JP5095948B2 - Terphenylyl-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.

  1,3,5-triazine analogues are attracting attention as materials for organic electroluminescent elements. For example, Patent Documents 1 to 3 disclose display devices using these.

US Pat. No. 6,225,467 JP 2004-63465 A International Publication No. 2004/07785 Pamphlet

  Conventionally, however, 1,3,5-triazine analogues have limited uses for electron transport materials and light-emitting materials, and development of applications to other sites has not been studied so far.

  The present inventors synthesized various analogs of 1,3,5-triazine derivatives having one terphenylyl group not specified in the literature so far, and measured their charge mobility. Electron mobility exceeding (8-quinolinolato) aluminum (III) (hereinafter referred to as Alq) was obtained. They also found that they exhibit high hole mobility. Furthermore, when an organic electroluminescence device comprising them as a constituent component was fabricated and the luminescence characteristics were measured, it showed high luminance and luminous efficiency, had a long lifetime, and had a luminescent color of CIE (Commission International de l'Eclairage: International Illumination). The present invention was completed by finding that it is very close to the chromaticity coordinates (x, y) = (0.14, 0.08) of pure blue determined by the committee.

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

［式中、Ａｒ^１およびＡｒ^２は、同一または相異なるフェニル基、ナフチル基またはビフェニリル基を示し、これらは炭素数１から４のアルキル基で１個以上置換されていても良い。］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 and Ar ² represent the same or different phenyl group, naphthyl group or biphenylyl group, and these may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. It is a 1,3,5-triazine derivative characterized by the above-mentioned.

  The present invention also provides a general formula (2)

［式中、Ｍ^１は−ＺｎＲ^１基、−ＭｇＲ^１基、−Ｓｎ（Ｒ^２）_３基、−Ｂ（ＯＨ）_２基、−ＢＲ^３基、−ＢＦ_３ ⁻（Ｚ^１）^＋基または−Ｓｉ（Ｒ^４）_３基を示す。但し、Ｒ^１は塩素原子、臭素原子またはヨウ素原子を示し、Ｒ^２は同一または相異なって炭素数１から４のアルキル基を示し、Ｒ^３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^４は同一または相異なってメチル基、エチル基、メトキシ基、エトキシ基または塩素原子を示す。］で表される置換ビフェニル化合物と、一般式（３）

[In the formula, M ¹ represents —ZnR ¹ group, —MgR ¹ group, —Sn (R ² ) ₃ group, —B (OH) ₂ group, —BR ³ group, —BF ₃ ^— (Z ¹ ) ⁺ group or —Si (R ⁴ ) ₃ groups are shown. Where R ¹ represents a chlorine atom, a bromine atom or an iodine atom, R ² is the same or different and represents an alkyl group having 1 to 4 carbon atoms, and R ³ represents 2,3-dimethylbutane-2,3-dioxy. Group, an ethylenedioxy group or a 1,3-propanedioxy group, (Z ¹ ) ⁺ represents an alkali metal ion or a quaternary ammonium ion, and R ⁴ is the same or different and is a methyl group, an ethyl group, a methoxy group, A group, an ethoxy group or a chlorine atom; A substituted biphenyl compound represented by the general formula (3)

［式中、Ａｒ^１およびＡｒ^２は前記と同じ内容を示し、Ｙ^１は脱離基を示す。］で表される１，３，５−トリアジン化合物とを、金属触媒の存在下でカップリング反応させることを特徴とする、一般式（１）で表される１，３，５−トリアジン誘導体の製造方法である。

[Wherein, Ar ¹ and Ar ² have the same contents as described above, and Y ¹ represents a leaving group. A 1,3,5-triazine compound represented by the general formula (1), wherein the 1,3,5-triazine compound represented by the general formula (1) is subjected to a coupling reaction in the presence of a metal catalyst. It is a manufacturing method.

  The present invention also provides a general formula (4)

［式中、Ａｒ^１およびＡｒ^２は前記と同じ内容を示し、Ｍ^２は−ＺｎＲ^５基、−ＭｇＲ^５基、−Ｓｎ（Ｒ^６）_３基、−Ｂ（ＯＨ）_２基、−ＢＲ^７基、−ＢＦ_３ ⁻（Ｚ^２）^＋基または−Ｓｉ（Ｒ^８）_３基を示す。但し、Ｒ^５は塩素原子、臭素原子またはヨウ素原子を示し、Ｒ^６は同一または相異なって炭素数１から４のアルキル基を示し、Ｒ^７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^２）^＋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^８は同一または相異なってメチル基、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１，３，５−トリアジン化合物と、一般式（５）

