JP5812584B2 - Pyrimidine derivative, method for producing the same, and organic electroluminescent device comprising the same - Google Patents

Description

  The present invention relates to a pyrimidine derivative having a 3,5-disubstituted phenyl group at the 2-position of the pyrimidine ring and a method for producing the same. The pyrimidine derivative is useful as a component of a fluorescent or phosphorescent organic electroluminescent device because it has good charge transport properties, and the present invention uses these in at least one organic compound layer of the organic electroluminescent device. The present invention relates to a high-efficiency organic electroluminescence device excellent in driveability and light emission.

  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 generated excitons are deactivated, and is applied to displays and the like.

  Patent Documents 1 and 2 disclose examples in which pyrimidines are used in an organic electroluminescent device, but these do not limit the substitution position on the phenyl group at the 2-position of the pyrimidine ring, but the pyrimidine of the present invention. Specific examples of pyrimidines substituted with 3,5-disubstituted phenyl groups such as derivatives are not described.

  Patent Documents 3 and 4 disclose examples in which pyrimidines having a 4-substituted phenyl group are used in an organic electroluminescent device, and these are characterized by having a 3,5-disubstituted phenyl group. Different from the pyrimidine derivatives of the present invention.

  An example in which pyrimidines having a phenyl group condensed with an aromatic hetero 5-membered ring is used in an organic electroluminescence device is disclosed in Patent Document 5, but these have a 3,5-disubstituted phenyl group. It is different from the characteristic pyrimidine derivative of the present invention.

  Further, in Synthesis Example 4 (paragraph 0072) of Patent Document 6, there is an example of a pyrimidine having a substituted phenyl group at the 2-position of the pyrimidine ring. The substituent at the 3- and 5-positions of this substituted phenyl group is “unsubstituted phenyl”. On the other hand, in the pyrimidine derivative of the present invention, the substituted phenyl group at the 2-position of the pyrimidine ring does not necessarily contain a substituted phenyl group having a substituent or a group 16 element. It is completely different in that it is a cyclic phenyl group, and this is a major feature of the present invention.

JP 2003-45662 A JP 2004-31004 A WO2004097786 WO2005105950 gazette WO20077069569 WO2005085387

  In the organic electroluminescence device, there is a problem that the light emission efficiency of the blue light emission is lower than that of the relatively low energy green or red light emission. In either case of a fluorescent or phosphorescent organic electroluminescent device, in order to obtain efficient light emission, high-energy excitons must be efficiently contained in the light emitting layer. For that purpose, it is necessary to use not only the host material used for the light emitting layer but also the charge transport material adjacent to the light emitting layer, a material that suppresses undesirable energy transfer from excitons.

  In particular, with respect to charge transport materials, materials that have inherent charge injection and transport characteristics and achieve efficient confinement of excitons, that is, materials that can drive a fluorescent or phosphorescent organic electroluminescent device with low voltage and high efficiency Cannot be found in conventional compounds, and new materials are desired.

  As a result of intensive studies to solve the above problems, the present inventors have found that the pyrimidine derivative (1) of the present invention into which a 3,5-disubstituted phenyl group is introduced is generally used for vacuum deposition, spin coating and the like. It was found that a thin film can be formed by a simple method and has good charge transport characteristics. In addition, fluorescent or phosphorescent organic electroluminescent devices using these as organic compound layers effectively contain excitons, resulting in lower device driving voltage and higher efficiency emission than when using general-purpose organic materials. It has been found that the above can be achieved simultaneously, and the present invention has been completed.

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

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。）で示されるピリミジン誘導体に関するものである。

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. Ar ³ represents a substituted phenyl group or a condensed phenyl group not containing a group 16 element, provided that Ar ³ does not contain a 1,3,5-trimethylphenyl group.)).

  Further, the present invention provides a compound represented by the general formula (2)

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ｙ^１は、塩素原子、臭素原子又はヨウ素原子を表す。）で示される化合物と、一般式（３）

(Wherein, Ar ¹ and Ar ² each independently represents an optionally substituted aromatic group; Y ¹ represents a chlorine atom, a bromine atom or an iodine atom) and a general formula (3)

（式中、Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。Ｍは、金属基又はヘテロ原子基を表す。）で示される化合物とを、場合によっては塩基の存在下に、パラジウム触媒の存在下にカップリング反応させることを特徴とする、一般式（１）

(In the formula, Ar ³ represents a substituted phenyl group or a condensed phenyl group not containing a group 16 element. However, Ar ³ does not contain a 1,3,5-trimethylphenyl group. M is a metal group or And a compound represented by the general formula (1), wherein the compound represented by formula (1) is subjected to a coupling reaction in the presence of a palladium catalyst, optionally in the presence of a base.

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。）で示されるピリミジン誘導体の製造方法に関するものである。

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. Ar ³ represents a substituted phenyl group or a condensed phenyl group not containing a group 16 element, provided that Ar ³ does not include a 1,3,5-trimethylphenyl group.), And relates to a method for producing a pyrimidine derivative represented by:

  The present invention also provides a general formula (4)

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ｒ^２は水素原子、炭素数１〜４のアルキル基又はフェニル基を表し、Ｂ（ＯＲ^２）_２の２つのＲ^２は同一又は異なっていてもよい。又、２つのＲ^２は一体となって酸素原子及びホウ素原子を含んで環を形成することもできる。）で示される化合物と、一般式（５）

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and B (OR ² ) two R ² ₂ may be the same or different. Furthermore, the compound represented by the two R ² may form a ring containing an oxygen atom and a boron atom together.) General formula (5)

（式中、Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。Ｙ^２は、塩素原子、臭素原子又はヨウ素原子を表す。）で示される化合物とを、塩基及びパラジウム触媒の存在下にカップリング反応させることを特徴とする、一般式（１）

(In the formula, Ar ³ represents a substituted phenyl group or a condensed phenyl group containing no group 16 element. However, Ar ³ does not contain a 1,3,5-trimethylphenyl group. Y ² represents a chlorine atom. , Which represents a bromine atom or an iodine atom), and is subjected to a coupling reaction in the presence of a base and a palladium catalyst.

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。）で示されるピリミジン誘導体の製造方法に関するものである。

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. Ar ³ represents a substituted phenyl group or a condensed phenyl group not containing a group 16 element, provided that Ar ³ does not include a 1,3,5-trimethylphenyl group.), And relates to a method for producing a pyrimidine derivative represented by:

  Furthermore, the present invention relates to a general formula (1)

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。）で示されるピリミジン誘導体を構成成分とする有機電界発光素子に関するものである。

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. Ar ³ represents a substituted phenyl group or a condensed phenyl group not containing a group 16 element, provided that Ar ³ does not contain a 1,3,5-trimethylphenyl group).

  Hereinafter, the present invention will be described in detail.

Examples of the optionally substituted aromatic group represented by Ar ¹ include an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted anthryl group, and optionally substituted. Examples thereof include a good phenanthryl group, an optionally substituted pyrenyl group, a pyridyl group, an optionally substituted pyrimidyl group, an optionally substituted quinolyl group, and an optionally substituted thienyl group. Hereinafter, more specific examples will be given, but the present invention is not limited thereto.

  Examples of the optionally substituted phenyl group include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 4-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group, and a 2-trifluoromethyl group. Fluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, mesityl group, 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 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl 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, 3-chlorophenyl group, 4-chlorophenyl group A substituted phenyl group such as 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3-bromophenyl group, 4-bromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenyl group, 4- In addition to biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 2-methylbiphenyl-4-yl group, 3-methylbiphenyl group Enyl-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-yl 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, 2-triflu Olomethylbiphenyl-4-yl group, 3-trifluoromethylbiphenyl-4-yl group, 2′-trifluoromethylbiphenyl-4-yl group, 4′-trifluoromethylbiphenyl-4-yl group, 6-trimethyl Fluoromethylbiphenyl-3-yl group, 5-trifluoromethylbiphenyl-3-yl group, 2′-trifluoromethylbiphenyl-3-yl group, 4′-trifluoromethylbiphenyl-3-yl group, 5-trimethyl Fluoromethylbiphenyl-2-yl group, 6-trifluoromethylbiphenyl-2-yl group, 2′-trifluoromethylbiphenyl-2-yl group, 4′-trifluoromethylbiphenyl-2-yl group, 3-ethyl Biphenyl-4-yl group, 4′-ethylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-triethylbiphenyl-4- 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-propylbiphenyl-3-yl group, 4′-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group, 2 ′, 4 ′, 6 '-Tripropylbiphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group, 4'-isopropylbiphenyl-4-yl group, 2', 4 ', 6'-triisopropylbiphenyl-4-yl 6-isopropylbiphenyl-3-yl group, 4′-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 4′-isopropylbiphenyl-2-yl group, 2 ′, 4 ′, 6 '-Triisopropylbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 4'-butylbiphenyl-4-yl group, 2', 4 ', 6'-tributylbiphenyl-4-yl group, 6 -Butylbiphenyl-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′-tri-tert-butyl Rubiphenyl-4-yl group, 6-tert-butylbiphenyl-3-yl group, 4′-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 4′-tert- Substituted biphenylyl group such as butylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tri-tert-butylbiphenyl-2-yl group, 1,1 ′: 4 ′, 1 ″ -terphenyl-3- Yl group, 1,1 ′: 4 ′, 1 ″ -terphenyl-4-yl group, 1,1 ′: 3 ′, 1 ″ -terphenyl-3-yl group, 1,1 ′: 3 ′, 1 "-Terphenyl-4-yl group, 1,1 ': 3', 1" -terphenyl-5'-yl group, 1,1 ': 2', 1 "-terphenyl-3-yl group, 1 , 1 ′: 2 ′, 1 ″ -terphenyl-4-yl group, 1,1 ′: 2 ′, 1 ″ -terphenyl- Terphenylyl group such as' -yl group, 3- (1-naphthyl) phenyl group, 4- (1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3 -(1-anthryl) phenyl group, 3- (2-anthryl) phenyl group, 3- (9-anthryl) phenyl group, 4- (1-anthryl) phenyl group, 4- (2-anthryl) phenyl group, 4 -(9-anthryl) phenyl group, 3- (1-perylenyl) phenyl group, 3- (2-perylenyl) phenyl group, 4- (1-perylenyl) phenyl group, 4- (2-perylenyl) phenyl group, 3 -Triphenylenylphenyl group, 4-triphenylenylphenyl 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, 2- (4-methylpyridin-2-yl) phenyl group, 2- (5-methylpyridin-2-yl) phenyl group, 2- (6-methylpyridin-2-yl) phenyl Group, 2- (4-methylpyridin-3-yl) phenyl group, 2- (5-methylpyridin-3-yl) phenyl group, 2- (6-methylpyridin-3-yl) phenyl group, 2- ( 2-methylpyridin-4-yl) phenyl group, 2- (3-methylpyridin-4-yl) phenyl group, 3- (4-methylpyridin-2-yl) phenyl group, 3- (5-methylpyridine- 2-yl) phenyl group, 3- (6-methylpyridin-2-yl) phenyl group, 3- (4-methylpyridin-3-yl) phenyl group, 3- (5-methylpyridin-3-yl) phenyl group, 3- (6- Methylpyridin-3-yl) phenyl group, 3- (2-methylpyridin-4-yl) phenyl group, 3- (3-methylpyridin-4-yl) phenyl group, 4- (4-methylpyridin-2- Yl) phenyl group, 4- (5-methylpyridin-2-yl) phenyl group, 4- (6-methylpyridin-2-yl) phenyl group, 4- (4-methylpyridin-3-yl) phenyl group, 4- (5-methylpyridin-3-yl) phenyl group, 4- (6-methylpyridin-3-yl) phenyl group, 4- (2-methylpyridin-4-yl) phenyl group, 4- (3- Methylpyridin-4-yl) pheni Group, 2- (4,6-dimethylpyridin-2-yl) phenyl group, 3- (4,6-dimethylpyridin-2-yl) phenyl group, 4- (4,6-dimethylpyridin-2-yl) Phenyl group, 2- (4-phenylpyridin-2-yl) phenyl group, 2- (5-phenylpyridin-2-yl) phenyl group, 2- (6-phenylpyridin-2-yl) phenyl group, 2- (4-phenylpyridin-3-yl) phenyl group, 2- (5-phenylpyridin-3-yl) phenyl group, 2- (6-phenylpyridin-3-yl) phenyl group, 2- (2-phenylpyridine) -4-yl) phenyl group, 2- (3-phenylpyridin-4-yl) phenyl group, 3- (4-phenylpyridin-2-yl) phenyl group, 3- (5-phenylpyridin-2-yl) Phenyl group 3- (6-phenylpyridin-2-yl) phenyl group, 3- (4-phenylpyridin-3-yl) phenyl group, 3- (5-phenylpyridin-3-yl) phenyl group, 3- (6- Phenylpyridin-3-yl) phenyl group, 3- (2-phenylpyridin-4-yl) phenyl group, 3- (3-phenylpyridin-4-yl) phenyl group, 4- (4-phenylpyridin-2- Yl) phenyl group, 4- (5-phenylpyridin-2-yl) phenyl group, 4- (6-phenylpyridin-2-yl) phenyl group, 4- (4-phenylpyridin-3-yl) phenyl group, 4- (5-phenylpyridin-3-yl) phenyl group, 4- (6-phenylpyridin-3-yl) phenyl group, 4- (2-phenylpyridin-4-yl) phenyl group, 4- (3- Feni Rupyridin-4-yl) phenyl group, 2- (4,6-diphenylpyridin-2-yl) phenyl group, 3- (4,6-diphenylpyridin-2-yl) phenyl group, 4- (4,6- Diphenylpyridin-2-yl) phenyl group, 2- (2,6-diphenylpyridin-2-yl) phenyl group, 3- (2,6-diphenylpyridin-2-yl) phenyl group, 4- (2,6 -Diphenylpyridin-2-yl) phenyl group, 4- (2,6-diphenylpyridin-4-yl) phenyl group, 2- (2-pyrimidyl) phenyl group, 3- (2-pyrimidyl) phenyl group, 4- (2-pyrimidyl) phenyl group, 2- (5-pyrimidyl) phenyl group, 3- (5-pyrimidyl) phenyl group, 4- (5-pyrimidyl) phenyl group, 2- (4,6-dimethylpyrimidine-2 Yl) phenyl group, 3- (4,6-dimethylpyrimidin-2-yl) phenyl group, 4- (4,6-dimethylpyrimidin-2-yl) phenyl group, 2- (4,6-diphenylpyrimidin-2) -Yl) phenyl group, 3- (4,6-diphenylpyrimidin-2-yl) phenyl group, 4- (4,6-diphenylpyrimidin-2-yl) phenyl group, 3- (2-quinolyl) phenyl group, 4- (2-quinolyl) phenyl group, 3- (4-quinolyl) phenyl group, 4- (4-quinolyl) phenyl group, 3- (2-thienyl) phenyl group, 4- (2-thienyl) phenyl group, 3- (2-furyl) phenyl group, 4- (2-furyl) phenyl group and the like can be mentioned.

