was cooled to room temperature, 200 mL of water was added, and the resulting precipitate was collected by filtration. The obtained precipitate was purified by recrystallization with o-xylene, and the target product, 2- [5-chloro-3- (dibenzothiophen-2-yl) phenyl] -4,6-diphenyl-1,3, was obtained. An off-white solid of 5-triazine (yield 1.79 g, 66.7% yield) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.49-7.51 (m, 2H), 7.56-7.64 (m, 6H), 7.80 (dd, J = 8.5 Hz) 1.8 Hz, 1H), 7.88-7.91 (m, 2H), 7.99 (d, J = 8.2 Hz, 1H), 8.27-8.29 (m, 1H). 43 (d, J = 1.3 Hz, 1H), 8.74 (dd, J = 2.1 Hz, 1.4 Hz, 1H) 8.78 (dd, J = 8.3 Hz, 1.8 Hz, 4H). 8.94 (t, J = 1.6 Hz, 1H).
Synthesis example-3

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（１４．８ｇ，３４．９ｍｍｏｌ）、４−（２−ピリジル）フェニルボロン酸（９．０４ｇ，４５．４ｍｍｏｌ）及びテトラキストリフェニルホスフィンパラジウム（８０８ｍｇ，０．６９９ｍｍｏｌ）をテトラヒドロフラン（２５０ｍＬ）に懸濁し、６０℃に加熱した。これに１０重量％ＮａＯＨ水溶液（４０ｍＬ，１０５ｍｍｏｌ）をゆっくりと滴下した後、３時間撹拌した。室温まで放冷後、反応混合物に水（９０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの白色固体（収量１５．４ｇ，収率８８．５％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．２７（ｄｄｄ，Ｊ＝５．７Ｈｚ，４．６Ｈｚ，２．３Ｈｚ，１Ｈ），７．５６−７．６５（ｍ，６Ｈ），７．７７−７．８５（ｍ，５Ｈ），８．１６（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．７２−８．７４（ｍ，２Ｈ），８．７７（ｄｄ，Ｊ＝８．２Ｈｚ，１．４Ｈｚ，４Ｈ），８．９２（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ）．
合成実施例−１

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (14.8 g, 34.9 mmol), 4- (2-pyridyl) phenylboronic acid ( 9.04 g, 45.4 mmol) and tetrakistriphenylphosphine palladium (808 mg, 0.699 mmol) were suspended in tetrahydrofuran (250 mL) and heated to 60 ° C. A 10 wt% NaOH aqueous solution (40 mL, 105 mmol) was slowly added dropwise thereto, and the mixture was stirred for 3 hours. After cooling to room temperature, water (90 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by recrystallization with toluene, and the target product, 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3, A white solid of 5-triazine (yield 15.4 g, yield 88.5%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.27 (ddd, J = 5.7 Hz, 4.6 Hz, 2.3 Hz, 1H), 7.56-7.65 (m, 6H), 7 .77-7.85 (m, 5H), 8.16 (d, J = 8.6 Hz, 2H), 8.72-8.74 (m, 2H), 8.77 (dd, J = 8. 2 Hz, 1.4 Hz, 4H), 8.92 (t, J = 1.6 Hz, 1H).
Synthesis Example-1

アルゴン気流下、合成例−１で得られた２−［５−クロロ−３−（ジベンゾチオフェン−４−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（０．５０ｇ，０．９５１ｍｍｏｌ）、４−（２−ピリジル）フェニルボロン酸（０．２４６ｇ，１．２４ｍｍｏｌ）、酢酸パラジウム（６．４０ｍｇ，０．０２８５ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（２７．２ｍｇ，０．０５７０ｍｍｏｌ）及びリン酸カリウム（０．５２４ｇ，２．４７ｍｍｏｌ）をジオキサン（１５ｍＬ）及び水（２ｍＬ）の混合溶媒に懸濁し、７０℃に加熱して１８時間加熱した。室温まで放冷後、反応混合物に水（２０ｍＬ）及びメタノール（２０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−（ジベンゾチオフェン−４−イル）−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−１５７）の白色固体（収量０．６００ｇ，収率９７．９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．２４−７．２９（ｍ，１Ｈ），７．４７−７．５１（ｍ，２Ｈ），７．５４−７．７２（ｍ，８Ｈ），７．７７−７．８８（ｍ，３Ｈ），７．９６（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．１９（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．２３−８．２６（ｍ，２Ｈ），８．２８（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），８．７３（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８０（ｄｄ，Ｊ＝８．３Ｈｚ，１．８Ｈｚ，４Ｈ），９．１２（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ），９．１５（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）． 合成実施例−２

2- [5-chloro-3- (dibenzothiophen-4-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (0.50 g, obtained in Synthesis Example-1 under an argon stream 0.951 mmol), 4- (2-pyridyl) phenylboronic acid (0.246 g, 1.24 mmol), palladium acetate (6.40 mg, 0.0285 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (27.2 mg, 0.0570 mmol) and potassium phosphate (0.524 g, 2.47 mmol) were suspended in a mixed solvent of dioxane (15 mL) and water (2 mL) and heated to 70 ° C. Heated for 18 hours. After allowing to cool to room temperature, water (20 mL) and methanol (20 mL) were added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by recrystallization from toluene, and the target product 2- [5- (dibenzothiophen-4-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4,6 -A white solid (yield 0.600 g, yield 97.9%) of diphenyl-1,3,5-triazine (compound A-157) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.24-7.29 (m, 1H), 7.47-7.51 (m, 2H), 7.54-7.72 (m, 8H) ), 7.77-7.88 (m, 3H), 7.96 (d, J = 8.5 Hz, 2H), 8.19 (d, J = 8.5 Hz, 2H), 8.23-8. .26 (m, 2H), 8.28 (t, J = 1.6 Hz, 1H), 8.73 (d, J = 4.8 Hz, 1H), 8.80 (dd, J = 8.3 Hz, 1.8 Hz, 4H), 9.12 (t, J = 1.7 Hz, 1H), 9.15 (t, J = 1.7 Hz, 1H). Synthesis Example-2

アルゴン気流下、合成例−２で得られた２−［５−クロロ−３−（ジベンゾチオフェン−２−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（０．５０ｇ，０．９５１ｍｍｏｌ）、４−（２−ピリジル）フェニルボロン酸（０．２４６ｇ，１．２４ｍｍｏｌ）、酢酸パラジウム（６．４０ｍｇ，０．０２８５ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（２７．２ｍｇ，０．０５７０ｍｍｏｌ）及び炭酸カリウム（０．３４１ｇ，２．４７ｍｍｏｌ）をジオキサン（１５ｍＬ）及び水（１．３ｍＬ）の混合溶媒に懸濁し、１００℃に加熱して１８時間加熱した。室温まで放冷後、反応混合物に水（２０ｍＬ）及びメタノール（２０ｍＬ）を加え、析出物をろ取した。得られた析出物をシリカゲルクロマトグラフィー（溶離液：クロロホルム及びヘキサンの混合溶媒（クロロホルム：ヘキサン（体積比）＝５０：５０〜１：０のグラジエント））により精製し、目的物である２−［５−（ジベンゾチオフェン−２−イル）−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−１５８）の白色固体（収量０．４７０ｇ，収率７６．６％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．２４−７．２９（ｍ，１Ｈ），７．４９−７．５１（ｍ，２Ｈ），７．５６−７．６４（ｍ，６Ｈ），７．７９（ｔｄ，Ｊ＝７．７Ｈｚ，１．９Ｈｚ，１Ｈ），７．８４（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．８８−７．９１（ｍ，２Ｈ），７．９５（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），８．０２（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．１８−８．２０（ｍ，１Ｈ），８．２０（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．２９−８．３２（ｍ，１Ｈ），８．５３（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ），８．７４（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．０Ｈｚ，１．９Ｈｚ，４Ｈ）．９．０６−９．０７（ｍ，２Ｈ）．
合成実施例−３

Under a stream of argon, 2- [5-chloro-3- (dibenzothiophen-2-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (0.50 g, obtained in Synthesis Example-2) 0.951 mmol), 4- (2-pyridyl) phenylboronic acid (0.246 g, 1.24 mmol), palladium acetate (6.40 mg, 0.0285 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (27.2 mg, 0.0570 mmol) and potassium carbonate (0.341 g, 2.47 mmol) were suspended in a mixed solvent of dioxane (15 mL) and water (1.3 mL), and heated to 100 ° C. And heated for 18 hours. After allowing to cool to room temperature, water (20 mL) and methanol (20 mL) were added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by silica gel chromatography (eluent: mixed solvent of chloroform and hexane (gradient of chloroform: hexane (volume ratio) = 50: 50 to 1: 0)), and the target 2- [ White solid (yield) of 5- (dibenzothiophen-2-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (Compound A-158) 0.470 g, yield 76.6%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.24-7.29 (m, 1H), 7.49-7.51 (m, 2H), 7.56-7.64 (m, 6H) ), 7.79 (td, J = 7.7 Hz, 1.9 Hz, 1H), 7.84 (d, J = 8.1 Hz, 1H), 7.88-7.91 (m, 2H), 7 .95 (d, J = 8.7 Hz, 2H), 8.02 (d, J = 8.2 Hz, 1H), 8.18-8.20 (m, 1H), 8.20 (d, J = 8.4 Hz, 2H), 8.29-8.32 (m, 1H), 8.53 (d, J = 1.6 Hz, 1H), 8.74 (d, J = 4.8 Hz, 1H), 8.81 (dd, J = 8.0 Hz, 1.9 Hz, 4H). 9.06-9.07 (m, 2H).
Synthesis Example-3

アルゴン気流下、合成例−３で得られた２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（１．４９ｇ，３．００ｍｍｏｌ）、２−ベンゾチオフェンボロン酸（０．６９４ｇ，３．９０ｍｍｏｌ）、酢酸パラジウム（１３．５ｍｇ，０．０６００ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（５７．２ｍｇ、０．１２０ｍｍｏｌ）及び炭酸カリウム（１．０８ｇ，７．８０ｍｍｏｌ）をテトラヒドロフラン（２０ｍＬ）及びに水（６．５ｍＬ）の混合溶媒に懸濁し、７０℃で４時間撹拌した。室温まで放冷後、反応混合物に水（２０ｍＬ）及びメタノール（２０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−（ベンゾチオフェン−２−イル）−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−１５９）の白色固体（収量１．７１ｇ，収率９５．８％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．２５−７．２９（ｍ，１Ｈ），７．３４−７．４２（ｍ，２Ｈ），７．５８−７．６６（ｍ，６Ｈ），７．７７−７．９１（ｍ，５Ｈ），７．９２（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．１８−８．２０（ｍ，１Ｈ），８．２０（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．７４（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．０Ｈｚ，１．６Ｈｚ，４Ｈ），９．０１（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），９．１０（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）．
合成実施例−４

Under an argon stream, 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (1. 49 g, 3.00 mmol), 2-benzothiopheneboronic acid (0.694 g, 3.90 mmol), palladium acetate (13.5 mg, 0.0600 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′- Triisopropylbiphenyl (57.2 mg, 0.120 mmol) and potassium carbonate (1.08 g, 7.80 mmol) were suspended in a mixed solvent of tetrahydrofuran (20 mL) and water (6.5 mL), and the mixture was stirred at 70 ° C. for 4 hours. did. After allowing to cool to room temperature, water (20 mL) and methanol (20 mL) were added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by recrystallization from toluene, and the desired product 2- [5- (benzothiophen-2-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4,6 -A white solid (yield 1.71 g, yield 95.8%) of diphenyl-1,3,5-triazine (compound A-159) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.25-7.29 (m, 1H), 7.34-7.42 (m, 2H), 7.58-7.66 (m, 6H) ), 7.77-7.91 (m, 5H), 7.92 (d, J = 8.5 Hz, 2H), 8.18-8.20 (m, 1H), 8.20 (d, J = 8.5 Hz, 2H), 8.74 (d, J = 4.8 Hz, 1H), 8.81 (dd, J = 8.0 Hz, 1.6 Hz, 4H), 9.01 (t, J = 1.6 Hz, 1 H), 9.10 (t, J = 1.7 Hz, 1 H).
Synthesis Example 4

アルゴン気流下、合成例−３で得られた２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（１．４９ｇ，３．００ｍｍｏｌ）、２−ベンゾフランボロン酸（０．６３２ｇ，３．９０ｍｍｏｌ）、酢酸パラジウム（１３．５ｍｇ，０．０６００ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（５７．２ｍｇ、０．１２０ｍｍｏｌ）及び炭酸カリウム（１．０８ｇ，７．８０ｍｍｏｌ）をテトラヒドロフラン（２０ｍＬ）及びに水（６．５ｍＬ）の混合溶媒に懸濁し、７０℃で４時間撹拌した。室温まで放冷後、反応混合物に水（２０ｍＬ）及びメタノール（２０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−（ベンゾフラン−２−イル）−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−３６３）の白色固体（収量１．５６ｇ，収率８９．９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．２４−７．３１（ｍ，３Ｈ），７．３４（ｔ，Ｊ＝７．３Ｈｚ，１Ｈ），７．５９−７．６８（ｍ，８Ｈ），７．８０（ｔ，Ｊ＝７．８Ｈｚ，１Ｈ），７．８４（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），７．９４（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．２０（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．３８（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），８．７５（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８２（ｄｄ，Ｊ＝８．０Ｈｚ，１．５Ｈｚ，４Ｈ），９．０２（ｔ，ｄ＝１．７Ｈｚ，１Ｈ），９．２０（ｔ，ｄ＝１．６Ｈｚ，１Ｈ）．
合成実施例−５