[Wherein, Ar ¹ and Ar ² have the same contents as described above, and M ² represents —ZnR ⁵ group, —MgR ⁵ group, —Sn (R ⁶ ) ₃ group, —B (OH) ₂ group, —BR ⁷ shows the ^{(Z 2) +} group or -Si ^(R _{8) 3} group - _group, ^-BF 3. However, R ⁵ represents a chlorine atom, a bromine atom or an iodine atom, R ⁶ represents the same or different alkyl group having 1 to 4 carbon atoms, and R ⁷ represents 2,3-dimethylbutane-2,3-dioxy. A group, an ethylenedioxy group or a 1,3-propanedioxy group, (Z ² ) ⁺ represents an alkali metal ion or a quaternary ammonium ion, and R ⁸ is the same or different and is a methyl group, an ethyl group, a methoxy group, A group, an ethoxy group or a chlorine atom; A substituted 1,3,5-triazine compound represented by the general formula (5)

［式中、Ｙ^２は脱離基を示す。］で表されるビフェニル化合物とを、金属触媒の存在下でカップリング反応させることを特徴とする、一般式（１）で表される１，３，５−トリアジン誘導体の製造方法である。

[Wherein Y ² represents a leaving group. And a biphenyl compound represented by the general formula (1), wherein the coupling reaction is carried out in the presence of a metal catalyst.

  Moreover, this invention is an organic electroluminescent element characterized by using 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 optionally substituted by one or more alkyl groups having 1 to 4 carbon atoms represented by Ar ¹ and Ar ² include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, 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-diethyl Phenyl 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-butyl Phenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2 , 4-di-tert-butylphenyl group or 3,5-di-tert-butylphenyl group.

  Phenyl group, p-tolyl group, m-tolyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group or the like in terms of good performance as a material for organic electroluminescent elements 4-tert-butylphenyl group is desirable, and phenyl group, p-tolyl group, m-tolyl group, 4-butylphenyl group or 4-tert-butylphenyl group is more desirable.

Examples of the biphenylyl group optionally substituted by one or more alkyl groups having 1 to 4 carbon atoms represented by Ar ¹ and Ar ² include a 4-biphenylyl group, a 4′-methylbiphenyl-4-yl group, and a 4 ′ group. -Ethylbiphenyl-4-yl group, 4'-propylbiphenyl-4-yl group, 4'-butylbiphenyl-4-yl group, 4'-tert-butylbiphenyl-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 or 3'-tert-butylbiphenyl A -3-yl group etc. are 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 in terms of good performance as a material for an organic electroluminescence device. 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 which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms represented by Ar ¹ and Ar ² include 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-ethyl Naphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5 -Ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalene 2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphtha N-2-yl group, 7-methylnaphthalen-2-yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group or 7-tert -A butylnaphthalen-2-yl group etc. are mentioned.

  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 an organic electroluminescent element, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group or 7 A -tert-butylnaphthalen-2-yl group is desirable, and a 1-naphthyl group or 2-naphthyl group is more desirable.

  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^２およびＭ^１は前記と同じ内容を示す。］
「工程Ａ−２」

[Wherein Y ² and M ¹ represent the same contents as described above. ]
"Process A-2"

［式中、Ａｒ^１、Ａｒ^２、Ｍ^１およびＹ^１は前記と同じ内容を示す。］
まず、「工程Ａ−１」では、一般式（５）で表されるビフェニル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）で表される置換ビフェニル化合物が得られる。

[Wherein Ar ¹ , Ar ² , M ¹ and Y ¹ represent the same contents as described above. ]
First, in “Step A-1”, a biphenyl compound represented by the general formula (5) is lithiated with butyllithium or tert-butyllithium, and then reacted with a coupling reagent. A substituted biphenyl compound represented by the general formula (2) which is a reactive species used is obtained.

Coupling reagents include dichloro (tetramethylethylenediamine) zinc (II), zinc chloride, zinc bromide, zinc iodide, trimethyltin chloride, tributyltin chloride, tributyltin hydride, hexamethyl distanan, hexabutyl distanan, boron acid, pinacolate borane, ethylene glycolate borane, 1,3-propanediol dioleate borane, bis (pinacolato) diborane, trimethoxysilane, can exemplified triethoxysilane or dichloride diethyl silane, M ¹ by reaction with these Are —ZnCl group, —ZnBr group, —ZnI group, —SnMe ₃ group, —SnBu ₃ group, —B (OH) ₂ group, —B (pinacolate) group, —B (ethylene glycolate) group, —B ( 1,3-propanediol dioleate) group, -Si _{(OMe) 3} group, -Si _OEt) can be obtained substituted biphenyl compound represented by a ₃ group or -SiEtCl ₂ group formula (2). 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 ₃ and M ^{1 -} K ⁺ group, -BF ₃ ^- Cs ⁺ group or _-BF ³ - _NBu ^{4 +} salts may be such as a group.