  Examples of the phenyl group which may be substituted from the viewpoint of good performance as a material for an organic electroluminescence device include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, and a 2,6-dimethylphenyl group. 4-tert-butylphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 1,1 ′: 4 ′, 1 ″ -terphenyl-4-yl group, 1,1 ′: 2 ′ , 1 ″ -terphenyl-4-yl group, 1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl group, 4- (1-naphthyl) phenyl group, 4- (9-anthryl) phenyl Group, 3- (2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl Group, 4- (4-pyridyl) phenyl group, 3 (6-Phenylpyridin-2-yl) phenyl group, 4- (6-phenylpyridin-2-yl) phenyl group and 4- (2,6-diphenylpyridin-4-yl) phenyl group are preferable and easy to synthesize In particular, a phenyl group, a p-tolyl group, a 4-biphenylyl group, a 2-biphenylyl group, and a 4- (3-pyridyl) phenyl group are more preferable.

  The naphthyl group which may be substituted includes 1-naphthyl group and 2-naphthyl group, 4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalen-1-yl group and 4-ethylnaphthalene. -1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5- Trifluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl Group, 6-methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylna Talen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalen-2-yl group 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group, 7-tert-butylnaphthalen-2-yl group, and the like.

  The naphthyl group which may be substituted is a 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl, in terms of good performance as a material for organic electroluminescent elements. Group, 5-methylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group , 7-methylnaphthalen-2-yl group or 7-tert-butylnaphthalen-2-yl group is preferable, and 2-naphthyl group is more preferable in terms of easy synthesis.

  Examples of the optionally substituted anthryl group include 1-anthryl group, 2-anthryl group, 9-anthryl group, 2-methylanthracen-1-yl group, 3-methylanthracen-1-yl group, 4- Methyl anthracen-1-yl group, 9-methylanthracen-1-yl group, 10-methylanthracen-1-yl group, 2-phenylanthracen-1-yl group, 3-phenylanthracen-1-yl group, 4- Phenylanthracen-1-yl group, 5-phenylanthracen-1-yl group, 6-phenylanthracen-1-yl group, 7-phenylanthracen-1-yl group, 8-phenylanthracen-1-yl group, 9- Phenylanthracen-1-yl group, 10-phenylanthracen-1-yl group, 1-methylanthracen-2-yl group, 3 Methyl anthracen-2-yl group, 4-methylanthracen-2-yl group, 9-methylanthracen-2-yl group, 10-methylanthracen-2-yl group, 1-phenylanthracen-2-yl group, 3- Phenylanthracen-2-yl group, 4-phenylanthracen-2-yl group, 5-phenylanthracen-2-yl group, 6-phenylanthracen-2-yl group, 7-phenylanthracen-2-yl group, 8- Phenylanthracen-2-yl group, 9-phenylanthracen-2-yl group, 10-phenylanthracen-2-yl group, 2-methylanthracen-9-yl group, 3-methylanthracen-9-yl group, 4- Methyl anthracen-9-yl group, 10-methylanthracen-9-yl group, 2-phenylanthracene-9-i Group, 3-phenylanthracen-9-yl group, 4-phenylanthracen-9-yl group, 5-phenylanthracen-9-yl group, 6-phenylanthracen-9-yl group, 7-phenylanthracen-9-yl Group, 1-phenylanthracen-9-yl group, 10-phenylanthracen-9-yl group and the like.

  As an anthryl group which may be substituted in terms of good performance as a material for an organic electroluminescent device, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 4-phenylanthracen-1-yl group, A 4-phenylanthracen-9-yl group is preferable, and a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group are more preferable in terms of low molecular weight.

  Examples of the optionally substituted phenanthryl group include 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 2-phenylphenanthren-1-yl group, 3- Phenylphenanthren-1-yl group, 4-phenylphenanthren-1-yl group, 9-phenylphenanthren-1-yl group, 1-phenylphenanthren-2-yl group, 3-phenylphenanthren-2-yl group, 4- Phenylphenanthren-2-yl group, 8-phenylphenanthren-2-yl group, 8-phenylphenanthren-3-yl group, 9-phenylphenanthren-2-yl group, 1-phenylphenanthren-3-yl group, 2- Phenylphenanthren-3-yl group, 4-phenylphenanthre -3-yl group, 9-phenylphenanthren-3-yl group, 1-phenylphenanthren-4-yl group, 2-phenylphenanthren-4-yl group, 3-phenylphenanthren-4-yl group, 9-phenylphenanthrene Examples include a -4-yl group, a 1-phenylphenanthren-9-yl group, a 2-phenylphenanthren-9-yl group, a 3-phenylphenanthren-9-yl group, and a 4-phenylphenanthren-9-yl group.

  Examples of the phenanthryl group which may be substituted in terms of good performance as a material for an organic electroluminescence device include 2-phenanthryl group, 3-phenanthryl group, 8-phenylphenanthren-2-yl group, and 8-phenylphenanthrene- A 3-yl group is preferable, and a 2-phenanthryl group and a 3-phenanthryl group are more preferable in terms of low molecular weight.

  Examples of the optionally substituted pyrenyl group include a 1-pyrenyl group and a 2-pyrenyl group, a 6-phenylpyren-1-yl group, a 7-phenylpyren-1-yl group, and an 8-phenylpyrene-1- Yl group, 6-phenylpyren-2-yl group, 7-phenylpyren-2-yl group, 8-phenylpyren-2-yl group and the like.

  As an optionally substituted pyrenyl group, a 1-pyrenyl group, a 2-pyrenyl group, and a 7-phenylpyren-2-yl group are preferable because the performance as a material for an organic electroluminescent element is good, and the molecular weight is low. In this respect, a 1-pyrenyl group is more preferable.

  Examples of the pyridyl group include a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group, and a 2-pyridyl group is more preferable in terms of easy synthesis.

  The pyrimidyl group which may be substituted includes 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 4,6-dimethylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl Groups and the like.

  As an optionally substituted pyrimidyl group, a 2-pyrimidyl group, a 4-pyrimidyl group, and a 4,6-diphenylpyrimidin-2-yl group are preferable because the performance as a material for an organic electroluminescent element is good. Are more preferable, 2-pyrimidyl group and 4-pyrimidyl group are more preferable.

  The quinolyl group which may be substituted includes a 2-quinolyl group, a 3-quinolyl group, a 4-quinolyl group, a 5-quinolyl group, a 6-quinolyl group, a 7-quinolyl group, an 8-quinolyl group, Methylquinolin-2-yl group, 2-methylquinolin-6-yl group, 2-methylquinolin-7-yl group, 2-methylquinolin-8-yl group, 3-phenylquinolin-2-yl group, 2- Examples thereof include a phenylquinolin-6-yl group, a 2-phenylquinolin-7-yl group, a 2-phenylquinolin-8-yl group, and a 5-phenylquinolin-8-yl group.

  As an optionally substituted quinolyl group, a 2-quinolyl group, a 6-quinolyl group, and a 5-phenylquinolin-8-yl group are preferable because the performance as a material for an organic electroluminescent element is good, and the molecular weight is low. In this respect, a 2-quinolyl group is more preferable.

  Examples of the optionally substituted thienyl group include 2-thienyl group and 3-thienyl group, 4-methylthiophen-2-yl group, 5-methylthiophen-2-yl group, 3,4,5-trimethyl. A thiophen-2-yl group, a 5-phenylthiophen-2-yl group, a 3,4,5-triphenylthiophen-2-yl group, and the like can be given.

