JP5019816B2 - 1,3,5-triazine derivative, process for producing the same, and organic electroluminescent device comprising the same - Google Patents

Description

  The present invention relates to a 1,3,5-triazine derivative, a method for producing the same, and an organic electroluminescent element comprising the same.

  The organic electroluminescent element has a structure in which a light emitting layer containing a light emitting compound is sandwiched between a hole transport layer and an electron transport layer. A device that uses light emission (fluorescence or phosphorescence) when excitons generated when holes and electrons are recombined by injecting holes and electrons into the light-emitting layer by attaching an anode and a cathode to the outside. is there.

  Although research on the hole transport material for the device is progressing, there are few examples of electron transport materials, and tris (8-quinolinolato) aluminum (III) (Alq) is most widely used. Sexual problems have been pointed out. On the other hand, 1,3,5-triazine analogues are also one of compounds expected to be long-lived electron transport materials because they have low energy levels of the lowest occupied molecular orbitals. For example, Patent Documents 1 to 4 disclose organic electroluminescent devices using, as an electron transport material, a compound in which a group in which an aromatic compound is linked to positions 2, 4, and 6 of a 1,3,5-triazine ring is substituted. Yes. However, no examples are given for 1,3,5-triazine derivatives containing pyridyl or pyridylene groups. In addition, these patent documents do not have a clear description regarding the glass transition temperature, the driving voltage, and the lifetime, which are indicators of the device lifetime.

US Pat. No. 6,225,467 JP 2003-045662 A JP 2003-282270 A JP 2004-022334 A

  However, the conventional electron transport material has a problem that the thermal stability is low, and the brightness and luminous efficiency of the organic electroluminescent device using the same and the device life are not sufficient.

  In order to solve the problem relating to the stability of the device, the present inventors have made extensive studies focusing on the effect of the pyridyl group. As a result, variously synthesized 1,3,5-triazine derivatives containing a pyridyl group or a pyridylene group have been obtained. It was found that the glass transition temperature and the melting point of each were thermally stable at 100 ° C. or higher. In addition, these 1,3,5-triazine derivatives could be formed into thin films by either vacuum deposition or spin coating. Furthermore, by using these as an electron transport material, it is possible to produce a device that is superior in terms of luminance, light emission efficiency, device life, and drive voltage compared to an organic electroluminescent device using Alq, which is a general-purpose electron transport material. The headline and the present invention were completed.

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

［式中、Ａｒ^１は、炭素数１から６のアルキル基で置換されていても良い、フェニル基、ナフチルフェニル基、ビフェニリル基またはナフチル基を示す。Ｒ^１およびＲ^２は水素原子またはメチル基を示す。Ｒ^３は、炭素数１から４のアルキル基を示し、ｍは０から２の整数を示す。ｍが２の時、Ｒ^３は同一または相異なっていても良い。Ｘは、炭素数１から４のアルキル基で置換されていても良い、１，３−フェニレン基、１，４−フェニレン基、１，４−ナフチレン基、１，５−ナフチレン基、２，６−ナフチレン基、２，４−ピリジレン基、２，５−ピリジレン基または２，６−ピリジレン基を示し、ｐは１または２を示す。ｐが２の時、Ｘは同一または相異なっていても良い。Ａｒ^２は、炭素数１から６のアルキル基で１つ以上置換されていても良い、フェニル基、１−ナフチル基、２−ナフチル基、２−ピリジル基、３−ピリジル基または４−ピリジル基を示す。但し、置換基である−（Ｘ）_ｐ−Ａｒ^２の中に少なくとも一つのピリジン環を含む。ａおよびｂは１または２を示し、ａ＋ｂは３である。ａが２のとき、Ａｒ^１は同一または相異なっていても良い。ｂが２のとき、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｘ、ｐおよびＡｒ^２は同一または相異なっていても良い。］で表されることを特徴とする１，３，５−トリアジン誘導体である。

[Wherein Ar ¹ represents a phenyl group, a naphthylphenyl group, a biphenylyl group or a naphthyl group, which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. R ³ represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 2. When m is 2, R ³ may be the same or different. X is a 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6, which may be substituted with an alkyl group having 1 to 4 carbon atoms. -A naphthylene group, a 2,4-pyridylene group, a 2,5-pyridylene group or a 2,6-pyridylene group, p represents 1 or 2. When p is 2, X may be the same or different. Ar ² is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group, which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms. Indicates. However, at least one pyridine ring is contained in the substituent — (X) _p —Ar ² . a and b represent 1 or 2, and a + b is 3. When a is 2, Ar ¹ may be the same or different. When b is 2, R ¹ , R ² , R ³ , m, X, p and Ar ² may be the same or different. It is a 1,3,5-triazine derivative characterized by the above-mentioned.

  The present invention also relates to a 1,3,5-triazine derivative represented by the general formula (1), which is represented by the general formula (2)

［式中、ＸおよびＡｒ^２は前記と同じ内容を示す。ｑは０またはｐ以下の整数を示す。Ｍは−ＺｎＲ^４基、−ＭｇＲ^４基、−ＳｎＲ^５Ｒ^６Ｒ^７基、−Ｂ（ＯＨ）_２基、−Ｂ＝Ｒ^８基、−ＢＦ_３ ⁻（Ｚ^１）^＋基、または−ＳｉＲ^９Ｒ^１０Ｒ^１１基を示す。Ｒ^４は塩素原子、臭素原子またはヨウ素原子を示し、Ｒ^５、Ｒ^６およびＲ^７は炭素数１から４のアルキル基を示し、Ｒ^８は２，３−ジメチルブタン−２，３−ジオキシ基、エチレンジオキシ基または１，３−プロパンジオキシ基を示し、（Ｚ^１）^＋はアルカリ金属イオンまたは四級アンモニウムイオンを示し、Ｒ^９、Ｒ^１０およびＲ^１１はメチル基、エチル基、メトキシ基、エトキシ基または塩素原子を示す。］で表される置換芳香族化合物と、一般式（３）

[Wherein, X and Ar ² represent the same contents as described above. q represents 0 or an integer of p or less. M represents —ZnR ⁴ group, —MgR ⁴ group, —SnR ⁵ R ⁶ R ⁷ group, —B (OH) ₂ group, —B═R ⁸ group, —BF ₃ ^— (Z ¹ ) ⁺ group, or —SiR. ^{The 9} R ¹⁰ R ¹¹ group is shown. R ⁴ represents a chlorine atom, a bromine atom or an iodine atom, R ⁵ , R ⁶ and R ⁷ represent an alkyl group having 1 to 4 carbon atoms, and R ⁸ represents a 2,3-dimethylbutane-2,3-dioxy group. Represents an ethylenedioxy group or a 1,3-propanedioxy group, (Z ¹ ) ⁺ represents an alkali metal ion or a quaternary ammonium ion, and R ⁹ , R ¹⁰ and R ¹¹ represent a methyl group, an ethyl group, a methoxy group, A group, an ethoxy group or a chlorine atom; A substituted aromatic compound represented by the general formula (3)

［式中、Ａｒ^１、ａ、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｘおよびｂは、前記と同じ内容を示し、ｒはｐ−ｑを示し、Ｙは脱離基を示す。］で表される１，３，５−トリアジン化合物との、金属触媒の存在下でのカップリング反応により得ることを特徴とする製造方法である。

[Wherein, Ar ¹ , a, R ¹ , R ² , R ³ , m, X and b represent the same contents as described above, r represents pq, and Y represents a leaving group. It is obtained by a coupling reaction in the presence of a metal catalyst with a 1,3,5-triazine compound represented by the formula:

  Furthermore, the present invention relates to a 1,3,5-triazine derivative represented by the general formula (1), the general formula (4)

［式中、Ａｒ^１、ａ、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｘ、ｂ、Ｍおよびｒは、前記と同じ内容を示す。］で表される置換１，３，５−トリアジン化合物と、一般式（５）

[Wherein Ar ¹ , a, R ¹ , R ² , R ³ , m, X, b, M and r have the same contents as described above. A substituted 1,3,5-triazine compound represented by the general formula (5)

［式中、Ｘ、Ｙ、ｑおよびＡｒ^２は前記と同じ内容を示す。］で表される芳香族化合物との、金属触媒の存在下でのカップリング反応により得ることを特徴とする製造方法である。

[Wherein, X, Y, q and Ar ² have the same contents as described above. It is obtained by a coupling reaction in the presence of a metal catalyst with an aromatic compound represented by the formula:

  Moreover, this invention is an organic electroluminescent element which uses the 1,3,5-triazine derivative represented by General formula (1) as a structural component. The present invention is described in further detail below.

Examples of the phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ¹ include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, and 2,4-dimethylphenyl. Group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propyl Phenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butyl Examples thereof include a phenyl 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-butyl Phenyl group, 3,5-di-tert-butylphenyl group, 2-pentylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 2,4-dipentylphenyl group, 3,5-dipentylphenyl group, 2 -Neopentylphenyl group, 3-neopentylphenyl group, 4-neopentylphenyl group, 2,4-dineopentylphenyl group, 3,5-dineopentylphenyl group, 2-hexylphenyl group, 3-hexylphenyl Group, 4-hexylphenyl group, 2,4-dihexylphenyl group, 3,5-dihexylphenyl group, 2-cyclohexyl Butylphenyl group, 3-phenyl group, 4-phenyl group, such as 2,4-dicyclohexyl phenyl or 3,5-dicyclohexyl phenyl group.

  Phenyl group, p-tolyl group, m-tolyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group in terms of good performance as a material for organic electroluminescent elements 4-tert-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group or 4-cyclohexylphenyl group are desirable, phenyl group, p-tolyl group, m-tolyl group, 3,5-dimethylphenyl group, 4-butylphenyl group or 4-tert-butylphenyl group is more desirable.

Examples of the naphthylphenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ¹ include 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- ( 1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 4- (4-methylnaphthalen-1-yl) phenyl group, 3- (4-methylnaphthalen-1-yl) phenyl group, 2-methyl -4- (1-naphthyl) phenyl group, 2-methyl-4- (2-naphthyl) phenyl group, 5-methyl-3- (1-naphthyl) phenyl group or 5-methyl-3- (2-naphthyl) A phenyl group etc. are mentioned. 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group or 3- (2-naphthyl) in terms of good performance as a material for organic electroluminescent elements. ) A phenyl group is preferred.

Examples of the biphenylyl group optionally substituted by an alkyl group having 1 to 6 carbon atoms represented by Ar ¹ include a 4-biphenylyl group, a 4′-methylbiphenyl-4-yl group, and a 4′-ethylbiphenyl-4- Yl group, 4′-propylbiphenyl-4-yl group, 4′-butylbiphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 4′-hexylbiphenyl-4-yl group, 3 -Biphenylyl group, 3'-methylbiphenyl-3-yl group, 3'-ethylbiphenyl-3-yl group, 3'-propylbiphenyl-3-yl group, 3'-butylbiphenyl-3-yl group, 3 ' -Tert-butylbiphenyl-3-yl group or 3'-hexylbiphenyl-3-yl group and the like can be mentioned. A 4-biphenylyl group, a 4′-methylbiphenyl-4-yl group, a 4′-tert-butylbiphenyl-4-yl group, a 3-biphenylyl group, and a 3 ′ group because the performance as a material for an organic electroluminescence device is good. A -methylbiphenyl-3-yl group or a 3'-tert-butylbiphenyl-3-yl group is desirable, and a 4-biphenylyl group or a 3-biphenylyl group is more desirable.

Examples of the naphthyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ¹ include a 1-naphthyl group, a 4-methylnaphthalen-1-yl group, and a 4-ethylnaphthalen-1-yl group. 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 4-hexylnaphthalen-1-yl group, 5-methylnaphthalene-1- Yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 5-hexylnaphthalene- 1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group, 6-butyl Naphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 6-hexylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group, 7-ethylnaphthalen-2-yl group, 7 Examples include -propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group, 7-tert-butylnaphthalen-2-yl group, and 7-hexylnaphthalen-2-yl group.

  1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group in terms of good performance as a material for organic electroluminescent elements 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 A 7-tert-butylnaphthalen-2-yl group is desirable, and a 1-naphthyl group or a 2-naphthyl group is more desirable.

R ¹ and R ² are preferably hydrogen atoms in terms of good performance as a material for an organic electroluminescence device.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, and cyclobutyl group. Or a cyclopropylmethyl group etc. are mentioned.

  m is preferably 0 or 1 and more preferably 0 in terms of performance as a material for an organic electroluminescent element.

  X represents 1,3-phenylene group, 2-methyl-1,3-phenylene group, 4-methyl-1,3-phenylene group, 5-methyl-1,3-phenylene group, 2-tert-butyl-1 , 3-phenylene group, 4-tert-butyl-1,3-phenylene group, 5-tert-butyl-1,3-phenylene group, 1,4-phenylene group, 2-methyl-1,4-phenylene group, 2-tert-butyl-1,4-phenylene group, 1,4-naphthylene group, 2-methyl-1,4-naphthylene group, 5-methyl-1,4-naphthylene group, 6-methyl-1,4- Naphthylene group, 1,4-naphthylene group, 2-tert-butyl-1,4-naphthylene group, 5-tert-butyl-1,4-naphthylene group, 6-tert-butyl-1,4-naphthylene group, 1 , 5-naphthylene group, 2- Til-1,5-naphthylene group, 3-methyl-1,5-naphthylene group, 4-methyl-1,5-naphthylene group, 2-tert-butyl-1,5-naphthylene group, 3-tert-butyl- 1,5-naphthylene group, 4-tert-butyl-1,5-naphthylene group and the like can be mentioned.

  2,6-naphthylene group, 1-methyl-2,6-naphthylene group, 3-methyl-2,6-naphthylene group, 4-methyl-2,6-naphthylene group, 1-tert-butyl-2,6 -Naphthylene group, 3-tert-butyl-2,6-naphthylene group, 4-tert-butyl-2,6-naphthylene group, 2,4-pyridylene group, 3-methyl-2,4-pyridylene group, 5- Methyl-2,4-pyridylene group, 6-methyl-2,4-pyridylene group, 3-tert-butyl-2,4-pyridylene group, 5-tert-butyl-2,4-pyridylene group, 6-tert- Butyl-2,4-pyridylene group, 2,5-pyridylene group, 3-methyl-2,5-pyridylene group, 4-methyl-2,5-pyridylene group, 6-methyl-2,5-pyridylene group, 3 -Tert-butyl-2, -Pyridylene group, 4-tert-butyl-2,5-pyridylene group, 6-tert-butyl-2,5-pyridylene group, 2,6-pyridylene group, 3-methyl-2,6-pyridylene group, 4- Examples thereof include a methyl-2,6-pyridylene group, a 3-tert-butyl-2,6-pyridylene group or a 4-tert-butyl-2,6-pyridylene group.

  A 1,4-phenylene group, a 2,5-pyridylene group, or a 2,6-pyridylene group is desirable in terms of good performance as a material for an organic electroluminescent element.

Ar ² is phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethyl Phenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl Group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-t Examples include tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group and the like.

  2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 2-pentylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 2,4-dipentylphenyl group 3,5-dipentylphenyl group, 2-neopentylphenyl group, 3-neopentylphenyl group, 4-neopentylphenyl group, 2,4-dinepentylphenyl group, 3,5-dineopentylphenyl group, 2-hexylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 2,4-dihexylphenyl group, 3,5-dihexylphenyl group, 2-cyclohexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group Group, 2,4-dicyclohexylphenyl group, 3,5-dicyclohexylphenyl group, 1- Fuchiru group, 4-methyl-naphthalen-1-yl group, 4-ethyl-1-yl group, 4-propyl-naphthalen-1-yl group, and 4-butyl-1-yl group.

  In addition, 4-tert-butylnaphthalen-1-yl group, 4-hexylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalene-1- Yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 5-hexylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 6-hexylnaphthalen-2-yl group Group, 7-methylnaphthalen-2-yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalene-2- Le group, 7-tert-butyl-2-yl group, or the like 7-hexyl-2-yl group.

  2-pyridyl group, 3-methylpyridin-2-yl group, 4-methylpyridin-2-yl group, 5-methylpyridin-2-yl group, 6-methylpyridin-2-yl group, 3-ethylpyridine 2-yl group, 4-ethylpyridin-2-yl group, 5-ethylpyridin-2-yl group, 6-ethylpyridin-2-yl group, 3-propylpyridin-2-yl group, 4-propylpyridine 2-yl group, 5-propylpyridin-2-yl group, 6-propylpyridin-2-yl group, 3-butylpyridin-2-yl group, 4-butylpyridin-2-yl group, 5-butylpyridine 2-yl group, 6-butylpyridin-2-yl group, 3-tert-butylpyridin-2-yl group, 4-tert-butylpyridin-2-yl group, 5-tert-butylpyridin-2-yl group Group, -Tert-butylpyridin-2-yl group, 3-pyridyl group, 2-methylpyridin-3-yl group, 4-methylpyridin-3-yl group, 5-methylpyridin-3-yl group, 6-methylpyridine Examples include a -3-yl group and a 2-ethylpyridin-3-yl group.