Further, the biphenyl compound represented by the general formula (5) is directly reacted with magnesium bromide or isopropylmagnesium bromide without lithiation, and represented by the general formula (2) in which M ¹ is a —MgBr group or the like. Substituted biphenyl compounds can also be obtained.

  The obtained substituted biphenyl compound represented by the general formula (2) may be isolated after the reaction, but may be subjected to the next “Step A-2” without isolation.

Yield a good point, dichloro (tetramethylethylenediamine) after lithiation zinc (II), zinc chloride, zinc bromide, zinc iodide, are reacted with trimethyltin chloride or tributyltin chloride, M ¹ is -ZnCl group, It is desirable to obtain a substituted biphenyl compound represented by the general formula (2) which is a —ZnBr group, a —ZnI group, a —SnMe ₃ group or a —SnBu ₃ group, and subject it to “Step A-2” without isolation. Reaction with dichloro (tetramethylethylenediamine) zinc (II) or trimethyltin chloride after lithiation gives a substituted biphenyl compound represented by the general formula (2) in which M ¹ is a —ZnCl group or a —SnMe ₃ group, It is more desirable to use for "process A-2" without isolating.

The leaving group represented by Y ² 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 biphenyl compound represented by General Formula (2) obtained in “Step A-1” is converted to 1,3 represented by General Formula (3) in the presence of a metal catalyst. By reacting with a 1,5-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, metal chloride salts, bromide salts, iodide salts, nitrates, sulfates, carbonates, oxalates, acetates or oxide salts, or olefin complexes. , A complex compound such as a phosphine complex, an amine complex, an ammine complex, or an acetylacetonato complex can be used. Further, these metals, metal salts or 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. In addition, palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, palladium sulfate, palladium cyanide, sodium hexachloroparadate, potassium hexachloroparadate, sodium tetrachloroparadate, Examples of the metal salt include potassium tetrachloroparadate, potassium tetrabromoparadate, ammonium tetrachloroparadate, and ammonium 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 (tri Enylphosphine) 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 may be any of the above metals, supported metals, metal salts, and complex compounds, but in terms of good yield, palladium chloride, palladium acetate, 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] palladium, palladium / alumina and paradi N / a carbon is desirable, 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 , Ethyl diphenyl phosphine, propyl diphenylphosphine, isopropyl diphenyl phosphine, butyl diphenylphosphine, and the like.

  In addition, isobutyldiphenylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 ′-(N, N-dimethylamino) biphenyl , (R)-(+)-2- (diphenylphosphino) -2′-methoxy-1,1′-binaphthyl, (−)-1,2-bis [(2R, 5R) -2,5-dimethyl Phosphorano] 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-diethylphosphorano] benzene, 1,1'-bis (diisopropylphosphino) ferrocene, (-)- , 1′-bis [(2S, 4S) -2,4-diethylphosphorano] ferrocene, (R)-(−)-1-[(S) -2- (dicyclohexylphosphino) ferrocenyl] ethyldicyclohexylphosphine, etc. Is exemplified.

  Also, (+)-1,2-bis [(2R, 5R) -2,5-diisopropylphosphorano] 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 (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dipentafluorophenylphosphino) Ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,4-bis (diphenylphosphino) pe Tan, 1,1′-bis (diphenylphosphino) ferrocene, (2R, 3R)-(−)-2,3-bis (diphenylphosphino) -bicyclo [2.2.1] hept-5-ene, etc. Is exemplified.

  (2S, 3S)-(+)-2,3-bis (diphenylphosphino) -bicyclo [2.2.1] hept-5-ene, (2S, 3S)-(−)-bis (diphenyl) Phosphino) butane, cis-1,2-bis (diphenylphosphino) ethylene, bis (2-diphenylphosphinoethyl) phenylphosphine, (2S, 4S)-(−)-2,4-1,4-bis (Diphenylphosphino) pentane, (2R, 4R)-(−)-2,4-1,4-bis (diphenylphosphino) pentane, 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) Hosuf Emissions, tris [3,5-bis (trifluoromethyl) phenyl] phosphine, tris (3-chlorophenyl) phosphine, tris (4-chlorophenyl) phosphine, tris (3,5-dimethylphenyl) phosphine and the like.

  Further, tris (3-fluorophenyl) phosphine, tris (4-fluorophenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2 , 4,6-trimethoxyphenyl) phosphine, 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) ben (R)-(+)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, (S)-(−)-2,2′-bis (diphenylphosphino) -1 , 1′-binaphthyl and the like.