  The thienyl group that may be substituted is preferably a 2-thienyl group and a 5-phenylthiophen-2-yl group in terms of good performance as a material for an organic electroluminescent element, and in terms of low molecular weight, 2- More preferred is a thienyl group.

Examples of the optionally substituted aromatic group represented by Ar ² include the groups exemplified for Ar ¹ .

The substituted phenyl group represented by Ar ³ includes a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms (however, 1,3,5-trimethylphenyl group is not included), substituted with a halogen atom Phenyl group, phenyl group substituted with an optionally substituted phenyl group, phenyl group substituted with an optionally substituted pyrimidyl group, optionally substituted thiazolyl group And a phenyl group substituted with a pyridyl group, a phenyl group substituted with a phenanthryl group, and the like. Hereinafter, more specific examples will be given, but the present invention is not limited thereto.

  Examples of the phenyl group substituted with an alkyl group having 1 to 4 carbon atoms include p-tolyl group, m-tolyl group, o-tolyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2- Trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, mesityl group, 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-dipropyl Phenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl 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, and the like.

  The phenyl group substituted with an alkyl group having 1 to 4 carbon atoms is a p-tolyl group, an m-tolyl group, an o-tolyl group, 4-trifluoro group in terms of good performance as an organic electroluminescent element material. A methylphenyl group and a 4-butylphenyl group are preferable, and a p-tolyl group and an m-tolyl group are more preferable in that they are inexpensive.

  Examples of the phenyl group substituted with a halogen atom include 3-chlorophenyl group, 4-chlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3-bromophenyl group, 4-bromophenyl group, 3,4 -A dibromophenyl group, a 3, 5- dibromophenyl group, etc. are mentioned. A 3-chlorophenyl group is preferred because it is easy to synthesize.

  Examples of the phenyl group substituted with an optionally substituted phenyl group include 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 2-methylbiphenyl-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′-trimethyl Biphenyl-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-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2 ' Methyl biphenyl-2-yl group, 4′-methylbiphenyl-2-yl group, 6,2′-dimethylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-trimethylbiphenyl-2-yl group, 2 -Trifluoromethylbiphenyl-4-yl group, 3-trifluoromethylbiphenyl-4-yl group, 2'-trifluoromethylbiphenyl-4-yl group, 4'-trifluoromethylbiphenyl-4-yl group, 6 -Trifluoromethylbiphenyl-3-yl group, 5-trifluoromethylbiphenyl-3-yl group, 2'-trifluoromethylbiphenyl-3-yl group, 4'-trifluoromethylbiphenyl-3-yl group, 5 -Trifluoromethylbiphenyl-2-yl group, 6-trifluoromethylbiphenyl-2-yl group, 2'-trifluoromethylbiphenyl- -Yl group, 4'-trifluoromethylbiphenyl-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-propylbiphenyl-3-yl group, 4′-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group, 2 ′, 4 ′ , 6'- Tripropylbiphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group, 4′-isopropylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-triisopropylbiphenyl-4-yl group, 6- Isopropylbiphenyl-3-yl group, 4′-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 4′-isopropylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tri Isopropylbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 4′-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tributylbiphenyl-4-yl group, 6-butylbiphenyl -3-yl group, 4'-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 4'-butylbiphenyl-2-yl group, 2 ', ', 6'-tributylbiphenyl-2-yl group, 3-tert-butylbiphenyl-4-yl group, 4'-tert-butylbiphenyl-4-yl group, 2', 4 ', 6'-tri-tert -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'-tri-tert-butylbiphenyl-2-yl group, 1,1 ': 4', 1 "-terphenyl-3-yl group, 1 , 1 ′: 4 ′, 1 ″ -terphenyl-4-yl group, 1,1 ′: 3 ′, 1 ″ -terphenyl-3-yl group, 1,1 ′: 3 ′, 1 ″ -terphenyl group -4-yl group, 1,1 ': 3', 1 "-terfe Ru-5′-yl group, 1,1 ′: 2 ′, 1 ″ -terphenyl-3-yl group, 1,1 ′: 2 ′, 1 ″ -terphenyl-4-yl group, 1,1 ′ : 2 ′, 1 ″ -terphenyl-4′-yl group, 2 ′-(2-pyridyl) biphenyl-2-yl group, 3 ′-(2-pyridyl) biphenyl-2-yl group, 4 ′-( 2-pyridyl) biphenyl-2-yl group, 2 ′-(3-pyridyl) biphenyl-2-yl group, 3 ′-(3-pyridyl) biphenyl-2-yl group, 4 ′-(3-pyridyl) biphenyl 2-yl group, 2 ′-(4-pyridyl) biphenyl-2-yl group, 3 ′-(4-pyridyl) biphenyl-2-yl group, 4 ′-(4-pyridyl) biphenyl-2-yl group 2 '-(2-pyridyl) biphenyl-3-yl group, 3'-(2-pyridyl) biphenyl-3-yl Group, 4 ′-(2-pyridyl) biphenyl-3-yl group, 2 ′-(3-pyridyl) biphenyl-3-yl group, 3 ′-(3-pyridyl) biphenyl-3-yl group, 4′- (3-pyridyl) biphenyl-3-yl group, 2 ′-(4-pyridyl) biphenyl-3-yl group, 3 ′-(4-pyridyl) biphenyl-3-yl group, 4 ′-(4-pyridyl) Biphenyl-3-yl group, 2 '-(2-pyridyl) biphenyl-4-yl group, 3'-(2-pyridyl) biphenyl-4-yl group, 4 '-(2-pyridyl) biphenyl-4-yl Group, 2 ′-(3-pyridyl) biphenyl-4-yl group, 3 ′-(3-pyridyl) biphenyl-4-yl group, 4 ′-(3-pyridyl) biphenyl-4-yl group, 2′- (4-pyridyl) biphenyl-4-yl group, 3 ′-(4-pyridy ) Biphenyl-4-yl group, 4 '- (4-pyridyl) biphenyl-4-yl group and the like.

  In terms of good performance as an organic electroluminescent device material, the phenyl group substituted with a phenyl group which may have a substituent includes 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1 , 1 ′: 3 ′, 1 ″ -terphenyl-5′-yl group, 2 ′-(2-pyridyl) biphenyl-3-yl group, 3 ′-(2-pyridyl) biphenyl-3-yl group, 4 A '-(2-pyridyl) biphenyl-3-yl group is preferable, and a 3-biphenylyl group and a 3'-(2-pyridyl) biphenyl-3-yl group are more preferable in terms of easy synthesis.

  Examples of the phenyl group substituted with an optionally substituted pyrimidyl group include 2- (2-pyrimidyl) phenyl group, 3- (2-pyrimidyl) phenyl group, 4- (2-pyrimidyl) phenyl group, 2- (4-pyrimidyl) phenyl group, 3- (4-pyrimidyl) phenyl group, 4- (4-pyrimidyl) phenyl group, 2- (5-pyrimidyl) phenyl group, 3- (5-pyrimidyl) phenyl group, 4- (5-pyrimidyl) phenyl group, 2- (4,6-dimethylpyrimidin-2-yl) phenyl group, 3- (4,6-dimethylpyrimidin-2-yl) phenyl group, 4- (4,6 -Dimethylpyrimidin-2-yl) phenyl group, 2- (4,6-diphenylpyrimidin-2-yl) phenyl group, 3- (4,6-diphenylpyrimidin-2-yl) phenyl group, 4- (4 6-diphenylpyrimidin-2-yl) phenyl group, 3- [4,6-di-p-tolylpyrimidin-2-yl] phenyl group, 4- [4,6-di-m-tolylpyrimidin-2-yl] ] Phenyl group, 3- [4,6-bis (3,5-dimethylphenyl) pyrimidin-2-yl] phenyl group, 4- [4,6-bis (2,6-dimethylphenyl) pyrimidin-2-yl ] Phenyl group, 3- [4,6-bis (2-biphenylyl) pyrimidin-2-yl] phenyl group, 4- [4,6-bis (3-biphenylyl) pyrimidin-2-yl] phenyl group, 3- Examples include [4,6-di (2-naphthyl) pyrimidin-2-yl] phenyl group, 4- [4,6-di (9-anthryl) pyrimidin-2-yl] phenyl group, and the like.

  As a phenyl group substituted with a pyrimidyl group which may have a substituent in terms of good performance as a material for an organic electroluminescence device, 4- (2-pyrimidyl) phenyl group, 4- (5-pyrimidyl) ) Phenyl group, 3- (4,6-dimethylpyrimidin-2-yl) phenyl group, 4- (4,6-dimethylpyrimidin-2-yl) phenyl group, 3- (4,6-diphenylpyrimidin-2-) Yl) phenyl group and 4- (4,6-diphenylpyrimidin-2-yl) phenyl group are preferred, and 4- (2-pyrimidyl) phenyl group and 4- (5-pyrimidyl) phenyl group are easy to synthesize. More preferred are groups.

  Examples of the phenyl group substituted with an optionally substituted thiazolyl group include 2- (2-thiazolyl) phenyl group, 3- (2-thiazolyl) phenyl group, 4- (2-thiazolyl) phenyl group, 2- (4-thiazolyl) phenyl group, 3- (4-thiazolyl) phenyl group, 4- (4-thiazolyl) phenyl group, 2- (5-thiazolyl) phenyl group, 3- (5-thiazolyl) phenyl group, 4- (5-thiazolyl) phenyl group, 3- (2-methylthiazol-4-yl) phenyl group, 4- (2-methylthiazol-5-yl) phenyl group, 2- (4,5-dimethylthiazole- 2-yl) phenyl group, 3- (4,5-dimethylthiazol-2-yl) phenyl group, 4- (4,5-dimethylthiazol-2-yl) phenyl group, 2- (2-phenylthiazo) Ru-4-yl) phenyl group, 3- (2-phenylthiazol-4-yl) phenyl group, 4- (2-phenylthiazol-4-yl) phenyl group, 4- (2-phenylthiazol-5-yl) ) Phenyl group, 2- (4,5-diphenylthiazol-2-yl) phenyl group, 3- (4,5-diphenylthiazol-2-yl) phenyl group, 4- (4,5-diphenylthiazol-2-yl) Yl) phenyl group, 2- (2-benzothiazolyl) phenyl group, 3- (2-benzothiazolyl) phenyl group, 4- (2-benzothiazolyl) phenyl group, 3- (2-naphthothiazolyl) phenyl group, 4- (2- Naphthiazolyl) phenyl group and the like.

  As a phenyl group substituted with a thiazolyl group which may have a substituent, the 3- (4,5-diphenylthiazol-2-yl) phenyl group may be used as a material for an organic electroluminescent element. 4- (4,5-diphenylthiazol-2-yl) phenyl group and 4- (2-benzothiazolyl) phenyl group are preferable, and 4- (2-benzothiazolyl) phenyl group is more preferable in terms of easy synthesis. .