Under an argon stream, 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (1. 49 g, 3.00 mmol), 2-benzofuranboronic acid (0.632 g, 3.90 mmol), palladium acetate (13.5 mg, 0.0600 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri Isopropyl biphenyl (57.2 mg, 0.120 mmol) and potassium carbonate (1.08 g, 7.80 mmol) were suspended in a mixed solvent of tetrahydrofuran (20 mL) and water (6.5 mL), and the mixture was stirred at 70 ° C. for 4 hours. . After allowing to cool to room temperature, water (20 mL) and methanol (20 mL) were added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by recrystallization with toluene, and the target product 2- [5- (benzofuran-2-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4,6- A white solid (yield 1.56 g, yield 89.9%) of diphenyl-1,3,5-triazine (Compound A-363) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.24-7.31 (m, 3H), 7.34 (t, J = 7.3 Hz, 1H), 7.59-7.68 (m 8H), 7.80 (t, J = 7.8 Hz, 1H), 7.84 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 8.5 Hz, 2H), 8 .20 (d, J = 8.6 Hz, 2H), 8.38 (t, J = 1.8 Hz, 1H), 8.75 (d, J = 4.8 Hz, 1H), 8.82 (dd, J = 8.0 Hz, 1.5 Hz, 4H), 9.02 (t, d = 1.7 Hz, 1H), 9.20 (t, d = 1.6 Hz, 1H).
Synthesis Example-5

アルゴン気流下、合成例−３で得られた２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（２．００ｇ，４．０２ｍｍｏｌ）、４−ジベンゾフランボロン酸（１．１１ｇ，５．２３ｍｍｏｌ）、酢酸パラジウム（２７．１ｍｇ，０．１２１ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１１５ｍｇ、０．２４１ｍｍｏｌ）をテトラヒドロフラン（２７．６ｇ）に懸濁し、６０℃に加熱した。これに２０重量％Ｋ_２ＣＯ_３水溶液（５．８ｍＬ，１０．５ｍｍｏｌ）をゆっくりと滴下した後、１時間撹拌した。室温まで放冷後、反応混合物に水（２０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−（ジベンゾフラン−４−イル）−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−３６１）の白色固体（収量１．７５ｇ，収率６９．２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．２４−７．２７（ｍ，１Ｈ），７．３９（ｔ，Ｊ＝７．５Ｈｚ，１Ｈ），７．４９（ｔｄ、Ｊ＝８．５Ｈｚ，１．４Ｈｚ，１Ｈ），７．５２（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．５５−７．６３（ｍ，６Ｈ），７．６５（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ）， ７．７８（ｔｄ，Ｊ＝７．８Ｈｚ，１．８Ｈｚ，１Ｈ），７．８１−７．８４（ｍ，２Ｈ），７．９５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．０１（ｄｄ，Ｊ＝７．７Ｈｚ，１．２Ｈｚ，１Ｈ），８．０３（ｄ，Ｊ＝７．５Ｈｚ，１Ｈ），８．１８（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．４２（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），８．７４（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．０Ｈｚ，１．８Ｈｚ，４Ｈ），９．０８（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ），９．３３（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）．
合成実施例−６

Under an argon stream, 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (2. 00 g, 4.02 mmol), 4-dibenzofuranboronic acid (1.11 g, 5.23 mmol), palladium acetate (27.1 mg, 0.121 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri Isopropyl biphenyl (115 mg, 0.241 mmol) was suspended in tetrahydrofuran (27.6 g) and heated to 60 ° C. A 20 wt% K ₂ CO ₃ aqueous solution (5.8 mL, 10.5 mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. After allowing to cool to room temperature, water (20 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by recrystallization from toluene, and the target product, 2- [5- (dibenzofuran-4-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4,6- A white solid (yield 1.75 g, yield 69.2%) of diphenyl-1,3,5-triazine (compound A-361) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.24-7.27 (m, 1H), 7.39 (t, J = 7.5 Hz, 1H), 7.49 (td, J = 8 .5 Hz, 1.4 Hz, 1 H), 7.52 (t, J = 7.7 Hz, 1 H), 7.55-7.63 (m, 6 H), 7.65 (d, J = 8.0 Hz, 1H), 7.78 (td, J = 7.8 Hz, 1.8 Hz, 1H), 7.81-7.84 (m, 2H), 7.95 (d, J = 8.5 Hz, 2H), 8.01 (dd, J = 7.7 Hz, 1.2 Hz, 1H), 8.03 (d, J = 7.5 Hz, 1H), 8.18 (d, J = 8.5 Hz, 2H), 8 .42 (t, J = 1.8 Hz, 1H), 8.74 (d, J = 4.8 Hz, 1H), 8.81 (dd, J = 8.0 Hz, 1.8 Hz, 4H), 9. 08 (t, J 1.7Hz, 1H), 9.33 (t, J = 1.7Hz, 1H).
Synthesis Example-6

アルゴン気流下、合成例−２で得られた２−［５−クロロ−３−（ジベンゾチオフェン−２−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（３．００ｇ，５．７０ｍｍｏｌ）、６−（２−ナフチル）−３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジン（２．６４ｇ，７．９８ｍｍｏｌ）、酢酸パラジウム（２５．６ｍｇ，０．１１４ｍｍｏｌ）及び２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１０９ｍｇ、０．２２８ｍｍｏｌ）をテトラヒドロフラン（１００ｍＬ）及び２０重量％炭酸カリウム水溶液（１０．２ｇ，１４．８ｍｍｏｌ）の混合溶媒に懸濁し、７０℃で４時間撹拌した。室温まで放冷後、反応混合物に水（１００ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、メタノール（４０ｍ）及びヘキサン（５０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−｛３−（ジベンゾチオフェン−２−イル）−５−［６−（２−ナフチル）ピリジン−３−イル）］フェニル｝−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−４８２）の白色固体（収量２．５５ｇ，収率６４．４％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４９−７．５４（ｍ，４Ｈ），７．５７−７．６６（ｍ，６Ｈ），７．８８−７．９１（ｍ，３Ｈ），８．００（ｄ，Ｊ＝８．９Ｈｚ，２Ｈ），８．０３（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．０８（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．１９（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ），８．２３−８．２６（ｍ，２Ｈ），８．２９−８．３１（ｍ，１Ｈ），８．５３（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ），８．６０（ｄ，Ｊ＝１．１Ｈｚ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．０Ｈｚ，１．８Ｈｚ，４Ｈ），９．１０（ｄｔ，Ｊ＝５．７Ｈｚ，１．４Ｈｚ，２Ｈ），９．２５（ｄｄ，Ｊ＝２．５Ｈｚ，０．８Ｈｚ，１Ｈ）．
合成例−４

Under an argon stream, 2- [5-chloro-3- (dibenzothiophen-2-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (3.00 g, obtained in Synthesis Example-2) 5.70 mmol), 6- (2-naphthyl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (2.64 g, 7.98 mmol), Palladium acetate (25.6 mg, 0.114 mmol) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (109 mg, 0.228 mmol) were added to tetrahydrofuran (100 mL) and a 20 wt% aqueous potassium carbonate solution ( (10.2 g, 14.8 mmol), and the mixture was stirred at 70 ° C. for 4 hours. After allowing to cool to room temperature, water (100 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with methanol (40 m) and hexane (50 mL). The obtained precipitate was purified by recrystallization with toluene, and the target product, 2- {3- (dibenzothiophen-2-yl) -5- [6- (2-naphthyl) pyridin-3-yl)] phenyl } -4,6-diphenyl-1,3,5-triazine (Compound A-482) was obtained as a white solid (yield 2.55 g, yield 64.4%).
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.49-7.54 (m, 4H), 7.57-7.66 (m, 6H), 7.88-7.91 (m, 3H) ), 8.00 (d, J = 8.9 Hz, 2H), 8.03 (d, J = 8.3 Hz, 1H), 8.08 (d, J = 8.4 Hz, 1H), 8.19. (T, J = 1.7 Hz, 1H), 8.23-8.26 (m, 2H), 8.29-8.31 (m, 1H), 8.53 (d, J = 1.3 Hz, 1H), 8.60 (d, J = 1.1 Hz, 1H), 8.81 (dd, J = 8.0 Hz, 1.8 Hz, 4H), 9.10 (dt, J = 5.7 Hz, 1 .4 Hz, 2H), 9.25 (dd, J = 2.5 Hz, 0.8 Hz, 1H).
Synthesis example 4

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（５．００ｇ，１１．８ｍｍｏｌ）、４−ジベンゾフランボロン酸（３．０１ｇ，１４．２ｍｍｏｌ）、炭酸カリウム（４．９０ｇ，３５．５ｍｍｏｌ）及びテトラキストリフェニルホスフィンパラジウム（４１０ｍｇ，０．３５４ｍｍｏｌ）をテトラヒドロフラン（１５０ｍＬ）及び水（３５ｍＬ）の混合溶液に懸濁し、７０℃で１９時間撹拌させて反応させた。反応混合物を室温まで冷却させた後、水を２００ｍＬ加え、得られた析出物をろ取した。得られた析出物をトルエンによる再結晶によって精製し、目的物である２−［５−クロロ−３−（ジベンゾフラン−４−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジンの灰白色固体（収量５．３３ｇ，収率８８．０％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４０（ｄｔ，Ｊ＝７．５Ｈｚ，０．９Ｈｚ，１Ｈ），７．４９−７．５３（ｍ，２Ｈ），７．５５−７．６４（ｍ，６Ｈ），７．６７（ｂｒｄ，Ｊ＝８．３Ｈｚ，１Ｈ），７．７５（ｄｄ，Ｊ＝７．６Ｈｚ，１．３Ｈｚ，１Ｈ），８．０２（ｄ，Ｊ＝７．８Ｈｚ，２Ｈ），８．１６（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），８．７７−８．８１（ｍ，５Ｈ），９．２５（ｔ，Ｊ＝１．５１，１Ｈ）．
合成例−５

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (5.00 g, 11.8 mmol), 4-dibenzofuranboronic acid (3.01 g, 14 .2 mmol), potassium carbonate (4.90 g, 35.5 mmol) and tetrakistriphenylphosphine palladium (410 mg, 0.354 mmol) are suspended in a mixed solution of tetrahydrofuran (150 mL) and water (35 mL), and the mixture is maintained at 70 ° C. for 19 hours. The reaction was allowed to stir. After the reaction mixture was cooled to room temperature, 200 mL of water was added, and the resulting precipitate was collected by filtration. The obtained precipitate was purified by recrystallization from toluene, and the desired 2- [5-chloro-3- (dibenzofuran-4-yl) phenyl] -4,6-diphenyl-1,3,5-triazine Of an off-white solid (yield 5.33 g, yield 88.0%).
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.40 (dt, J = 7.5 Hz, 0.9 Hz, 1H), 7.49-7.53 (m, 2H), 7.55-7 .64 (m, 6H), 7.67 (brd, J = 8.3 Hz, 1H), 7.75 (dd, J = 7.6 Hz, 1.3 Hz, 1H), 8.02 (d, J = 7.8 Hz, 2H), 8.16 (t, J = 1.8 Hz, 1H), 8.77-8.81 (m, 5H), 9.25 (t, J = 1.51, 1H).
Synthesis example-5

窒素気流下、フェナシルピリジニウムブロミド（３．００ｇ，８．４０ｍｍｏｌ）、（Ｅ）−カルコン（１．７５ｇ，８．４０ｍｍｏｌ）、酢酸アンモニウム（３２．３ｇ，４２０ｍｍｏｌ）、酢酸（１２０ｍＬ）及びジメチルホルムアミド（９５ｍＬ）を５００ｍＬ４つ口フラスコに加え、１６０℃で３時間撹拌した。室温まで放冷後、反応混合物に水（３００ｍＬ）を加え、析出物をろ取した。ろ取した析出物を純水で洗浄し、白色粉末を得た。得られた灰白色粉末をトルエン（３０ｍＬ）とメタノール（２５ｍＬ）の混合溶媒で再結晶することにより精製し、２−（４−ブロモフェニル）−４，６−ジフェニルピリジンの灰白色粉末（収量１．１４ｇ，収率３５．２％）を得た。

Under a nitrogen stream, phenacylpyridinium bromide (3.00 g, 8.40 mmol), (E) -chalcone (1.75 g, 8.40 mmol), ammonium acetate (32.3 g, 420 mmol), acetic acid (120 mL) and dimethylformamide (95 mL) was added to a 500 mL four-necked flask and stirred at 160 ° C. for 3 hours. After allowing to cool to room temperature, water (300 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with pure water to obtain a white powder. The resulting off-white powder was purified by recrystallization from a mixed solvent of toluene (30 mL) and methanol (25 mL) to give an off-white powder of 2- (4-bromophenyl) -4,6-diphenylpyridine (yield 1.14 g). Yield 35.2%).