  (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, 2,2′-bis (diphenylphosphino) -1,1′-biphenyl, (S)-(+ ) -4,12-bis (diphenylphosphino)-[2.2] -paracyclophane, (R)-(−)-4,12-bis (diphenylphosphino)-[2.2] -paracyclo Fan, (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-diaminosi Rohexane, (1S, 2S)-(+)-N, N′-bis (2′-diphenylphosphinobenzoyl) -1,2-diaminocyclohexane, (±) -N, N′-bis (2′-diphenyl) Examples include phosphinobenzoyl) -1,2-diaminocyclohexane and the like.

  (1S, 2S)-(−)-N, N′-bis (2-diphenylphosphino-1-naphthoyl) -1,2-diaminocyclohexane, (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] ethyl di-tert-butylphosphi Bis (p-sulfonatophenyl) phenylphosphine dipotassium salt, 2-dicyclohexylphosphino-2 ′-(N, N-dimethylamino) biphenyl, (S)-(−)-1- (2-diphenylphosphino -1-naphthyl) isoquinoline and the like.

  Further, tris (trimethylsilyl) phosphine 2-di-tert-butylphosphino-2 ′-(N, N-dimethylamino) biphenyl, 2-di-tert-butylphosphino-2′-methylbiphenyl, 2- (dicyclohexyl) Phosphino) biphenyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl and 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′-triisopropyl-1,1 ′ -Biphenyl etc. can be illustrated.

  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 , 1′-binaphthyl, (S)-(−)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl and (±) -2,2′-bis (diphenylphosphino) -1 1,1′-binaphthyl is preferred.

  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′-binaphthyl Desirable in La.

  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, potassium phosphate, triethylamine, butylamine, diisopropylamine or ethyl. Examples thereof include inorganic bases such as diisopropylamine or organic bases. The reaction proceeds sufficiently even without the addition of a base.

Examples of the leaving group represented by Y ¹ include 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.

  The molar ratio of butyllithium or tert-butyllithium used for lithiation in “Step A-1” to the biphenyl compound represented by the general formula (5) is preferably 1: 1 to 5: 1, and the yield is From 1: 1 to 1: 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 and the like, and these may be used in appropriate combination. It is desirable to use tetrahydrofuran alone in terms of good yield.

  The concentration of the biphenyl compound represented by the general formula (5) in “Step A-1” is preferably 10 mmol / L to 10,000 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 biphenyl compound represented by the general formula (5) in “Step A-1” is preferably 1: 1 to 1:10, and 1: 1.5 in terms of good yield. To 1: 3 is 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.

  The molar ratio of the substituted biphenyl compound represented by the general formula (2) and the 1,3,5-triazine compound represented by the general formula (3) in “Step A-2” is from 1: 0.5. 1: 5 is desirable, and 1: 0.75 to 1: 2 is more desirable in terms of good yield.

  The molar ratio of the metal catalyst in “Step A-2” to the 1,3,5-triazine compound (3) represented by the general formula (3) is preferably 0.001: 1 to 0.5: 1. From the viewpoint of good yield, 0.01: 1 to 0.1: 1 is more desirable.

  As a solvent that can be used in "Step A-2", methanol, ethanol, isopropyl alcohol, N, N-dimethylformamide, 1,4-dioxane, diethyl ether, xylene, toluene, benzene, tetrahydrofuran, acetonitrile, dichloromethane, dimethyl Examples thereof include sulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphoric triamide, and these may be used in appropriate combination. In view of good yield, 1,4-dioxane, diethyl ether, toluene or tetrahydrofuran is desirable. When the substituted biphenyl compound represented by the general formula (2) produced in “Step A-1” is subjected to “Step A-2” without isolation, the solvent used in “Step A-1” is used as it is. You can also.

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

  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、Ａｒ^２、Ｙ^１およびＭ^２は前記と同じ内容を示す。］
「工程Ｂ−２」

[Wherein Ar ¹ , Ar ² , Y ¹ and M ² have the same contents as described above. ]
"Process B-2"

［式中、Ａｒ^１、Ａｒ^２、Ｍ^２およびＹ^２は前記と同じ意味を示す。］
まず、「工程Ｂ−１」では、一般式（３）で表される１，３，５−トリアジン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（４）で表される置換１，３，５−トリアジン化合物が得られる。

[Wherein Ar ¹ , Ar ² , M ² and Y ² have the same meaning as described above. ]
First, in “Step B-1”, the 1,3,5-triazine compound represented by the general formula (3) is lithiated with butyllithium or tert-butyllithium, and then reacted with a coupling reagent. Thus, a substituted 1,3,5-triazine compound represented by the general formula (4), which is a reactive species usually used in the coupling reaction, is obtained.