  Examples of the phenyl group substituted with a pyridyl group include 2- (2-pyridyl) phenyl group, 3- (2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, and 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 4-phenyl-2- (2-pyridyl) phenyl group, 5-phenyl-2- (2-pyridyl) phenyl group, 4-phenyl-3- (2-pyridyl) phenyl group, 5-phenyl-3- ( 2-pyridyl) phenyl group, 6-phenyl-3- (2-pyridyl) phenyl group, 3-phenyl-4- (2-pyridyl) phenyl group, 3-phenyl-2- (3-pyridyl) phenyl group, 4 -Phenyl- -(3-pyridyl) phenyl group, 4-phenyl-3- (3-pyridyl) phenyl group, 5-phenyl-3- (3-pyridyl) phenyl group, 6-phenyl-3- (3-pyridyl) phenyl group 2-phenyl-4- (3-pyridyl) phenyl group, 4-phenyl-2- (4-pyridyl) phenyl group, 4-phenyl-3- (4-pyridyl) phenyl group, 5-phenyl-3- ( 4-pyridyl) phenyl group, 3-phenyl-4- (4-pyridyl) phenyl group, 3,4-di (2-pyridyl) phenyl group, 3,4-di (3-pyridyl) phenyl group, 3,4 -Di (4-pyridyl) phenyl group, 3- (2-pyridyl) -4- (3-pyridyl) phenyl group, 3- (2-pyridyl) -4- (4-pyridyl) phenyl group, 3- (3 -Pyridyl) -4- (2-pyridyl) fur Nyl group, 3- (4-pyridyl) -4- (2-pyridyl) phenyl group, 3,5-di (2-pyridyl) phenyl group, 3,5-di (3-pyridyl) phenyl group, 3,5 -Di (4-pyridyl) phenyl group etc. are mentioned.

  The phenyl group substituted with a pyridyl group is a 2- (2-pyridyl) phenyl group, a 3- (2-pyridyl) phenyl group, a 4- (2- Pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 5-phenyl-3 -(2-pyridyl) phenyl group, 5-phenyl-3- (3-pyridyl) phenyl group, 5-phenyl-3- (4-pyridyl) phenyl group, 3,5-di (2-pyridyl) phenyl group In terms of easy synthesis, 2- (2-pyridyl) phenyl group, 3- (2-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group Is more preferable.

  Examples of the phenyl group substituted with a phenanthroyl group include 2- (2-phenanthroyl) phenyl group, 3- (2-phenanthroyl) phenyl group, 4- (2-phenanthrolyl) phenyl group, and 2- (3-phenanthroyl) phenyl group. 3- (3-phenanthroyl) phenyl group, 4- (3-phenanthrolyl) phenyl group, 2- (4-phenanthrolyl) phenyl group, 3- (4-phenanthrolyl) phenyl group, 4- (4-phenanthrolyl) phenyl group Etc.

  Examples of the phenyl group substituted with a phenanthroyl group include a 3- (2-phenanthroyl) phenyl group, a 4- (2-phenanthroyl) phenyl group, and 3- (3- A phenanthroyl) phenyl group and a 4- (3-phenanthroyl) phenyl group are preferable, and a 4- (2-phenanthroyl) phenyl group is more preferable in terms of easy synthesis.

As the condensed ring phenyl group not containing a group 16 element represented by Ar ³ , it is essential that the ring structure does not contain a group 16 element of the periodic table such as an oxygen atom and a sulfur atom, and a 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group, 5-quinolyl group, 6-quinolyl group, Examples include 7-quinolyl group, 8-quinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group and the like.

  A 2-ringyl group, a 9-anthryl group, a 3-phenanthryl group, and a 6-quinolyl group are preferable as a condensed phenyl group in terms of good performance as a material for an organic electroluminescent element, and synthesis is easy. , 6-quinolyl group is more preferable.

  The compound represented by the general formula (2) is, for example, The Journal of Organic Chemistry, 1951, 16, 461-465, Macromolecules, 2001, 6, 477-480, or Organic Letters, 2003, 5, It can be manufactured using the method disclosed in 1551-1554.

Examples of the metal group represented by M include Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl ₂ , AlBr ₂ , Al (Me) ₂ , Al (Et) ₂ , and Al ( ⁱ Bu) _2. , Sn (Me) ₃ , Sn (Bu) ₃ , ZnR ^{1 and the} like. Examples of ZnR ¹ include ZnCl, ZnBr, and ZnI.

  In terms of good reaction yield, the metal group is preferably ZnCl, and more preferably ZnCl (TMEDA) coordinated with tetramethylethylenediamine.

Examples of the heteroatom group represented by M include Si (Ph) ₃ , SnF ₃ , B (OR ² ) _{2 and the} like. As B (OR ² ) ₂ , B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) _{2 and the} like. Examples of B (OR ² ) ₂ in the case where two R ² are combined to form a ring containing an oxygen atom and a boron atom include groups represented by the following (I) to (VI): The group represented by (II) is preferable because it can be exemplified and the yield is good.

Ｙ^１及びＹ^２は、塩素原子、臭素原子又はヨウ素原子を表す。合成が容易な点で臭素原子、塩素原子が好ましい。

Y ¹ and Y ² represent a chlorine atom, a bromine atom or an iodine atom. A bromine atom and a chlorine atom are preferable in terms of easy synthesis.

  Next, the manufacturing method of this invention is demonstrated.

  The pyrimidine derivative (1) of the present invention has the following reaction formula:

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。Ｙ^１は、塩素原子、臭素原子又はヨウ素原子を表す。Ｍは、金属基又はヘテロ原子基を表す。）で示される工程１によって製造することができる。

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. Ar ³ represents a substituted phenyl group or a condensed phenyl group not containing a group 16 element, provided that Ar ³ does not contain a 1,3,5-trimethylphenyl group, Y ¹ represents a chlorine atom, a bromine atom or an iodine atom, M represents a metal group or a heteroatom group. Can be manufactured.

  “Step 1” is a method in which the compound (2) is reacted with the compound (3) in the presence of a palladium catalyst, optionally in the presence of a base, to obtain the pyrimidine derivative (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 target 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. Further, 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 preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is particularly preferable in terms of a good reaction yield. preferable. The molar ratio of the palladium catalyst to the compound (2) is preferably 1: 200 to 1: 2, and more preferably 1:50 to 1:10 in terms of a good reaction yield.

  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. 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.

  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.

In the case of the Suzuki-Miyaura reaction where M is B (OR ² ) ₂ , the reaction of “Step 1” can improve the yield by carrying out the reaction in the presence of a base. 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. Cesium carbonate and the like can be exemplified, and cesium carbonate is preferable in terms of a good yield. The molar ratio of the base and the compound (3) is preferably 1: 2 to 10: 1 and more preferably 1: 1 to 3: 1 in terms of a good yield.

  The reaction of “Step 1” can be carried out in a solvent. Examples of the solvent that can be used in “Step 1” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. It is desirable to use toluene or tetrahydrofuran in terms of a good yield.

  “Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is preferably performed at 40 ° C. to 110 ° C. in terms of a good yield.

  The pyrimidine derivative (1) of the present invention can be obtained by performing a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

  The pyrimidine derivative (1) of the present invention has the following reaction formula:

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ａｒ^３は、置換フェニル基、又は１６族元素を含まない縮環フェニル基を表す。ただし、Ａｒ^３は１，３，５−トリメチルフェニル基を含まない。Ｙ^２は、塩素原子、臭素原子又はヨウ素原子を表す。Ｒ^２は水素原子、炭素数１から４のアルキル基又はフェニル基を表し、Ｂ（ＯＲ^２）_２の２つのＲ^２は同一又は異なっていてもよい。又、２つのＲ^２は一体となって酸素原子及びホウ素原子を含んで環を形成することもできる。）で示される工程によっても製造することができる。

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. Ar ³ represents a substituted phenyl group or a condensed phenyl group not containing a group 16 element, provided that Ar ³ does not contain a 1,3,5-trimethylphenyl group, Y ² represents a chlorine atom, a bromine atom or an iodine atom, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group. , B (oR ²⁾ two R ² ₂ may be the same or different. Furthermore, the two R ² may form a ring containing an oxygen atom and a boron atom together.) in It can also be manufactured by the steps shown.

  “Step 2” is a method in which compound (4) is reacted with compound (5) in the presence of a palladium catalyst and a base to obtain pyrimidine derivative (1) of the present invention. Reaction of a general Suzuki-Miyaura reaction By applying the conditions, the target product can be obtained with good yield.

  Examples of the palladium catalyst that can be used in “Step 2” include the palladium salts and complex compounds exemplified in “Step 1”. Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is particularly preferable in terms of a good reaction yield. preferable. The molar ratio of the palladium catalyst to the compound (4) is preferably 1: 200 to 1: 2, and more preferably 1:50 to 1:10 in terms of a good reaction yield.

  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 tertiary phosphine exemplified in “Step 1”. Among them, 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.

  It is essential to carry out “Step 2” in the presence of a base. Examples of the base that can be used in “Step 2” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, fluoride. Cesium carbonate and the like can be exemplified, and cesium carbonate is preferable in terms of a good yield. The molar ratio of base to compound (4) is preferably from 1: 2 to 10: 1, and more preferably from 1: 1 to 4: 1 in terms of good yield.

  The molar ratio of the compound (4) and the compound (5) used in “Step 2” is preferably 1:10 to 2: 1, and more preferably 1: 2 to 1: 4 in terms of a good yield.

  The reaction of “Step 2” can be carried out in a solvent. Examples of the solvent that can be used in “Step 2” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. It is desirable to use a mixed solvent of toluene and water in terms of good yield.

  “Step 2” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 40 ° C. to 110 ° C. in terms of a good yield.

  The pyrimidine derivative (1) of the present invention can be obtained by performing a normal treatment after completion of “Step 2”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

  Compound (4), which is a raw material of “Step 2” for producing the pyrimidine derivative (1) of the present invention, has, for example, the following reaction formula:

（式中、Ａｒ^１及びＡｒ^２は、各々独立に置換されていてもよい芳香族基を表す。Ｙ^１は、塩素原子、臭素原子又はヨウ素原子を表す。Ｒ^２は水素原子、炭素数１から４のアルキル基又はフェニル基を表し、Ｂ（ＯＲ^２）_２の２つのＲ^２は同一又は異なっていてもよい。又、２つのＲ^２は一体となって酸素原子及びホウ素原子を含んで環を形成することもできる。）で示した方法により製造することができる。

(In the formula, Ar ¹ and Ar ² each independently represent an optionally substituted aromatic group. Y ¹ represents a chlorine atom, a bromine atom or an iodine atom. R ² represents a hydrogen atom and 1 carbon atom. 4 represents an alkyl group or a phenyl group, and two R ² of B (OR ² ) ₂ may be the same or different, and the two R ² together include an oxygen atom and a boron atom. A ring can also be formed.).

  "Step 3" is a reaction of reacting compound (2) with a borane compound represented by general formula (6) or a diboron compound represented by general formula (7) in the presence of a base and a palladium catalyst. 2 ”, which is disclosed, for example, in The Journal of OrganicC Chemistry, 60, 7508-7510, 1995 or Journal of Organic Chemistry, 65, 164-168, 2000. By applying the reaction conditions described above, the target product can be obtained with a high reaction yield.

  Examples of the palladium catalyst that can be used in "Step 3" include the same palladium salts or complex compounds exemplified in "Step 1". Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is particularly preferable in terms of a good reaction yield. preferable. The molar ratio of the palladium catalyst to the compound (2) is preferably 1: 200 to 1: 2, and more preferably 1:50 to 1:10 in terms of a good reaction yield.

  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 tertiary phosphine exemplified in “Step 1”. Among them, 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.