  4-ethylpyridin-3-yl group, 5-ethylpyridin-3-yl group, 6-ethylpyridin-3-yl group, 2-propylpyridin-3-yl group, 4-propylpyridin-3-yl group 5-propylpyridin-3-yl group, 6-propylpyridin-3-yl group, 2-butylpyridin-3-yl group, 4-butylpyridin-3-yl group, 5-butylpyridin-3-yl group 6-butylpyridin-3-yl group, 2-tert-butylpyridin-3-yl group, 4-tert-butylpyridin-3-yl group, 5-tert-butylpyridin-3-yl group, 6-tert -Butylpyridin-3-yl group, 4-pyridyl group, 2-methylpyridin-4-yl group, 3-methylpyridin-4-yl group, 2-ethylpyridin-4-yl group, 3-ethylpyridin-4 Yl group, 2-propylpyridin-4-yl group, 3-propylpyridin-4-yl group, 2-butylpyridin-4-yl group, 3-butylpyridin-4-yl group, 2-tert-butylpyridine- Examples thereof include a 4-yl group and a 3-tert-butylpyridin-4-yl group.

  A phenyl group, a p-tolyl group, an m-tolyl group, a 2-tert-butylphenyl group, a 3-tert-butylphenyl group, and a 4-tert-butylphenyl group in terms of good performance as a material for an organic electroluminescence device. 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 2-pyridyl group, 3-tert-butylpyridin-2-yl group, 4-tert-butylpyridine-2 -Yl group, 5-tert-butylpyridin-2-yl group, 6-tert-butylpyridin-2-yl group, 3-pyridyl group or 4-pyridyl group are desirable, phenyl group, p-tolyl group, m- A tolyl group, 4-tert-butylphenyl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group is more desirable.

It is essential that at least one pyridine ring is present in the substituent-(X) _p -Ar ² composed of X and Ar ² described above. Examples of the substituent-(X) _p -Ar ² include groups represented by the basic skeletons of AI to A-XXXVIII described in Tables 1, 2, and 3. However, the present invention is limited to these. is not.

一般式（１）で表される１，３，５−トリアジン誘導体として、以上の、Ａｒ^１、ａ、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｘ、ｐ、Ａｒ^２およびｂのいずれの組合せからなる化合物でも良いが、有機電界発光素子用材料としての性能が良い点で、２，４−ビス（４−ｔｅｒｔ−ブチルフェニル）−６−［４’−（２−ピリジル）ビフェニル−４−イル］−１，３，５−トリアジン、２−［４−（６−フェニルピリジン−２−イル）フェニル］−４，６−ジ−ｍ−トリル−１，３，５−トリアジン、２−［４−（５−フェニルピリジン−２−イル）フェニル］−４，６−ジ−ｍ−トリル−１，３，５−トリアジン、２−［４’−（２−ピリジル）ビフェニル−４−イル］−４，６−ジ−ｍ−トリル−１，３，５−トリアジン、２，４−ビス（４−ｔｅｒｔ−ブチルフェニル）−６−［４−（５−フェニルピリジン−２−イル）フェニル］−１，３，５−トリアジン、２−｛４−［５−（４−ｔｅｒｔ−ブチルフェニル）ピリジン−２−イル］フェニル｝−４，６−ジ−ｍ−トリル−１，３，５−トリアジン等が好ましい。

As the 1,3,5-triazine derivative represented by the general formula (1), any combination of the above Ar ¹ , a, R ¹ , R ² , R ³ , m, X, p, Ar ² and b However, 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-phenyl] -4-phenyl (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-phenyl] may be used. Yl] -1,3,5-triazine, 2- [4- (6-phenylpyridin-2-yl) phenyl] -4,6-di-m-tolyl-1,3,5-triazine, 2- [ 4- (5-phenylpyridin-2-yl) phenyl] -4,6-di-m-tolyl-1,3,5-triazine, 2- [4 ′-(2-pyridyl) biphenyl-4-yl] -4,6-di-m-tolyl-1,3,5-triazine, 2,4-bis (4-te t-butylphenyl) -6- [4- (5-phenylpyridin-2-yl) phenyl] -1,3,5-triazine, 2- {4- [5- (4-tert-butylphenyl) pyridine- 2-yl] phenyl} -4,6-di-m-tolyl-1,3,5-triazine is preferred.

  In addition, 6- {4- [4,6-bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl, 5- {4- [ 4,6-bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl, 2,4-bis (4-tert-butylphenyl)- 6- [4 ′-(5-phenylpyridin-2-yl) biphenyl-4-yl] -1,3,5-triazine, 2,4-bis (4-tert-butylphenyl) -6- [4 ′ '-(2-pyridyl) -1,1': 4 ', 1' '-terphenyl-4-yl] -1,3,5-triazine, 2,4-bis (4-biphenylyl) -6- [ 4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine, 2,4 Bis (1-naphthyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine, 6- [4- (4,6-di-m-tolyl-1) , 3,5-triazin-2-yl) phenyl] -2,2′-bipyridyl, 6- {4- [4,6-bis (4-biphenylyl) -1,3,5-triazin-2-yl] Phenyl} -2,2′-bipyridyl and the like are preferable.

  2,4-bis (4-tert-butylphenyl) -6- [4 '-(3-pyridyl) biphenyl-4-yl] -1,3,5-triazine, 2,4-bis (4-biphenylyl) ) -6- [3 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine, 4- {4- [4,6-bis (4-biphenylyl) -1,3,5 -Triazin-2-yl] phenyl} -2,2'-bipyridyl, 2- (4-biphenylyl) -4,6-bis [4 '-(2-pyridyl) biphenyl-4-yl] -1,3 5-triazine, 5- {4- [4,6-bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,4′-bipyridyl, 5- {4 -[4,6-bis (4-biphenylyl) -1,3,5-triazin-2-yl] Enyl} -2,4′-bipyridyl, 2,4-bis (4-biphenylyl) -6- [4 ′-(3-pyridyl) biphenyl-4-yl] -1,3,5-triazine or 2,4 -Bis (4-biphenylyl) -6- [4 '-(4-pyridyl) biphenyl-4-yl] -1,3,5-triazine is desirable.

  Next, the manufacturing method of this invention is demonstrated. The 1,3,5-triazine derivative represented by the general formula (1) of the present invention can be produced by the following [Production Method-A] or [Production Method-B].

[Manufacturing method-A] consists of “Step A-1” and “Step A-2”.
[Production Method-A]
"Process A-1"

［式中、Ｙ、Ｘ、ｑ、Ａｒ^２およびＭは前記と同じ内容を表す。］
「工程Ａ−２」

[Wherein Y, X, q, Ar ² and M represent the same contents as described above. ]
"Process A-2"

［式中、Ｍ、Ｘ、ｑ、Ａｒ^２、Ａｒ^１、ａ、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、ｒ、Ｙ、ｂおよびｐは前記と同じ内容を示す。］
まず、「工程Ａ−１」では、一般式（５）で表される芳香族化合物をブチルリチウムまたはｔｅｒｔ−ブチルリチウム等でリチオ化後、カップリング用試薬を反応させることにより、カップリング反応に通常用いられる反応種である一般式（２）で表される置換芳香族化合物が得られる。

[Wherein, M, X, q, Ar ² , Ar ¹ , a, R ¹ , R ² , R ³ , m, r, Y, b and p have the same contents as described above. ]
First, in “Step A-1”, the aromatic compound represented by the general formula (5) is lithiated with butyllithium, tert-butyllithium, or the like, and then reacted with a coupling reagent. A substituted aromatic compound represented by the general formula (2), which is a commonly used reactive species, is obtained.

Coupling reagents include dichloro (tetramethylethylenediamine) zinc (II), zinc chloride, zinc bromide, zinc iodide, trimethyltin chloride, tributyltin chloride, tributyltin hydride, hexamethyldistanan, hexabutyldistanan, Boric acid, (2,3-dimethylbutane-2,3-dioxy) borane, ethylenedioxyborane, 1,3-propanedioxyborane, bis (2,3-dimethylbutane-2,3-dioxy) diborane, Examples thereof include trimethoxysilane, triethoxysilane, and diethyldichloride silane. By reaction with these, M is -ZnCl species, -ZnBr species, -ZnI species, -SnMe ₃ species, -SnBu ₃ species, -B (OH ) _two, -B (2,3-dimethylbutane-2,3-dioxy) species, -B (ethylenedioxy Obtaining seeds, -B (1,3-propane-dioxy) species, -Si _{(OMe) 3} species, a compound represented by -Si _(OEt) formula is _three or -SiEtCl ₂ or (2) Can do.

When reacted with boric acid, after the reaction is reacted with hydrogen fluoride water, potassium carbonate, by treatment with cesium carbonate or tetrabutylammonium fluoride, etc., -BF the M ₃ ^- K ⁺ species, -BF ₃ ^- Cs ⁺ species or _-BF ³ - _NBu ^{4 +} salts may be such as seeds. Alternatively, the aromatic compound (5) can be directly reacted with magnesium bromide or isopropylmagnesium bromide without lithiation to obtain a substituted aromatic compound (2) in which M is a —MgBr species or the like. As the substituted aromatic compound (2) containing boron in M, a commercially available product can be used as it is. It can also be produced by a method that does not involve lithiation as described in Journal of Organic Chemistry, Vol. 60, 7508-7510, 1995.

Although these obtained substituted aromatic compounds (2) may be isolated after the reaction, they may be subjected to the next “Step A-2” without isolation. In terms of good yield, after lithiation, dichloro (tetramethylethylenediamine) zinc (II), zinc chloride, zinc bromide, zinc iodide, trimethyltin chloride or tributyltin chloride is reacted, and M is -ZnCl species,- A substituted aromatic compound (2) that is ZnBr species, —ZnI species, —SnMe ₃ species, or —SnBu ₃ species is obtained, and is used for “Step A-2” without isolation, or commercially available —B (OH) It is desirable to use _two compounds. After lithiation, reaction with dichloro (tetramethylethylenediamine) zinc (II) or trimethyltin chloride gives a substituted aromatic compound (2) in which M is —ZnCl species or —SnMe ₃ species; or subjected to a-2 ", or commercially available -B _(OH) it is more desirable to use _two compounds.

  The leaving group represented by Y can be exemplified by a chlorine atom, a bromine atom, an iodine atom or a trifluoromethylsulfonyloxy group, but a bromine atom or an iodine atom is desirable in terms of a good yield.

  In “Step A-2”, the substituted aromatic compound represented by the general formula (2) obtained in “Step A-1” is converted into the 1, 1 represented by the general formula (3) in the presence of a metal catalyst. By reacting with a 3,5-triazine compound, a 1,3,5-triazine derivative represented by the general formula (1) of the present invention can be obtained.

  Examples of the metal catalyst that can be used in “Step A-2” include a palladium catalyst, a nickel catalyst, an iron catalyst, a ruthenium catalyst, a platinum catalyst, a rhodium catalyst, an iridium catalyst, an osmium catalyst, and a cobalt catalyst. These metal catalysts include metals, supported metals and metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates or oxides, metal salts such as olefin complexes, phosphine complexes, amines. A complex compound such as a complex, an ammine complex, or an acetylacetonato complex can be used. Further, these metals, metal salts and complex compounds and tertiary phosphine ligands can be used in combination. A palladium catalyst, an iron catalyst or a nickel catalyst is desirable in terms of a good yield, and a palladium catalyst is more desirable.

  More specifically, examples of the palladium catalyst include palladium metals such as palladium black and palladium sponge, and palladium / alumina, palladium / carbon, palladium / silica, palladium / Y-type zeolite, palladium / A-type zeolite, Examples thereof include supported palladium metals such as palladium / X-type zeolite, palladium / mordenite, and palladium / ZSM-5. Palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, palladium sulfate, palladium cyanide, sodium hexachloroparadate, potassium hexachloroparadate, disodium tetrachloroparadate And metal salts such as dipotassium tetrachloroparadate, dipotassium tetrabromoparadate, diammonium tetrachloroparadate, and tetraammonium hexachloroparadate.

  In addition, π-allyl palladium chloride dimer, palladium acetylacetonato, borofluorinated tetra (acetonitrile) palladium, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) di Palladium, dichlorodiammine palladium, tetraammine palladium nitrate, tetraammine palladium tetrachloroparadate, dichlorodipyridine palladium, dichloro (2,2'-bipyridyl) palladium, dichloro (phenanthroline) palladium, nitrate (tetramethylphenanthroline) palladium, diphenanthroline nitrate Palladium, bis (tetramethylphenanthroline) palladium nitrate, dichlorobis (to Phenylphosphine) palladium, dichlorobis (tricyclohexylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, dichloro [1,3-bis (diphenylphosphino) propane ] Complex compounds such as palladium, dichloro [1,4-bis (diphenylphosphino) butane] palladium and dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium.

  The palladium catalyst used in “Step A-2” may be any of the above metals, supported metals, metal salts, and complex compounds, but palladium chloride, palladium acetate, π-allyl palladium chloride dimer in terms of good yield. Bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, Dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenylphosphino) butane] palladium, dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium, palladium / Al Na and palladium / carbon is preferably tetrakis (triphenylphosphine) palladium is more preferable.

  These palladium catalysts may be used alone or in combination with a tertiary phosphine. The tertiary phosphine that can be used is triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-tert-butylphosphine, trineopentylphosphine, tricyclohexylphosphine , Trioctylphosphine, tris (hydroxymethyl) phosphine, tris (2-hydroxyethyl) phosphine, tris (3-hydroxypropyl) phosphine, tris (2-cyanoethyl) phosphine, (+)-1,2-bis [(2R , 5R) -2,5-diethylphosphorano] ethane, triallylphosphine, triamylphosphine, cyclohexyldiphenylphosphine, methyldiphenylphosphite And the like.

  Also, ethyl diphenylphosphine, propyldiphenylphosphine, isopropyldiphenylphosphine, butyldiphenylphosphine, isobutyldiphenylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphine) Fino) -2 '-(N, N-dimethylamino) biphenyl, (R)-(+)-2- (diphenylphosphino) -2'-methoxy-1,1'-binaphthyl, (-)-1, 2-bis [(2R, 5R) -2,5-dimethylphosphorano] benzene, (+)-1,2-bis [(2S, 5S) -2,5-dimethylphosphorano] benzene, (−) — 1,2-bis ((2R, 5R) -2,5-diethylphosphorano) benzene, (+)-1,2-bis (2S, 5S) -2,5- diethyl phosphoramide Roh] benzene and the like.

  Also, 1,1′-bis (diisopropylphosphino) ferrocene, (−)-1,1′-bis [(2S, 4S) -2,4-diethylphosphorano] ferrocene, (R)-(−)-1 -[(S) -2- (dicyclohexylphosphino) ferrocenyl] ethyldicyclohexylphosphine, (+)-1,2-bis [(2R, 5R) -2,5-di-isopropylphosphorano] benzene, (-) -1,2-bis [(2S, 5S) -2,5-di-isopropylphosphorano] benzene, (±) -2- (di-tert-butylphosphino) -1,1′-binaphthyl, 2- (Di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (dicyclohexylphosphino) -2′-methylbiphenyl, bis (diphenylphosphine) Roh) methane, 1,2-bis (diphenylphosphino) ethane and the like.

  Further, 1,2-bis (dipentafluorophenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,4-bis (diphenylphosphino) ) Pentane, 1,1′-bis (diphenylphosphino) ferrocene, (2R, 3R)-(−)-2,3-bis (diphenylphosphino) -bicyclo [2.2.1] hept-5-ene , (2S, 3S)-(+)-2,3-bis (diphenylphosphino) -bicyclo [2.2.1] hept-5-ene, (2S, 3S)-(−)-bis (diphenylphos Fino) butane, cis-1,2-bis (diphenylphosphino) ethylene, bis (2-diphenylphosphinoethyl) phenylphosphine, (2S, 4S)-(−)-2,4-1,4- Scan (diphenylphosphino) pentane, (2R, 4R) - (-) - 2,4-1,4- bis (diphenylphosphino) pentane, and the like.