Examples of coupling reagents include dichloro (tetramethylethylenediamine) zinc (II), zinc chloride, zinc bromide, zinc iodide, trimethyltin chloride, tributyltin chloride, tributyltin hydride, hexa, exemplified in “Step A-1”. Methyl distanane, hexabutyl distanane, boric acid, pinacolate borane, ethylene glycolate borane, 1,3-propanediolate borane, bis (pinacolato) diborane, trimethoxysilane, triethoxysilane or diethylchloride disilane etc. By reaction with these, M ² is —ZnCl group, —ZnBr group, —ZnI group, —SnMe ₃ group, —SnBu ₃ group, —B (OH) ₂ group, —B (pinacolato) group, —B (Ethylene glycolate) group, -B (1,3-propanediolate) group, -S A substituted 1,3,5-triazine compound represented by the general formula (4) which is i (OMe) ₃ group, -Si (OEt) ₃ group or -SiEtCl ₂ group 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., -BF ₃ and M ^{2 -} K ⁺ group, -BF ₃ ^- Cs ⁺ group or _-BF ³ - _NBu ^{4 +} salts may be such as a group.

Further, the 1,3,5-triazine compound represented by the general formula (3) is generally reacted with magnesium bromide or isopropylmagnesium bromide without lithiation, and M ² is a —MgBr group or the like A substituted 1,3,5-triazine compound represented by the formula (4) can also be obtained.

  The obtained substituted 1,3,5-triazine compound represented by the general formula (4) may be isolated after the reaction, but may be subjected to “Step B-2” without isolation.

In terms of a good yield, dichloro after lithiation (tetramethylethylenediamine) zinc (II), zinc chloride, zinc bromide, zinc iodide, are reacted with trimethyltin chloride or tributyltin chloride, M ² is -ZnCl group, A substituted 1,3,5-triazine compound represented by the general formula (4) which is —ZnBr group, —ZnI group, —SnMe ₃ group or —SnBu ₃ group is obtained, and “Step B-2” is obtained without isolation. It is desirable to use. Substitution 1,3,5 represented by the general formula (4) in which M ² is a —ZnCl group or a —SnMe ₃ group by reacting with dichloro (tetramethylethylenediamine) zinc (II) or trimethyltin chloride after lithiation. -It is further desirable to obtain a triazine compound and subject it to "Step B-2" without isolation.

Examples of the leaving group represented by Y ¹ include 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 B-2”, the substituted 1,3,5-triazine compound represented by General Formula (4) obtained in “Step B-1” is converted into General Formula (5) in the presence of a metal catalyst. By reacting with the biphenyl compound represented, 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 metals, supported metals, metal chloride salts, bromide salts, iodide salts, nitrates, sulfates, carbonates, oxalates, acetates or oxide salts, or olefin complexes. , A complex compound such as a phosphine complex, an amine complex, an ammine complex, or an acetylacetonato complex can be used. Further, these metals, metal salts or 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. Examples of the tertiary phosphine that can be used include 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) -1,1′-binaphthyl , (S)-(−)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl and (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl Etc. can be illustrated.

  In “Step B-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, potassium phosphate, triethylamine, butylamine, diisopropylamine or ethyl. Examples thereof include inorganic bases such as diisopropylamine or organic bases. The reaction proceeds sufficiently even without the addition of a base.

The leaving group represented by Y ² 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.

  The molar ratio of butyl lithium or tert-butyl lithium used for lithiation in “Step B-1” to the 1,3,5-triazine compound represented by the general formula (3) is 1: 1 to 5: 1. Is desirable, and 1: 1 to 3: 1 is more desirable in terms of a good yield.

  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 and the like, and these may be used in appropriate combination. It is desirable to use tetrahydrofuran alone in terms of good yield.

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

  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 and the 1,3,5-triazine compound represented by the general formula (3) in “Step B-1” is preferably 1: 1 to 1:10, and the yield is good. 1: 1 to 1: 3 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.

  The molar ratio of the substituted 1,3,5-triazine compound represented by the general formula (4) and the biphenyl compound represented by the general formula (5) in “Step B-2” is from 1: 0.25. 1: 5 is desirable, and 1: 0.5 to 1: 1.5 is more desirable in terms of good yield.

  The molar ratio of the metal catalyst and the biphenyl compound represented by the general formula (5) in “Step B-2” is preferably 0.001: 1 to 0.5: 1, and is preferably 0.00 in terms of good yield. More preferred is 01: 1 to 0.1: 1.

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

  The concentration of the biphenylyl compound represented by the general formula (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 a 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, preparative thin layer chromatography, and sublimation. 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. When used for an organic electroluminescent device, purification by sublimation is particularly desirable.

  Although there is no restriction | limiting in the synthesis method of the 1,3,5-triazine compound represented by General formula (3), For example, the following method can be used.