  It is essential to carry out the reaction of “Step 3” in the presence of a base. Examples of the base that can be used in “Step 3” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, fluoride. Cesium carbonate and the like can be exemplified, and cesium carbonate is preferable in terms of a good yield. The molar ratio of base to compound (2) is preferably 1: 2 to 10: 1, and more preferably 2: 1 to 4: 1 in terms of good yield.

  The molar ratio of the borane compound (6) or diboron compound (7) and the compound (2) used in “Step 3” is preferably 1: 1 to 5: 1, and 2: 1 to 3 in that the reaction yield is good. : 1 is more preferred.

  The reaction of “Step 3” can be carried out in a solvent. Examples of the solvent that can be used in “Step 3” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. It is desirable to use tetrahydrofuran in terms of a good yield.

  “Step 3” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 40 ° C. to 80 ° C. in terms of a good yield.

  The compound (4) obtained in this step may be isolated after the reaction or may be subjected to “Step 2” without isolation.

There is no particular limitation on the method for producing a thin film for an organic electroluminescent device comprising the pyrimidine derivative (1) of the present invention, and a desired thin film is prepared by a vacuum deposition method, a spin coating method, an inkjet method, a casting method, a dipping method, or the like. can do. For example, the 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 ⁻⁵ Pa which can be reached by the The deposition rate is preferably 0.005 to 1.0 nm / second, depending on the thickness of the film to be formed. In addition, since the pyrimidine derivative (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, inkjet Film formation by a method, a casting method, a dip method or the like is also possible.

  The thin film comprising the pyrimidine derivative (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection characteristics, etc. It is useful as a material for an organic electroluminescence device, and 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.

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

EXAMPLES Hereinafter, although an Example and a reference example are given and this invention is demonstrated further in detail, this invention is not limited to these.
Example-1

アルゴン気流下、２−（３，５−ジクロロフェニル）−４，６−ジフェニルピリミジン（１．５０ｇ，３．９８ｍｍｏｌ）、４−（２−ピリジル）フェニルボロン酸（１．７４ｇ，８．７５ｍｍｏｌ）、炭酸セシウム（２．８５ｇ，８．７５ｍｍｏｌ）、酢酸パラジウム（３６ｍｇ，０．１５９ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１５２ｍｇ，０．３１８ｍｍｏｌ）を１，４−ジオキサン（８０ｍＬ）に懸濁し、１７時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：クロロホルム）で精製し、目的の２−［４，４”−ジ（２−ピリジル）−１，１’：３’，１”−テルフェニル−５’−イル］−４，６−ジフェニルピリミジンの白色固体（収量２．１９ｇ，収率９０％）を得た。

Under an argon stream, 2- (3,5-dichlorophenyl) -4,6-diphenylpyrimidine (1.50 g, 3.98 mmol), 4- (2-pyridyl) phenylboronic acid (1.74 g, 8.75 mmol), Cesium carbonate (2.85 g, 8.75 mmol), palladium acetate (36 mg, 0.159 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (152 mg, 0.318 mmol), Suspended in 4-dioxane (80 mL) and refluxed for 17 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: chloroform), and the desired 2- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained. A white solid (-5.19 g, 90% yield) of -5′-yl] -4,6-diphenylpyrimidine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.19-7.23 (m, 2H), 7.53-7.50 (m, 6H), 7.70-7.79 (m, 4H), 7. 88 (d, J = 8.5 Hz, 4H), 8.01-8.02 (m, 2H), 8.11 (d, J = 8.3 Hz, 4H), 8.25-8.29 (m , 4H), 8.68 (d, J = 4.5 Hz, 2H), 8.95 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 110.7 (CH), 120.5 (CH × 2), 122.2 (CH × 2), 126.6 (CH × 2), 127.4 (CH × 4) ), 127.5 (CH × 4), 127.9 (CH × 4), 128.2 (CH), 129.0 (CH × 4), 130.9 (CH × 2), 136.8 (CH X2), 137.5 (quart. X2), 138.7 (quart. X2), 139.5 (quart.), 141.6 (quart.), 141.8 (quart.), 149. 9 (CH × 2), 157.1 (quart.), 164.4 (CH), 165.0 (CH × 2).
Example-2

アルゴン気流下、２−（３，５−ジブロモフェニル）−４，６−ジフェニルピリミジン（１．５９ｇ，３．４３ｍｍｏｌ）、２−［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）フェニル］ピリジン（２．０２ｇ，７．２０ｍｍｏｌ）、炭酸セシウム（２．３４ｇ，７．２０ｍｍｏｌ）、酢酸パラジウム（３１ｍｇ，０．１３７２ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１３１ｍｇ，０．２７４ｍｍｏｌ）をテトラヒドロフラン（６０ｍＬ）に懸濁し、５５時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：ヘキサン／クロロホルム＝１／１）で精製し、目的の２−［３，３”−ジ（２−ピリジル）−１，１’：３’，１”−テルフェニル−５’−イル］−４，６−ジフェニルピリミジンの白色固体（収量１．６９ｇ，収率８０％）を得た。

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-diphenylpyrimidine (1.59 g, 3.43 mmol), 2- [3- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) phenyl] pyridine (2.02 g, 7.20 mmol), cesium carbonate (2.34 g, 7.20 mmol), palladium acetate (31 mg, 0.1372 mmol), 2-dicyclohexylphosphino -2 ', 4', 6'-triisopropylbiphenyl (131 mg, 0.274 mmol) was suspended in tetrahydrofuran (60 mL) and refluxed for 55 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: hexane / chloroform = 1/1) to obtain the desired 2- [3,3 ″ -di (2-pyridyl) -1,1 ′: 3 ′. , 1 ″ -terphenyl-5′-yl] -4,6-diphenylpyrimidine (yield 1.69 g, yield 80%).

¹ H-NMR (CDCl ₃ ): δ 7.17-7.23 (m, 2H), 7.49-7.61 "(m, 8H), 7.68-7.83 (m, 6H), 7 .98 (t, J = 0.9 Hz, 1H), 8.02 (s, 1H), 8.04 (t, J = 1.8 Hz, 2H), 8.24-8.28 (m, 4H) , 8.33 (t, J = 1.8 Hz, 2H), 8.65-8.68 (m, 2H), 8.93 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 111.0 (CH), 121.2 (CH × 2), 122.7 (CH × 2), 126.56 (CH × 2), 126.59 (CH × 2) ), 127.0 (CH × 2), 127.8 (CH × 4), 128.7 (CH × 2), 129.1 (CH), 129.4 (CH × 4), 129.7 (CH × 2), 131.2 (CH × 2), 137.2 (CH × 2), 137.9 (quart. × 2), 140.0 (quart.), 140.4 (quart. × 2), 142.3 (quart. X2), 142.5 (quart. X2), 150.1 (CH x2), 157.8 (quart. X2), 164.9 (quart.), 165.3 (Quart. × 2).
Example-3

アルゴン気流下、４，６−ビス（２−ビフェニリル）−２−（３，５−ジクロロフェニル）ピリミジン（１．１４ｇ，２．１５ｍｍｏｌ）、４−（２−ピリジル）フェニルボロン酸（０．９０ｇ，４．５２ｍｍｏｌ）、炭酸セシウム（１．４７ｇ，４．５２ｍｍｏｌ）、酢酸パラジウム（１９ｍｇ，０．０８６ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（８２ｍｇ，０．１７２ｍｍｏｌ）をテトラヒドロフラン（４０ｍＬ）に懸濁し、１８時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：ヘキサン／クロロホルム＝１／１）で精製し、目的の４，６−ビス（２−ビフェニリル）−２−［４，４”−ジ（２−ピリジル）−１，１’：３’，１”−テルフェニル−５’−イル］ピリミジンの白色固体（収量０．６０ｇ，収率３７％）を得た。

Under a stream of argon, 4,6-bis (2-biphenylyl) -2- (3,5-dichlorophenyl) pyrimidine (1.14 g, 2.15 mmol), 4- (2-pyridyl) phenylboronic acid (0.90 g, 4.52 mmol), cesium carbonate (1.47 g, 4.52 mmol), palladium acetate (19 mg, 0.086 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (82 mg, 0.85 mmol). 172 mmol) was suspended in tetrahydrofuran (40 mL) and refluxed for 18 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: hexane / chloroform = 1/1) to obtain the desired 4,6-bis (2-biphenylyl) -2- [4,4 "-di (2 -Pyridyl) -1,1 ': 3', 1 "-terphenyl-5'-yl] pyrimidine was obtained as a white solid (yield 0.60 g, yield 37%).

¹ H-NMR (CDCl ₃ ): δ 7.04 (s, 1H), 7.22-7.36 (m, 10H), 7.45-7.59 (m, 8H), 7.80-7. 89 (m, 8H), 7.96 (t, J = 1.8 Hz, 1H), 8.18 (d, J = 8.3 Hz, 4H), 8.25 (d, J = 1.8 Hz, 2H) ), 8.78 (bd, J = 4.8 Hz, 2H).
Example-4

アルゴン気流下、２−（３，５−ジクロロフェニル）−４，６−ジ（２−ピリジル）ピリミジン（０．５０ｇ、１．３２ｍｍｏｌ）、４−（２−ピリジル）フェニルボロン酸（０．５５ｇ，２．７６ｍｍｏｌ）、炭酸セシウム（０．９０ｇ，２．７７ｍｍｏｌ）、酢酸パラジウム（２４ｍｇ，０．１０６ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１０１ｍｇ，０．２１１ｍｍｏｌ）をテトラヒドロフラン（３０ｍＬ）に懸濁し、１７時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：クロロホルム）で精製し、目的の２−［４，４”−ジ（２−ピリジル）−１，１’：３’，１”−テルフェニル−５’−イル］−４，６−ジ（２−ピリジル）ピリミジンの白色固体（収量０．４６ｇ，収率５６％）を得た。

Under an argon stream, 2- (3,5-dichlorophenyl) -4,6-di (2-pyridyl) pyrimidine (0.50 g, 1.32 mmol), 4- (2-pyridyl) phenylboronic acid (0.55 g, 2.76 mmol), cesium carbonate (0.90 g, 2.77 mmol), palladium acetate (24 mg, 0.106 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (101 mg, 0.86 mmol). 211 mmol) was suspended in tetrahydrofuran (30 mL) and refluxed for 17 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: chloroform), and the desired 2- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained. A white solid (yield 0.46 g, yield 56%) of -5′-yl] -4,6-di (2-pyridyl) pyrimidine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.17-7.26 (m, 2H), 7.40 (ddd, J = 7.5, 4.8, 1.0 Hz, 2H), 7.69-7 .78 (m, 4H), 7.83-7.89 (m, 6H), 8.00 (t, J = 1.6 Hz, 1H), 8.12 (d, J = 8.3 Hz, 4H) , 8.67-8.70 (m, 4H), 8.74 (d, J = 4.0 Hz, 2H), 8.94 (d, J = 1.8 Hz, 2H), 9.31 (s, 1H).
¹³ C-NMR (CDCl ₃ ): δ 112.0 (CH), 120.6 (CH × 2, CH × 2), 122.0 (CH × 2), 122.3 (CH × 2), 125.4 (CH × 2), 126.5 (CH × 4), 127.5 (CH × 4), 127.9 (CH), 136.9 (CH × 2), 137.1 (CH × 2), 138 .7 (quart. × 2), 139.2 (quart.), 141.7 (quart. × 2), 141.8 (quart. × 2), 149.7 (CH × 2), 149.8 ( CH × 2), 154.7 (quart. × 2), 157.1 (quart. × 2), 163.9 (quart.), 164.5 (quart. × 2).
Example-5