  R-(+)-1,2-bis (diphenylphosphino) propane, (2S, 3S)-(+)-1,4-bis (diphenylphosphino) -2,3-O-isopropylidene- 2,3-butanediol, tri (2-furyl) phosphine, tri (1-naphthyl) phosphine, tris [3,5-bis (trifluoromethyl) phenyl] phosphine, tris (3-chlorophenyl) phosphine, tris (4 -Chlorophenyl) phosphine, tris (3,5-dimethylphenyl) phosphine, tris (3-fluorophenyl) phosphine, tris (4-fluorophenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) Phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4,6-tri Tokishifeniru) phosphine, and the like.

  Also, tris (pentafluorophenyl) phosphine, tris [4- (perfluorohexyl) phenyl] phosphine, tris (2-thienyl) phosphine, tris (m-tolyl) phosphine, tris (o-tolyl) phosphine, tris (p -Tolyl) phosphine, tris (4-trifluoromethylphenyl) phosphine, tri (2,5-xylyl) phosphine, tri (3,5-xylyl) phosphine, 1,2-bis (diphenylphosphino) benzene, (R )-(+)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, (S)-(−)-2,2′-bis (diphenylphosphino) -1,1′- Binaphthyl, (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, 2,2′-bis (diphenylphosphine) Roh) -1,1'-biphenyl, (S) - (+) - 4,12- bis (diphenylphosphino) - [2.2] - paracyclophane and the like.

  Also, (R)-(−)-4,12-bis (diphenylphosphino)-[2.2] -paracyclophane, (R)-(+)-2,2′-bis (di-p- Tolylphosphino) -1,1′-binaphthyl, (S)-(−)-2,2′-bis (di-p-tolylphosphino) -1,1′-binaphthyl, bis (2-methoxyphenyl) phenylphosphine, 1 , 2-bis (diphenylphosphino) benzene, (1R, 2R)-(+)-N, N′-bis (2′-diphenylphosphinobenzoyl) -1,2-diaminocyclohexane, (1S, 2S) — (+)-N, N′-bis (2′-diphenylphosphinobenzoyl) -1,2-diaminocyclohexane, (±) -N, N′-bis (2′-diphenylphosphinobenzoyl) -1,2 -Diaminocyclohexa , (1S, 2S) - (-) - N, N'- bis (2-diphenylphosphino-1-naphthoyl) -1,2-diaminocyclohexane, and the like.

  Also, (1R, 2R)-(+)-N, N′-bis (2-diphenylphosphino-1-naphthoyl) -1,2-diaminocyclohexane, (±) -N, N′-bis (2- Diphenylphosphino-1-naphthoyl) diaminocyclohexane, tris (diethylamino) phosphine, bis (diphenylphosphino) acetylene, bis (2-diphenylphosphinophenyl) ether, (R)-(−)-1-[(S) -2- (dicyclohexylphosphino) ferrocenyl] ethyldiphenylphosphine, (R)-(−)-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethyldi-tert-butylphosphine, bis (p-sulfo) Natophenyl) phenylphosphine dipotassium salt, 2-dicyclohexylphosphino-2 ′-(N, N-di Chiruamino) biphenyl, (S) - (-) - 1- (2- diphenylphosphino-1-naphthyl) isoquinoline and tris (trimethylsilyl) phosphine and the like.

  The tertiary phosphine used may be any of the above tertiary phosphines, but in terms of good yield, triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, Trioctylphosphine, 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 1,2-bis ( Diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, (R)-(+) -2,2'-bis (diphenylphosphino)- , 1′-binaphthyl, (S)-(−)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl and (±) -2,2′-bis (diphenylphosphino) -1 1,1′-binaphthyl is preferred.

  Especially triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, trioctylphosphine, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 1 , 2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, (R )-(+)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, (S)-(−)-2,2′-bis (diphenylphosphino) -1,1′- Binaphthyl and (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphth Le is further desirable.

  In “Step A-2”, a base may be added to improve the yield. Examples of the base to be added include lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, sodium hydroxide, potassium hydroxide, tripotassium phosphate, triethylamine, butylamine, diisopropylamine or An inorganic base or organic base such as ethyldiisopropylamine can be exemplified. The reaction proceeds sufficiently even without the addition of a base.

  The molar ratio of butyllithium or tert-butyllithium used for lithiation in “Step A-1” to the aromatic compound (5) is preferably 1: 1 to 5: 1, and 1: 1 in terms of good yield. To 3: 1 is more desirable.

  Examples of the solvent used in the reaction with the lithiation and coupling reagent in “Step A-1” include tetrahydrofuran, toluene, benzene, diethyl ether, xylene, chloroform, dichloromethane and the like, which are used in appropriate combinations. May be. It is desirable to use tetrahydrofuran alone in terms of good yield.

  The concentration of the aromatic compound (5) in “Step A-1” is preferably 10 mmol / L to 1000 mmol / L, and more preferably 50 mmol / L to 200 mmol / L in terms of a good yield.

  The reaction temperature during lithiation in “Step A-1” is preferably −150 ° C. to −20 ° C., and more preferably a temperature appropriately selected from −100 ° C. to −60 ° C. in terms of a good yield.

  The reaction time for lithiation in “Step A-1” is preferably 1 minute to 3 hours, and more preferably 15 minutes to 1 hour in terms of good yield.

  The molar ratio of the coupling reagent to the aromatic compound (5) in “Step A-1” is preferably 1: 1 to 1:10, and 1: 1.5 to 1: 3 in terms of good yield. More desirable.

  The reaction temperature after adding the coupling reagent in “Step A-1” is preferably raised from a low temperature region of −150 ° C. to −20 ° C. to a high temperature region of −20 ° C. to 50 ° C. It is more desirable to raise the temperature from a low temperature region of −100 ° C. to −60 ° C. to a high temperature region of 0 ° C. to 30 ° C. in terms of good rate.

  The reaction time with the coupling reagent in “Step A-1” varies depending on the substrate and reaction scale and is not particularly limited, but the reaction in the low temperature region is preferably 1 minute to 1 hour, and the yield is good. 5 to 30 minutes is more desirable. The reaction in the high temperature region is desirably 10 minutes to 10 hours, and more desirably 30 minutes to 5 hours in terms of a good yield.

  In the “Step A-2”, when a = 1 (b = 1) of the 1,3,5-triazine compound (3), the substituted aromatic compound (2) is converted into the 1,3,5-triazine compound (3). On the other hand, when 1 equivalent or more is reacted, the 1,3,5-triazine derivative of a = 2 (b = 1) in the general formula (1) can be obtained with high yield. Further, when a = 1 (b = 2) of the 1,3,5-triazine compound (3), the substituted aromatic compound (2) is 2 etc. with respect to the 1,3,5-triazine compound (3). When the reaction is carried out in an amount or more, the 1,3,5-triazine derivative of a = 1 (b = 2) in the general formula (1) can be obtained with good yield.

  The molar ratio of the metal catalyst and the 1,3,5-triazine compound (3) in “Step A-2” is preferably from 0.001: 1 to 0.5: 1, and is preferably 0. More preferred is 01: 1 to 0.1: 1.

  As a solvent that can be used in "Step A-2", methanol, ethanol, isopropyl alcohol, N, N-dimethylformamide, dioxane, diethyl ether, xylene, toluene, benzene, tetrahydrofuran, acetonitrile, dichloromethane, dimethyl sulfoxide, N- Examples thereof include methyl-2-pyrrolidone and hexamethylphosphoric triamide, and these may be used in appropriate combination. Dioxane, diethyl ether, toluene or tetrahydrofuran is desirable in terms of good yield. When the substituted aromatic compound (2) produced in “Step A-1” is subjected to “Step A-2” without being isolated, the solvent used in “Step A-1” can be used as it is.

  The concentration of the 1,3,5-triazine compound (3) in “Step A-2” is preferably 5 mmol / L to 1000 mmol / L, and more preferably 10 mmol / L to 200 mmol / L in terms of good yield.

  The reaction temperature in “Step A-2” is preferably a temperature appropriately selected from the reflux temperature of the solvent used from 0 ° C., and more preferably the solvent reflux temperature in terms of a good yield.

  The reaction time in “Step A-2” is preferably 10 minutes to 48 hours, and more preferably 30 minutes to 24 hours in terms of good yield.

Next, [Production Method-B] will be described. [Manufacturing method-B] consists of “Step B-1” and “Step B-2”.
[Production Method-B]
"Process B-1"

［式中、Ａｒ^１、ａ、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｘ、ｒ、Ｙ、ｂおよびＭは前記と同じ内容を示す。］
「工程Ｂ−２」

[Wherein Ar ¹ , a, R ¹ , R ² , R ³ , m, X, r, Y, b and M have the same contents as described above. ]
"Process B-2"

［式中、Ａｒ^１、ａ、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｍ、ｂ、Ｙ、Ｘ、ｐ、ｑおよびＡｒ^２は前記と同じ内容を示す。］
まず、「工程Ｂ−１」では、１，３，５−トリアジン化合物（３）をブチルリチウムまたはｔｅｒｔ−ブチルリチウム等でリチオ化後、カップリング用試薬を反応させることにより、カップリング反応に通常用いられる反応種である置換１，３，５−トリアジン化合物（４）が得られる。カップリング用試薬としては、「工程Ａ−１」で例示した、ジクロロ（テトラメチルエチレンジアミン）亜鉛（ＩＩ）、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、塩化トリメチルスズ、塩化トリブチルスズ、水素化トリブチルスズ、ヘキサメチルジスタナン、ヘキサブチルジスタナン、ホウ酸、（２，３−ジメチルブタン−２，３−ジオキシ）ボラン、エチレンジオキシボラン、１，３−プロパンジオキシボラン、ビス（２，３−ジメチルブタン−２，３−ジオキシ）ジボラン、トリメトキシシラン、トリエトキシシランまたは二塩化ジエチルシラン等が例示でき、これらとの反応によりＭ^２が−ＺｎＣｌ種、−ＺｎＢｒ種、−ＺｎＩ種、−ＳｎＭｅ_３種、−ＳｎＢｕ_３種、−Ｂ（ＯＨ）_２種、−Ｂ（２，３−ジメチルブタン−２，３−ジオキシ）種、−Ｂ（エチレンジオキシ）種、−Ｂ（１，３−プロパンジオキシ）種、−Ｓｉ（ＯＭｅ）_３種、−Ｓｉ（ＯＥｔ）_３種または−ＳｉＥｔＣｌ_２種である置換１，３，５−トリアジン化合物（４）を得ることができる。

[Wherein Ar ¹ , a, R ¹ , R ² , R ³ , m, M, b, Y, X, p, q and Ar ² have the same contents as described above. ]
First, in “Step B-1,” the 1,3,5-triazine compound (3) is lithiated with butyllithium, tert-butyllithium, or the like, and then reacted with a coupling reagent. The substituted 1,3,5-triazine compound (4) which is the reactive species used is obtained. Examples of the coupling reagent include dichloro (tetramethylethylenediamine) zinc (II), zinc chloride, zinc bromide, zinc iodide, trimethyltin chloride, tributyltin chloride, tributyltin hydride, exemplified in “Step A-1”. Hexamethyl distanane, hexabutyl distanane, boric acid, (2,3-dimethylbutane-2,3-dioxy) borane, ethylenedioxyborane, 1,3-propanedioxyborane, bis (2,3-dimethyl) Butane-2,3-dioxy) diborane, trimethoxysilane, triethoxysilane or diethylsilanedisilane and the like, and by reaction with these, M ² is -ZnCl species, -ZnBr species, -ZnI species, -SnMe ₃ Species, -SnBu ₃ species, -B (OH) ₂ species, -B (2,3-dimethylbutane-2,3-dioxy ) Species, -B (ethylenedioxy) species, -B (1,3-propanedioxy) species, -Si (OMe) ₃ species, -Si (OEt) ₃ species or -SiEtCl ₂ species substituted 1, A 3,5-triazine compound (4) can be obtained.

When reacted with boric acid, after the reaction is reacted with hydrogen fluoride water, potassium carbonate, by treatment with cesium carbonate or tetrabutylammonium fluoride, etc., M ² a -BF ₃ ^- K ⁺ species, -BF ₃ ^- Cs ⁺ species or _-BF ³ - _NBu ^{4 +} salts may be such as seeds. In addition, the 1,3,5-triazine compound (3) is directly reacted with magnesium bromide or isopropylmagnesium bromide without lithiation to obtain a compound (4) in which M ² is -MgBr species or the like. You can also. The substituted 1,3,5-triazine compound (4) containing boron in M can also be produced by a method without lithiation as described in Journal of Organic Chemistry, 60, 7508-7510, 1995. Commercial products can also be used as they are.

The obtained substituted 1,3,5-triazine compound (4) may be isolated after the reaction, but may be subjected to “Step B-2” without isolation. In terms of good yield, after lithiation, dichloro (tetramethylethylenediamine) zinc (II), zinc chloride, zinc bromide, zinc iodide, trimethyltin chloride or tributyltin chloride is reacted, and M is -ZnCl species,- It is desirable to obtain a substituted 1,3,5-triazine compound (4) which is a ZnBr species, a -ZnI species, a -SnMe ₃ species or a -SnBu ₃ species, and subjecting it to "Step B-2" without isolation. After lithiation, reaction with dichloro (tetramethylethylenediamine) zinc (II) or trimethyltin chloride gives a substituted 1,3,5-triazine compound (4) in which M is —ZnCl species or —SnMe ₃ species. It is more desirable to use for "process B-2" without releasing.

  In "Step B-2", the substituted 1,3,5-triazine compound (4) obtained in "Step B-1" is reacted with the aromatic compound (5) in the presence of a metal catalyst, The 1,3,5-triazine derivative represented by the general formula (1) of the present invention is obtained.

  The metal catalyst that can be used in “Step B-2” is the palladium catalyst, nickel catalyst, iron catalyst, ruthenium catalyst, platinum catalyst, rhodium catalyst, iridium catalyst, osmium catalyst, and cobalt catalyst exemplified in “Step A-2”. Etc. can be listed. These metal catalysts include metal salts such as metal salts, chloride salts, bromide salts, iodide salts, nitrate salts, sulfate salts, carbonate salts, oxalate salts, acetate salts or oxide salts, olefin complexes, phosphine complexes, A complex compound such as an amine complex, an ammine complex, or an acetylacetonato complex can be used. Further, these metals, metal salts and complex compounds and tertiary phosphine ligands can be used in combination. A palladium catalyst, an iron catalyst or a nickel catalyst is desirable in terms of a good yield, and a palladium catalyst is more desirable.

  More specifically, examples of the palladium catalyst include metals such as palladium black, supported metals such as palladium / alumina and palladium / carbon, metal salts such as palladium chloride and palladium acetate exemplified in “Step A-2”, π -Allyl palladium chloride dimer, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ) Ethane] palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenylphosphino) butane] palladium, dichloro [1,1′-bis (diphenylphosphino) Ferrocene Complex compounds such as palladium may be mentioned. Tetrakis (triphenylphosphine) palladium is desirable because of its good yield.

  These metals, supported metals, metal salts and complex compounds may be used alone or in combination with tertiary phosphine. As the tertiary phosphine that can be used, triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, trioctylphosphine, exemplified in “Step A-2”, 9 , 9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 1,2-bis (diphenylphosphino) ethane 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, (R)-(+)-2,2 ′ -Bis (diphenylphosphino) -1,1'-binaphth (S)-(−)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl and (±) -2,2′-bis (diphenylphosphino) -1,1′- Binaphthyl and the like can be exemplified.

The molar ratio of butyllithium or tert-butyllithium used for lithiation in “Step B-1” to 1,3,5-triazine compound (3) is preferably 2: 1 to 5: 1, and the yield is good. More preferably, 2: 1 to 3: 1.
Examples of the solvent used in the reaction with the lithiation and coupling reagent in “Step B-1” include tetrahydrofuran, toluene, benzene, diethyl ether, xylene, chloroform, dichloromethane and the like, and these are used in appropriate combinations. May be. It is desirable to use tetrahydrofuran alone in terms of good yield.

  The concentration of the 1,3,5-triazine compound (3) in “Step B-1” is preferably 5 mmol / L to 1000 mmol / L, and more preferably 10 mmol / L to 200 mmol / L in terms of good yield.

  The reaction temperature at the time of lithiation in “Step B-1” is preferably −150 ° C. to −20 ° C., and more preferably a temperature appropriately selected from −100 ° C. to −60 ° C. in terms of a good yield.

  The reaction time for lithiation in “Step B-1” is preferably 1 minute to 3 hours, and more preferably 5 minutes to 1 hour in terms of good yield.

  The molar ratio of the coupling reagent to the 1,3,5-triazine compound (3) in “Step B-1” is preferably 2: 1 to 10: 1, and 2: 1 to 3 in terms of good yield. : 1 is more desirable.