¹ H-NMR (CDCl ₃ ); 8.17 (d, 2H), 8.07 (d, 2H), 7.88 (s, 1H), 7.82 (s, 1H), 7.71 (d , 2H), 7.62 (d, 2H), 7.52-7.44 (m, 6H).
Synthesis Example-6

アルゴン気流下、合成例−５で得られた２−（４−ブロモフェニル）−４，６−ジフェニルピリジン（１ｇ，２．５９ｍｍｏｌ）をテトラヒドロフラン（１３ｍＬ）に溶解させ、−７８℃に冷却した。ここに、２．８５ｍｍｏｌのｎ−ブチルリチウムを含むヘキサン溶液１．７２ｍＬをゆっくり加え、この温度で３０分撹拌した。この混合物にホウ酸トリイソプロピル（０．７７ｍＬ，３．３７ｍｍｏｌ）をゆっくり加え、１時間撹拌した。得られた混合物を室温まで昇温後、１９時間撹拌した。ここに１．５ＮのＮａＯＨ水溶液を４．５ｍＬ滴下し、晶析してきた析出物を濾取した。得られた析出物を水（１５ｍＬ）で洗浄し、白色粉末を得た。得られた白色粉末を真空乾燥させ、４−（４，６−ジフェニルピリジン−２−イル）フェニルボロン酸の白色粉末（収量４８９ｍｇ，収率５３．８％）を得た。

Under an argon stream, 2- (4-bromophenyl) -4,6-diphenylpyridine (1 g, 2.59 mmol) obtained in Synthesis Example-5 was dissolved in tetrahydrofuran (13 mL) and cooled to -78 ° C. To this, 1.72 mL of a hexane solution containing 2.85 mmol of n-butyllithium was slowly added and stirred at this temperature for 30 minutes. To this mixture, triisopropyl borate (0.77 mL, 3.37 mmol) was slowly added and stirred for 1 hour. The resulting mixture was warmed to room temperature and stirred for 19 hours. 4.5 mL of 1.5N NaOH aqueous solution was dripped here, and the deposit which crystallized was filtered. The obtained precipitate was washed with water (15 mL) to obtain a white powder. The obtained white powder was vacuum dried to obtain white powder of 4- (4,6-diphenylpyridin-2-yl) phenylboronic acid (yield 489 mg, yield 53.8%).

  Synthesis Example-7

アルゴン気流下、合成例−４で得られた２−［５−クロロ−３−（ジベンゾフラン−４−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（２．００ｇ，３．９２ｍｍｏｌ）、合成例−６で得られた４−（４，６−ジフェニルピリジン−２−イル）フェニルボロン酸（１．９８ｇ，５．６５ｍｍｏｌ）、酢酸パラジウム（８．８０ｍｇ，０．０３９ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（３７．３ｍｇ、０．０７８ｍｍｏｌ）及び炭酸カリウム（１．６３ｇ，１１．８ｍｍｏｌ）をテトラヒドロフラン（５０ｍＬ）及び水（１１ｍＬ）の混合溶媒に懸濁し、７０℃で１７時間撹拌した。室温まで放冷後、反応混合物に水（１００ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（３０ｍＬ）、メタノール（３０ｍ）及びヘキサン（３０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−（ジベンゾフラン−４−イル）−４’−（４，６−ジフェニルピリジン−２−イル）−ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−４７１）の白色固体（収量２．５５ｇ，収率６４．４％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４０（ｄｄｄ，Ｊ＝７．４Ｈｚ，７．４Ｈｚ，０．９Ｈｚ，１Ｈ），７．４４−７．６４（ｍ，１４Ｈ），７．６７（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．７８（ｄｄ，Ｊ＝８．３Ｈｚ，１．２Ｈｚ，２Ｈ），７．８５（ｄｄ，Ｊ＝７．６Ｈｚ，１．２Ｈｚ，１Ｈ），７．９２（ｄ，Ｊ＝１．４Ｈｚ，１Ｈ），７．９９−８．０５（ｍ，５Ｈ），８．２５（ｄｄ，Ｊ＝８．３Ｈｚ，１．４Ｈｚ，２Ｈ），８．４１（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．４６（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ），８．８３（ｄｄ，Ｊ＝８．１Ｈｚ，１．９Ｈｚ，４Ｈ），９．１２（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），９．３５（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）．
合成例７

Under an argon stream, 2- [5-chloro-3- (dibenzofuran-4-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (2.00 g, 3) obtained in Synthesis Example-4 .92 mmol), 4- (4,6-diphenylpyridin-2-yl) phenylboronic acid (1.98 g, 5.65 mmol) obtained in Synthesis Example-6, palladium acetate (8.80 mg, 0.039 mmol) 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (37.3 mg, 0.078 mmol) and potassium carbonate (1.63 g, 11.8 mmol) in tetrahydrofuran (50 mL) and water (11 mL) And the mixture was stirred at 70 ° C. for 17 hours. After allowing to cool to room temperature, water (100 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (30 mL), methanol (30 m) and hexane (30 mL). The obtained precipitate was purified by recrystallization from toluene, and the desired product 2- [5- (dibenzofuran-4-yl) -4 ′-(4,6-diphenylpyridin-2-yl) -biphenyl-3 was obtained. -Il] -4,6-diphenyl-1,3,5-triazine (Compound A-471) was obtained as a white solid (yield 2.55 g, yield 64.4%).
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.40 (ddd, J = 7.4 Hz, 7.4 Hz, 0.9 Hz, 1H), 7.44-7.64 (m, 14H), 7 .67 (d, J = 8.2 Hz, 1H), 7.78 (dd, J = 8.3 Hz, 1.2 Hz, 2H), 7.85 (dd, J = 7.6 Hz, 1.2 Hz, 1H) ), 7.92 (d, J = 1.4 Hz, 1H), 7.9-8.05 (m, 5H), 8.25 (dd, J = 8.3 Hz, 1.4 Hz, 2H), 8 .41 (d, J = 8.5 Hz, 2H), 8.46 (t, J = 1.7 Hz, 1H), 8.83 (dd, J = 8.1 Hz, 1.9 Hz, 4H), 9. 12 (t, J = 1.6 Hz, 1H), 9.35 (t, J = 1.7 Hz, 1H).
Synthesis example 7

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（２５．０ｇ，５９．１ｍｍｏｌ）、３−ピリジンボロン酸（１２．０ｇ，９７．６ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（２．０５ｇ，１．７７ｍｍｏｌ）及び炭酸カリウム（２４．５ｇ，１７７ｍｍｏｌ）を、テトラヒドロフラン（５００ｍＬ）及び水（１７７ｍＬ）の混合溶媒に懸濁し、７０℃に加熱して１８時間撹拌した。撹拌した後、反応溶媒を留去し、クロロホルム及び水を加えて再度溶解させた。有機層のみを取り出し、硫酸マグネシウムを加えて脱水した後、ろ過した。得られた有機層の低沸点成分を留去して得られた灰白色固体を、トルエンによる再結晶により精製し、目的物である２−［５−クロロ−３−（３−ピリジル）フェニル］−４，６−ジフェニル−１，３，５−トリアジンの灰白色固体（収量２２．６ｇ，収率９０．９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：７．４５（ｄｄ，Ｊ＝７．６Ｈｚ，４．８Ｈｚ，１Ｈ），７．５６−７．６５（ｍ，６Ｈ），７．７８（ｔ，Ｊ＝１．９Ｈｚ，１Ｈ），７．９９（ｄ，Ｊ＝７．９Ｈｚ，１Ｈ），８．６８（ｄｄ，Ｊ＝４．８Ｈｚ，１．６Ｈｚ，１Ｈ），８．７４−８．７６（ｍ，１Ｈ），８．７６（ｄ，Ｊ＝６．５Ｈｚ，４Ｈ），８．８６（ｂｒｓ，１Ｈ），８．９９（ｄ，Ｊ＝２．２Ｈｚ，１Ｈ）．
合成例−８

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (25.0 g, 59.1 mmol), 3-pyridineboronic acid (12.0 g, 97 .6 mmol), tetrakistriphenylphosphine palladium (2.05 g, 1.77 mmol) and potassium carbonate (24.5 g, 177 mmol) are suspended in a mixed solvent of tetrahydrofuran (500 mL) and water (177 mL) and heated to 70 ° C. And stirred for 18 hours. After stirring, the reaction solvent was distilled off, and chloroform and water were added and dissolved again. Only the organic layer was taken out, dehydrated by adding magnesium sulfate, and then filtered. An off-white solid obtained by distilling off the low-boiling components of the obtained organic layer was purified by recrystallization with toluene, and the desired product 2- [5-chloro-3- (3-pyridyl) phenyl]- An off-white solid (yield 22.6 g, yield 90.9%) of 4,6-diphenyl-1,3,5-triazine was obtained.
¹ H-NMR (CDCl ₃ ): 7.45 (dd, J = 7.6 Hz, 4.8 Hz, 1H), 7.56-7.65 (m, 6H), 7.78 (t, J = 1) .9 Hz, 1H), 7.9 (d, J = 7.9 Hz, 1H), 8.68 (dd, J = 4.8 Hz, 1.6 Hz, 1H), 8.74-8.76 (m, 1H), 8.76 (d, J = 6.5 Hz, 4H), 8.86 (brs, 1H), 8.99 (d, J = 2.2 Hz, 1H).
Synthesis Example-8

アルゴン気流下、２−ジベンゾチオフェンボロン酸（３．００ｇ，１３．２ｍｍｏｌ）、ｐ−ブロモクロロベンゼン（２．５１ｇ，１３．２ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（４５６ｍｇ，０．３９４ｍｍｏｌ）及び炭酸カリウム（５．４５ｇ，３９．５ｍｍｏｌ）をテトラヒドロフラン（７９ｍＬ）及び水（３９ｍＬ）の混合溶媒に懸濁し、７０℃で１７時間撹拌した。室温まで放冷後、反応混合物に水（１００ｍＬ）及びクロロホルム（２００ｍＬ）を加えた。得られた混合物を振り混ぜた後、有機層のみを取り出した。得られた有機層を硫酸マグネシウムで脱水した後、低沸点成分を留去した。得られた生成物を、シリカゲルクロマトグラフィー（溶離液＝ヘキサン）により精製し、目的物である２−（４−クロロフェニル）ジベンゾチオフェンの白色固体（収量３．２９ｇ，収率８４．９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：７．４４（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．４５−７．４８（ｍ，２Ｈ），７．６２（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．６２−７．６５（ｍ，１Ｈ），７．８６（ｄｄｄ，Ｊ＝５．９Ｈｚ，３．３Ｈｚ，０．７Ｈｚ，１Ｈ），７．９０（ｄｄ，Ｊ＝８．３Ｈｚ，０．５Ｈｚ，１Ｈ），８．２０（ｄｄｄ，Ｊ＝５．８Ｈｚ，３．３Ｈｚ，０．５Ｈｚ，１Ｈ），８．２９（ｄｄ，Ｊ＝２．０Ｈｚ，０．５Ｈｚ，１Ｈ）．
合成例−９

Under a stream of argon, 2-dibenzothiopheneboronic acid (3.00 g, 13.2 mmol), p-bromochlorobenzene (2.51 g, 13.2 mmol), tetrakistriphenylphosphine palladium (456 mg, 0.394 mmol) and potassium carbonate ( 5.45 g, 39.5 mmol) was suspended in a mixed solvent of tetrahydrofuran (79 mL) and water (39 mL), and the mixture was stirred at 70 ° C. for 17 hours. After cooling to room temperature, water (100 mL) and chloroform (200 mL) were added to the reaction mixture. After the obtained mixture was shaken and mixed, only the organic layer was taken out. The obtained organic layer was dehydrated with magnesium sulfate, and then the low boiling point component was distilled off. The obtained product was purified by silica gel chromatography (eluent = hexane), and a white solid (yield 3.29 g, yield 84.9%) of 2- (4-chlorophenyl) dibenzothiophene as the target product was obtained. Obtained.
¹ H-NMR (CDCl ₃ ): 7.44 (d, J = 8.7 Hz, 2H), 7.45-7.48 (m, 2H), 7.62 (d, J = 8.7 Hz, 2H) ), 7.62-7.65 (m, 1H), 7.86 (ddd, J = 5.9 Hz, 3.3 Hz, 0.7 Hz, 1H), 7.90 (dd, J = 8.3 Hz, 0.5Hz, 1H), 8.20 (ddd, J = 5.8Hz, 3.3Hz, 0.5Hz, 1H), 8.29 (dd, J = 2.0Hz, 0.5Hz, 1H).
Synthesis Example-9