アルゴン気流下、２−（３，５−ジブロモフェニル）−４，６−ジ−ｐ−トリルピリミジン（０．４０ｇ，０．８１ｍｍｏｌ）、４−［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］ピリジン（０．４８ｇ，１．７０ｍｍｏｌ）、炭酸セシウム（０．５５ｇ，１．７０ｍｍｏｌ）、酢酸パラジウム（７ｍｇ，０．０３２ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（３１ｍｇ，０．０６５ｍｍｏｌ）をテトラヒドロフラン（２０ｍＬ）に懸濁し、８７時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：クロロホルム／メタノール＝１００／１）で精製し、目的の２−［４，４”−ジ（４−ピリジル）−１，１’：３’，１”−テルフェニル−５’−イル］−４，６−ジ−ｐ−トリルピリミジンの白色固体（収量０．３０ｇ，収率５８％）を得た。

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-di-p-tolylpyrimidine (0.40 g, 0.81 mmol), 4- [4- (4,4,5,5-tetra Methyl-1,3,2-dioxaborolan-2-yl) phenyl] pyridine (0.48 g, 1.70 mmol), cesium carbonate (0.55 g, 1.70 mmol), palladium acetate (7 mg, 0.032 mmol), 2 -Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (31 mg, 0.065 mmol) was suspended in tetrahydrofuran (20 mL) and refluxed for 87 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: chloroform / methanol = 100/1) to obtain the desired 2- [4,4 ″ -di (4-pyridyl) -1,1 ′: 3 ′. , 1 "-terphenyl-5'-yl] -4,6-di-p-tolylpyrimidine (yield 0.30 g, yield 58%).

¹ H-NMR (CDCl ₃ ): δ 2.50 (s, 6H), 7.41 (d, J = 8.0 Hz, 4H), 7.63 (dd, J = 4.5, 1.5 Hz, 4H) ), 7.84 (d, J = 8.3 Hz, 4H), 7.95 (d, J = 8.3 Hz, 4H), 8.03 (t, J = 1.8 Hz, 1H), 8.05 (S, 1H), 8.24 (d, J = 8.0 Hz, 4H), 8.73 (dd, J = 4.5, 1.5 Hz, 4H), 9.02 (d, J = 1. 8Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.6 (CH ₃ ), 31.0 (CH 3), 110.1 (CH), 121.5 (CH × 4), 126.7 (CH × 2), 127. 3 (CH × 4), 127.5 (CH × 4), 128.2 (CH × 4), 129.7 (CH × 4), 134.7 (quart. × 2), 137.3 (quart. X2), 139.9 (quart.), 141.2 (quart. X2), 141.3 (quart. X2), 142.0 (quart. X2), 147.9 (quart. X2) ), 150.4 (CH × 4), 164.0 (quart.), 164.7 (quart. × 2).
Example-6

アルゴン気流下、２−（３，５−ジブロモフェニル）−４，６−ジ（２−ナフチル）ピリミジン（０．５０ｇ，０．８８ｍｍｏｌ）、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］−１，１０−フェナントロリン（０．９５ｇ，２．８２ｍｍｏｌ）、炭酸セシウム（０．６３ｇ，１．９４ｍｍｏｌ）、酢酸パラジウム（８ｍｇ，０．０３５ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（３４ｍｇ，０．０７０ｍｍｏｌ）をトルエン（４０ｍＬ）に懸濁し、１４時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：クロロホルム）で精製し、目的の２−［４，４”−ビス（１，１０−フェナントロリン−２−イル）−１，１’；３’，１”−テルフェニル−５’−イル］−４，６−ジ（２−ナフチル）ピリミジンの黄色固体（収量０．２５ｇ，収率３１％）を得た。

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-di (2-naphthyl) pyrimidine (0.50 g, 0.88 mmol), 2- [4- (4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1,10-phenanthroline (0.95 g, 2.82 mmol), cesium carbonate (0.63 g, 1.94 mmol), palladium acetate (8 mg, 0.035 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (34 mg, 0.070 mmol) was suspended in toluene (40 mL) and refluxed for 14 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: chloroform) to obtain the desired 2- [4,4 ″ -bis (1,10-phenanthrolin-2-yl) -1,1 ′; 3 ′. , 1 ″ -terphenyl-5′-yl] -4,6-di (2-naphthyl) pyrimidine (yield 0.25 g, yield 31%).

¹ H-NMR (CDCl ₃ ): δ 7.52-7.55 (m, 4H), 7.61 (dd, J = 4.4, 0.3 Hz, 2H), 7.73-7.82 (m , 4H), 7.88-7.92 (m, 2H), 8.00-8.09 (m, 8H), 8.13 (bs, 1H), 8.12-8.24 (m, 4H) ), 8.31 (d, J = 8.5 Hz, 2H), 8.34 (s, 1H), 8.46 (d, J = 8.3 Hz, 2H), 8.53 (d, J = 8 .0 Hz, 4H), 8.85 (bs, 2H), 9.10 (bs, 2H), 9.23 (d, J = 4.3 Hz, 2H).
Example-7

アルゴン気流下、２−［３，５−ビス（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］−４，６−ジフェニルピリミジン（０．１８ｇ，０．３２ｍｍｏｌ）、３−（４−ブロモフェニル）ピリジン（０．１９ｇ，０．８２ｍｍｏｌ）、炭酸セシウム（０．２５ｇ，０．７６ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２３ｍｇ，０．０３３ｍｍｏｌ）をテトラヒドロフラン（１０ｍＬ）に懸濁し、１２時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／クロロホルム＝１／１）で精製し、目的の２−［４，４”−ジ（３−ピリジル）−１，１’：３’，１”−テルフェニル−５’−イル｝−４，６−ジフェニルピリミジンの白色固体（収量７７ｍｇ，収率３９％）を得た。

Under an argon stream, 2- [3,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenylpyrimidine (0.18 g, 0.32 mmol), 3- (4-bromophenyl) pyridine (0.19 g, 0.82 mmol), cesium carbonate (0.25 g, 0.76 mmol), dichlorobis (triphenylphosphine) palladium (23 mg, 0.033 mmol) Was suspended in tetrahydrofuran (10 mL) and refluxed for 12 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane / chloroform = 1/1) to obtain the desired 2- [4,4 ″ -di (3-pyridyl) -1,1 ′: 3. A white solid (yield 77 mg, 39% yield) of “, 1” -terphenyl-5′-yl} -4,6-diphenylpyrimidine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.30-7.35 (m, 2H), 7.39-7.50 (m, 6H), 7.67 (d, J = 7.8 Hz, 4H), 7.84 (d, J = 7.8 Hz, 4H), 7.86-7.93 (m, 2H), 7.98 (s, 1H), 8.22-8.24 (m, 5H), 8.55 (d, J = 4.3 Hz, 2H), 8.88 (bs, 2H), 8.91 (bs, 2H). Example-8

アルゴン気流下、２−（３，５−ジブロモフェニル）−４−（２−ナフチル）−６−ｐ−トリルピリミジン（０．４０ｇ，０．７５ｍｍｏｌ）、５−［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］ピリミジン（０．４７ｇ，１．６６ｍｍｏｌ）、炭酸セシウム（０．５４ｇ，１．６６ｍｍｏｌ）、酢酸パラジウム（７ｍｇ，０．０３０ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（２９ｍｇ，０．０６０ｍｍｏｌ）をテトラヒドロフラン（１５ｍＬ）に懸濁し、１５時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：ヘキサン／クロロホルム＝１／１）で精製し、目的の２−［４，４”−ジ（５−ピリミジル）−１，１’：３’，１”−テルフェニル−５’−イル］−４−（２−ナフチル）−６−ｐ−トリルピリミジンの白黄色固体（収量０．２８ｇ，収率５４％）を得た。

Under an argon stream, 2- (3,5-dibromophenyl) -4- (2-naphthyl) -6-p-tolylpyrimidine (0.40 g, 0.75 mmol), 5- [4- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] pyrimidine (0.47 g, 1.66 mmol), cesium carbonate (0.54 g, 1.66 mmol), palladium acetate (7 mg,. 030 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (29 mg, 0.060 mmol) was suspended in tetrahydrofuran (15 mL) and refluxed for 15 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: hexane / chloroform = 1/1) to obtain the desired 2- [4,4 ″ -di (5-pyrimidyl) -1,1 ′: 3 ′. , 1 ″ -terphenyl-5′-yl] -4- (2-naphthyl) -6-p-tolylpyrimidine was obtained as a white yellow solid (yield 0.28 g, yield 54%).

¹ H-NMR (CDCl ₃ ): δ 2.40 (s, 3H), 7.32 (d, J = 8.0 Hz, 2H), 7.46-7.54 (m, 2H), 7.68 ( d, J = 8.3 Hz, 4H), 7.83-7.97 (m, 8H), 8.08 (s, 1H), 8.17 (d, J = 8.0 Hz, 2H), 8. 33 (dd, J = 8.8, 0.1 Hz, 1H), 8.68 (bs, 1H), 8.94 (d, J = 1.5 Hz, 2H), 8.98 (bs, 4H), 9.12 (bs, 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.5 (CH ₃ ), 110.7 (CH), 124.3 (CH), 126.7 (CH), 126.8 (CH), 127.3 (CH × 2, CH × 2), 127.5 (CH × 4), 127.9 (CH), 128.0 (CH), 128.5 (CH × 4), 128.8 (CH), 129.1 ( CH), 129.8 (CH × 2), 133.3 (quart.), 133.5 (quart. × 2), 134.0 (quart. × 2), 134.6 (quart.), 134. 7 (quart.), 134.9 (quart.), 139.9 (quart.), 141.1 (quart. X2), 141.5 (quart.), 141.9 (quart. X2), 154.9 (CH × 4) 157.7 (CH), 164.1 (qu art.), 154.8 (quart.), 164.9 (quart.).
Example-9

アルゴン気流下、２−［３，５−ビス（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］−４，６−ジフェニルピリミジン（０．１５ｇ，０．２６ｍｍｏｌ）、２−（４−ブロモフェニル）−１，３−ベンゾチアゾール（０．１９ｇ，０．６６ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（７７ｍｇ，０．０６６ｍｍｏｌ）を２Ｍ−炭酸ナトリウム水溶液（３ｍＬ）とトルエン（６ｍＬ）に懸濁し、２４時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：クロロホルム／メタノール＝１００／１）で精製し、目的の２−［４，４”−ジ（２−ベンゾチアゾリル）−１，１’：３’，１”−テルフェニル−５’−イル］−４，６−ジフェニルピリミジンの白色固体（収量０．１２ｇ，収率６５％）を得た。