  That is, the general formula (6)

［式中、Ｙ^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（７）

[Wherein Y ¹ represents the same content as described above. A substituted benzoyl chloride derivative represented by the general formula (7)

［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、および一般式（８）

[Wherein Ar ¹ represents the same content as described above. And a substituted benzonitrile derivative represented by the general formula (8):

［式中、Ａｒ^２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 ² represents the same content as described above. And a substituted benzonitrile derivative represented by the general formula (9):

［式中、Ａｒ^１、Ａｒ^２およびＹ^１は前記と同じ内容を示し、（Ｚ^３）⁻は陰イオンを示す。］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製造することができる。

[Wherein Ar ¹ , Ar ² and Y ¹ represent the same contents as described above, and (Z ³ ) ⁻ represents an anion. The 1,3,5-oxadianyl-1-ium salt derivative represented by the following formula can be obtained and treated with aqueous ammonia.

  It is essential that the molar ratio of the substituted benzonitrile derivatives represented by the general formulas (7) and (8) is 1: 1.

  The molar ratio of the substituted benzoyl chloride derivative represented by the general formula (6) and the substituted benzonitrile derivative represented by the general formula (7) or (8) is high in a wide range of 1:10 to 10: 1. The reaction proceeds sufficiently even with the stoichiometric ratio.

  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 1,3,5-oxadianyl-1-ium salt derivative represented by the general formula (9) can be isolated, but may be subjected to the next reaction operation in the form of a solution. When isolated as a salt, (Z ³ ) ⁻ of the 1,3,5-oxadianyl-1-ium salt derivative represented by the general formula (9) is not particularly limited as long as it is an anion. Tetrafluoroborate ion, chlorotrifluoroborate ion, tetrachloroaluminate ion, tetrachloroiron (III) ion, pentachlorotin (IV) acid in which fluoride ion or chloride ion is bonded to the listed Lewis acid Yields are good when ions or hexachloroantimonate (V) ions are obtained as counter anions.

  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.

There is no particular limitation on the method for producing a thin film composed of the 1,3,5-triazine derivative represented by the general formula (1), but in the case of producing as a thin film for an organic electroluminescence device, film formation by a vacuum evaporation method is possible. It is. 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, electron transport ability, hole blocking ability, hole transport ability, blue fluorescence emission. Therefore, it can be used as a material for an organic electroluminescent element, 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. Accordingly, the thin film composed of the 1,3,5-triazine derivative represented by the general formula (1) can be used as a constituent component of an organic electroluminescent element, an organic transistor, an organic photoreceptor, electronic paper, and the like.

  According to the present invention, a 1,3,5-triazine derivative having one terphenylyl group can be obtained with high yield. The organic electroluminescent device comprising the 1,3,5-triazine derivative as a component exhibits high luminance and high luminous efficiency, has a long lifetime, and has a luminescent color of CIE (Commission International de l'Eclairage: International Lighting Commission). ) Has pure blue chromaticity coordinates.

  Hereinafter, although the reference example and Example of this invention are demonstrated, this invention is not limited to these 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. After drying the white precipitate, 150 ml of chloroform was added thereto, and the suspension was heated to reflux and filtered. Further, 50 ml of chloroform was added to the insoluble component separated by filtration, and this was heated to reflux and then filtered twice. 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 (naphthalen-1-yl) -1,3,5-triazine 1.10 g of 4-bromobenzoyl chloride and naphthalene-1-carbohydrate 1.53 g of nitrile 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-di (naphthalen-1-yl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was gradually added to 100 mL of 28% aqueous ammonia solution at 0 ° C. To form 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. 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-di (naphthalene). A white solid (yield 0.91 g, yield 37%) of -1-yl) -1,3,5-triazine 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 3 Synthesis of 2,4-bis (biphenyl-4-yl) -6- (4-bromophenyl) -1,3,5-triazine 4.39 g of 4-bromobenzoyl chloride and 4-biphenylcarbonitrile 7.17 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 (biphenyl-4-yl) -6- (4-bromophenyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was gradually added to 300 mL of 28% aqueous ammonia solution at 0 ° C. To form 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 the suspension was heated to reflux and filtered. Further, 50 ml of chloroform was added to the insoluble component separated by filtration, and this was heated to reflux 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 (biphenyl-4-yl) -6- (4-bromophenyl)- A white solid of 1,3,5-triazine (yield 9.48 g, yield 88%) was obtained.

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.