アルゴン気流下、合成例−８で得られた２−（４−クロロフェニル）ジベンゾチオフェン（１．００ｇ，３．３９ｍｍｏｌ）、ビス（ピナコラート）ジボロン（１．０３ｇ，４．０７ｍｍｏｌ）、酢酸パラジウム（１５．２ｍｇ，０．０６７ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（６４．７ｍｇ、０．０１３５ｍｍｏｌ）及び酢酸カリウム（０．９９８ｇ，１０．２ｍｍｏｌ）を１，４−ジオキサン（１０ｍＬ）に懸濁し、１００℃で２４時間撹拌した。室温まで放冷後、反応混合物に水（２０ｍＬ）及びクロロホルム（５０ｍＬ）を加えた。得られた混合物を振り混ぜた後、有機層のみを取り出した。得られた有機層を硫酸マグネシウムで脱水した後、低沸点成分を留去した。得られた生成物を、シリカゲルクロマトグラフィー（溶離液＝クロロホルム／ヘキサンの混合溶液）により精製し、目的物である２−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］ジベンゾチオフェンの白色固体（収量１．２３ｇ，収率９３．９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：１．３６（ｓ，１２Ｈ），７．４５−７．４７（ｍ，２Ｈ），７．６９−７．７３（ｍ，３Ｈ），７．８３−７．８７（ｍ，１Ｈ），７．９０（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．９２（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．２０−８．２４（ｍ，１Ｈ），８．３６（ｂｒｄ，Ｊ＝１．４Ｈｚ，１Ｈ）．
合成実施例−８

Under an argon stream, 2- (4-chlorophenyl) dibenzothiophene (1.00 g, 3.39 mmol), bis (pinacolato) diboron (1.03 g, 4.07 mmol), palladium acetate (15) obtained in Synthesis Example-8. .2 mg, 0.067 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (64.7 mg, 0.0135 mmol) and potassium acetate (0.998 g, 10.2 mmol) Suspended in 4-dioxane (10 mL) and stirred at 100 ° C. for 24 hours. After cooling to room temperature, water (20 mL) and chloroform (50 mL) were added to the reaction mixture. After the obtained mixture was shaken and mixed, only the organic layer was taken out. The obtained organic layer was dehydrated with magnesium sulfate, and then the low boiling point component was distilled off. The obtained product was purified by silica gel chromatography (eluent = chloroform / hexane mixed solution), and the desired product 2- [4- (4,4,5,5-tetramethyl-1,3, was obtained. A white solid (yield 1.23 g, yield 93.9%) of 2-dioxaborolan-2-yl) phenyl] dibenzothiophene was obtained.
¹ H-NMR (CDCl ₃ ): 1.36 (s, 12H), 7.45-7.47 (m, 2H), 7.69-7.73 (m, 3H), 7.83-7. 87 (m, 1H), 7.90 (d, J = 8.1 Hz, 1H), 7.92 (d, J = 8.3 Hz, 2H), 8.20-8.24 (m, 1H), 8.36 (brd, J = 1.4 Hz, 1H).
Synthesis Example-8

アルゴン気流下、合成例−７で得られた２−［５−クロロ−３−（３−ピリジル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（３００ｍｇ，０．７１ｍｍｏｌ）、合成例−９で得られた２−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］ジベンゾチオフェン（３３０ｍｇ，０．８６ｍｍｏｌ）、酢酸パラジウム（１．６０ｍｇ，０．００７１ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（６．８ｍｇ、０．０１４ｍｍｏｌ）及び炭酸カリウム（２９５ｍｇ，２．１４ｍｍｏｌ）をテトラヒドロフラン（５ｍＬ）及び水（２ｍＬ）の混合溶媒に懸濁し、７０℃で１８時間撹拌した。室温まで放冷後、反応混合物に水（１０ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（１０ｍＬ）、メタノール（１０ｍ）及びヘキサン（１０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［４’−（２−ジベンゾチオフェン）−５−（３−ピリジル）−ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−５４５）の白色固体（収量４１４ｍｇ，収率９０．２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４６−７．５２（ｍ，３Ｈ），７．５７−７．６６（ｍ，６Ｈ），７．７９（ｄｄ，Ｊ＝８．３Ｈｚ，１．９Ｈｚ，１Ｈ），７．８７−７．９６（ｍ，６Ｈ），８．０８（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），８．１１（ｄｄｄ，Ｊ＝７．８Ｈｚ，２．３Ｈｚ，１．６Ｈｚ，１Ｈ），８．２５−８．２７（ｍ，１Ｈ），８．４４（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ），８．７０（ｄｄ，Ｊ＝４．８Ｈｚ，１．６Ｈｚ，１Ｈ），８．８０（ｄｄ，Ｊ＝８．３Ｈｚ，１．８Ｈｚ，４Ｈ），８．９９（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），９．１０（ｔ，Ｊ＝１．７Ｈｚ，２Ｈ）．
合成例−１０

2- [5-chloro-3- (3-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (300 mg, 0.71 mmol) obtained in Synthesis Example-7 under an argon stream, 2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] dibenzothiophene (330 mg, 0.86 mmol) obtained in Synthesis Example-9, acetic acid Palladium (1.60 mg, 0.0071 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (6.8 mg, 0.014 mmol) and potassium carbonate (295 mg, 2.14 mmol) were added to tetrahydrofuran. (5 mL) and water (2 mL) were suspended in a mixed solvent, and the mixture was stirred at 70 ° C. for 18 hours. After allowing to cool to room temperature, water (10 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (10 mL), methanol (10 m) and hexane (10 mL). The resulting precipitate was purified by recrystallization from toluene, and the target product, 2- [4 ′-(2-dibenzothiophene) -5- (3-pyridyl) -biphenyl-3-yl] -4,6- A white solid (yield 414 mg, yield 90.2%) of diphenyl-1,3,5-triazine (compound A-545) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.46-7.52 (m, 3H), 7.57-7.66 (m, 6H), 7.79 (dd, J = 8.3 Hz) , 1.9 Hz, 1H), 7.87-7.96 (m, 6H), 8.08 (t, J = 1.8 Hz, 1H), 8.11 (ddd, J = 7.8 Hz, 2. 3 Hz, 1.6 Hz, 1 H), 8.25-8.27 (m, 1 H), 8.44 (d, J = 1.6 Hz, 1 H), 8.70 (dd, J = 4.8 Hz, 1 .6 Hz, 1H), 8.80 (dd, J = 8.3 Hz, 1.8 Hz, 4H), 8.99 (t, J = 1.6 Hz, 1H), 9.10 (t, J = 1. 7Hz, 2H).
Synthesis Example-10

合成例−８と同様な反応条件及び方法で、目的物である５−クロロ−２−（２−ナフチル）ピリジンを合成した。

The target product, 5-chloro-2- (2-naphthyl) pyridine, was synthesized under the same reaction conditions and method as in Synthesis Example-8.

  Synthesis Example-11

アルゴン気流下、５−クロロ−２−（２−ナフチル）ピリジン（２．５５ｇ，１０．６ｍｍｏｌ）、ビス（ピナコラート）ジボロン（２．９７ｇ，１１．７ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（２９１ｍｇ，０．３８１ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（４５５ｍｇ、０．９５４ｍｍｏｌ）及び酢酸カリウム（３．１２ｇ，３１．８ｍｍｏｌ）を１，４−ジオキサン（４０ｍＬ）に懸濁し、８０℃で１７時間撹拌した。室温まで放冷後、反応混合物に水（５０ｍＬ）を加え、晶析してきた析出物を濾過した。得られた濾過物を、水（５０ｍＬ）によって洗浄し、目的の６−（２−ナフチル）−３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジンの白色固体（収量３．３５ｇ，収率９５．４％）を得た。

Under an argon stream, 5-chloro-2- (2-naphthyl) pyridine (2.55 g, 10.6 mmol), bis (pinacolato) diboron (2.97 g, 11.7 mmol), tris (dibenzylideneacetone) dipalladium ( 291 mg, 0.381 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (455 mg, 0.954 mmol) and potassium acetate (3.12 g, 31.8 mmol) in 1,4-dioxane (40 mL) and stirred at 80 ° C. for 17 hours. After allowing to cool to room temperature, water (50 mL) was added to the reaction mixture, and the crystallized precipitate was filtered. The filtrate obtained was washed with water (50 mL) and the desired 6- (2-naphthyl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl ) A white solid of pyridine (yield 3.35 g, yield 95.4%) was obtained.

  Synthesis Example-9

アルゴン気流下、合成例−４で得られた２−［５−クロロ−３−（ジベンゾフラン−４−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（３．００ｇ，５．８８ｍｍｏｌ）、合成例−１１で得られた６−（２−ナフチル）−３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジン（２．５３ｇ，７．６５ｍｍｏｌ）、酢酸パラジウム（３９．６ｍｇ，０．１７６ｍｍｏｌ）及び２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１６８ｍｇ、０．３５３ｍｍｏｌ）をテトラヒドロフラン（６０ｍＬ）及び２０重量％炭酸カリウム水溶液（１０．６ｇ，１５．３ｍｍｏｌ）の混合溶媒に懸濁し、７５℃で２時間撹拌した。室温まで放冷後、反応混合物に水（１００ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、メタノール（３０ｍ）及びヘキサン（５０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−｛３−（ジベンゾフラン−４−イル）−５−［６−（２−ナフチル）ピリジン−３−イル）］フェニル｝−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−４９３）の白色固体（収量３．６５，収率９１．５％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４８−７．５４（ｍ，４Ｈ），７．５７−７．６５（ｍ，６Ｈ），７．８８−７．９１（ｍ，３Ｈ），７．９８−８．００（ｍ，２Ｈ），８．０３（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．０８（ｄｄ，Ｊ＝８．３Ｈｚ，０．８Ｈｚ，１Ｈ），８．１９（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），８．２３−８．２６（ｍ，２Ｈ），８．２９−８．３３（ｍ，１Ｈ），８．５３（ｂｒｄ，Ｊ＝１．６Ｈｚ，１Ｈ），８．６０（ｂｒｓ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．１Ｈｚ，１．８Ｈｚ，４Ｈ），９．０９−９．１１（ｍ，２Ｈ），９．２５（ｄｄ，Ｊ＝２．４Ｈｚ，０．８Ｈｚ，１Ｈ）．
合成実施例−１０

Under an argon stream, 2- [5-chloro-3- (dibenzofuran-4-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (3.00 g, 5) obtained in Synthesis Example-4 .88 mmol), 6- (2-naphthyl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine obtained in Synthesis Example-11 (2. 53 g, 7.65 mmol), palladium acetate (39.6 mg, 0.176 mmol) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (168 mg, 0.353 mmol) in tetrahydrofuran (60 mL) and The suspension was suspended in a mixed solvent of a 20 wt% aqueous potassium carbonate solution (10.6 g, 15.3 mmol) and stirred at 75 ° C. for 2 hours. After allowing to cool to room temperature, water (100 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with methanol (30 m) and hexane (50 mL). The obtained precipitate was purified by recrystallization with toluene, and the target product, 2- {3- (dibenzofuran-4-yl) -5- [6- (2-naphthyl) pyridin-3-yl)] phenyl} A white solid (yield 3.65, yield 91.5%) of -4,6-diphenyl-1,3,5-triazine (Compound A-493) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.48-7.54 (m, 4H), 7.57-7.65 (m, 6H), 7.88-7.91 (m, 3H) ), 7.98-8.00 (m, 2H), 8.03 (d, J = 8.3 Hz, 1H), 8.08 (dd, J = 8.3 Hz, 0.8 Hz, 1H), 8 .19 (t, J = 1.8 Hz, 1H), 8.23-8.26 (m, 2H), 8.29-8.33 (m, 1H), 8.53 (brd, J = 1. 6 Hz, 1H), 8.60 (brs, 1H), 8.81 (dd, J = 8.1 Hz, 1.8 Hz, 4H), 9.09-9.11 (m, 2H), 9.25 ( dd, J = 2.4 Hz, 0.8 Hz, 1H).
Synthesis Example-10

アルゴン気流下、合成例−４で得られた２−［５−クロロ−３−（ジベンゾフラン−４−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（２．００ｇ，３．９２ｍｍｏｌ）、１−ピレンボロン酸（１．１６ｇ，４．７１ｍｍｏｌ）、酢酸パラジウム（８．８１ｍｇ，０．０３９ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（３７．４ｍｇ、０．０７８ｍｍｏｌ）及び炭酸カリウム（１．６３ｇ，１１．８ｍｍｏｌ）をテトラヒドロフラン（６７ｍＬ）及び水（１１ｍＬ）の混合溶媒に懸濁し、７０℃で１９時間撹拌した。室温まで放冷後、反応混合物に水（１００ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（４０ｍＬ）、メタノール（４０ｍ）及びヘキサン（４０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［３−（ジベンゾフラン−４−イル）−５−（１−ピレニル）−フェニル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−３３７）の白色固体（収量２．１８ｇ，収率８２．２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．３８（ｄｄｄ，Ｊ＝７．５Ｈｚ，７．５Ｈｚ，０．９Ｈｚ，１Ｈ），７．４６−７．６１（ｍ，８Ｈ），７．６５（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），７．８８（ｄｄ，Ｊ＝７．８Ｈｚ，１．２Ｈｚ，１Ｈ），８．０３（ｄ，Ｊ＝７．４Ｈｚ，２Ｈ），８．０３−８．０５（ｍ，１Ｈ），８．１２（ｄ，Ｊ＝９．４Ｈｚ，１Ｈ），８．１５（ｄ，Ｊ＝３．３Ｈｚ，２Ｈ），８．２０−８．２４（ｍ，３Ｈ），８．３４（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．４３（ｄ，Ｊ＝９．０Ｈｚ，１Ｈ），８．４６（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），７．８０（ｄｄ，Ｊ＝８．５Ｈｚ，１．６Ｈｚ，４Ｈ），９．０７（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）．９．４９（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）．
合成実施例−１１