Under an argon stream, 2- [3,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenylpyrimidine (0.15 g, 0.26 mmol), 2- (4-bromophenyl) -1,3-benzothiazole (0.19 g, 0.66 mmol), tetrakis (triphenylphosphine) palladium (77 mg, 0.066 mmol) in 2M sodium carbonate aqueous solution (3 mL) and toluene (6 mL) were suspended and refluxed for 24 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/1) to obtain the desired 2- [4,4 ″ -di (2-benzothiazolyl) -1,1 ′: 3. A white solid (yield 0.12 g, yield 65%) of “, 1” -terphenyl-5′-yl] -4,6-diphenylpyrimidine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.30-7.36 (m, 2H), 7.42-7.56 (m, 8H), 7.78-7.87 (m, 6H), 7. 95-7.97 (m, 1H), 7.9 (s, 1H), 8.04 (d, J = 7.8 Hz, 2H), 8.18 (d, J = 8.3 Hz, 4H), 8.22-8.26 (m, 4H), 8.94 (d, J = 1.8 Hz, 2H).
Example-10

アルゴン気流下、６−ブロモキノリン（０．３４ｇ，１．６２ｍｍｏｌをテトラヒドロフラン（７ｍＬ）に溶解し、ブチルリチウム（１．６３ｍｍｏｌ）を含むヘキサン溶液（１．０３ｍＬ）を−７８℃で滴下した。混合物を−７８℃で３０分間攪拌後、ジクロロ（テトラメチルエチレンジアミン）亜鉛（０．４１ｇ，１．６３ｍｍｏｌ）を加え、室温まで昇温した後１時間攪拌した。この混合物に２−（３，５−ジブロモフェニル）−４，６−ジ−ｐ−トリルピリミジン（０．２０ｇ，０．４１ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（１９ｍｇ，０．０１６ｍｍｏｌ）、テトラヒドロフラン（３ｍＬ）を加えて懸濁し、加熱還流下で１７時間攪拌した。室温まで冷却後、減圧下で低沸点成分を留去した後、析出した固体をろ別した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／クロロホルム＝１／１）で精製し、目的の２−［３，５−＋ジ（６−キノリル）フェニル］−４，６−ジ−ｐ−トリルピリミジンの白色固体（収量０．１６ｇ、収率６５％）を得た。

Under an argon stream, 6-bromoquinoline (0.34 g, 1.62 mmol was dissolved in tetrahydrofuran (7 mL), and a hexane solution (1.03 mL) containing butyllithium (1.63 mmol) was added dropwise at −78 ° C. After stirring at −78 ° C. for 30 minutes, dichloro (tetramethylethylenediamine) zinc (0.41 g, 1.63 mmol) was added, and the mixture was warmed to room temperature and stirred for 1 hour. Dibromophenyl) -4,6-di-p-tolylpyrimidine (0.20 g, 0.41 mmol), tetrakis (triphenylphosphine) palladium (19 mg, 0.016 mmol), tetrahydrofuran (3 mL) were added and suspended, and heated. The mixture was stirred for 17 hours under reflux, cooled to room temperature, distilled off low-boiling components under reduced pressure, and then precipitated. The resulting crude product was purified by silica gel column chromatography (developing solvent: hexane / chloroform = 1/1) to obtain the desired 2- [3,5- + di (6-quinolyl) phenyl. ] -4,6-di-p-tolylpyrimidine was obtained as a white solid (yield 0.16 g, yield 65%).

¹ H-NMR (CDCl ₃ ): δ 2.49 (s, 6H), 7.33-7.38 (m, 2H), 7.41 (d, J = 8.0 Hz, 4H), 8.03 ( t, J = 1.8 Hz, 1H), 8.05 (s, 1H), 8.09-8.34 (m, 8H), 8.24 (d, J = 8.0 Hz, 4H), 8. 92 (dd, J = 4.3, 1.5 Hz, 2H), 9.02 (d, J = 1.8 Hz, 2H).
Example-11

アルゴン気流下、２−（３，５−ジクロロフェニル）−４，６−ビス［４−（３−ピリジル）フェニル］ピリミジン（０．４５ｇ，０．８５ｍｍｏｌ）、ｍ−ビフェニルボロン酸（０．３７ｇ，１．８７ｍｍｏｌ）、リン酸カリウム（０．３９ｇ，１．８６ｍｍｏｌ）、酢酸パラジウム（８ｍｇ，０．０３４ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（３２ｍｇ，０．０６８ｍｍｏｌ）をテトラヒドロフラン（２０ｍＬ）に懸濁し、６６時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：クロロホルム）で精製し、目的の４，６−ビス［４−（３−ピリジル）フェニル］−２−（１，１’：３’，１”：３”，１”’：３”’，１””−キンクフェニル−５”−イル）ピリミジンの白色固体（収量０．４２ｇ，収率６４％）を得た。

Under an argon stream, 2- (3,5-dichlorophenyl) -4,6-bis [4- (3-pyridyl) phenyl] pyrimidine (0.45 g, 0.85 mmol), m-biphenylboronic acid (0.37 g, 1.87 mmol), potassium phosphate (0.39 g, 1.86 mmol), palladium acetate (8 mg, 0.034 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (32 mg, 0 .068 mmol) was suspended in tetrahydrofuran (20 mL) and refluxed for 66 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: chloroform), and the desired 4,6-bis [4- (3-pyridyl) phenyl] -2- (1,1 ′: 3 ′, 1 A white solid (yield 0.42 g, yield 64%) of “: 3”, 1 ″ ′: 3 ″ ′, 1 ″ ″-kinkphenyl-5 ″ -yl) pyrimidine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.28-7.44 (m, 8H), 7.51-7.66 (m, 8H), 7.71-7.75 (m, 6H), 7. 89 (t, J = 1.9 Hz, 2H), 7.91-7.94 (m, 2H), 7.98 (t, J = 1.6 Hz, 1H), 8.08 (s, 1H), 8.38 (d, J = 8.3 Hz, 4H), 8.58 (dd, J = 4.8, 1.5 Hz, 2H), 8.88 (d, J = 2.3 Hz, 2H), 8 .93 (d, J = 1.8 Hz, 2H).
Example-12

アルゴン気流下、２−（３，５−ジブロモフェニル）−４，６−ジフェニルピリミジン（５．００ｇ，１０．７ｍｍｏｌ）、３−クロロフェニルボロン酸（３．７０ｇ，２３．６ｍｍｏｌ）、炭酸セシウム（７．６９ｇ，２３．６ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（３００ｍｇ，０．４３ｍｍｏｌ）をテトラヒドロフラン（１００ｍＬ）に懸濁し、１５時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒：ヘキサン／クロロホルム＝１／１）で精製し、目的の２−（３，３”−ジクロロ−１，１’：３’，１”−テルフェニル−５’−イル）−４，６−ジフェニルピリミジンの白色固体（収量３．５８ｇ，収率６３％）を得た。

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-diphenylpyrimidine (5.00 g, 10.7 mmol), 3-chlorophenylboronic acid (3.70 g, 23.6 mmol), cesium carbonate (7 .69 g, 23.6 mmol) and dichlorobis (triphenylphosphine) palladium (300 mg, 0.43 mmol) were suspended in tetrahydrofuran (100 mL) and refluxed for 15 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent: hexane / chloroform = 1/1) to obtain the desired 2- (3,3 ″ -dichloro-1,1 ′: 3 ′, 1 ″ -tel A white solid of phenyl-5′-yl) -4,6-diphenylpyrimidine (yield 3.58 g, yield 63%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.32-7.43 (m, 4H), 7.51-7.55 (m, 6H), 7.60 (dt, J = 7.3, 1.5 Hz) , 2H), 7.69 (t, J = 1.5 Hz, 2H), 7.79 (t, J = 1.8 Hz, 1H), 8.01 (s, 1H), 8.22-8.26. (M, 4H), 8.84 (d, J = 1.8 Hz, 2H).
Example-13

アルゴン気流下、２−（３，３”−ジクロロ−１，１’：３’，１”−テルフェニル−５’−イル）−４，６−ジフェニルピリミジン（０．５０ｇ，０．９４ｍｍｏｌ）、２−ベンゾフリルボロン酸（０．６７ｇ，４．１６ｍｍｏｌ）、炭酸セシウム（１．３５ｇ，４．１６ｍｍｏｌ）、酢酸パラジウム（８ｍｇ，０．０３８ｍｍｏｌ）、２−ジシクロへキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（３６ｍｇ，０．０７５ｍｍｏｌ）を１，４−ジオキサン（２０ｍＬ）に懸濁し、１４時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒 ヘキサン：クロロホルム＝１：１）で精製し、目的の２−［３，３”−ジ（２−ベンゾフリル）−１，１’：３’，１”−テルフェニル−５’−イル］−４，６−ジフェニルピリミジンの白色固体（収量０．１６ｇ，収率２５％）を得た。

Under an argon stream, 2- (3,3 ″ -dichloro-1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl) -4,6-diphenylpyrimidine (0.50 g, 0.94 mmol), 2-benzofurylboronic acid (0.67 g, 4.16 mmol), cesium carbonate (1.35 g, 4.16 mmol), palladium acetate (8 mg, 0.038 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-Triisopropylbiphenyl (36 mg, 0.075 mmol) was suspended in 1,4-dioxane (20 mL) and refluxed for 14 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 1) to obtain the desired 2- [3,3 ″ -di (2-benzofuryl) -1,1 ′: 3 ′, A white solid (yield 0.16 g, yield 25%) of 1 ″ -terphenyl-5′-yl] -4,6-diphenylpyrimidine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.09 (s, 2H), 7.15-7.27 (m, 4H), 7.48-7.59 (m, 12H), 7.74 (bd, J = 7.7 Hz, 2H), 7.87 (bd, J = 7.8 Hz, 2H), 8.01 (t, J = 1.8 Hz, 1H), 8.03 (s, 1H), 8. 23-8.30 (m, 6H), 8.96 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 101.9 (CH × 2), 110.8 (CH), 111.3 (CH × 2), 121.0 (CH × 2), 123.0 (CH × 2) ), 124.1 (CH × 2), 124.2 (CH × 2), 124.5 (CH × 2), 126.8 (CH × 2), 127.4 (CH × 4), 127.9 (CH × 2), 128.6 (CH), 129.1 (CH × 4), 129.3 (quart. × 2), 129.4 (CH × 2), 131.0 (CH × 2), 131.2 (quart. X2), 137.5 (quart. X2), 139.6 (quart.), 141.9 (quart. X2), 142.0 (quart. X2), 155. 1 (quart. X2), 155.9 (quart. X2), 164.4 (quart.), 165.0 (q art. × 2).
Reference Example-1

アルゴン気流下、２−（３，５−ジブロモフェニル）−４，６−ジフェニルピリミジン（１．００ｇ，２．１５ｍｍｏｌ）、ビスピナコラートジボロン（１．２０ｇ，４．７３ｍｍｏｌ）、酢酸カリウム（０．７０ｇ，７．０９ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（９１ｍｇ，０．１２９ｍｍｏｌ）をテトラヒドロフラン（２０ｍＬ）に懸濁し、７７時間還流した。室温まで冷却後、減圧下で低沸点成分を除去した後、析出した固体をろ別した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒 ヘキサン：クロロホルム＝１：１）で精製し、目的の２−［３，５−ビス（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］−４，６−ジフェニルピリミジンの白色固体（収量０．６８ｇ，収率５６％）を得た。

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-diphenylpyrimidine (1.00 g, 2.15 mmol), bispinacolatodiboron (1.20 g, 4.73 mmol), potassium acetate (0 .70 g, 7.09 mmol) and dichlorobis (triphenylphosphine) palladium (91 mg, 0.129 mmol) were suspended in tetrahydrofuran (20 mL) and refluxed for 77 hours. After cooling to room temperature, low-boiling components were removed under reduced pressure, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 1) to obtain the desired 2- [3,5-bis (4,4,5,5-tetramethyl-1,3). , 2-Dioxaborolan-2-yl) phenyl] -4,6-diphenylpyrimidine was obtained as a white solid (yield 0.68 g, yield 56%).