  The reaction temperature after adding the coupling reagent in “Step B-1” is preferably raised from a low temperature region of −150 ° C. to −20 ° C. to a high temperature region of −20 ° C. to 50 ° C. It is more desirable to raise the temperature from a low temperature region of −100 ° C. to −60 ° C. to a high temperature region of 0 ° C. to 30 ° C. in terms of good rate.

  The reaction time with the coupling reagent in “Step B-1” varies depending on the substrate and reaction scale and is not particularly limited, but the reaction in the low temperature region is preferably 1 minute to 3 hours, and the yield is good. 5 minutes to 1 hour is more desirable. The reaction in the high temperature region is desirably 10 minutes to 10 hours, and more desirably 30 minutes to 5 hours in terms of a good yield.

  In "Step B-2", when the aromatic compound (5) is reacted with the substituted 1,3,5-triazine compound (4) at 2 equivalents or more, 1,3,5- of the general formula (1) is obtained. A triazine derivative can be obtained with good yield.

  The molar ratio of the metal catalyst to the aromatic compound (5) in “Step B-2” is preferably 0.001: 1 to 0.5: 1, and 0.01: 1 to 0 in terms of good yield. .1: 1 is more desirable.

  As a solvent that can be used in "Step B-2", methanol, ethanol, isopropyl alcohol, N, N-dimethylformamide, dioxane, diethyl ether, xylene, toluene, benzene, tetrahydrofuran, acetonitrile, dichloromethane, dimethyl sulfoxide, N- Examples thereof include methyl-2-pyrrolidone and hexamethylphosphoric triamide, and these may be used in appropriate combination. Dioxane, diethyl ether, toluene or tetrahydrofuran is desirable in terms of good yield. It is more desirable that the substituted 1,3,5-triazine compound (4) produced in “Step B-1” is subjected to “Step B-2” without isolation in terms of a good yield. Tetrahydrofuran used in “B-1” can be used as it is.

  The concentration of the aromatic compound (5) in “Step B-2” is preferably 5 mmol / L to 1000 mmol / L, and more preferably 10 mmol / L to 200 mmol / L in terms of good yield.

  The reaction temperature in “Step B-2” is preferably a temperature appropriately selected from the reflux temperature of the solvent used from 0 ° C., and more preferably the solvent reflux temperature in terms of a good yield.

  The reaction time in “Step B-2” is preferably 1 hour to 120 hours, and more preferably 6 hours to 72 hours in terms of good yield.

  The crude product of the 1,3,5-triazine derivative represented by the general formula (1) is obtained by distilling off the solvent after completion of “Step A-2” or “Step B-2”. Examples of the purification method of the crude product include recrystallization, column purification, sublimation and the like. For example, in recrystallization, it can be easily purified by either a method of dissolving in a good solvent or a combination of a good solvent and a poor solvent and cooling, or a method of dissolving in a good solvent and adding the poor solvent. Although depending on the solubility of the crude product, a method of adding methanol after dissolving in dichloromethane is desirable. When performing column purification, it is desirable to use silica gel. The eluent is preferably a combination of hexane-dichloromethane or hexane-chloroform in terms of a good yield. The volume ratio of hexane and dichloromethane or hexane and chloroform can be appropriately selected according to the degree of separation / elution from a range of 1: 0 to 0: 1. These ratios may be changed as appropriate during purification.

Aromatic compound represented by the general formula (5), using the _{Y-X-Y, Y- (} X) p -Y, Y-Ar 2 or Y-X-Ar ² or the like, for example, J. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, Ltd, West Sussex, 2004. It can be easily obtained by a coupling reaction using the general-purpose metal catalyst described in 1. In that case, the catalyst, solvent, and reaction conditions exemplified in “Step A-2” or “Step B-2” can be applied. The aromatic compound (5) in which Y is a bromine atom is described in Journal of Organic Chemistry, 68, 2028-2029, 2003. Can also be easily obtained. That is, the general formula (6)

［式中、Ｘ、ｑおよびＡｒ^２は前記と同じ内容を示す。］で表される芳香族化合物を２−ジメチルアミノエトキシエタノール存在下でブチルリチウムでリチオ化後、四臭化炭素と反応させることにより得ることもできる。

[Wherein X, q and Ar ² represent the same contents as described above. ] Can be obtained by reacting with carbon tetrabromide after lithiation with butyllithium in the presence of 2-dimethylaminoethoxyethanol.

  As a synthesis method of the 1,3,5-triazine compound represented by the general formula (3), for example, a method described in JP-A-2006-62962 can be used.

  That is, the general formula (7)

［式中、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｘ、ｒおよびＹは前記と同じ内容を示す。］で表される置換ベンゾイルクロリド誘導体と一般式（８）

[Wherein R ¹ , R ² , R ³ , m, X, r and Y have the same contents as described above. A substituted benzoyl chloride derivative represented by the general formula (8)

［式中、Ａｒ^１は前記と同じ内容を示す。］で表される置換ベンゾニトリル誘導体とを、ルイス酸の存在下で反応させて一般式（９）

[Wherein Ar ¹ represents the same content as described above. And a substituted benzonitrile derivative represented by the general formula (9):

［式中、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｘ、ｒおよびＹは前記と同じ内容を示し、Ｚ^２は陰イオンを示す。］で表されるで１，３，５−オキサジアニル−１−イウム塩誘導体を得、これをアンモニア水で処理することにより、ａ＝２（ｂ＝１）の一般式（３）の１，３，５−トリアジン化合物を得ることができる。

[Wherein, Ar ¹ , Ar ² , R ¹ , R ² , R ³ , m, X, r and Y have the same contents as described above, and Z ² represents an anion. The 1,3,5-oxadianyl-1-ium salt derivative represented by the formula (1) is treated with ammonia water to give 1,3 of the general formula (3) of a = 2 (b = 1). , 5-triazine compound can be obtained.

  Further, the general formula (10)

［式中、Ａｒ^１は前記と同じ内容を示す。］で表される置換ベンゾイルクロリド誘導体と一般式（１１）

[Wherein Ar ¹ represents the same content as described above. A substituted benzoyl chloride derivative represented by the general formula (11)

［式中、Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ｙ、Ｘおよびｒは前記と同じ内容を示す。］で表される置換ベンゾニトリル誘導体とを、ルイス酸の存在下で反応させて一般式（１２）

[Wherein R ¹ , R ² , R ³ , m, Y, X, and r represent the same contents as described above. And a substituted benzonitrile derivative represented by the general formula (12):

で表される１，３，５−オキサジアニル−１−イウム塩誘導体を得、これをアンモニア水で処理することにより、ａ＝１（ｂ＝２）の一般式（３）の１，３，５−トリアジン化合物を得ることができる。

1,3,5-oxadianyl-1-ium salt derivative represented by the formula (1) is treated with aqueous ammonia to obtain 1,3,5 of the general formula (3) of a = 1 (b = 2). -A triazine compound can be obtained.

  Either of the molar ratios of the benzoyl chloride derivatives represented by the general formulas (7) and (10) and the benzonitrile derivatives represented by the general formulas (8) and (11) may be excessive. The reaction proceeds sufficiently even with the theoretical amount.

  Examples of the solvent used in the reaction include chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, chlorobenzene, and 1,2-dichlorobenzene. From the viewpoint of good yield, dichloromethane or chloroform is desirable.

  Examples of the Lewis acid include boron trifluoride, aluminum trichloride, iron trichloride, tin tetrachloride, and antimony pentachloride. Antimony pentachloride is desirable because of its good yield.

The salt of the general formula (9) or (12) can be isolated, but may be subjected to the next reaction operation in the form of a solution. In the case of isolation as a salt, Z ² in the general formula (9) or (12) is not particularly limited as long as it is an anion, but a tetraion in which a fluoride ion or a chloride ion is bound to the Lewis acid listed above. When a fluoroboric acid ion, a chlorotrifluoroboric acid ion, a tetrachloroaluminum acid ion, a tetrachloroiron (III) acid ion, a pentachlorotin (IV) acid ion or a hexachloroantimonic (V) acid ion is obtained as a counter anion Yield is good.

  Although there is no restriction | limiting in particular in the density | concentration of the ammonia water to be used, 5 to 50% is preferable and reaction advances fully even if it is 28% on the market.

  Although there is no restriction | limiting in particular in reaction temperature, It is preferable to react at the temperature suitably selected from -50 degreeC-solvent recirculation | reflux temperature. The reaction time is 30 minutes to 24 hours depending on the reaction temperature.

Although there is no particular limitation on the method for producing a thin film for an organic electroluminescent element comprising the 1,3,5-triazine derivative represented by the general formula (1), film formation by a vacuum vapor deposition method is possible. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is determined by taking into account the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device, and commonly used diffusion pumps, turbo molecular pumps, cryopumps, etc. 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa which can be reached by the above is desirable. The deposition rate is preferably 0.005 to 1.0 nm / second, depending on the thickness of the film to be formed. In addition, the 1,3,5-triazine derivative represented by the general formula (1) has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran, or the like. Film formation by the spin coat method, ink jet method, cast method, dipping method, or the like used is also possible.

  The thin film comprising the 1,3,5-triazine derivative represented by the general formula (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking ability, redox resistance, water resistance. Therefore, it can be used as a material for an organic electroluminescence device, and in particular, can be used as an electron transport material, a hole blocking material, a light emitting material, a light emitting host material, and the like. Therefore, the thin film composed of the 1,3,5-triazine derivative represented by the general formula (1) can be used as a component of the organic electroluminescence device.

  The 1,3,5-triazine derivative represented by the general formula (1) of the present invention, when used as a constituent component of an organic electroluminescence device, improves the electron injection efficiency and consequently reduces the driving voltage. In addition, a decrease in drive voltage results in an increase in electron lifetime. This is presumably because the nitrogen atom of the pyridyl group as a substituent can interact with various electrodes through its lone pair (Langmuir, 19, p. 132, 2003). As mentioned above, if the compound of this invention is used, the organic electroluminescent element excellent in the light emission characteristic and durability can be produced.

  Hereinafter, although the reference example and Example of this invention are demonstrated, this invention is not limited to these Examples at all.

Reference Example 1 Synthesis of 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine 6.58 g of 4-bromobenzoyl chloride and 4-tert- 9.55 g of butylbenzonitrile was dissolved in 200 mL of chloroform, and 8.97 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour and then refluxed for 8 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was added to 300 mL of 28% aqueous ammonia solution at 0 ° C. When added slowly, a white precipitate formed. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. The white precipitate was dried, dissolved in dimethylformamide heated to 153 ° C., and filtered. Further, the insoluble component separated by filtration was added to dimethylformamide heated to 153 ° C., and then filtered three times. All filtrates were collected and cooled, and the white precipitate formed again was filtered and dried to give 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3, A white solid of 5-triazine (yield 10.41 g, yield 69%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 1.44 (s, 18H), 7.63 (d, J = 8.6 Hz, 4H), 7.73 (d, J = 8.6 Hz, 2H), 8. 67 (d, J = 8.6 Hz, 2H), 8.69 (d, J = 8.6 Hz, 4H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 125.6, 127.2, 128.8, 130.4, 131.8, 133.4, 135.4, 156.2, 170 6, 171.6.

Reference Example 2 Synthesis of 2- (4-bromophenyl) -4,6-di-m-tolyl-1,3,5-triazine 8.78 g of 4-bromobenzoyl chloride and 9.37 g of 3-methylbenzonitrile Was dissolved in 120 mL of chloroform, and 11.96 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 30 minutes and then refluxed for 16 hours. After cooling to room temperature, it was filtered under argon. The obtained antimony hexachloride salt of oxadianium was washed with dichloromethane and dried under reduced pressure. When a oxadianium salt was gradually added to 400 mL of 28% aqueous ammonia at 0 ° C., a white precipitate was formed. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. The white precipitate was dried, dissolved in boiling dimethylformamide, and filtered. Further, the operation of adding the insoluble component separated by filtration to boiling dimethylformamide and then filtering was performed three times. All the filtrates were collected and cooled, and the white precipitate formed again was filtered and dried. ^{From 1} H, ¹³ C-NMR, it was confirmed that the obtained white precipitate was 2- (4-bromophenyl) -4,6-di-m-tolyl-1,3,5-triazine (yield 12 .58 g, 76% yield).

¹ H-NMR (CDCl ₃ ): δ 2.56 (s, 6H), 7.42-7.55 (m, 4H), 7.74 (d, J = 8.6 Hz, 4H), 8.54- 8.62 (m, 4H), 8.68 (d, J = 8.6 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.5, 126.2, 127.3, 128.5, 129.4, 130.4, 131.8, 133.4, 135.2, 136.0, 138 .3, 170.6, 171.7.

Reference Example 3 Synthesis of 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine 4.39 g of 4-bromobenzoyl chloride and 4-biphenylcarbonitrile 17 g was dissolved in 40 mL of chloroform, and 5.98 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 13 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate is gradually added to 300 mL of 28% aqueous ammonia solution at 0 ° C. And a white precipitate formed. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 150 ml of chloroform was added thereto, and this suspension was stirred under heating to reflux and filtered. Further, 50 ml of chloroform was added to the insoluble component separated by filtration, and this was stirred under heating and refluxing, and then filtered twice. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the obtained solid was recrystallized from dichloromethane-methanol to obtain 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1, A white solid of 3,5-triazine was obtained (yield 9.48 g, yield 88%).

¹ H-NMR (CDCl ₃ ): δ 7.30-7.39 (m, 2H), 7.39-7.49 (m, 4H), 7.59-7.68 (m, 4H), 7. 65 (d, J = 8.6 Hz, 2H), 7.74 (d, J = 8.5 Hz, 4H), 8.59 (d, J = 8.6 Hz, 2H), 8.76 (d, J = 8.5 Hz, 4H).
¹³ C-NMR (CDCl ₃ ): δ 127.2, 127.3, 127.4, 128.0, 128.9, 129.4, 130.4, 131.8, 134.9, 135.2, 140 .3, 145.2, 170.7, 171.4.

Reference Example 4 Synthesis of 2- (4-bromophenyl) -4,6-bis (1-naphthyl) -1,3,5-triazine 1.10 g of 4-bromobenzoyl chloride and naphthalene-1-carbonitrile 1 .53 g was dissolved in 100 mL of chloroform, and 1.50 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour and then refluxed for 8 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (4-bromophenyl) -4,6-bis (1-naphthyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate is gradually added to 100 mL of 28% aqueous ammonia solution at 0 ° C. And a white precipitate formed. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. The white precipitate was dried and purified by silica gel column chromatography (developing solvent hexane: chloroform = 1: 1), recrystallized from dichloromethane-methanol, and 2- (4-bromophenyl) -4,6-bis (1 -White solid of naphthyl) -1,3,5-triazine (yield 0.91 g, yield 37%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.59 (ddd, J = 8.0, 6.8, 1.2 Hz, 2H), 7.64 (ddd, J = 8.5, 6.8, 1. 5 Hz, 2H), 7.68 (dd, J = 8.0, 7.4 Hz, 2H), 7, 73 (d, J = 8.6 Hz, 2H), 7.98 (brd, J = 8.0 Hz) , 2H), 8.10 (brd, J = 8.0 Hz, 2H), 8.56 (dd, J = 7.4, 1.2 Hz, 2H), 8.66 (d, J = 8.6 Hz, 2H), 9.17 (brd, J = 8.5 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 125.2, 126.0, 126.2, 127.4, 127.8, 128.8, 130.6, 130.9, 131.3, 132.1, 132 5, 133.6, 134.2, 135.1, 170.4, 174.4.

Reference Example 5 Synthesis of 2- (4′-bromobiphenyl-4-yl) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine 4′-bromobiphenyl-4- 2.96 g of carbonyl chloride and 3.18 g of 4-tert-butylbenzonitrile were dissolved in 30 mL of chloroform, and 2.99 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 13 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (4′-bromobiphenyl-4-yl) -4,6-bis (4-tert-butylphenyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was dissolved in 28% aqueous ammonia solution. Slow addition to 150 mL at 0 ° C. produced a white precipitate. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 150 ml of chloroform was added thereto, and this suspension was stirred under heating to reflux and filtered. Further, 50 ml of chloroform was added to the insoluble component separated by filtration, and this was stirred under heating and refluxing, and then filtered twice. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the obtained solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 9: 1 to 4: 1) and recrystallized from dichloromethane-methanol to give 2- (4′-bromobiphenyl-4-yl). ) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine was obtained as a white solid (yield 3.81 g, yield 66%).