Under an argon stream, 2- [5-chloro-3- (dibenzofuran-4-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (2.00 g, 3) obtained in Synthesis Example-4 .92 mmol), 1-pyreneboronic acid (1.16 g, 4.71 mmol), palladium acetate (8.81 mg, 0.039 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (37 .4 mg, 0.078 mmol) and potassium carbonate (1.63 g, 11.8 mmol) were suspended in a mixed solvent of tetrahydrofuran (67 mL) and water (11 mL), and the mixture was stirred at 70 ° C. for 19 hours. After allowing to cool to room temperature, water (100 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (40 mL), methanol (40 m) and hexane (40 mL). The obtained precipitate was purified by recrystallization from toluene, and the target product, 2- [3- (dibenzofuran-4-yl) -5- (1-pyrenyl) -phenyl] -4,6-diphenyl-1, A white solid (yield 2.18 g, yield 82.2%) of 3,5-triazine (compound A-337) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.38 (ddd, J = 7.5 Hz, 7.5 Hz, 0.9 Hz, 1 H), 7.46-7.61 (m, 8H), 7 .65 (d, J = 8.3 Hz, 1H), 7.88 (dd, J = 7.8 Hz, 1.2 Hz, 1H), 8.03 (d, J = 7.4 Hz, 2H), 8. 03-8.05 (m, 1H), 8.12 (d, J = 9.4 Hz, 1H), 8.15 (d, J = 3.3 Hz, 2H), 8.20-8.24 (m 3H), 8.34 (d, J = 7.8 Hz, 1H), 8.43 (d, J = 9.0 Hz, 1H), 8.46 (t, J = 1.8 Hz, 1H), 7 .80 (dd, J = 8.5 Hz, 1.6 Hz, 4H), 9.07 (t, J = 1.7 Hz, 1H). 9.49 (t, J = 1.7 Hz, 1H).
Synthesis Example-11

アルゴン気流下、合成例−２で得られた２−［５−クロロ−３−（ジベンゾチオフェン−２−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（３００ｍｇ，０．５７ｍｍｏｌ）、９−フェナントレンボロン酸（１５８ｍｇ，０．６９ｍｍｏｌ）、酢酸パラジウム（２．５９ｍｇ，０．０１１ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１１．０ｍｇ、０．０２３ｍｍｏｌ）及び炭酸カリウム（２３９ｍｇ，１．７３ｍｍｏｌ）をテトラヒドロフラン（５ｍＬ）及び水（１．７ｍＬ）の混合溶媒に懸濁し、７０℃で４時間撹拌した。室温まで放冷後、反応混合物に水（１５ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（１０ｍＬ）、メタノール（２０ｍ）及びヘキサン（２０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［３−（ジベンゾチオフェン−２−イル）−５−（９−フェナントリル）−フェニル］３，５−ジフェニル−１，３，５−トリアジン（化合物Ａ−１１０）の白色固体（収量３７７ｍｇ，収率９７．９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４６−７．５０（ｍ，２Ｈ），７．５２−７．６２（ｍ，７Ｈ），７．６６（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．７２（ｔ，Ｊ＝７．８Ｈｚ，２Ｈ），７．８７−７．８９（ｍ，１Ｈ），７．９１（ｓ，１Ｈ），７．９３（ｄｄ，Ｊ＝８．３Ｈｚ，１．７Ｈｚ，１Ｈ），７．９８（ｂｔｄ，７．８Ｈｚ，１Ｈ），８．０１（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．０５（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．１２（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），８．２５−８．２７（ｍ，１Ｈ），８．５４（ｂｒｄ，Ｊ＝１．４Ｈｚ，１Ｈ），８．７６−８．７９（ｍ，５Ｈ），８．８４（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．９５（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），９．１９（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）．
合成例−１２

Under a stream of argon, 2- [5-chloro-3- (dibenzothiophen-2-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (300 mg, 0.3 g) obtained in Synthesis Example-2. 57 mmol), 9-phenanthreneboronic acid (158 mg, 0.69 mmol), palladium acetate (2.59 mg, 0.011 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (11.0 mg) , 0.023 mmol) and potassium carbonate (239 mg, 1.73 mmol) were suspended in a mixed solvent of tetrahydrofuran (5 mL) and water (1.7 mL), and the mixture was stirred at 70 ° C. for 4 hours. After allowing to cool to room temperature, water (15 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (10 mL), methanol (20 m) and hexane (20 mL). The obtained precipitate was purified by recrystallization from toluene, and the desired product 2- [3- (dibenzothiophen-2-yl) -5- (9-phenanthryl) -phenyl] 3,5-diphenyl-1, A white solid (yield 377 mg, yield 97.9%) of 3,5-triazine (compound A-110) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.46-7.50 (m, 2H), 7.52-7.62 (m, 7H), 7.66 (t, J = 7.7 Hz) , 1H), 7.72 (t, J = 7.8 Hz, 2H), 7.87-7.89 (m, 1H), 7.91 (s, 1H), 7.93 (dd, J = 8 .3 Hz, 1.7 Hz, 1 H), 7.98 (btd, 7.8 Hz, 1 H), 8.01 (d, J = 8.2 Hz, 1 H), 8.05 (d, J = 8.2 Hz, 1H), 8.12 (t, J = 1.8 Hz, 1H), 8.25-8.27 (m, 1H), 8.54 (brd, J = 1.4 Hz, 1H), 8.76- 8.79 (m, 5H), 8.84 (d, J = 8.3 Hz, 1H), 8.95 (t, J = 1.6 Hz, 1H), 9.19 (t, J = 1.7 Hz) , 1H).
Synthesis example-12

アルゴン気流下、４−ジベンゾフランボロン酸（１．６２ｇ，７．６５ｍｍｏｌ）、ｐ−ブロモクロロベンゼン（１．４６ｇ，７．６５ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（２６５ｍｇ，０．２２９ｍｍｏｌ）及び炭酸カリウム（３．１７ｇ，２３．０ｍｍｏｌ）をテトラヒドロフラン（４４ｍＬ）及び水（２２ｍＬ）の混合溶媒に懸濁し、７０℃で１８時間撹拌した。室温まで放冷後、反応混合物に水（１００ｍＬ）及びクロロホルム（２００ｍＬ）を加えた。得られた混合物を振り混ぜた後、有機層のみを取り出した。得られた有機層を硫酸マグネシウムで脱水した後、低沸点成分を留去した。得られた生成物を、シリカゲルクロマトグラフィー（溶離液＝ヘキサン）により精製し、目的物である４−（４−クロロフェニル）ジベンゾフランの白色固体（収量２．０６ｇ，収率９６．６％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：７．３５（ｄｔ，Ｊ＝７．３Ｈｚ，１．０Ｈｚ，１Ｈ），７．４１（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．４５（ｄｄ，Ｊ＝８．３Ｈｚ，１．４Ｈｚ，１Ｈ），７．４９（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），７．５５（ｄｄ，Ｊ＝７．７Ｈｚ，１．３Ｈｚ，１Ｈ），７．５８（ｂｒｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．８４（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），７．９４（ｄｄ，Ｊ＝７．７Ｈｚ，１．３Ｈｚ，１Ｈ），７．９８（ｄｄｄ，Ｊ＝７．７Ｈｚ，１．４Ｈｚ，０．７Ｈｚ，１Ｈ）．
合成例−１３

Under a stream of argon, 4-dibenzofuranboronic acid (1.62 g, 7.65 mmol), p-bromochlorobenzene (1.46 g, 7.65 mmol), tetrakistriphenylphosphine palladium (265 mg, 0.229 mmol) and potassium carbonate (3 .17 g, 23.0 mmol) was suspended in a mixed solvent of tetrahydrofuran (44 mL) and water (22 mL), and stirred at 70 ° C. for 18 hours. After cooling to room temperature, water (100 mL) and chloroform (200 mL) were added to the reaction mixture. After the obtained mixture was shaken and mixed, only the organic layer was taken out. The obtained organic layer was dehydrated with magnesium sulfate, and then the low boiling point component was distilled off. The obtained product was purified by silica gel chromatography (eluent = hexane) to obtain a white solid (yield 2.06 g, yield 96.6%) of 4- (4-chlorophenyl) dibenzofuran which was the target product. It was.
¹ H-NMR (CDCl ₃ ): 7.35 (dt, J = 7.3 Hz, 1.0 Hz, 1H), 7.41 (t, J = 7.7 Hz, 1H), 7.45 (dd, J = 8.3 Hz, 1.4 Hz, 1 H), 7.49 (d, J = 8.8 Hz, 2 H), 7.55 (dd, J = 7.7 Hz, 1.3 Hz, 1 H), 7.58 ( brd, J = 8.2 Hz, 1H), 7.84 (d, J = 8.8 Hz, 2H), 7.94 (dd, J = 7.7 Hz, 1.3 Hz, 1H), 7.98 (ddd , J = 7.7 Hz, 1.4 Hz, 0.7 Hz, 1 H).
Synthesis Example-13

アルゴン気流下、２−［５−クロロ−３−（３−ピリジル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（１０．０ｇ，２３．８ｍｍｏｌ）、ビス（ピナコラト）ジボロン（９．０７ｇ，３５．７ｍｍｏｌ），酢酸カリウム（７．０１ｇ，７１．４ｍｍｏｌ）、酢酸パラジウム（５３．４ｍｇ，０．２３８ｍｍｏｌ）及び２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（２２７ｍｇ，０．４７６ｍｍｏｌ）を１，４−ジオキサン（４００ｍＬ）に懸濁し、１００℃に加熱して１８時間撹拌した。次いで、反応溶液にクロロホルム５００ｍＬ及び水１００ｍＬ加えて振り混ぜ、有機層のみを取り出した。有機層に硫酸マグネシウムを加えて脱水し、ろ過した。得られた有機層の低沸点成分を留去した後、１５０ｍＬのクロロホルムに溶解させた。これに１０００ｍＬのヘキサンを加えて１時間撹拌し、生成した析出物をろ取することにより、目的の４，６−ジフェニル−２−［３−（３−ピリジル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］−１，３，５−トリアジンの白色固体（９．５８ｇ，収率７８．６％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：１．４２（ｓ，１２Ｈ），７．４３（ｄｄｄ，Ｊ＝７．８Ｈｚ，４．８Ｈｚ，０．７Ｈｚ，１Ｈ），７．５６−７．６４（ｍ，６Ｈ），８．０６（ｄｄｄ，Ｊ＝７．８Ｈｚ，２．３Ｈｚ，１．６Ｈｚ，１Ｈ），８．２３（ｄｄ，Ｊ＝２．１Ｈｚ，１．０Ｈｚ，１Ｈ），８．６５（ｄｄ，Ｊ＝４．９Ｈｚ，１．６Ｈｚ，１Ｈ），８．７９（ｄｄ，Ｊ＝８．０Ｈｚ，１．４Ｈｚ，４Ｈ），９．０４（ｄｄ，Ｊ＝２．５Ｈｚ，０．８Ｈｚ，１Ｈ），９．０８（ｔ，Ｊ＝１．９Ｈｚ，１Ｈ），９．１６（ｄｄ，Ｊ＝１．７Ｈｚ，１．１Ｈｚ，１Ｈ）．
合成実施例−１２

Under an argon stream, 2- [5-chloro-3- (3-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (10.0 g, 23.8 mmol), bis (pinacolato) diboron ( 9.07 g, 35.7 mmol), potassium acetate (7.01 g, 71.4 mmol), palladium acetate (53.4 mg, 0.238 mmol) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropyl. Biphenyl (227 mg, 0.476 mmol) was suspended in 1,4-dioxane (400 mL), heated to 100 ° C. and stirred for 18 hours. Next, 500 mL of chloroform and 100 mL of water were added to the reaction solution and shaken to remove only the organic layer. Magnesium sulfate was added to the organic layer for dehydration and filtered. After distilling off low-boiling components of the obtained organic layer, it was dissolved in 150 mL of chloroform. 1000 mL of hexane was added thereto and stirred for 1 hour, and the resulting precipitate was collected by filtration to obtain the desired 4,6-diphenyl-2- [3- (3-pyridyl) -5- (4,4,4). A white solid (9.58 g, yield 78.6%) of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1,3,5-triazine was obtained.
¹ H-NMR (CDCl ₃ ): 1.42 (s, 12H), 7.43 (ddd, J = 7.8 Hz, 4.8 Hz, 0.7 Hz, 1H), 7.56-7.64 (m , 6H), 8.06 (ddd, J = 7.8 Hz, 2.3 Hz, 1.6 Hz, 1H), 8.23 (dd, J = 2.1 Hz, 1.0 Hz, 1H), 8.65 ( dd, J = 4.9 Hz, 1.6 Hz, 1H), 8.79 (dd, J = 8.0 Hz, 1.4 Hz, 4H), 9.04 (dd, J = 2.5 Hz, 0.8 Hz, 1H), 9.08 (t, J = 1.9 Hz, 1H), 9.16 (dd, J = 1.7 Hz, 1.1 Hz, 1H).
Synthesis Example-12