Example 1 Synthesis of 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Under an argon stream, 1.9 mL of a hexane solution containing 2.9 mmol of butyl lithium was slowly added to 20 mL of tetrahydrofuran in which 0.61 g of 4-bromobiphenyl was dissolved and cooled to −78 ° C. After stirring at −78 ° C. for 30 minutes, 0.79 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 (40 mL) in which 0.12 g was dissolved was added, and the mixture was stirred for 2 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 (developing solvent hexane: chloroform = 5: 1 to 3: 1) and recrystallized again with dichloromethane / methanol to obtain the desired 2,4-bis (4-tert -Butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine was obtained as a white solid (yield 1.05 g, yield 91%). It was.

¹ H-NMR (CDCl ₃ ): δ 1.45 (s, 18H), 7.38-7.46 (m, 1H), 7.46-7.56 (m, 2H), 7.64 (d, J = 8.5 Hz, 4H), 7.67-7.74 (m, 2H), 7.78 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8.5 Hz, 2H) ), 7.89 (d, J = 8.5 Hz, 2H), 8.74 (d, J = 8.5 Hz, 4H), 8.89 (d, J = 8.5 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 125.6, 127.1, 127.1, 127.5, 127.6, 127.6, 128.8, 128.9, 129 5, 133.7, 135.5, 139.3, 140.6, 140.8, 144.4, 156.0, 171.1, 171.5.

Example 2 Synthesis of 2,4-di (naphthalen-1-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Argon Under a stream of air, 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-di (naphthalen-1-yl) -1,3,5-triazine obtained in Reference Example 2 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 reaction solution was concentrated under reduced pressure, and the resulting solid was washed with chloroform to obtain the desired 2,4-di (naphthalen-1-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4. A white solid (yield 1.19 g, yield 71%) of -yl-1,3,5-triazine 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 3 Synthesis of 2,4-bis (biphenyl-4-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Argon Under a stream of air, 2.1 mL of a hexane solution containing 3.3 mmol of butyllithium 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 (biphenyl-4-yl) -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 stirred for 2 hours while heating under reflux. 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 (biphenyl-). 4-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine was obtained as a white solid (yield 1.09 g, yield 71%). It was.

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 4 Preparation of charge mobility measuring element and measurement of charge mobility A glass substrate with an ITO transparent electrode on which a 2 mm wide ITO (indium tin oxide) film was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. The inside of the vacuum deposition tank was depressurized to 4.0 × 10 ⁻⁴ Pa, the material for measuring the mobility was heated by a resistance heating method, and vacuum deposited on the substrate at a deposition rate of 0.3 to 0.5 nm / second. The film thickness of the deposited film was measured with a stylus type film thickness meter (DEKTAK). Next, a metal mask was arranged on the substrate so as to be orthogonal to the ITO stripe, and a 2 mm wide Al film was vacuum deposited to a thickness of 100 nm to obtain a 2 mm square operation area. This substrate was sealed in a nitrogen atmosphere glove box having an oxygen / water concentration of 1 ppm or less. For the sealing, an epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) was used.

  The charge mobility was measured using a time-of-flight mobility measurement method. The measurement was performed at room temperature, and the mobility was determined from the moving speed of the charge generated when the nitrogen laser was irradiated from the ITO transparent electrode side to the Al electrode.

Example 4 Transfer of 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Degree measurement 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5- synthesized in Example 1 The charge mobility of triazine was measured according to Reference Example 4. The film thickness of the vapor deposition film was 1.5 μm.

The obtained electron mobility was 1.0 × 10 ⁻⁴ cm ² / V · sec. This value was 10 times as large as 1.0 × 10 ⁻⁵ cm ² / V · sec of Alq (Japanese Patent Laid-Open No. 2002-158091), which is a general-purpose electron transport material. Further, this element was confirmed to have a hole mobility, and exhibited a hole mobility of 1.0 × 10 ⁻⁴ cm ² / V · sec, which was the same as the electron mobility. From the above results, 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine was used. It was revealed that the thin film prepared in this way is an excellent bipolar compound exhibiting fast electron transport properties and hole transport properties.

Example 5 Mobility of 2,4-di (naphthalen-1-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Measurement 2,4-di (naphthalen-1-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine synthesized in Example 2 Then, device fabrication and charge mobility measurement were performed in the same manner as in Example 4. The electron mobility obtained was 4 × 10 ⁻⁴ cm ² / V · sec, and the hole mobility was 1 × 10 ⁻⁵ cm ² / V · sec. 2,4-di (naphthalen-1-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine is also a compound exhibiting bipolar properties. It became clear that there was.

Example 6 Mobility of 2,4-bis (biphenyl-4-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Measurement 2,4-bis (biphenyl-4-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine synthesized in Example 3 Then, device fabrication and charge mobility measurement were performed in the same manner as in Example 4. The obtained electron mobility was 7 × 10 ⁻⁴ cm ² / V · sec, and the hole mobility was 1 × 10 ⁻⁶ cm ² / V · sec. 2,4-bis (biphenyl-4-yl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine is also a compound exhibiting bipolar properties. It became clear that.