¹ H-NMR (CDCl ₃ ): δ 1.42 (s, 18H), 7.57 (d, J = 8.5 Hz, 2H), 7.61 (d, J = 8.5 Hz, 4H), 7. 62 (d, J = 8.5 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 8.70 (d, J = 8.5 Hz, 4H), 8.82 (d, J = 8.4 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 122.3, 125.6, 127.0, 128.8, 128.8, 129.5, 132.0, 133.6, 135 .8, 139.4, 143.6, 156.1, 171.0, 171.5.

Reference Example 6 Synthesis of 2- (4-biphenylyl) -4,6-bis (4-bromophenyl) -1,3,5-triazine 2.17 g of 4-biphenylcarbonyl chloride and 4-bromobenzonitrile 64 g was dissolved in 60 mL of chloroform, and 2.99 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 15 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (4-biphenylyl) -4,6-bis (4-bromophenyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate is gradually added to 150 mL of 28% aqueous ammonia solution at 0 ° C. And a white precipitate formed. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 150 ml of chloroform was added thereto, and this suspension was stirred under heating to reflux and filtered. Further, 50 ml of chloroform was added to the insoluble component separated by filtration, and this was stirred under heating and refluxing, and then filtered twice. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol to give 2- (4-biphenylyl) -4,6-bis (4-bromophenyl) -1, A white solid of 3,5-triazine (yield 3.23 g, yield 59%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.40-7.45 (m, 1H), 7.48-7.53 (m, 2H), 7.69-7.75 (m, 2H), 7. 72 (d, J = 8.5 Hz, 4H), 7.81 (d, J = 8.3 Hz, 2H), 8.64 (d, J = 8.5 Hz, 4H), 8.80 (d, J = 8.3 Hz, 2H).

Reference Example 7 Synthesis of 2,4-bis (4-biphenylyl) -6- (4′-bromobiphenyl-4-yl) -1,3,5-triazine 4′-bromobiphenyl-4-carbonyl chloride 11 .82 g and 14.34 g of 4-biphenylcarbonitrile were dissolved in 200 mL of chloroform, and 11.96 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 12 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The resulting 2,4-bis (4-biphenylyl) -6- (4′-bromobiphenyl-4-yl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was added to 600 mL of 28% aqueous ammonia solution. When added slowly at 0 ° C., a white precipitate formed. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 300 ml of chloroform was added thereto, and this suspension was stirred under heating to reflux and filtered. Further, 100 ml of chloroform was added to the insoluble component separated by filtration, and this was stirred under heating and refluxing, and then filtered twice. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol to give 2,4-bis (4-biphenylyl) -6- (4′-bromobiphenyl-4-). Yl) -1,3,5-triazine was obtained as a white solid (yield 19.88 g, yield 81%).

¹ H-NMR (CDCl ₃ ): δ 7.40-7.45 (m, 2H), 7.48-7.53 (m, 4H), 7.54 (d, J = 8.5 Hz, 2H), 7.61 (d, J = 8.5 Hz, 2H), 7.68-7.72 (m, 4H), 7.73 (d, J = 8.4 Hz, 2H), 7.79 (d, J = 8.4 Hz, 4H), 8.81 (d, J = 8.4 Hz, 2H), 8.82 (d, J = 8.4 Hz, 4H).
¹³ C-NMR (CDCl ₃ ): δ 122.3, 127.0, 127.3, 128.0, 128.8, 128.9, 129.4, 129.5, 132.0, 135.1, 135 .6, 139.3, 140.4, 143.7, 145.1, 171.1, 171.3.

Reference Example 8 Synthesis of 2,4-bis (4-biphenylyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Under argon flow Then, 2.1 mL of a hexane solution containing 3.3 mmol of butyl lithium was slowly added to 30 mL of tetrahydrofuran in which 0.69 g of 4-bromobiphenyl was dissolved and cooled to −78 ° C. After stirring at −78 ° C. for 15 minutes, 0.91 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2.5 hours. To this solution, 1.35 g of 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine obtained in Reference Example 3 and tetrakis (triphenylphosphine) palladium (0) 60 mL of tetrahydrofuran in which 0.12 g was dissolved was added, and the mixture was stirred for 2 hours under heating and refluxing. The solid obtained by concentrating the reaction solution under reduced pressure was purified by silica gel column chromatography (developing solvent hexane: chloroform = 2: 1-chloroform) and recrystallized from dichloromethane-methanol to obtain the desired 2,4-bis (4- Biphenylyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine was obtained as a white solid (yield 1.09 g, yield 71%).

¹ H-NMR (CDCl ₃ ): δ 7.37-7.45 (m, 3H), 7.46-7.54 (m, 6H), 7.68 (brd, J = 8.4 Hz, 2H), 7.73 (brd, J = 8.3 Hz, 4H), 7.74 (d, J = 8.4 Hz, 2H), 7.81 (d, J = 8.4 Hz, 2H), 7.83 (d , J = 8.4 Hz, 4H), 7.87 (d, J = 8.4 Hz, 2H), 8.88 (d, J = 8.4 Hz, 4H), 8.89 (d, J = 8. 4Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 127.1, 127.2, 127.3, 127.4, 127.5, 127.6, 127.7, 128.0, 128.9, 128.9, 129 5, 129.6, 135.2, 135.3, 139.3, 140.4, 140.6, 140.9, 144.6, 145.2, 171.4, 171.4.

Reference Example 9 Synthesis of 2,4-bis (1-naphthyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Under argon flow Then, 2.8 mL of a hexane solution containing 4.3 mmol of butyllithium was slowly added to 15 mL of tetrahydrofuran in which 0.91 g of 4-bromobiphenyl was dissolved and cooled to −78 ° C. After stirring at −78 ° C. for 15 minutes, 1.19 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.47 g of 2- (4-bromophenyl) -4,6-bis (1-naphthyl) -1,3,5-triazine obtained in Reference Example 4 and tetrakis (triphenylphosphine) palladium (0) 80 mL of tetrahydrofuran in which 0.14 g was dissolved was added, and the mixture was stirred for 13 hours with heating under reflux. The solid obtained by concentrating the reaction solution under reduced pressure was washed with chloroform, and the desired 2,4-bis (1-naphthyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl was obtained. A white solid of -1,3,5-triazine (yield 1.19 g, yield 71%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.36-7.41 (m, 1H), 7.46-7.52 (m, 2H), 7.57-7.62 (m, 2H), 7. 63-7.72 (m, 4H), 7.68 (dd, J = 8.0, 7.3 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.81 (d , J = 8.4 Hz, 2H), 7.88 (d, J = 8.5 Hz, 2H), 7.99 (brd, J = 8.0 Hz, 2H), 8.10 (brd, J = 8. 0 Hz, 2H), 8.60 (dd, J = 7.3 Hz, 1.2 Hz, 2H), 8.88 (d, J = 8.5 Hz, 2H), 9.23 (brd, J = 8.6 Hz) , 2H).
¹³ C-NMR (CDCl ₃ ): δ 125.2, 126.1, 127.1, 127.3, 127.4, 127.5, 127.6, 127.7, 128.7, 128.9, 129 7, 130.8, 131.4, 132.4, 133.9, 134.3, 135.1, 139.1, 140.1, 141.0, 144.9, 170.9, 174.3 .

Example 1 Synthesis of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine Under an argon stream, Slowly add 3.5 mL of pentane solution containing 5.2 mmol of tert-butyllithium to 15 mL of tetrahydrofuran cooled to −78 ° C., and further add 10 mL of tetrahydrofuran in which 0.61 g of 2- (4-bromophenyl) pyridine is dissolved. Added. After stirring at −78 ° C. for 30 minutes, 1.64 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.00 g of 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine obtained in Reference Example 1 and tetrakis (triphenylphosphine) palladium. (0) Tetrahydrofuran (35 mL) in which 0.12 g was dissolved was added, and the mixture was stirred with heating under reflux for 13 hours. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: dichloromethane = 3: 2 to 4: 3) and recrystallized again from dichloromethane-methanol to obtain the desired 2,4-bis (4-tert A white solid (yield 1.00 g, yield 87%) of -butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine was obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CD ₂ Cl ₂ ): δ 1.47 (s, 18 H), 7.32 (ddd, J = 6.8 Hz, 4.9 Hz, 1.8 Hz, 1 H), 7.69 (d, J = 8.7 Hz, 4H),
7.81-7.94 (m, 2H), 7.92 (d, J = 8.6 Hz, 2H), 7.96 (d, J = 8.6 Hz, 2H), 8.23 (d, J = 8.6 Hz, 2H), 8.71-8.80 (m, 1H), 8.77 (d, J = 8.6 Hz, 4H), 8.93 (d, J = 8.5 Hz, 2H) .
¹³ C-NMR (CD ₂ Cl ₂ ): δ 31.4, 35.4, 120.6, 122.6, 126.0, 127.5, 127.6, 127.8, 129.1, 129.8 134.0, 136.0, 137.1, 139.3, 141.0, 144.6, 150.1, 156.6, 156.8, 171.5, 171.8.

(Example 2) Synthesis of 2- [4- (6-phenylpyridin-2-yl) phenyl] -4,6-di-m-tolyl-1,3,5-triazine Dissolve 2.08 g of 2- (4-bromophenyl) -4,6-di-m-tolyl-1,3,5-triazine synthesized in 3.9 mL of a hexane solution containing 0.5 mmol. Slowly added to 100 mL of tetrahydrofuran cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 1.16 g of trimethyltin chloride was added, and the mixture was stirred at −78 ° C. for 30 minutes and then at room temperature for 30 minutes. After the tetrahydrofuran was distilled off under reduced pressure and dried, 150 mL of toluene in which 1.36 g of 2-bromo-6-phenylpyridine was dissolved and 0.58 g of tetrakis (triphenylphosphine) palladium (0) were added to the obtained solid. The mixture was stirred with heating under reflux for an hour. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (developing solvent hexane: dichloromethane = 3: 1 to 3: 2) and then recrystallized again from dichloromethane / methanol to obtain the desired 2- [4- (6-phenyl). A white solid (yield 1.09 g, yield 44%) of pyridin-2-yl) phenyl] -4,6-di-m-tolyl-1,3,5-triazine was obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CDCl ₃ ): δ 2.58 (s, 6H), 7.43-7.61 (m, 7H), 7.77-7.96 (m, 3H), 8.19-8. 27 (m, 2H), 8.42 (d, J = 8.7 Hz, 2H), 8.59-8.67 (m, 4H), 8.95 (d, J = 8.6 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.6, 119.1, 119.3, 126.2, 127.1, 127.2, 128.6, 128.7, 129.2, 129.3, 129 5, 133.3, 136.3, 136.8, 137.7, 138.3, 139.2, 142.9, 155.9, 157.0, 171.3, 171.8.

(Example 3) Synthesis of 2- [4- (5-phenylpyridin-2-yl) phenyl] -4,6-di-m-tolyl-1,3,5-triazine Then, 3.08 mL of hexane solution containing 2 mmol was dissolved in 1.58 g of 2- (4-bromophenyl) -4,6-di-m-tolyl-1,3,5-triazine obtained in Reference Example 2, and dissolved in -78. Slowly added to 80 mL of tetrahydrofuran cooled to ° C. After stirring at −78 ° C. for 15 minutes, 0.87 g of trimethyltin chloride was added, followed by stirring at −78 ° C. for 45 minutes and then at room temperature for 30 minutes. Tetrahydrofuran was distilled off under reduced pressure and dried, and 120 mL of toluene in which 1.07 g of 2-bromo-5-phenylpyridine was dissolved and 0.44 g of tetrakis (triphenylphosphine) palladium (0) were added to the obtained solid. The mixture was stirred with heating under reflux for a day. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 3: 2 to 1: 1) and then recrystallized again from dichloromethane-methanol to obtain the desired 2- [4- (5-phenyl). A white solid (yield 0.14 g, yield 8%) of pyridin-2-yl) phenyl] -4,6-di-m-tolyl-1,3,5-triazine was obtained. The melting points are shown in Table 4. A clear glass transition point was not observed.

¹ H-NMR (CDCl ₃ ): δ 2.48 (s, 6H), 7.33-7.51 (m, 7H), 7.56-7.64 (m, 2H), 7.84-7. 99 (m, 2H), 8.21 (d, J = 8.5 Hz, 2H), 8.49-8.58 (m, 4H), 8.84 (d, J = 8.6 Hz, 2H), 8.95 (d, J = 1.7 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 21.6, 120.9, 126.3, 127.0, 127.1, 128.3, 128.6, 129.2, 129.5, 133.3, 135 3, 135.6, 136.2, 136.9, 137.4, 138.3, 142.4, 148.2, 155.2, 171.2, 171.8.

(Example 4) Synthesis of 2- [4 '-(2-pyridyl) biphenyl-4-yl] -4,6-di-m-tolyl-1,3,5-triazine Then, 3.3 mL of a hexane solution containing 1.6 mmol was dissolved in 1.75 g of 2- (4-bromophenyl) -4,6-di-m-tolyl-1,3,5-triazine obtained in Reference Example 2 to obtain −78. Slowly added to 100 mL of tetrahydrofuran cooled to ° C. After stirring at −78 ° C. for 15 minutes, 0.96 g of trimethyltin chloride was added, and the mixture was stirred at −78 ° C. for 1 hour and then at room temperature for 30 minutes. Tetrahydrofuran was distilled off under reduced pressure and dried, and 150 mL of toluene in which 1.17 g of 2- (4-bromophenyl) pyridine was dissolved and 0.49 g of tetrakis (triphenylphosphine) palladium (0) were added to the obtained solid. The mixture was stirred for 24 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: dichloromethane = 3: 2 to 0: 1) and recrystallized again from dichloromethane-methanol to obtain the desired 2- [4 ′-(2- A white solid (yield 0.43 g, yield 21%) of pyridyl) biphenyl-4-yl] -4,6-di-m-tolyl-1,3,5-triazine was obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CD ₂ Cl ₂ ): δ 2.59 (s, 6H), 7.32 (ddd, J = 6.7 Hz, 4.9 Hz, 1.8 Hz, 1H), 7.47-7.60 (M, 4H), 7.79-7.94 (m, 4H), 7.91 (d, J = 8.6 Hz, 2H), 7.96 (d, J = 8.6 Hz, 2H), 8 .23 (d, J = 8.5 Hz, 2H), 8.60-8.71 (m, 4H), 8.72-8.79 (m, 1H), 8.93 (d, J = 8. 5Hz, 2H).
¹³ C-NMR (CD ₂ Cl ₂ ): δ 21.7, 120.7, 122.7, 126.5, 127.6, 127.7, 127.8, 128.9, 129.7, 129.8 , 133.7, 135.9, 136.6, 137.1, 139.0, 139.4, 141.0, 144.8, 150.1, 156.9, 171.6, 172.1.

Example 5 Synthesis of 2,4-bis (4-tert-butylphenyl) -6- [4- (5-phenylpyridin-2-yl) phenyl] -1,3,5-triazine Under an argon stream, 3.5 mL of pentane solution containing 5.2 mmol of tert-butyllithium was slowly added to 15 mL of tetrahydrofuran cooled to −78 ° C., and 10 mL of tetrahydrofuran in which 0.61 g of 2-bromo-5-phenylpyridine was dissolved was added dropwise to this solution. . After stirring at −78 ° C. for 30 minutes, 1.64 g of dichloro (tetramethylethylenedi) zinc (II) was added, and stirred at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.00 g of 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine synthesized by the method of Reference Example 1 and tetrakis (triphenyl) were added. 35 mL of tetrahydrofuran in which 0.12 g of phosphine) palladium (0) was dissolved was added and stirred for 10 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: dichloromethane = 3: 2 to 4: 3) and recrystallized again from dichloromethane-methanol to obtain the desired 2,4-bis (4-tert A white solid (yield 1.05 g, yield 91%) of -butylphenyl) -6- [4- (5-phenylpyridin-2-yl) phenyl] -1,3,5-triazine was obtained. The melting points are shown in Table 4. A clear glass transition point was not observed.

¹ H-NMR (CDCl ₃ ): δ 1.45 (s, 18H), 7.44-7.60 (m, 3H), 7.65 (d, J = 8.6 Hz, 4H), 7.88 ( d, J = 8.5 Hz, 2H), 7.88-7.94 (m, 1H), 8.07-8.15 (m, 3H), 8.74 (d, J = 8.6 Hz, 4H) ), 8.93 (d, J = 8.5 Hz, 2H), 9.09 (d, J = 1.7 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 120.3, 125.6, 126.9, 127.0, 128.8, 129.1, 129.6, 133.6, 134 1, 135.1, 136.2, 138.8, 141.2, 148.1, 156.1, 156.6, 170.9, 171.5.