¹ H-NMR (CDCl ₃ ): δ 1.32 (s, 24H), 7.49-7.52 (m, 6H), 7.94 (s, 1H), 8.23-8.27 (m, 4H), 8.34 (bs, 1H), 9.09 (d, J = 1.3 Hz, 2H).
Element Example-1
Fabrication and Performance Evaluation of Organic Electroluminescent Device Containing Pyrimidine Derivatives As a substrate, a glass substrate with an ITO transparent electrode in which a 2 mm-wide indium-tin oxide (ITO) film 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. First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa. Thereafter, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4 and an electron transport layer 5 are sequentially formed as an organic compound layer on the glass substrate shown in FIG. 1, and then a cathode layer 6 is formed. Filmed. As the hole injection layer 2, sublimation-purified phthalocyanine copper (II) was vacuum-deposited with a film thickness of 25 nm. As the hole transport layer 3, N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 45 nm.

  As the light emitting layer 4, 4,4′-bis (2,2-diphenylethen-1-yl) diphenyl (DPVBi) and 4,4′-bis [4- (di-p-tolylamino) phenylethene-1- [Il] biphenyl (DPAVBi) was vacuum-deposited at a thickness of 97 nm and a thickness of 40 nm. As the electron transport layer 5, 2- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl] -4 synthesized in Example-1 was used. , 6-Diphenylpyrimidine was vacuum deposited with a thickness of 20 nm. Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 nm / second to 0.5 nm / second. Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed. The cathode layer 6 was made into a two-layer structure by vacuum-depositing lithium fluoride and aluminum with thicknesses of 0.5 nm and 100 nm, respectively. 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. Sealing was performed using a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation).

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 light emission characteristics, voltage (V), luminance (cd / m ² ), current efficiency (cd / A), and power efficiency (lm / W) when a current density of 20 mA / cm ² is passed are measured, and when continuously lit The luminance half time of was measured.

The measured value of the produced blue fluorescent element was 5.8 V, 2160 cd / m ² , 10.8 cd / A, 5.9 lm / W. The luminance half time of this element was 171 hours.
Element Example-2
In place of the light emitting layer 4 of the device example-1, an organic electroluminescent device in which Alq (tris (8-quinolinolato) aluminum (III)) was vacuum-deposited with a film thickness of 40 nm was prepared in the same manner as the device example-1. did.

The measured value of the produced green fluorescent element was 5.1 V, 958 cd / m ² , 4.8 cd / A, 2.9 lm / W. The luminance half time of this device was 1618 hours.
Element Example-3
Under the element production conditions of element example-1, sublimation-purified phthalocyanine copper (II) was vacuum-deposited as a hole injection layer 2 with a film thickness of 10 nm. As the hole transport layer 3, N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 30 nm. 4,4′-bis (carbazol-9-yl) biphenyl (CBP) is used as the host material of the light-emitting layer 4, and tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3) is used as the dopant. The film was co-deposited to a thickness of 30 nm using a dope concentration of 6%. As the electron transport layer 5, 2- [4,4 "-di (2-pyridyl) -1,1 ': 3', 1"-terphenyl-5'-yl] -4,6-diphenyl of the present invention is used. Pyrimidine was vacuum deposited with a film thickness of 50 nm.

The measured values of the produced green phosphorescent element were 7.5 V, 6610 cd / m ² , 33.5 cd / A, and 13.9 lm / W. The luminance half time of this device was 230 hours.
Element Example 4
In place of the electron transport layer 5 of device example-1, 2- [3,3 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl] -4 An organic electroluminescent device obtained by vacuum-depositing 1,6-diphenylpyrimidine with a film thickness of 20 nm was produced in the same manner as in Device Example-1.

The measured value of the produced blue fluorescent element was 6.3 V, 2110 cd / m ² , 10.6 cd / A, 5.3 lm / W. The luminance half time of this device was 165 hours.
Device comparison example-1
Instead of the electron transport layer 5 of the device example-1, an organic electroluminescent device in which Alq was vacuum-deposited with a film thickness of 20 nm was produced in the same manner as the device example-1.

The measured values of the produced blue fluorescent element were 7.1 V, 1883 cd / m ² , 9.4 cd / A, and 4.2 lm / W. The luminance half time of this device was 163 hours.
Device comparison example-2
In place of the electron transport layer 5 of the device example-2, an organic electroluminescent device in which Alq was vacuum-deposited with a film thickness of 20 nm was produced in the same manner as the device example-2.

The measured value of the produced green fluorescent element was 5.6 V, 957 cd / m ² , 4.8 cd / A, 2.6 lm / W. The luminance half time of this device was 1318 hours.
Device comparison example-3
Instead of the electron transport layer 5 of the device example-3, an organic electroluminescent device in which Alq was vacuum-deposited with a film thickness of 50 nm was produced in the same manner as the device example-2.

The measured values of the produced green phosphorescent element were 7.7 V, 3850 cd / m ² , 16.9 cd / A, and 6.7 lm / W. The luminance half time of this device was 271 hours.
Device comparison example-4
Instead of the electron transport layer 5 of the device example-3, organic electroluminescence obtained by vacuum depositing BAlq (bis (2-methyl-8-quinolinolato) 4-phenylphenolato-aluminum) with a thickness of 5 nm and Alq with a thickness of 45 nm. The device was fabricated in the same manner as in Device Example-3.

The measured value of the produced green phosphorescent element was 9.3 V, 6170 cd / m ² , 30.9 cd / A, 10.4 lm / W. The luminance half time of this element was 202 hours.

  As described above, it has been confirmed that the use of the pyrimidine derivative of the present invention can achieve lower power consumption and longer life in a wide range of fluorescent elements and phosphorescent elements as compared with existing materials. In addition to the light emitting layer of this example, the compound of the present invention can be applied to organic electroluminescent devices using other fluorescent light emitting materials and phosphorescent materials, and can also be applied to coating-based devices. In addition to flat panel display applications, it is also effective for lighting applications that require both low power consumption and long life.

  The present invention provides a pyrimidine derivative having a novel structure that enables low-voltage driving and high-efficiency light emission of an element by using it as an electron transport layer of a fluorescent or phosphorescent organic electroluminescent element, and further provides a low voltage using the compound. The present invention provides an organic electroluminescent device having a structure.

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

Claims (7)

General formula (1)

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group, 2-biphenyl group, pyridyl group, p-tolyl group, naphthyl group, 4- (3-pyridyl) phenyl group. Ar ³ represents carbon. Phenyl group substituted with an alkyl group of 1 to 4, phenyl group substituted with phenyl group, phenyl group substituted with pyrimidyl group, 4- (2-benzothiazolyl) phenyl group , phenyl group substituted with pyridyl group Represents a phenyl group substituted with a phenanthryl group, a phenyl group substituted with a phenanthryl group, a 3- (2-benzofuryl) phenyl group, or a quinolyl group ) . General formula (2)

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group, a 2-biphenyl group, a pyridyl group, a p-tolyl group, a naphthyl group, or a 4- (3-pyridyl) phenyl group. Y ¹ represents chlorine. An atom, a bromine atom or an iodine atom) and a general formula (3)

(In the formula, Ar ³ is a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with a phenyl group, a phenyl group substituted with a pyrimidyl group, or a 4- (2-benzothiazolyl) phenyl group. Represents a phenyl group substituted with a pyridyl group, a phenyl group substituted with a phenanthryl group, a phenyl group substituted with a phenanthryl group, a 3- (2-benzofuryl) phenyl group, or a quinolyl group, where M is a metal group or And a compound represented by the general formula (1), wherein the compound is subjected to a coupling reaction in the presence of a palladium catalyst, optionally in the presence of a base.

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group, 2-biphenyl group, pyridyl group, p-tolyl group, naphthyl group, 4- (3-pyridyl) phenyl group. Ar ³ represents carbon. Phenyl group substituted with an alkyl group of 1 to 4, phenyl group substituted with phenyl group, phenyl group substituted with pyrimidyl group, 4- (2-benzothiazolyl) phenyl group , phenyl group substituted with pyridyl group And represents a phenyl group substituted with a phenanthryl group, a phenyl group substituted with a phenanthryl group, a 3- (2-benzofuryl) phenyl group, or a quinolyl group ) . The metal group or heteroatom group represented by M is ZnR ¹ or B (OR ² ) ₂ (where R ¹ represents a halogen atom, R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or phenyl. It represents a group, B (oR ²⁾ two R ² ₂ may be the same or different. Furthermore, the two R ² may form a ring containing an oxygen atom and a boron atom together The method for producing a pyrimidine derivative according to claim 2, wherein the group is a group represented by the formula: General formula (4)

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group, a 2-biphenyl group, a pyridyl group, a p-tolyl group, a naphthyl group, or a 4- (3-pyridyl) phenyl group. R ² represents a hydrogen atom. Represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and two R ² of B (OR ² ) ₂ may be the same or different, and the two R ² are combined with an oxygen atom and boron. A ring including an atom can be formed.) And a compound represented by the general formula (5)

(In the formula, Ar ³ is a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with a phenyl group, a phenyl group substituted with a pyrimidyl group, or a 4- (2-benzothiazolyl) phenyl group. Y ² represents a chlorine atom, a phenyl group substituted with a pyridyl group, a phenyl group substituted with a phenanthryl group, a phenyl group substituted with a phenanthryl group, a 3- (2-benzofuryl) phenyl group, or a quinolyl group. , Which represents a bromine atom or an iodine atom), and a compound represented by the general formula (1), wherein the compound is subjected to a coupling reaction in the presence of a base and a palladium catalyst.

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group, 2-biphenyl group, pyridyl group, p-tolyl group, naphthyl group, 4- (3-pyridyl) phenyl group. Ar ³ represents carbon. Phenyl group substituted with an alkyl group of 1 to 4, phenyl group substituted with phenyl group, phenyl group substituted with pyrimidyl group, 4- (2-benzothiazolyl) phenyl group , phenyl group substituted with pyridyl group And represents a phenyl group substituted with a phenanthryl group, a phenyl group substituted with a phenanthryl group, a 3- (2-benzofuryl) phenyl group, or a quinolyl group ) . The method for producing a pyrimidine derivative according to any one of claims 2 to 4, wherein the palladium catalyst is a palladium catalyst having tertiary phosphine as a ligand. The method for producing a pyrimidine derivative according to claim 5, wherein the tertiary phosphine is triphenylphosphine. General formula (1)

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group, 2-biphenyl group, pyridyl group, p-tolyl group, naphthyl group, 4- (3-pyridyl) phenyl group. Ar ³ represents carbon. Phenyl group substituted with an alkyl group of 1 to 4, phenyl group substituted with phenyl group, phenyl group substituted with pyrimidyl group, 4- (2-benzothiazolyl) phenyl group , phenyl group substituted with pyridyl group An organic electroluminescence device comprising a pyrimidine derivative represented by any one of the following: a phenyl group substituted with a phenanthryl group, a phenyl group substituted with a phenanthryl group, a 3- (2-benzofuryl) phenyl group, or a quinolyl group ) .

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