アルゴン気流下、合成例−１３で得られた４，６−ジフェニル−２−［３−（３−ピリジル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］−１，３，５−トリアジン（３．００ｇ，５．８５ｍｍｏｌ）、合成例−１２で得られた４−（４−クロロフェニル）ジベンゾフラン（１．９６ｇ，７．０３ｍｍｏｌ）、酢酸パラジウム（１３．１ｍｇ，０．０５８ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（５５．８ｍｇ、０．１１７ｍｍｏｌ）及び炭酸カリウム（２．４３ｇ，１７．６ｍｍｏｌ）をテトラヒドロフラン（４５ｍＬ）及び水（１７ｍＬ）の混合溶媒に懸濁し、７０℃で１９時間撹拌した。室温まで放冷後、反応混合物に水（１００ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（３０ｍＬ）、メタノール（３０ｍ）及びヘキサン（３０ｍＬ）にて洗浄した。得られた析出物をシリカゲルクロマトグラフィー（溶離液＝クロロホルム／ヘキサン）により精製し、目的物である２−［４’−（４−ジベンゾフラン）−５−（３−ピリジル）−ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−５５６）の白色固体（収量２．３８ｇ，収率５８．８％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．３８（ｄｔ，Ｊ＝７．３Ｈｚ，０．９Ｈｚ，１Ｈ），７．４５−７．５１（ｍ，３Ｈ），７．５８−７．６６（ｍ，７Ｈ），７．７０（ｄｄ，Ｊ＝７．７Ｈｚ，１．２Ｈｚ，１Ｈ），７．９６−７．９９（ｍ，３Ｈ），８．０１（ｄｄｄ，Ｊ＝７．８Ｈｚ，１．４Ｈｚ，０．６Ｈｚ，１Ｈ），８．０９−８．１３（ｍ，４Ｈ），８．７０（ｄｄ，Ｊ＝４．８Ｈｚ，１．７Ｈｚ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．１Ｈｚ，１．９Ｈｚ，４Ｈ），９．００（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），９．１０（ｄｄ，Ｊ＝２．５Ｈｚ，０．８Ｈｚ，１Ｈ），９．１２（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ）．
合成例−１４

Under a stream of argon, 4,6-diphenyl-2- [3- (3-pyridyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane] obtained in Synthesis Example-13 2-yl) phenyl] -1,3,5-triazine (3.00 g, 5.85 mmol), 4- (4-chlorophenyl) dibenzofuran (1.96 g, 7.03 mmol) obtained in Synthesis Example-12 , Palladium acetate (13.1 mg, 0.058 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (55.8 mg, 0.117 mmol) and potassium carbonate (2.43 g, 17. 6 mmol) was suspended in a mixed solvent of tetrahydrofuran (45 mL) and water (17 mL), and the mixture was stirred at 70 ° C. for 19 hours. After allowing to cool to room temperature, water (100 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (30 mL), methanol (30 m) and hexane (30 mL). The resulting precipitate was purified by silica gel chromatography (eluent = chloroform / hexane), and the desired product 2- [4 ′-(4-dibenzofuran) -5- (3-pyridyl) -biphenyl-3-yl ] -4,6-diphenyl-1,3,5-triazine (Compound A-556) was obtained as a white solid (yield 2.38 g, yield 58.8%).
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.38 (dt, J = 7.3 Hz, 0.9 Hz, 1H), 7.45-7.51 (m, 3H), 7.58-7 .66 (m, 7H), 7.70 (dd, J = 7.7 Hz, 1.2 Hz, 1H), 7.96-7.99 (m, 3H), 8.01 (ddd, J = 7. 8 Hz, 1.4 Hz, 0.6 Hz, 1 H), 8.09-8.13 (m, 4 H), 8.70 (dd, J = 4.8 Hz, 1.7 Hz, 1 H), 8.81 (dd , J = 8.1 Hz, 1.9 Hz, 4H), 9.00 (t, J = 1.6 Hz, 1H), 9.10 (dd, J = 2.5 Hz, 0.8 Hz, 1H), 9. 12 (t, J = 1.6 Hz, 1H).
Synthesis Example-14

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（８．４６ｇ，２０．０ｍｍｏｌ）、４−ビフェニルボロン酸（４．３６ｇ，２２．０ｍｍｏｌ）及びテトラキストリフェニルホスフィンパラジウム（４６２ｍｇ，０．４０ｍｍｏｌ）をテトラヒドロフラン（１００ｍＬ）に懸濁させ、これに４ＮのＮａＯＨ水溶液（１５．０ｍＬ，６０ｍｍｏｌ）を３分間かけて滴下した。得られた混合物を７５℃で１６時間撹拌した。室温まで放冷後、反応混合物に水（１５０ｍＬ）を加え、析出物をろ取した。得られた固体を水、メタノール、及びヘキサンで洗浄した。個体を再結晶（トルエン）することにより、目的物である２−（５−クロロ−１，１’：４’，１’’−テルフェニル−３−イル）−４，６−ジフェニル−１，３，５−トリアジンの白色固体（収量９．４８ｇ，収率９５．６％）を得た。

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (8.46 g, 20.0 mmol), 4-biphenylboronic acid (4.36 g, 22) 0.0 mmol) and tetrakistriphenylphosphine palladium (462 mg, 0.40 mmol) were suspended in tetrahydrofuran (100 mL), and 4N NaOH aqueous solution (15.0 mL, 60 mmol) was added dropwise thereto over 3 minutes. The resulting mixture was stirred at 75 ° C. for 16 hours. After allowing to cool to room temperature, water (150 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The obtained solid was washed with water, methanol, and hexane. By recrystallizing the solid (toluene), the target product 2- (5-chloro-1,1 ′: 4 ′, 1 ″ -terphenyl-3-yl) -4,6-diphenyl-1, A white solid of 3,5-triazine (yield 9.48 g, yield 95.6%) was obtained.

  Synthesis Example-13

アルゴン気流下、合成例１４で得られた２−（５−クロロ−１，１’：４’，１’’−テルフェニル−３−イル）−４，６−ジフェニル−１，３，５−トリアジン（１．２７ｇ、２．５６ｍｍｏｌ）、２−ジベンゾチオフェンボロン酸（７００ｍｇ、３．０７ｍｍｏｌ）、酢酸パラジウム（１１．５ｍｇ、０．０５１１ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（４８．７ｍｇ、０．１０２ｍｍｏｌ）及び炭酸カリウム（１．０６ｇ、７．６７ｍｍｏｌ）をテトラヒドロフラン（３５ｍＬ）及び水（７ｍＬ）の混合溶媒に懸濁し、７０℃で１９時間撹拌した。室温まで放冷後、反応混合物に水（３０ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（３０ｍＬ）、メタノール（３０ｍＬ）及びヘキサン（３０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−（ジベンゾチオフェン−２−イル）−［１，１’：４’，１’’］−テルフェニル−３−イル］−４，６−ジフェル−１，３，５−トリアジン（Ａ−９８）の白色固体（収量１．１９ｇ、収率７２．２％）を得た。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ（ｐｐｍ）：７．３８（ｔ，Ｊ＝７．５Ｈｚ，１Ｈ），７．４７−７．５２（ｍ，４Ｈ），７．５７−７．６４（ｍ，６Ｈ），７．７０（ｄｄ，Ｊ＝８．５Ｈｚ，１．４Ｈｚ，２Ｈ），７．７９（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．８９−７．９３（ｍ，４Ｈ），８．０２（ｄｄ，Ｊ＝８．３Ｈｚ，０．４Ｈｚ，１Ｈ），８．１２（ｔ，Ｊ＝１．８Ｈｚ，１Ｈ），８．２９−８．３１（ｍ，１Ｈ），８．５２（ｄ，Ｊ＝１．４Ｈｚ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．０Ｈｚ，１．９Ｈｚ，４Ｈ），９．０６（ｄ，Ｊ＝１．８Ｈｚ，２Ｈ）．
合成実施例−１４

2- (5-Chloro-1,1 ′: 4 ′, 1 ″ -terphenyl-3-yl) -4,6-diphenyl-1,3,5-obtained in Synthesis Example 14 under an argon stream Triazine (1.27 g, 2.56 mmol), 2-dibenzothiopheneboronic acid (700 mg, 3.07 mmol), palladium acetate (11.5 mg, 0.0511 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (48.7 mg, 0.102 mmol) and potassium carbonate (1.06 g, 7.67 mmol) were suspended in a mixed solvent of tetrahydrofuran (35 mL) and water (7 mL), and the mixture was stirred at 70 ° C. for 19 hours. . After allowing to cool to room temperature, water (30 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (30 mL), methanol (30 mL) and hexane (30 mL). The obtained precipitate was purified by recrystallization from toluene, and the target 2- [5- (dibenzothiophen-2-yl)-[1,1 ′: 4 ′, 1 ″]-terphenyl-3 was obtained. -Il] -4,6-Difel-1,3,5-triazine (A-98) was obtained as a white solid (yield 1.19 g, yield 72.2%).
1H-NMR (CDCl3) δ (ppm): 7.38 (t, J = 7.5 Hz, 1H), 7.47-7.52 (m, 4H), 7.57-7.64 (m, 6H) ), 7.70 (dd, J = 8.5 Hz, 1.4 Hz, 2H), 7.79 (d, J = 8.3 Hz, 2H), 7.89-7.93 (m, 4H), 8 .02 (dd, J = 8.3 Hz, 0.4 Hz, 1H), 8.12 (t, J = 1.8 Hz, 1H), 8.29-8.31 (m, 1H), 8.52 ( d, J = 1.4 Hz, 1H), 8.81 (dd, J = 8.0 Hz, 1.9 Hz, 4H), 9.06 (d, J = 1.8 Hz, 2H).
Synthesis Example-14

アルゴン気流下、合成例１で得られた２−［５−クロロ−３−（ジベンゾチオフェン−４−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（１．５０ｇ、２．８５ｍｍｏｌ）、６−フェニル−３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジン（９６２ｍｇ、３．４２ｍｍｏｌ）、酢酸パラジウム（１２．８ｍｇ、０．０５７０ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（５４．３ｍｇ、０．１１４ｍｍｏｌ）及び炭酸カリウム（１．１８ｇ、８．５５ｍｍｏｌ）をテトラヒドロフラン（ＴＨＦ）（３５０ｍＬ）及び水（９ｍＬ）の混合溶媒に懸濁し、７０℃で２時間撹拌した。続いて、酢酸パラジウム（１２．８ｍｇ、０．０５７０ｍｍｏｌ）、及び２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（５４．３ｍｇ、０．１１４ｍｍｏｌ）をＴＨＦ（５ｍＬ）に溶解させた溶液を反応溶液に加え、７０℃で１９時間撹拌した。室温まで放冷後、反応混合物に水（１５０ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（１００ｍＬ）、メタノール（１００ｍ）及びヘキサン（１００ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［３−（ジベンゾチオフェン−２−イル）−５−（６−フェニルピリジン−３−イル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（Ａ−４２６）の白色固体（収量１．９６ｇ、収率８９．０％）を得た。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ（ｐｐｍ）：７．４５−７．６３（ｍ，１１Ｈ），７．８９−７．９２（ｍ，２Ｈ），７．９３（ｄｄ，Ｊ＝８．３Ｈｚ，０．９Ｈｚ，１Ｈ），８．０３（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），８．１１（ｄｄ，Ｊ＝８．５Ｈｚ，１．４Ｈｚ，２Ｈ），８．１７（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），８．２１（ｄｄ，Ｊ＝８．４Ｈｚ，２．４Ｈｚ，１Ｈ），８．２９−８．３２（ｍ，１Ｈ），８．５３（ｄｄ，Ｊ＝１．８Ｈｚ，０．４Ｈｚ，１Ｈ），８．８１（ｄｄ，Ｊ＝８．２Ｈｚ，１．８Ｈｚ，４Ｈ），９．０８（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ），９．１１（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ），９．２０（ｄｄ，Ｊ＝２．５Ｈｚ，０．８Ｈｚ，１Ｈ）．
合成例−１５

Under an argon stream, 2- [5-chloro-3- (dibenzothiophen-4-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (1.50 g, 2 obtained in Synthesis Example 1) .85 mmol), 6-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (962 mg, 3.42 mmol), palladium acetate (12.8 mg, 0.0570 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (54.3 mg, 0.114 mmol) and potassium carbonate (1.18 g, 8.55 mmol) in tetrahydrofuran (THF) ( 350 mL) and water (9 mL), and the mixture was stirred at 70 ° C. for 2 hours. Subsequently, palladium acetate (12.8 mg, 0.0570 mmol) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (54.3 mg, 0.114 mmol) are dissolved in THF (5 mL). The solution was added to the reaction solution and stirred at 70 ° C. for 19 hours. After allowing to cool to room temperature, water (150 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (100 mL), methanol (100 m) and hexane (100 mL). The obtained precipitate was purified by recrystallization with toluene, and the target product 2- [3- (dibenzothiophen-2-yl) -5- (6-phenylpyridin-3-yl) phenyl] -4,6 -A white solid (yield 1.96 g, yield 89.0%) of diphenyl-1,3,5-triazine (A-426) was obtained.
1H-NMR (CDCl3) δ (ppm): 7.45-7.63 (m, 11H), 7.89-7.92 (m, 2H), 7.93 (dd, J = 8.3 Hz, 0 .9 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 8.11 (dd, J = 8.5 Hz, 1.4 Hz, 2H), 8.17 (t, J = 1. 6 Hz, 1 H), 8.21 (dd, J = 8.4 Hz, 2.4 Hz, 1 H), 8.29-8.32 (m, 1 H), 8.53 (dd, J = 1.8 Hz, 0 .4 Hz, 1H), 8.81 (dd, J = 8.2 Hz, 1.8 Hz, 4H), 9.08 (t, J = 1.6 Hz, 1H), 9.11 (t, J = 1. 7 Hz, 1H), 9.20 (dd, J = 2.5 Hz, 0.8 Hz, 1H).
Synthesis Example-15