Example 6 Synthesis of 2- {4- [5- (4-tert-butylphenyl) pyridin-2-yl] phenyl} -4,6-di-m-tolyl-1,3,5-triazine Argon Under a stream of air, 5.3 mL of a pentane solution containing 7.8 mmol of tert-butyllithium was slowly added to 25 mL of tetrahydrofuran cooled to −78 ° C., and 2-bromo-5- (4-tert-butylphenyl) pyridine 1. 15 mL of tetrahydrofuran in which 13 g was dissolved was added dropwise. After stirring at −78 ° C. for 30 minutes, 2.47 g of dichloro (tetramethylethylenedi) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.25 g of 2- (4-bromophenyl) -4,6-di-m-tolyl-1,3,5-triazine synthesized by the method of Reference Example 2 and tetrakis (triphenylphosphine) palladium ( 0) 50 mL of tetrahydrofuran in which 0.17 g was dissolved was added, and the mixture was stirred for 3 hours under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: dichloromethane = 3: 2 to 4: 3) and recrystallized again from dichloromethane-methanol to obtain the desired 2- {4- [5- ( 4-tert-Butylphenyl) pyridin-2-yl] phenyl} -4,6-di-m-tolyl-1,3,5-triazine was obtained as a white solid (yield 1.55 g, yield 94%). . The melting points are shown in Table 4. A clear glass transition point was not observed.

¹ H-NMR (CDCl ₃ ): δ 1.32 (s, 18H), 2.48 (s, 6H), 7.32-7.43 (m, 4H), 7.47 (d, J = 8. 7 Hz, 2H), 7.74-7.83 (m, 1H), 7.79 (d, J = 8.6 Hz, 2H), 7.95 (d, J = 8.6 Hz, 2H), 7. 99 (dd, J = 8.3 Hz, 2.4 Hz, 1H), 8.48-8.57 (m, 4H), 8.83 (d, J = 8.6 Hz, 2H), 8.98 (d , J = 1.7 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 21.6, 31.3, 34.7, 120.1, 125.8, 126.2, 126.6, 126.9, 128.5, 129.4, 129 .7, 133.3, 133.7, 135.0, 135.9, 136.0, 136.2, 138.3, 141.4, 148.0, 152.4, 156.7, 171.0 , 171.7.

Example 7 Synthesis of 6- {4- [4,6-Bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl Then, 1.4 mL of a hexane solution containing 2.2 mmol of butyl lithium was added to 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5 obtained in Reference Example 1. -1.00 g of triazine was dissolved and slowly added to 40 mL of tetrahydrofuran cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.61 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 20 mL of tetrahydrofuran in which 0.56 g of 6-bromo-2,2′-bipyridyl and 0.12 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 20 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (developing solvent hexane: chloroform = 1: 1 to 0: 1) and recrystallized again with dichloromethane-methanol to obtain the desired 6- {4- [4,6 A white solid (yield 0.82 g, yield 71%) of -bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl was obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CDCl ₃ ): δ 1.45 (s, 18 H), 7.39 (ddd, J = 7.5 Hz, 4.7 Hz, 1.2 Hz, 1 H), 7.65 (d, J = 8 .6 Hz, 4H), 7.88-8.03 (m, 3H), 8.40 (d, J = 8.6 Hz, 2H), 8.48 (dd, J = 7.2 Hz, 1.6 Hz, 1H), 8.69-8.78 (m, 2H), 8.75 (d, J = 8.6 Hz, 4H), 8.94 (d, J = 8.5 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 119.9, 120.7, 121.4, 123.8, 125.6, 127.0, 128.8, 129.3, 133 7, 136.9, 136.9, 137.8, 142.8, 149.0, 155.6, 155.8, 156.0, 156.2, 171.0, 171.5.

Example 8 Synthesis of 5- {4- [4,6-bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl Then, 0.35 mL of a hexane solution containing 0.55 mmol of butyl lithium was added to 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5 obtained in Reference Example 1. -0.25 g of triazine was dissolved and slowly added to 15 mL of tetrahydrofuran cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.15 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 5 mL of tetrahydrofuran in which 0.14 g of 5-bromo-2,2′-bipyridyl and 0.03 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 15 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 1: 1 to 0: 1) and recrystallized again with dichloromethane-methanol to obtain the desired 5- {4- [4,6 A white solid (yield 0.16 g, yield 56%) of -bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl was obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CDCl ₃ ): δ 1.45 (s, 18 H), 7.38 (ddd, J = 7.5 Hz, 4.8 Hz, 1.1 Hz, 1 H), 7.65 (d, J = 8 .6 Hz, 4H), 7.84-7.95 (m, 1H), 7.90 (d, J = 8.5 Hz, 2H), 8.14 (dd, J = 8.3 Hz, 2.4 Hz, 1H), 8.52 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 8.2 Hz, 1H), 8.69-8.79 (m, 1H), 8.74 ( d, J = 8.6 Hz, 4H), 8.93 (d, J = 8.5 Hz, 2H), 9.08 (d, J = 1.8 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 121.1, 121.2, 123.8, 125.6, 127.1, 128.8, 129.6, 133.6, 135 3, 135.7, 136.3, 137.0, 141.2, 147.7, 149.3, 155.4, 155.7, 156.1, 170.9, 171.6.

Example 9 of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(5-phenylpyridin-2-yl) biphenyl-4-yl] -1,3,5-triazine Synthesis Under a stream of argon, 0.35 mL of a hexane solution containing 0.55 mmol of butyllithium was obtained by 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1, 0.25 g of 3,5-triazine was dissolved and slowly added to 15 mL of tetrahydrofuran cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.15 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution were added 5 mL of tetrahydrofuran in which 0.19 g of 2- (4-bromophenyl) -5-phenylpyridine and 0.03 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 14 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The resulting crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 1: 1 to 4: 5) and recrystallized again with dichloromethane-methanol to obtain the desired 2,4-bis (4-tert -Butylphenyl) -6- [4 '-(5-phenylpyridin-2-yl) biphenyl-4-yl] -1,3,5-triazine as a white solid (0.14 g, 43% yield) Obtained. The melting points are shown in Table 4. A clear glass transition point was not observed.

¹ H-NMR (CDCl ₃ ): δ 1.45 (s, 18H), 7.43-7.59 (m, 3H), 7.65 (d, J = 8.6 Hz, 4H), 7.78- 7.85 (m, 2H), 7.85-7.94 (m, 5H), 8.03-8.14 (m, 3H), 8.74 (d, J = 8.6 Hz, 4H), 8.91 (d, J = 8.5 Hz, 2H), 9.06 (d, J = 1.7 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 120.4, 125.6, 126.9, 127.2, 127.5, 128.0, 128.8, 129.1, 129 5, 133.7, 134.3, 135.0, 135.7, 137.2, 138.9, 140.1, 144.1, 148.0, 156.1, 156.3, 171.1 171.6.

Example 10 2,4-Bis (4-tert-butylphenyl) -6- [4 ″-(2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl-4-yl Synthesis of 1,3,5-triazine Under an argon stream, 0.88 mL of a pentane solution containing 1.3 mmol of tert-butyllithium was slowly added to 3 mL of tetrahydrofuran cooled to −78 ° C., and 4-bromo-4 was added to this solution. 7 mL of tetrahydrofuran in which 0.20 g of '-(2-pyridyl) -1,1'-biphenyl was dissolved was added dropwise. After stirring at −78 ° C. for 30 minutes, 0.41 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 0.25 g of 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine obtained in Reference Example 1 and tetrakis (triphenylphosphine) palladium. 10 mL of tetrahydrofuran in which 0.03 g of (0) was dissolved was added, and the mixture was stirred for 2 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The resulting crude product was purified by silica gel column chromatography (eluent hexane: dichloromethane = 1: 1 to 0: 1) and recrystallized again from dichloromethane-methanol to obtain the desired 2,4-bis (4-tert -Butylphenyl) -6- [4 ″-(2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl-4-yl] -1,3,5-triazine white solid (yield 0.20 g, 61% yield). The melting points are shown in Table 4. A clear glass transition point was not observed.

¹ H-NMR (CD ₂ Cl ₂ ): δ 1.34 (s, 18 H), 7.18 (ddd, J = 6.7 Hz, 4.9 Hz, 1.8 Hz, 1 H), 7.56 (d, J = 8.6 Hz, 4 H), 7.67-7.79 (m, 8 H), 7.83 (d, J = 8.6 Hz, 2 H), 8.08 (d, J = 8.5 Hz, 2 H) , 8.59-8.64 (m, 1H), 8.64 (d, J = 8.6 Hz, 4H), 8.80 (d, J = 8.5 Hz, 2H).
¹³ C-NMR (CD ₂ Cl ₂ ): δ 31.3, 35.4, 120.6, 122.6, 126.1, 127.5, 127.6, 127.8, 128.0, 129.1 , 129.8, 134.0, 135.9, 137.1, 138.9, 139.7, 140.4, 141.2, 144.7, 150.1, 156.6, 157.0, 171 .5, 171.9.

Example 11 Synthesis of 2,4-bis (4-biphenylyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine tert-Butyl under an argon stream 4.1 mL of a pentane solution containing 6.0 mmol of lithium was slowly added to 15 mL of tetrahydrofuran cooled to −78 ° C., and 10 mL of tetrahydrofuran in which 0.70 g (3.0 mmol) of 2- (4-bromophenyl) pyridine was further dissolved in this solution. Was dripped. After stirring at −78 ° C. for 30 minutes, 1.89 g (7.5 mmol) of dichloro (tetramethylethylenediamine) zinc (II) was added, and stirred at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.35 g (2.5 mmol) of 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine obtained in Reference Example 3 and tetrakis (triphenylphosphine) were obtained. ) 60 mL of tetrahydrofuran in which 0.12 g (0.10 mmol) of palladium (0) was dissolved was added, and the mixture was stirred for 13 hours with heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: dichloromethane = 2: 1 to 2: 3) and alumina gel column chromatography (eluent hexane: dichloromethane = 2: 1 to 1: 2). And recrystallized again from dichloromethane-methanol to obtain the white 2,4-bis (4-biphenylyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine A solid (yield 1.19 g, 77% yield) was obtained.

¹ H-NMR (CD ₂ Cl ₂ ): δ 7.28 (ddd, J = 7.3, 4.8, 1.2 Hz, 1H), 7.40-7.46 (m, 2H), 7.48 -7.54 (m, 4H), 7.72-7.77 (m, 4H), 7.80 (ddd, J = 7.6, 7.3, 1.8 Hz, 1H), 7.82- 7.88 (m, 1H), 7.85 (d, J = 8.4 Hz, 4H), 7.86 (d, J = 8.4 Hz, 2H), 7.91 (d, J = 8.4 Hz) , 2H), 8.18 (d, J = 8.4 Hz, 2H), 8.72 (brd, J = 4.8 Hz, 1H), 8.88 (d, J = 8.4 Hz, 4H), 8 .89 (d, J = 8.4 Hz, 2H).
¹³ C-NMR (CD ₂ Cl ₂ ): δ 120.7, 122.7, 127.6, 127.6, 127.7, 127.8, 127.8, 128.4, 129.3, 129.8 , 129.9, 135.6, 135.8, 137.1, 139.4, 140.6, 141.0, 144.8, 145.5, 150.1, 156.9, 171.7, 171 .7.

Example 12 Synthesis of 2,4-bis (1-naphthyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine tert-butyl under an argon stream 4.1 mL of a pentane solution containing 6.0 mmol of lithium was slowly added to 15 mL of tetrahydrofuran cooled to −78 ° C., and 10 mL of tetrahydrofuran in which 0.70 g of 2- (4-bromophenyl) pyridine was dissolved was further added dropwise to this solution. After stirring at −78 ° C. for 30 minutes, 1.89 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.22 g of 2- (4-bromophenyl) -4,6-bis (1-naphthyl) -1,3,5-triazine obtained in Reference Example 4 and tetrakis (triphenylphosphine) palladium (0). Tetrahydrofuran (65 mL) in which 0.12 g was dissolved was added, and the mixture was stirred for 16 hours with heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The resulting crude product was purified by silica gel column chromatography (eluent hexane: dichloromethane = 2: 1 to chloroform) and alumina gel column chromatography (eluent hexane: dichloromethane = 2: 1 to chloroform), and then again dichloromethane- Recrystallization from methanol gave the desired 2,4-bis (1-naphthyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a white solid (yield 1 0.23 g, 87% yield).

¹ H-NMR (CD ₂ Cl ₂ ): δ 7.29-7.38 (m, 1H), 7.62 (ddd, J = 8.0, 6.8, 1.3 Hz, 2H), 7.67 (Ddd, J = 8.6, 6.8, 1.5 Hz, 2H), 7.72 (dd, J = 8.1, 7.3 Hz, 2H), 7.84-7.92 (m, 2H ), 7.89 (d, J = 8.3 Hz, 2H), 7.94 (d, J = 8.5 Hz, 2H), 8.02 (brd, J = 8.0 Hz, 2H), 8.14 (Brd, J = 8.1 Hz, 2H), 8.21 (d, J = 8.3 Hz, 2H), 8.58 (dd, J = 7.3, 1.2 Hz, 2H), 8.71− 8.76 (m, 1H), 8.89 (d, J = 8.5 Hz, 2H), 9.21 (brd, J = 8.6 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 120.5, 122.3, 125.2, 126.1, 127.3, 127.5, 127.6, 128.7, 129.7, 130.8, 131 4, 132.4, 133.9, 134.3, 135.2, 136.8, 139.0, 140.7, 144.8, 149.8, 156.8, 170.9, 174.3 .

Example 13 Synthesis of 6- [4- (4,6-di-m-tolyl-1,3,5-triazin-2-yl) phenyl] -2,2′-bipyridyl Butyllithium under an argon stream 2.1 mL of a hexane solution containing 3.3 mmol of 2- (4-bromophenyl) -4,6-di-m-tolyl-1,3,5-triazine obtained in Reference Example 2 was dissolved. Slowly added to 60 mL of tetrahydrofuran cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.91 g of dichloro (tetramethylethylenediamine) zinc (II) was added, and stirred at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 20 mL of tetrahydrofuran in which 0.85 g of 6-bromo-2,2′-bipyridyl and 0.14 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 14 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (developing solvent hexane: chloroform = 1: 1 to 1: 2) and recrystallized again from dichloromethane-methanol to obtain the desired 6- [4- (4,6 A white solid (yield 0.89 g, yield 61%) of -di-m-tolyl-1,3,5-triazin-2-yl) phenyl] -2,2′-bipyridyl was obtained. The melting points are shown in Table 4. A clear glass transition point was not observed.

¹ H-NMR (CDCl ₃ ): δ 2.54 (s, 6H), 7.36 (ddd, J = 7.4, 4.8, 1.1 Hz, 1H), 7.41-7.45 (m , 2H), 7.48 (brdd, J = 7.5, 7.5 Hz, 2H), 7.86-7.92 (m, 2H), 7.94 (dd, J = 7.8, 6. 7 Hz, 1H), 8.36 (d, J = 8.5 Hz, 2H), 8.46 (brd, J = 7.6 Hz, 1H), 8.57-8.62 (m, 4H), 8. 69 (brd, J = 7.8 Hz, 1H), 8.73 (brd, J = 4.8 Hz, 1H), 8.90 (d, J = 8.5 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.7, 120.1, 120.9, 121.6, 124.0, 126.3, 127.1, 128.6, 129.4, 129.5, 133 4, 136.3, 136.9, 137.4, 137.9, 138.4, 142.9, 148.8, 155.5, 155.7, 156.0, 171.2, 171.8 .

Example 14 Synthesis of 6- {4- [4,6-bis (4-biphenylyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl Butyl under an argon stream 2.1 mL of a hexane solution containing 3.3 mmol of lithium was added to 1.62 g of 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine obtained in Reference Example 3. Slowly added to 70 mL of tetrahydrofuran dissolved and cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.91 g of dichloro (tetramethylethylenediamine) zinc (II) was added, and stirred at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 20 mL of tetrahydrofuran in which 0.85 g of 6-bromo-2,2′-bipyridyl and 0.14 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 4 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was washed with chloroform, and the desired 6- {4- [4,6-bis (4-biphenylyl) -1,3,5-triazin-2-yl] phenyl} -2,2 ′ was obtained. -A white solid of bipyridyl (yield 1.24 g, 67% yield) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.36 (ddd, J = 7.4, 4.8, 1.2 Hz, 1H), 7.41-7.45 (m, 2H), 7.50-7 .54 (m, 4H), 7.72-7.76 (m, 4H), 7.84 (d, J = 8.5 Hz, 4H), 7.90 (ddd, J = 7.7, 7. 4, 1.9 Hz, 1 H), 7.93 (dd, J = 7.8, 1.2 Hz, 1 H), 7.97 (dd, J = 7.8, 7.7 Hz, 1 H), 8.40. (D, J = 8.6 Hz, 2H), 8.46 (brdd, J = 7.7, 1.2 Hz, 1H), 8.69-8.72 (m, 1H), 8.73 (ddd, J = 4.8, 1.9, 0.9 Hz, 1H), 8.90 (d, J = 8.5 Hz, 4H), 8.96 (d, J = 8.6 Hz, 2H).