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（１０．０ｇ，２３．７３ｍｍｏｌ）、合成例−６で得られた４−（４，６−ジフェニルピリジン−２−イル）フェニルボロン酸（１０．０ｇ，２８．５ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（８２３ｍｇ，０．７１１ｍｍｏｌ）及び炭酸カリウム（９．８４ｇ，７１．２ｍｍｏｌ）を、テトラヒドロフラン（２６１ｍＬ）及び水（７１ｍＬ）の混合溶媒に懸濁した。得られた混合物を７０℃で２３時間撹拌した。放冷後、水（５００ｍＬ）を加え、析出した固体を濾別し、水、メタノール、ヘキサンで固体を洗浄した後、再結晶（トルエン）することで、目的中間体である２−［５−クロロ−４’−（４，６−ジフェニルピリジン−２−イル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの灰白色固体（収量１３．７ｇ、収率８９．１％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７，４４−７．６５（ｍ，１２Ｈ），７．７７（ｄｄ，Ｊ＝８．４Ｈｚ，１．４Ｈｚ，２Ｈ），７．８５−７．８８（ｍ，３Ｈ），７．９２（ｄ，Ｊ＝１．４Ｈｚ，１Ｈ），７．９７（ｄ，Ｊ＝１．４Ｈｚ，１Ｈ），８．２３（ｂｒｄ，Ｊ＝７．２Ｈｚ，２Ｈ），８．３８（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．７４（ｄｄ，Ｊ＝２．０Ｈｚ，１．５Ｈｚ，１Ｈ），８．７９（ｄｄ，Ｊ＝８．０Ｈｚ，１．８Ｈｚ，４Ｈ），８．９５（ｔ，Ｊ＝１．６Ｈｚ，１Ｈ）．
合成実施例−１５

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (10.0 g, 23.73 mmol), 4- (obtained in Synthesis Example-6) 4,6-diphenylpyridin-2-yl) phenylboronic acid (10.0 g, 28.5 mmol), tetrakis (triphenylphosphine) palladium (823 mg, 0.711 mmol) and potassium carbonate (9.84 g, 71.2 mmol) Was suspended in a mixed solvent of tetrahydrofuran (261 mL) and water (71 mL). The resulting mixture was stirred at 70 ° C. for 23 hours. After standing to cool, water (500 mL) was added, the precipitated solid was filtered off, washed with water, methanol and hexane, and then recrystallized (toluene) to give the target intermediate 2- [5- Chloro-4 ′-(4,6-diphenylpyridin-2-yl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (yield 13.7 g, yield 89.). 1%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7, 44-7.65 (m, 12H), 7.77 (dd, J = 8.4 Hz, 1.4 Hz, 2H), 7.85-7 .88 (m, 3H), 7.92 (d, J = 1.4 Hz, 1H), 7.97 (d, J = 1.4 Hz, 1H), 8.23 (brd, J = 7.2 Hz, 2H), 8.38 (d, J = 8.4 Hz, 2H), 8.74 (dd, J = 2.0 Hz, 1.5 Hz, 1H), 8.79 (dd, J = 8.0 Hz, 1 .8 Hz, 4H), 8.95 (t, J = 1.6 Hz, 1H).
Synthesis Example-15

アルゴン気流下、合成例１５で得られた２−［５−クロロ−４’−（４，６−ジフェニルピリジン−２−イル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（１．５０ｇ、２．３１ｍｍｏｌ）、２−ジベンゾチオフェンボロン酸（６３２ｍｇ、２．７７ｍｍｏｌ）、酢酸パラジウム（１０．４ｍｇ、０．０４６２ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（４４．０ｍｇ、０．０９２４ｍｍｏｌ）及び炭酸カリウム（９５８ｍｇ、６．９３ｍｍｏｌ）をテトラヒドロフラン（７０ｍＬ）及び水（７ｍＬ）の混合溶媒に懸濁し、７０℃で２０時間撹拌した。室温まで放冷後、反応混合物に水（５０ｍＬ）を加え、析出物をろ取した。ろ取した析出物を、水（５０ｍＬ）、メタノール（５０ｍＬ）及びヘキサン（５０ｍＬ）にて洗浄した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−［５−（ジベンゾチオフェン−２−イル）−４’−（４，６−ジフェニルピリジン−２−イル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（Ａ−４２３）の白色固体（収量１．３３ｇ、収率７２．１％）を得た。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ（ｐｐｍ）：７．４９−７．５１（ｍ，２Ｈ），７．５７−７．６３（ｍ，１３Ｈ），７．８３−７．９３（ｍ，４Ｈ），８．０１−８．１８（ｍ，６Ｈ），８．２４（ｂｒｓ，１Ｈ），８．３３−８．３６（ｍ，３Ｈ），８．５５（ｂｒｓ，１Ｈ），８．８２（ｄｄ，Ｊ＝７．９Ｈｚ，１．８Ｈｚ，４Ｈ），９．０８（ｂｒｓ，１Ｈ），９．１０（ｂｒｓ，１Ｈ）．
素子評価に用いた化合物の構造式及びその略称を以下に示す。

2- [5-Chloro-4 ′-(4,6-diphenylpyridin-2-yl) biphenyl-3-yl] -4,6-diphenyl-1,3, obtained in Synthesis Example 15 under an argon stream 5-triazine (1.50 g, 2.31 mmol), 2-dibenzothiopheneboronic acid (632 mg, 2.77 mmol), palladium acetate (10.4 mg, 0.0462 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′ , 6′-triisopropylbiphenyl (44.0 mg, 0.0924 mmol) and potassium carbonate (958 mg, 6.93 mmol) were suspended in a mixed solvent of tetrahydrofuran (70 mL) and water (7 mL) and stirred at 70 ° C. for 20 hours. . After allowing to cool to room temperature, water (50 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with water (50 mL), methanol (50 mL) and hexane (50 mL). The obtained precipitate was purified by recrystallization with toluene, and the target product 2- [5- (dibenzothiophen-2-yl) -4 ′-(4,6-diphenylpyridin-2-yl) biphenyl-3 was obtained. A white solid (yield 1.33 g, yield 72.1%) of -yl] -4,6-diphenyl-1,3,5-triazine (A-423) was obtained.
1H-NMR (CDCl3) δ (ppm): 7.49-7.51 (m, 2H), 7.57-7.63 (m, 13H), 7.83-7.93 (m, 4H), 8.01-8.18 (m, 6H), 8.24 (brs, 1H), 8.33-8.36 (m, 3H), 8.55 (brs, 1H), 8.82 (dd, J = 7.9 Hz, 1.8 Hz, 4H), 9.08 (brs, 1H), 9.10 (brs, 1H).
The structural formulas and abbreviations of the compounds used for device evaluation are shown below.

素子実施例−１
基板には、２ｍｍ幅の酸化インジウム−スズ（ＩＴＯ）膜がストライプ状にパターンされたＩＴＯ透明電極付きガラス基板を用いた。この基板をイソプロピルアルコールで洗浄した後、オゾン紫外線洗浄にて表面処理を行った。洗浄後の基板に、真空蒸着法で各層の真空蒸着を行い、断面図を図１に示すような発光面積４ｍｍ^２有機電界発光素子を作製した。なお、各有機材料は抵抗加熱方式により成膜した。

Element Example-1
As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG. Each organic material was formed by a resistance heating method.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa.

  Then, as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. 1, a hole injection layer 2, a charge generation layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and an electron injection layer 7 and the cathode layer 8 were both deposited in this order, and were formed by vacuum deposition.

  As the hole injection layer 2, a sublimated HIL film having a thickness of 65 nm was formed at a rate of 0.15 nm / second.

  As the charge generation layer 3, sublimation-purified HAT was deposited to a thickness of 5 nm at a rate of 0.05 nm / second.

  As the hole transport layer 4, HTL was formed to a thickness of 10 nm at a rate of 0.15 nm / second.

  As the light emitting layer 5, EML-1 and EML-2 were formed to a thickness of 25 nm at a ratio of 95: 5 (weight ratio) (deposition rate of 0.18 nm / second).

  As the electron transport layer 6, 2- [5- (dibenzothiophen-4-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4, obtained in Synthesis Example-1 of the present invention, A film of 6-diphenyl-1,3,5-triazine (Compound A-157) and Liq was formed at a ratio of 50:50 (weight ratio) to 30 nm (co-evaporation, film formation rate of 0.15 nm / second).

  Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 7 was formed. The cathode layer 7 is formed of silver / magnesium (weight ratio 1/10) and silver in this order at 80 nm (film formation rate 0.5 nm / second) and 20 nm (film formation rate 0.2 nm / second), respectively. And it was set as the 2 layer structure.

  Each film thickness was measured with a stylus type film thickness meter (DEKTAK).

Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.
Element Example-2
In Device Example-1, 2- [5- (dibenzothiophen-2-yl) -4 ′-(2-pyridyl) biphenyl-3-yl]-obtained in Synthesis Example-2 on the electron transport layer 6 was used. An organic electroluminescent element was produced in the same manner as in Example 1 except that 4,6-diphenyl-1,3,5-triazine (Compound A-158) was used.
Element Example-3
In Device Example-1, 2- [5- (dibenzofuran-4-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4, synthesized in Synthesis Example-5 on the electron transport layer 6, An organic electroluminescent element was produced in the same manner as in Example 1 except that 6-diphenyl-1,3,5-triazine (Compound A-361) was used.
Element Example 4
In Device Example-1, 2- {3- (dibenzothiophen-2-yl) -5- [6- (2-naphthyl) pyridin-3-yl] synthesized in Synthesis Example-6 on the electron transport layer 6 ] An organic electroluminescence device was prepared in the same manner as in Device Example 1 except that phenyl} -4,6-diphenyl-1,3,5-triazine (Compound A-482) was used.
Element Example-5
In device example-1, 2- [5- (dibenzofuran-4-yl) -4 ′-(4,6-diphenylpyridin-2-yl) -biphenyl- synthesized in Synthesis example-7 in the electron transport layer 6 An organic electroluminescence device was prepared in the same manner as in Device Example 1 except that 3-yl] -4,6-diphenyl-1,3,5-triazine (Compound A-471) was used.
Element Example-6
In Device Example-1, 2- [4 ′-(2-dibenzothiophene) -5- (3-pyridyl) -biphenyl-3-yl] -4, synthesized in Synthesis Example-8 on the electron transport layer 6, An organic electroluminescent element was prepared in the same manner as in Example 1 except that 6-diphenyl-1,3,5-triazine (Compound A-545) was used.
Element Example-7
In Device Example-1, 2- {3- (dibenzofuran-4-yl) -5- [6- (2-naphthyl) pyridin-3-yl)] synthesized in Synthesis Example-9 on the electron transport layer 6 An organic electroluminescent device was produced in the same manner as in Device Example 1 except that phenyl} -4,6-diphenyl-1,3,5-triazine (Compound A-493) was used.
Element Example-8
In Device Example-1, 2- [4 ′-(4-dibenzofuran) -5- (3-pyridyl) -biphenyl-3-yl] -4,6 synthesized in Synthesis Example-12 on the electron transport layer 6 -An organic electroluminescent element was prepared in the same manner as in Example 1 except that diphenyl-1,3,5-triazine (Compound A-556) was used.
Element Example-9
In Device Example-1, 2- [5- (benzothiophen-2-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4 synthesized in Synthesis Example-3 on the electron transport layer 6 An organic electroluminescent device was prepared in the same manner as in Device Example 1 except that 1,6-diphenyl-1,3,5-triazine (Compound A-159) was used.
Element Example-10
In Device Example-1, 2- [5- (benzofuran-2-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4, synthesized in Synthesis Example-4 on the electron transport layer 6, An organic electroluminescent device was prepared in the same manner as in Device Example 1 except that 6-diphenyl-1,3,5-triazine (Compound A-363) was used.
Element Example-11
In Device Example-1, 2- [3- (dibenzothiophen-2-yl) -5- (9-phenanthryl) -phenyl] 3,5-diphenyl- synthesized in Synthesis Example-11 on the electron transport layer 6 An organic electroluminescent element was produced in the same manner as in Example 1 except that 1,3,5-triazine (Compound A-110) was used.
Element Example-12
In Device Example-1, 2- [5- (dibenzothiophen-2-yl) -4 ′-(4,6-diphenylpyridin-2-yl) biphenyl synthesized in Synthesis Example-15 on the electron transport layer 6 An organic electroluminescent device was prepared in the same manner as in Device Example 1 except that -3-yl] -4,6-diphenyl-1,3,5-triazine (Compound A-423) was used.
Element Example-13
In Device Example-1, 2- [3- (dibenzothiophen-2-yl) -5- (6-phenylpyridin-3-yl) phenyl] -4 synthesized in Synthesis Example-14 on the electron transport layer 6 An organic electroluminescence device was prepared in the same manner as in Device Example 1 except that 1,6-diphenyl-1,3,5-triazine (Compound A-426) was used.
Element Example-14
In Device Example-1, 2- [5- (dibenzothiophen-2-yl)-[1,1 ′: 4 ′, 1 ″]-terphenyl synthesized in Synthesis Example-13 on the electron transport layer 6 An organic electroluminescent device was produced in the same manner as in Device Example 1 except that -3-yl] -4,6-difel-1,3,5-triazine (Compound A-98) was used.