Example 15 Synthesis of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(3-pyridyl) biphenyl-4-yl] -1,3,5-triazine Under an argon stream, 2- (4′-bromobiphenyl-4-yl) -4,6-bis (4-tert-butylphenyl) -1, obtained in Reference Example 5 with 1.4 mL of a hexane solution containing 2.2 mmol of butyllithium, 1.15 g of 3,5-triazine was dissolved and slowly added to 50 mL of tetrahydrofuran cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.61 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 10 mL of tetrahydrofuran in which 0.38 g of 3-bromopyridine and 0.09 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 4 hours while heating under reflux. The solid obtained by concentrating the reaction solution under reduced pressure was subjected to silica gel column chromatography (eluent hexane: chloroform = 2: 1 to chloroform) and alumina gel column chromatography (eluent hexane: chloroform = 2: 1 to 3: 2). After purification, recrystallization from dichloromethane-methanol and the desired 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(3-pyridyl) biphenyl-4-yl] -1,3,5 -A white solid of triazine (yield 0.71 g, 62% yield) was obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CDCl ₃ ): δ1.42 (s, 18H), 7.43 (brdd, J = 7.8, 4.8 Hz, 1H), 7.61 (d, J = 8.5 Hz, 4H) ), 7.72 (d, J = 8.3 Hz, 2H), 7.83 (d, J = 8.3 Hz, 2H), 7.84 (d, J = 8.4 Hz, 2H), 7.95. −8.00 (m, 1H), 8.64 (brdd, J = 4.8, 1.5 Hz, 1H), 8.71 (d, J = 8.5 Hz, 4H), 8.86 (d, J = 8.4 Hz, 2H), 8.94 (brd, J = 1.9 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 123.8, 125.6, 127.2, 127.6, 128.0, 128.8, 129.5, 133.6, 134 7, 135.8, 136.3, 137.0, 140.3, 144.0, 147.7, 148.1, 156.0, 171.0, 171.5.

Example 16 Synthesis of 2,4-bis (4-biphenylyl) -6- [3 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine tert-Butyl under an argon stream 4.1 mL of a pentane solution containing 6.0 mmol of lithium was slowly added to 20 mL of tetrahydrofuran cooled to −78 ° C., and 10 mL of tetrahydrofuran in which 0.70 g of 2- (3-bromophenyl) pyridine was dissolved was further added dropwise to this solution. After stirring at −78 ° C. for 30 minutes, 1.89 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.35 g of 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine obtained in Reference Example 3 and tetrakis (triphenylphosphine) palladium (0) 50 mL of tetrahydrofuran in which 0.12 g was dissolved was added, and the mixture was stirred for 15 hours with heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent hexane: chloroform = 2: 1 to chloroform) and alumina gel column chromatography (eluent hexane: chloroform = 2: 1 to chloroform). Of the desired 2,4-bis (4-biphenylyl) -6- [3 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine A white solid (yield 1.29 g, 84% yield) was obtained.

¹ H-NMR (CD ₂ Cl ₂ ): δ 7.32 (ddd, J = 7.2, 4.8, 1.2 Hz, 1H), 7.41-7.45 (m, 2H), 7.50 −7.55 (m, 4H), 7.63 (brdd, J = 7.7, 7.7 Hz, 1H), 7.74-7.78 (m, 4H), 7.80-7.90 ( m, 3H), 7.87 (d, J = 8.5 Hz, 4H), 7.96 (d, J = 8.5 Hz, 2H), 8.07 (ddd, J = 7.7, 1.3). , 1.2 Hz, 1H), 8.42-8.44 (m, 1H), 8.74 (ddd, J = 4.8, 1.7, 1.0 Hz, 1H), 8.90 (d, J = 8.5 Hz, 4H), 8.92 (d, J = 8.5 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 120.8, 122.4, 126.0, 126.6, 127.4, 127.4, 127.6, 127.9, 128.1, 129.0, 129 4, 129.6, 135.3, 135.4, 136.9, 140.2, 140.5, 141.1, 145.1, 145.3, 149.9, 157.3, 171.5 .

Example 17 Synthesis of 4- {4- [4,6-bis (4-biphenylyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl Reference under argon stream 0.54 g of 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine obtained in Example 3 and 4-tributylstannyl-2,2′-bipyridyl A toluene solution (20 ml) in which 63 g and tetrakis (triphenylphosphine) palladium (0) (0.12 g) were dissolved was stirred for 15 hours with heating under reflux. The solid obtained by concentrating the reaction solution under reduced pressure was purified by alumina gel column chromatography (eluent hexane: chloroform = 1: 1-chloroform) and recrystallized from dichloromethane-methanol to obtain the desired 4- {4- [4 , 6-Bis (4-biphenylyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl was obtained as a white solid (0.48 g, 78% yield).

¹ H-NMR (CDCl ₃ ): δ 7.39-7.45 (m, 3H), 7.48-7.53 (m, 4H), 7.68 (dd, J = 5.1, 1.7 Hz) , 1H), 7.69-7.73 (m, 4H), 7.81 (d, J = 8.5 Hz, 4H), 7.93 (ddd, J = 7.8, 7.7, 1.. 5 Hz, 1H), 7.99 (d, J = 8.4 Hz, 2H), 8.59 (brd, J = 7.8 Hz, 1H), 8.78 (brd, J = 4.8 Hz, 1H), 8.80 (brd, J = 5.1 Hz, 1H), 8.84 (d, J = 8.5 Hz, 4H), 8.87 (brs, 1H), 8.90 (d, J = 8.4 Hz) , 2H).
¹³ C-NMR (CDCl ₃ ): δ 119.3, 121.6, 121.8, 124.1, 127.3, 127.4, 127.5, 128.1, 129.0, 129.6, 129 .7, 135.1, 137.1, 137.3, 140.4, 142.1, 145.3, 148.9, 149.2, 149.7, 155.8, 156.6, 171.1 171.5.

Example 18 Synthesis of 2- (4-biphenylyl) -4,6-bis [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine tert-Butyl under an argon stream 6.0 mL of pentane solution containing 8.8 mmol of lithium was slowly added to 20 mL of tetrahydrofuran cooled to −78 ° C., and 10 mL of tetrahydrofuran in which 1.03 g of 2- (4-bromophenyl) pyridine was dissolved was further added dropwise to this solution. After stirring at −78 ° C. for 30 minutes, 2.78 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.09 g of 2- (4-biphenylyl) -4,6-bis (4-bromophenyl) -1,3,5-triazine obtained in Reference Example 6 and tetrakis (triphenylphosphine) palladium (0) Tetrahydrofuran (60 mL) in which 0.23 g was dissolved was added, and the mixture was stirred for 16 hours with heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent hexane: chloroform = 2: 1 to chloroform) and alumina gel column chromatography (eluent hexane: chloroform = 2: 1 to chloroform). , Recrystallized from dichloromethane-methanol to give the desired 2- (4-biphenylyl) -4,6-bis [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a white solid (Yield 1.06 g, yield 77%) was obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CD ₂ Cl ₂ ): δ 7.33-7.40 (m, 2H), 7.41-7.46 (m, 1H), 7.50-7.55 (m, 2H), 7.74-7.79 (m, 2H), 7.88 (d, J = 8.4 Hz, 2H), 7.88-7.93 (m, 8H), 7.95 (d, J = 8 .4 Hz, 4H), 8.23 (d, J = 8.3 Hz, 4H), 8.75 (brd, J = 4.7 Hz, 2H), 8.91 (d, J = 8.4 Hz, 2H) , 8.93 (d, J = 8.4 Hz, 4H).
¹³ C-NMR (CDCl ₃ ): δ 120.6, 122.3, 127.4, 127.4, 127.5, 127.7, 128.1, 129.0, 129.6, 129.6, 129 6, 135.3, 135.5, 136.9, 139.0, 140.5, 140.9, 144.6, 145.3, 149.9, 156.9, 171.4, 171.5 .

Example 19 Synthesis of 5- {4- [4,6-bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,4′-bipyridyl Then, 2.1 mL of a hexane solution containing 3.2 mmol of butyl lithium was added to 2- (4-bromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5 obtained in Reference Example 1. -1.50 g of triazine was dissolved and slowly added to 50 mL of tetrahydrofuran cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.83 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 30 mL of tetrahydrofuran in which 0.74 g of 5-bromo-2,4′-bipyridyl and 0.14 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 13 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent hexane: chloroform = 2: 1-chloroform) and alumina gel column chromatography (eluent hexane: chloroform = 1: 1), and then dichloromethane. Recrystallization from methanol and the desired 5- {4- [4,6-bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,4′-bipyridyl Of a white solid (yield 0.97 g, yield 56%). The melting points are shown in Table 4. A clear glass transition point was not observed.

¹ H-NMR (CDCl ₃ ): δ1.42 (s, 18H), 7.61 (d, J = 8.5 Hz, 4H), 7.83 (d, J = 8.4 Hz, 2H), 7. 92 (brd, J = 8.2 Hz, 1H), 8.00 (d, J = 6.1 Hz, 2H), 8.10 (dd, J = 8.2, 2.4 Hz, 1H), 8.70 (D, J = 8.5 Hz, 4H), 8.76 (d, J = 6.1 Hz, 2H), 8.88 (d, J = 8.4 Hz, 2H), 9.08 (brd, J = 2.4 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 31.3, 35.2, 120.9, 121.2, 125.7, 127.3, 128.9, 129.8, 133.6, 135.5, 136 2, 136.7, 140.7, 146.5, 148.7, 149.9, 153.5, 156.3, 170.8, 171.7.

Example 20 Synthesis of 5- {4- [4,6-bis (4-biphenylyl) -1,3,5-triazin-2-yl] phenyl} -2,4′-bipyridyl Butyl under a stream of argon 1.62 g of 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine obtained in Reference Example 3 was added to 2.2 mL of a hexane solution containing 3.3 mmol of lithium. Slowly added to 60 mL of tetrahydrofuran dissolved and cooled to -78 ° C. After stirring at −78 ° C. for 15 minutes, 0.91 g of dichloro (tetramethylethylenediamine) zinc (II) was added, and stirred at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution was added 30 mL of tetrahydrofuran in which 0.71 g of 5-bromo-2,4′-bipyridyl and 0.14 g of tetrakis (triphenylphosphine) palladium (0) were dissolved, and the mixture was stirred for 14 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The resulting compositional organism was purified by silica gel column chromatography (eluent hexane: chloroform = 2: 1 to chloroform) and alumina gel column chromatography (eluent hexane: chloroform = 1: 1), and then recrystallized from dichloromethane-methanol. White solid (yield: 1.00 g) of the desired 5- {4- [4,6-bis (4-biphenylyl) -1,3,5-triazin-2-yl] phenyl} -2,4′-bipyridyl Yield 54%).

¹ H-NMR (CDCl ₃ ): δ 7.40-7.45 (m, 2H), 7.48-7.54 (m, 4H), 7.69-7.75 (m, 4H), 7. 82 (d, J = 8.4 Hz, 4H), 7.86 (d, J = 8.4 Hz, 2H), 7.93 (brd, J = 8.2 Hz, 1H), 7.98 (d, J = 6.1 Hz, 2H), 8.12 (dd, J = 8.2, 2.4 Hz, 1H), 8.77 (d, J = 6.1 Hz, 2H), 8.86 (d, J = 8.4 Hz, 4H), 8.92 (d, J = 8.4 Hz, 2H), 9.10 (brd, J = 2.4 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 120.9, 121.1, 127.3, 127.3, 127.4, 128.1, 129.0, 129.6, 129.9, 135.1, 135 5, 136.0, 136.5, 140.4, 140.9, 145.4, 146.1, 148.7, 150.4, 153.8, 171.1, 171.5.

Example 21 Synthesis of 2,4-bis (4-biphenylyl) -6- [4 ′-(3-pyridyl) biphenyl-4-yl] -1,3,5-triazine Reference Example 7 under an argon stream 2,4-bis (4-biphenylyl) -6- (4′-bromobiphenyl-4-yl) -1,3,5-triazine 2.47 g and 3-pyridineboronic acid 0.54 g obtained in Dibenzylideneacetone) dipalladium (0) 0.04 g, tricyclohexylphosphine 0.03 g dissolved 1,4-dioxane solution 70 ml, aqueous solution of tripotassium phosphate 1.44 g dissolved 5.7 ml was added and heated for 13 hours Stir under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was dissolved in chloroform. The organic layer was washed with water and then dried over magnesium sulfate. Magnesium sulfate was removed by filtration, chloroform was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent hexane: chloroform = 2: 1 to 1: 2) and then recrystallized from dichloromethane-methanol. Of 2,4-bis (4-biphenylyl) -6- [4 ′-(3-pyridyl) biphenyl-4-yl] -1,3,5-triazine (yield 2.24 g, 91% yield) ) . The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CDCl ₃ ): δ 7.38-7.45 (m, 3H), 7.48-7.54 (m, 4H), 7.69-7.75 (m, 6H), 7. 79-7.85 (m, 2H), 7.81 (d, J = 8.3 Hz, 4H), 7.85 (d, J = 8.4 Hz, 2H), 7.92-7.96 (m , 1H), 8.64 (brdd, J = 4.8, 1.5 Hz, 1H), 8.86 (d, J = 8.3 Hz, 4H), 8.87 (d, J = 8.4 Hz, 2H), 8.94 (brd, J = 2.0 Hz, 1H).
¹³ C-NMR (CDCl ₃ ): δ 123.7, 127.3, 127.3, 127.4, 127.7, 128.0, 128.1, 129.0, 129.6, 129.6, 134 3, 135.2, 135.6, 136.1, 137.5, 140.2, 140.5, 144.3, 145.2, 148.3, 148.8, 171.3, 171.4 .

Example 22 Synthesis of 2,4-bis (4-biphenylyl) -6- [4 ′-(4-pyridyl) biphenyl-4-yl] -1,3,5-triazine Reference Example 7 under an argon stream 2,4-bis (4-biphenylyl) -6- (4′-bromobiphenyl-4-yl) -1,3,5-triazine 2.47 g and 4-pyridineboronic acid 0.54 g obtained in Dibenzylideneacetone) dipalladium (0) 0.04 g, tricyclohexylphosphine 0.03 g dissolved 1,4-dioxane solution 70 ml, aqueous solution of tripotassium phosphate 1.44 g dissolved 5.7 ml was added and heated to reflux for 14 hours Stirred under. The reaction solution was concentrated under reduced pressure, and the resulting solid was dissolved in chloroform. The organic layer was washed with water and then dried over magnesium sulfate. Magnesium sulfate was filtered off and chloroform was distilled off under reduced pressure. The resulting solid was purified by silica gel column chromatography (eluent hexane: chloroform = 2: 1-chloroform) and recrystallized from dichloromethane-methanol to obtain the desired 2 , 4-Bis (4-biphenylyl) -6- [4 ′-(4-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a white solid (yield 2.35 g, yield 96%) Obtained. The melting point and glass transition temperature are shown in Table 4.

¹ H-NMR (CDCl ₃ ): δ 7.41-7.45 (m, 2H), 7.48-7.54 (m, 4H), 7.68 (d, J = 6.2 Hz, 2H), 7.70-7.74 (m, 4H), 7.78-7.87 (m, 6H), 7.82 (d, J = 8.4 Hz, 4H), 8.72 (d, J = 6) .2 Hz, 2H), 8.86 (d, J = 8.4 Hz, 4H), 8.88 (d, J = 8.5 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 122.0, 127.3, 127.4, 127.7, 128.1, 128.2, 129.0, 129.6, 129.7, 135.2, 135 .9, 136.8, 140.4, 141.8, 143.9, 145.3, 148.5, 149.6, 171.2, 171.5.