Element Reference Example-1
In device example-1, 2- [5- (9-phenanthryl) -4 ′-(2-pyrimidyl) biphenyl-3-yl] -4, described in JP-A-2010-183145 is used for the electron transport layer 6. An organic electroluminescent element was produced in the same manner as in Example 1 except that 6-diphenyl-1,3,5-triazine (the above formula, represented by ETL-1) was used.

A direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As the light emission characteristics, voltage (V) and current efficiency (cd / A) when a current density of 10 mA / cm ² was passed were measured, and a luminance half time during continuous lighting was measured. In addition, the luminance decay time during continuous lighting when the initial luminance was driven at 800 cd / m ² was measured. The time when the luminance (cd / m ² ) is reduced by 30% is shown as the element lifetime (h) below.

素子比較例−１
素子実施例−１において、電子輸送層６に特願２００７−５５０１６６に開示の化合物Ｅ２２に記載されている２−［３，５−ビス（ジベンゾチオフェン−２−イル）］−３，５−ジフェニル−ピリミジン（上記式、ＥＴＬ−２で表される）を用いた以外は、素子実施例−１と同じ方法で有機電界発光素子を作成した。初期輝度を８００ｃｄ／ｍ^２で駆動したときの連続点灯時の輝度減衰時間を測定し、輝度（ｃｄ／ｍ^２）が３０％減じた時の時間は１９２時間だった。この様に、本願化合物と比較して、素子寿命に大きな差があると言える。

Device comparison example-1
In Device Example-1, 2- [3,5-bis (dibenzothiophen-2-yl)]-3,5-diphenyl described in Compound E22 disclosed in Japanese Patent Application No. 2007-550166 is used for the electron transport layer 6. -The organic electroluminescent element was created by the same method as element example-1 except having used pyrimidine (it is expressed with the above-mentioned formula and ETL-2). Initial brightness was measured to 800 cd / ^{m 2} luminance decay time at the time of continuous lighting when driven in, the time when the luminance (cd / ^{m 2)} is obtained by subtracting 30% was 192 hours. Thus, it can be said that there is a large difference in the device lifetime as compared with the present compound.

  From Table 1, it can be seen that the characteristics of the organic electroluminescent device using the azine compound of the present invention are improved in voltage, current efficiency and device lifetime as compared with the device reference example.

  The cyclic azine compound of the present invention is used as an electron transport material excellent in durability, driving voltage, and power efficiency. Furthermore, according to the present invention, an organic EL element with low power consumption and excellent element lifetime can be provided.

  Moreover, since the cyclic azine compound of this invention has high Tg, it can provide the element which is excellent in heat resistance. In addition, since the cyclic azine compound of the present invention has good thermal stability during sublimation purification, it is excellent in sublimation purification operability, and can provide a material with less impurities that cause element degradation of an organic electroluminescent element. . In addition, since the cyclic azine compound of the present invention is excellent in the stability of the deposited film, it is possible to provide a long-life organic electroluminescence device.

  In addition, the thin film comprising the cyclic azine compound (1) of the present invention or the thin film comprising the cyclic azine compound (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking. Performance, redox resistance, water resistance, oxygen resistance, electron injection characteristics, and the like, it is useful as a material for organic electroluminescent devices. In particular, it can be used as an electron transport material, a hole blocking material, a light emitting host material and the like. Further, since it is a wide band gap compound, it can be applied not only to conventional fluorescent device applications but also to phosphorescent devices. Therefore, the thin film comprising the cyclic azine compound (1) of the present invention or the thin film comprising the cyclic azine compound (1) of the present invention is expected to be used as a component of the organic electroluminescence device.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Charge generation layer 4. 4. Hole transport layer Light emitting layer 6. 6. Electron transport layer Cathode layer

Claims (17)

General formula (1)

(In general formula (1),
Two Ar ¹ represent the same substituent.
Ar ¹ represents a phenyl group or a naphthyl group (these substituents may have a fluorine atom, a methyl group, a phenyl group, or a pyridyl group as a substituent).
Ar ² is an aromatic hydrocarbon group having 6 to 18 carbon atoms or a heteroaromatic group having 3 to 13 carbon atoms composed of only C, H and N formed by a 6-membered ring (these substituents are fluorine atoms) , May be substituted with a methyl group or a phenyl group.
X is each independently a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group or a divalent divalent hydrocarbon having 5 to 9 carbon atoms which may be substituted with a methyl group. Represents a nitrogen-containing heteroaromatic group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom.
T represents a substituent represented by the following general formula (T-1) or (T-2).

(In General Formulas (T-1) and (T-2), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ each independently represents a hydrogen atom or a methyl group. Represents a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group or a phenyl group. )
The cyclic azine compound shown by these. The cyclic azine compound according to claim 1, wherein T is a substituent represented by the following general formula (T-3) or (T-4).

(In General Formulas (T-3) and (T-4), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ each independently represents a hydrogen atom or a methyl group. And represents a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group, or a phenyl group. * Represents a bonding position.) Ar ² is phenyl, biphenyl, naphthyl, phenanthryl, anthryl, fluoranthenyl, chrycenyl, triphenylenyl, pyridyl, pyrimidyl, pyrazyl, triazyl, quinolyl, isoquinolyl, or phenolyl The cyclic azine compound according to claim 1 or 2, which is a nantridyl group (these substituents may be substituted with a methyl group or a phenyl group). Ar ² is a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluoranthenyl group, a chrycenyl group, or a triphenylenyl group (these substituents may be substituted with a methyl group or a phenyl group). The cyclic azine compound according to claim 1, 2 or 3.   X is independently phenylene group, biphenylene group, naphthylene group, phenanthrylene group, anthrylene group, pyrenylene group, pyridylene group, methylpyridylene group, dimethylpyridylene group, pyrazylene group, methylpyrazylene group, dimethylpyrazylene group, pyrimidylene group. The cyclic azine compound according to claim 1, 2, 3, or 4, which is a methylpyrimidylene group or a dimethylpyrimidylene group.   The cyclic azine compound according to claim 1, 2, 3, 4, or 5, wherein X is a phenylene group or a pyridylene group. General formula (1)

(In general formula (1),
Two Ar ¹ represent the same substituent.
Ar ¹ represents a phenyl group (which may have a phenyl group, a methyl group or a pyridyl group as a substituent).
Ar ² is phenyl, biphenyl, naphthyl, phenanthryl, anthryl, fluoranthenyl, chrysenyl, triphenylenyl, pyridyl, phenyl-pyridyl, diphenyl-pyridyl, pyrimidyl, phenyl-pyrimidyl , Diphenyl-pyrimidyl group, pyrazyl group, triazyl group, diphenyl-triazyl group, quinolyl group, isoquinolyl group, or phenanthridyl group.
X is independently phenylene group, biphenylene group, naphthylene group, phenanthrylene group, anthrylene group, pyrenylene group, pyridylene group, methylpyridylene group, dimethylpyridylene group, pyrazylene group, methylpyrazylene group, dimethylpyrazylene group, pyrimidylene group. Represents a methylpyrimidylene group or a dimethylpyrimidylene group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom.
T represents a substituent represented by the following general formula (T-3) or (T-4).

(In General Formulas (T-3) and (T-4), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ each independently represents a hydrogen atom or a methyl group. And represents a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group or a phenyl group. * Represents a bonding position.)
The cyclic azine compound shown by these.   T is a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group or a benzofuranyl group (these groups may be substituted with a methyl group, a pyridyl group or a phenyl group), Item 8. The cyclic azine compound according to Item 7.   The cyclic azine compound according to claim 7 or 8, wherein X is a phenylene group or a pyridylene group. General formula (1)

(In general formula (1),
Two Ar ¹ represent the same substituent.
Ar ¹ represents a phenyl group.
Ar ² represents a 2-pyridyl group, a phenyl group, a 2-naphthyl group, a 4,6-diphenylpyridyl group, a pyrenyl group, an anthryl group, or a phenanthryl group.
X represents each independently a phenylene group or a pyridylene group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom.
T is a cyclic azine compound which is a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group or a benzofuranyl group. The compound represented by the general formula (2) and the compound represented by the general formula (3) and the general formula (4) are sequentially or simultaneously in the presence of a palladium catalyst in the presence or absence of a base. A method for producing a cyclic azine compound represented by the general formula (1), wherein a coupling reaction is performed.

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ represents a phenyl group or a naphthyl group (these substituents may have a fluorine atom, a methyl group, a phenyl group, or a pyridyl group as a substituent).
Ar ² is an aromatic hydrocarbon group having 6 to 18 carbon atoms or a heteroaromatic group having 3 to 13 carbon atoms composed of only C, H and N formed by a 6-membered ring (these substituents are fluorine atoms) , May be substituted with a methyl group or a phenyl group.
X is each independently a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group or a divalent divalent hydrocarbon having 5 to 9 carbon atoms which may be substituted with a methyl group. Represents a nitrogen-containing heteroaromatic group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom.
T represents a substituent represented by the following general formula (T-1) or (T-2).

(In General Formulas (T-1) and (T-2), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ each independently represents a hydrogen atom or a methyl group. Represents a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group or a phenyl group.)
Y ¹ and Y ² each independently represent a leaving group.
M ¹ represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together.
M ² represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together. ) The compound represented by the general formula (5) and the compound represented by the general formula (6) are subjected to a coupling reaction in the presence of a palladium catalyst in the presence of a base or in the absence of a base. The manufacturing method of the cyclic azine compound shown by General formula (1).

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ represents a phenyl group or a naphthyl group (these substituents may have a fluorine atom, a methyl group, a phenyl group, or a pyridyl group as a substituent).
Ar ² is an aromatic hydrocarbon group having 6 to 18 carbon atoms or a heteroaromatic group having 3 to 13 carbon atoms composed of only C, H and N formed by a 6-membered ring (these substituents are fluorine atoms) , May be substituted with a methyl group or a phenyl group.
X is each independently a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group or a divalent divalent hydrocarbon having 5 to 9 carbon atoms which may be substituted with a methyl group. Represents a nitrogen-containing heteroaromatic group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom.
T represents a substituent represented by the following general formula (T-1) or (T-2).

(In General Formulas (T-1) and (T-2), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ each independently represents a hydrogen atom or a methyl group. Represents a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group or a phenyl group.)
Y ³ each independently represents a leaving group.
M ³ represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together. ) The compound represented by the general formula (7) and the compound represented by the general formula (8) are subjected to a coupling reaction in the presence of a palladium catalyst in the presence of a base or in the absence of a base. The manufacturing method of the cyclic azine compound shown by General formula (1).

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ represents a phenyl group or a naphthyl group (these substituents may have a fluorine atom, a methyl group, a phenyl group, or a pyridyl group as a substituent).
Ar ² is an aromatic hydrocarbon group having 6 to 18 carbon atoms or a heteroaromatic group having 3 to 13 carbon atoms composed of only C, H and N formed by a 6-membered ring (these substituents are fluorine atoms) , May be substituted with a methyl group or a phenyl group.
X is each independently a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group or a divalent divalent hydrocarbon having 5 to 9 carbon atoms which may be substituted with a methyl group. Represents a nitrogen-containing heteroaromatic group.
p and q each independently represent 0, 1 or 2.
Z represents a nitrogen atom.
T represents a substituent represented by the following general formula (T-1) or (T-2).

(In General Formulas (T-1) and (T-2), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ each independently represents a hydrogen atom or a methyl group. Represents a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group or a phenyl group.)
Y ⁴ each independently represents a leaving group.
M ⁴ represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together. )   The production method according to claim 11, 12 or 13, wherein the palladium catalyst is a palladium catalyst having a tertiary phosphine as a ligand.   The palladium catalyst is a palladium catalyst having triphenylphosphine or 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl as a ligand. The manufacturing method as described in. A triazine compound represented by the general formula (10).

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ represents a phenyl group or a naphthyl group (these substituents may have a fluorine atom, a methyl group, a phenyl group, or a pyridyl group as a substituent).
X is each independently a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group or a divalent divalent hydrocarbon having 5 to 9 carbon atoms which may be substituted with a methyl group. Represents a nitrogen-containing heteroaromatic group.
q represents 0, 1 or 2.
Z represents a nitrogen atom.
T represents a substituent represented by the following general formula (T-1) or (T-2).

(In General Formulas (T-1) and (T-2), W ¹ and W ² each independently represent an oxygen atom or a sulfur atom. Ar ³ each independently represents a hydrogen atom or a methyl group. Represents a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group or a phenyl group.)
Y ¹ represents a chlorine atom, a bromine atom, an iodine atom or a triflate.   An organic electroluminescent device comprising the cyclic azine compound according to any one of claims 1 to 10.

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