(Example 23) Organic containing 2,4-bis (4-tert-butylphenyl) -6- [4 '-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a constituent component Production and Performance Evaluation of Electroluminescent Device A glass substrate with an ITO transparent electrode on which a 2 mm-wide indium-tin oxide (ITO) film was patterned in a stripe shape was used as the substrate. 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 glass substrate was introduced into a vacuum evaporation tank and the pressure was 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 indicated by 1 in FIG. 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 (naphthylene-1-yl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 45 nm. As the light emitting layer 4, Alq was vacuum-deposited with a film thickness of 40 nm. As the electron transport layer 5, 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3, obtained in Example 1, was used. 5-Triazine 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 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. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

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, luminance (cd / m ² ), light emission efficiency (cd / m ² ), and light emission wavelength (nm) at a voltage of 6.0 V were measured. The element lifetime was set to the luminance half time (h) of the initial luminance by constant current driving, with the value obtained by passing a current of 1 mA as the initial luminance. The results are shown in Table 5. Furthermore, the driving voltage (V), luminance (cd / m ² ), power efficiency (lm / W), and emission wavelength (nm) when a current of 1 mA was applied were measured. The results are shown in Table 6.

(Example 24) Organic comprising 2,4-bis (4-tert-butylphenyl) -6- [4- (5-phenylpyridin-2-yl) phenyl] -1,3,5-triazine as a constituent component Production and performance evaluation of electroluminescence device 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5- of Example 23 2,4-bis (4-tert-butylphenyl) -6- [4- (5-phenylpyridin-2-yl) phenyl] -1,3,5-triazine obtained in Example 5 instead of triazine An organic electroluminescent device was prepared in the same manner as in Example 23 by vacuum-depositing with a thickness of 20 nm as an electron transport layer 5.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Example 25) 2- {4- [5- (4-tert-butylphenyl) pyridin-2-yl] phenyl} -4,6-di-m-tolyl-1,3,5-triazine as a constituent component And performance evaluation of the organic electroluminescent device of 2,23-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3 of Example 23 2- {4- [5- (4-tert-butylphenyl) pyridin-2-yl] phenyl} -4,6-di-m-tolyl-1 obtained in Example 6 instead of 1,5-triazine An organic electroluminescent device was prepared in the same manner as in Example 23 using 2,3,5-triazine as the electron transport layer 5 and vacuum-deposited with a thickness of 20 nm.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Comparative Example 1)
General-purpose electron transporting material instead of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine in Example 23 An organic electroluminescent device obtained by vacuum-depositing Alq as an electron transport layer 5 with a film thickness of 20 nm was produced in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Table 5.

(Example 26) An organic electroluminescent device comprising 2,4-bis (4-biphenylyl) -6- [4 '-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a constituent component Preparation and Performance Evaluation of Example 23 in place of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine 2,4-bis (4-biphenylyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine obtained in Example 11 was used as the electron transport layer 5. An organic electroluminescence device vacuum-deposited with a thickness of 20 nm was produced in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Example 27) Organic electroluminescent device comprising 2,4-bis (1-naphthyl) -6- [4 '-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a constituent component Preparation and Performance Evaluation of Example 23 in place of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine Then, 2,4-bis (1-naphthyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine obtained in Example 12 was used as the electron transport layer 5. An organic electroluminescence device vacuum-deposited with a thickness of 20 nm was produced in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

Example 28 5- {4- [4,6-bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2,2′-bipyridyl as a constituent And performance evaluation of organic electroluminescent device to produce 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3 of Example 23 5- {4- [4,6-Bis (4-tert-butylphenyl) -1,3,5-triazin-2-yl] phenyl} -2 obtained in Example 8 instead of 5-triazine, An organic electroluminescent element obtained by vacuum-depositing with 2′-bipyridyl as an electron transport layer 5 in a thickness of 20 nm was produced in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Example 29) Organic electroluminescence containing 6- [4- (4,6-di-m-tolyl-1,3,5-triazin-2-yl) phenyl] -2,2'-bipyridyl as a constituent component Device Preparation and Performance Evaluation To 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine of Example 23 Instead, the 6- [4- (4,6-di-m-tolyl-1,3,5-triazin-2-yl) phenyl] -2,2′-bipyridyl obtained in Example 13 was used as the electron transport layer. As in Example 23, an organic electroluminescence device having a thickness of 20 nm as a result of vacuum deposition was prepared.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Example 30) Organic electroluminescent device comprising 2- (4-biphenylyl) -4,6-bis [4 '-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a constituent component Preparation and Performance Evaluation of Example 23 in place of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine Then, 2- (4-biphenylyl) -4,6-bis [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine obtained in Example 18 was used as the electron transport layer 5. An organic electroluminescent element vacuum-deposited with a film thickness of 20 nm was produced in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Example 31) Organic electroluminescence device comprising 2,4-bis (4-biphenylyl) -6- [4 '-(3-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a constituent component Preparation and Performance Evaluation of Example 23 in place of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine Thus, 2,4-bis (4-biphenylyl) -6- [4 ′-(3-pyridyl) biphenyl-4-yl] -1,3,5-triazine obtained in Example 21 was used as the electron transport layer 5. An organic electroluminescence device vacuum-deposited with a thickness of 20 nm was produced in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Example 32) An organic electroluminescent device comprising 2,4-bis (4-biphenylyl) -6- [4 '-(4-pyridyl) biphenyl-4-yl] -1,3,5-triazine as a constituent component Preparation and Performance Evaluation of Example 23 in place of 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5-triazine Thus, 2,4-bis (4-biphenylyl) -6- [4 ′-(4-pyridyl) biphenyl-4-yl] -1,3,5-triazine obtained in Example 22 was used as the electron transport layer 5. An organic electroluminescent element vacuum-deposited with a film thickness of 20 nm was produced in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Tables 5 and 6.

(Comparative Example 2)
Using the same element as in Comparative Example 1, the same evaluation as in Example 23 was performed. The results are shown in Table 6.

Comparative Example 3 Containing 2,4-bis (4-biphenylyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Preparation and performance evaluation of organic electroluminescence device 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5 of Example 23 -2,4-bis (4-biphenylyl) -6- [1,1 ': 4', 1 "] terphenyl-4-yl-1,3,5 obtained in Reference Example 8 instead of triazine -An organic electroluminescent device in which triazine was vacuum-deposited as an electron transport layer 5 to a thickness of 20 nm was prepared in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Table 6.

(Comparative Example 4) 2,4-bis (1-naphthyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine as a constituent component Preparation and performance evaluation of organic electroluminescence device 2,4-bis (4-tert-butylphenyl) -6- [4 ′-(2-pyridyl) biphenyl-4-yl] -1,3,5 of Example 23 -2,4-bis (1-naphthyl) -6- [1,1 ': 4', 1 "] terphenyl-4-yl-1,3,5 obtained in Reference Example 9 instead of triazine -An organic electroluminescent element obtained by vacuum-depositing triazine as the electron transport layer 5 in a thickness of 20 nm was prepared in the same manner as in Example 23.

  Evaluation of the produced organic electroluminescent element was performed in the same manner as in Example 23. The results are shown in Table 6.

6 is a cross-sectional view of an organic electroluminescent element produced in Example 23. FIG.

Explanation of symbols

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 (25)

General formula (1)

[Wherein Ar ¹ represents a phenyl group, a naphthylphenyl group, a biphenylyl group or a naphthyl group, which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. R ³ represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 2. When m is 2, R ³ may be the same or different. X is a 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6, which may be substituted with an alkyl group having 1 to 4 carbon atoms. -A naphthylene group, a 2,4-pyridylene group, a 2,5-pyridylene group or a 2,6-pyridylene group, p represents 1 or 2. When p is 2, X may be the same or different. Ar ² is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group, which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms. Indicates. However, at least one pyridine ring is contained in the substituent — (X) _p —Ar ² . a and b represent 1 or 2, and a + b is 3. When a is 2, Ar ¹ may be the same or different. When b is 2, R ¹ , R ² , R ³ , m, X, p and Ar ² may be the same or different. ] The 1,3,5-triazine derivative characterized by the above-mentioned. X is 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 2,4-pyridylene group, 2,5-pyridylene group The 1,3,5-triazine derivative according to claim 1, which is a 2,6-pyridylene group. The 1,3,5-triazine derivative according to claim 1, wherein R ¹ and R ² are hydrogen atoms. The 1,3,5-triazine derivative according to any one of claims 1 to 3, wherein m is 0. Ar ¹ is a phenyl group, p-tolyl group, m-tolyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4 -Tert-butylphenyl group, 4-hexylphenyl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) Phenyl group, 4-biphenylyl group, 4′-methylbiphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 3-biphenylyl group, 3′-methylbiphenyl-3-yl group, 3 ′ -Tert-butylbiphenyl-3-yl group, 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphth Len-1-yl group, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalene The 1,3,5-triazine derivative according to any one of claims 1 to 4, which is a 2-yl group or a 7-tert-butylnaphthalen-2-yl group. Ar ² is phenyl group, p-tolyl group, m-tolyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4- The 1,3,5-triazine derivative according to any one of claims 1 to 5, which is a tert-butylphenyl group, a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. General formula (1)

[Wherein Ar ¹ represents a phenyl group, a naphthylphenyl group, a biphenylyl group or a naphthyl group, which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. R ³ represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 2. When m is 2, R ³ may be the same or different. X is a 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6, which may be substituted with an alkyl group having 1 to 4 carbon atoms. -A naphthylene group, a 2,4-pyridylene group, a 2,5-pyridylene group or a 2,6-pyridylene group, p represents 1 or 2. When p is 2, X may be the same or different. Ar ² is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group, which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms. Indicates. However, at least one pyridine ring is contained in the substituent — (X) _p —Ar ² . a and b represent 1 or 2, and a + b is 3. When a is 2, Ar ¹ may be the same or different. When b is 2, R ¹ , R ² , R ³ , m, X, p and Ar ² may be the same or different. 1,3,5-triazine derivative represented by the general formula (2)

[Wherein, X and Ar ² represent the same contents as described above. q represents 0 or an integer of p or less. M represents —ZnR ⁴ group, —MgR ⁴ group, —SnR ⁵ R ⁶ R ⁷ group, —B (OH) ₂ group, —B═R ⁸ group, —BF ₃ ^— (Z ¹ ) ⁺ group, or —SiR. ^{The 9} R ¹⁰ R ¹¹ group is shown. R ⁴ represents a chlorine atom, a bromine atom or an iodine atom, R ⁵ , R ⁶ and R ⁷ represent an alkyl group having 1 to 4 carbon atoms, and R ⁸ represents a 2,3-dimethylbutane-2,3-dioxy group. Represents an ethylenedioxy group or a 1,3-propanedioxy group, (Z ¹ ) ⁺ represents an alkali metal ion or a quaternary ammonium ion, and R ⁹ , R ¹⁰ and R ¹¹ represent a methyl group, an ethyl group, a methoxy group, A group, an ethoxy group or a chlorine atom; A substituted aromatic compound represented by the general formula (3)

[Wherein, Ar ¹ , a, R ¹ , R ² , R ³ , m, X and b represent the same contents as described above, r represents pq, and Y represents a leaving group. And a 1,3,5-triazine compound represented by the following formula: X is 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 2,4-pyridylene group, 2,5-pyridylene group Or the manufacturing method of Claim 7 which is a 2, 6- pyridylene group. The production method according to claim 7 or 8, wherein R ¹ and R ² are hydrogen atoms. The manufacturing method according to any one of claims 7 to 9, wherein m is 0. Ar ¹ is a phenyl group, p-tolyl group, m-tolyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4 -Tert-butylphenyl group, 4-hexylphenyl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) Phenyl group, 4-biphenylyl group, 4′-methylbiphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 3-biphenylyl group, 3′-methylbiphenyl-3-yl group, 3 ′ -Tert-butylbiphenyl-3-yl group, 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphth Len-1-yl group, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalene The production method according to any one of claims 7 to 10, which is a 2-yl group or a 7-tert-butylnaphthalen-2-yl group. Ar ² is phenyl group, p-tolyl group, m-tolyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4- The production method according to any one of claims 7 to 11, which is a tert-butylphenyl group, a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group. General formula (1)

[Wherein Ar ¹ represents a phenyl group, a naphthylphenyl group, a biphenylyl group or a naphthyl group, which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. R ³ represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 2. When m is 2, R ³ may be the same or different. X is a 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6, which may be substituted with an alkyl group having 1 to 4 carbon atoms. -A naphthylene group, a 2,4-pyridylene group, a 2,5-pyridylene group or a 2,6-pyridylene group, p represents 1 or 2. When p is 2, X may be the same or different. Ar ² is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group, which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms. Indicates. However, at least one pyridine ring is contained in the substituent — (X) _p —Ar ² . a and b represent 1 or 2, and a + b is 3. When a is 2, Ar ¹ may be the same or different. When b is 2, R ¹ , R ² , R ³ , m, X, p and Ar ² may be the same or different. 1,3,5-triazine derivative represented by the general formula (4)

[Wherein Ar ¹ , a, R ¹ , R ² , R ³ , m, X, and b represent the same contents as described above. r represents pq, M represents —ZnR ⁴ group, —MgR ⁴ group, —SnR ⁵ R ⁶ R ⁷ group, —B (OH) ₂ group, —B═R ⁸ group, —BF ₃ ^— (Z ¹ ) A ⁺ group or a -SiR ⁹ R ¹⁰ R ¹¹ group is shown. A substituted 1,3,5-triazine compound represented by the general formula (5)

[Wherein, X and Ar ² have the same contents as described above. Y represents a leaving group, and q represents 0 or an integer of p or less. ] The manufacturing method characterized by obtaining by the coupling reaction in presence of a metal catalyst with the aromatic compound represented by this. X is 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 2,4-pyridylene group, 2,5-pyridylene group Or the manufacturing method of Claim 13 which is a 2, 6- pyridylene group. The production method according to claim 13 or 14, wherein R ¹ and R ² are hydrogen atoms. The manufacturing method according to claim 13, wherein m is 0. Ar ¹ is a phenyl group, p-tolyl group, m-tolyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4 -Tert-butylphenyl group, 4-hexylphenyl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) Phenyl group, 4-biphenylyl group, 4′-methylbiphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 3-biphenylyl group, 3′-methylbiphenyl-3-yl group, 3 ′ -Tert-butylbiphenyl-3-yl group, 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphth Len-1-yl group, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalene The production method according to claim 13, which is a 2-yl group or a 7-tert-butylnaphthalen-2-yl group. Ar ² is phenyl group, p-tolyl group, m-tolyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4- The production method according to claim 13, which is a tert-butylphenyl group, a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group. The production method according to any one of claims 7 to 18, wherein the metal catalyst is a palladium catalyst, a nickel catalyst, or an iron catalyst. General formula (1)

[Wherein Ar ¹ represents a phenyl group, a naphthylphenyl group, a biphenylyl group or a naphthyl group, which may be substituted with an alkyl group having 1 to 6 carbon atoms. R ¹ and R ² represent a hydrogen atom or a methyl group. R ³ represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 2. When m is 2, R ³ may be the same or different. X is a 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6, which may be substituted with an alkyl group having 1 to 4 carbon atoms. -A naphthylene group, a 2,4-pyridylene group, a 2,5-pyridylene group or a 2,6-pyridylene group, p represents 1 or 2. When p is 2, X may be the same or different. Ar ² is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group or 4-pyridyl group, which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms. Indicates. However, at least one pyridine ring is contained in the substituent — (X) _p —Ar ² . a and b represent 1 or 2, and a + b is 3. When a is 2, Ar ¹ may be the same or different. When b is 2, R ¹ , R ² , R ³ , m, X, p and Ar ² may be the same or different. ] The organic electroluminescent element which uses the 1,3,5-triazine derivative represented by this as a structural component. X is 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 2,4-pyridylene group, 2,5-pyridylene group An organic electroluminescent device comprising the 1,3,5-triazine derivative according to claim 20 as a constituent component, which is a 2,6-pyridylene group. The organic electroluminescence device comprising the 1,3,5-triazine derivative according to claim 20 or 21, wherein R ¹ and R ² are hydrogen atoms. m is 0, The organic electroluminescent element which uses the 1,3,5-triazine derivative in any one of Claims 20-22 as a structural component. Ar ¹ is a phenyl group, p-tolyl group, m-tolyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4 -Hexylphenyl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 4-biphenylyl group, 4'-methylbiphenyl-4-yl group, 4'-tert-butylbiphenyl-4-yl group, 3-biphenylyl group, 3'-methylbiphenyl-3-yl group, 3'-tert-butylbiphenyl-3- Yl group, 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5-te t-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 24. An organic electroluminescent device comprising the 1,3,5-triazine derivative according to any one of claims 20 to 23, which is a -butylnaphthalen-2-yl group. Ar ² is phenyl group, p-tolyl group, m-tolyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 2- 25. An organic electroluminescence device comprising the 1,3,5-triazine derivative according to any one of claims 20 to 24, which is a pyridyl group, a 3-pyridyl group, or a 4-pyridyl group.

Images