Reference Example 5 Production of Organic Electroluminescent Device and Evaluation of Luminescent Characteristics The configuration of the organic electroluminescent device used is shown in FIG. The substrate 1 was a glass substrate with an ITO transparent electrode in which a 2 mm wide ITO (indium tin oxide) film was patterned in a stripe shape. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. The substrate 1 is introduced into the vacuum deposition tank and the pressure is reduced to 1.0 × 10 ⁻⁴ Pa. On the substrate, the hole injection layer 2, the hole transport layer 3, the light emitting layer 4, the electron transport layer 5, and the electron injection are introduced. Layer 6 was sequentially formed by vacuum vapor deposition, and cathode layer 7 was further formed.

As the hole injection layer 2, sublimation-purified copper phthalocyanine was vacuum deposited at 25 nm. As the hole transport layer 3, NPD (N, N′-di (naphthalen-1-yl) -N, N′-diphenyl) benzidine was vacuum-deposited at 45 nm. As the light emitting layer 4, Alq was vacuum-deposited by 30 nm. Subsequently, the electron transport layer 5 and the electron injection layer 6 were vacuum deposited. Each layer was vacuum deposited by a resistance heating method at a film forming rate of 0.3 to 0.5 nm / second. Next, a cathode layer 7 was formed by arranging a metal mask so as to be orthogonal to the ITO stripe on the substrate thus laminated. The cathode layer 7 was vacuum-deposited with a thickness of 0.5 nm and 100 nm using a two-layer structure of LiF and Al, respectively. Each film thickness was measured with a stylus type film thickness meter (DEKTAK). Through the above operation, an organic electroluminescent element having a light emitting area of 4 mm ² was produced.

  Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen / water concentration of 1 ppm or less. For sealing, a glass sealing cap and a 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. The light emission characteristics were evaluated by luminance (cd / m ² ) at a voltage of 6 V, light emission efficiency (cd / A), and light emission wavelength (nm). 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.

Reference Example 6 Synthesis of 4,6-bis (4-tert-butylphenyl) -2- [4- (2,2′-bipyridin-6-yl) phenyl] -1,3,5-triazine 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′-bipyridine 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 4,6-bis (4-tert A white solid (yield 0.82 g, yield 71%) of -butylphenyl) -2- [4- (2,2′-bipyridin-6-yl) phenyl] -1,3,5-triazine was obtained.

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 = 8.6 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 7 2,4-Bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine was converted to an electron Evaluation of Organic Electroluminescent Device as Transport Material In the device of Reference Example 5, 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: synthesized in Example 1 as the electron transport layer 5: 4,6-bis (4-tert-butylphenyl) -2 synthesized in Reference Example 6 using 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine as an electron injection layer 6 at 20 nm. -[4- (2,2′-bipyridin-6-yl) phenyl] -1,3,5-triazine was vacuum-deposited at 10 nm, respectively. There was no dark spot on the light emitting surface of the fabricated device, and light was emitted uniformly. This is because 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine is highly amorphous. This indicates that it is not crystallized in a thin film state. Table 1 shows the measurement results of the light emission characteristics.

(Comparative example 1) Evaluation of the organic electroluminescent element which uses Alq as an electron transport material It replaced with the electron transport layer 5 and the electron injection layer 6 of Example 7, and vacuum-deposited Alq which is a general purpose electron transport material by 30 nm. Table 1 shows the measurement results of the light emission characteristics.

  From the results in Table 1, it was revealed that Example 7 can obtain higher luminance and higher luminous efficiency than the conventional element using Alq. Further, since the emission wavelength was not different from that of Comparative Example 1, no adverse effect on the emission color was observed. Furthermore, the device life was longer than that of Comparative Example 1, and the durability was improved.

（参考例７） 色純度測定用素子作成および色純度測定
用いた有機電界発光素子の構成を図２に示す。基板１には２ｍｍ幅のＩＴＯ（酸化インジウム錫）膜がストライプ状にパターンされたＩＴＯ透明電極付きガラス基板を用いた。この基板をイソプロピルアルコールで洗浄した後、オゾン紫外線洗浄にて表面処理を行った。真空蒸着槽内に基板１を導入して１．０×１０^−４Ｐａまで減圧し、この基板上に正孔注入層２、正孔輸送層３、発光層４、電子輸送層５を順次真空蒸着により成膜し、さらに、陰極層６を成膜した。

Reference Example 7 Preparation of Color Purity Measuring Element and Color Purity Measurement The configuration of the organic electroluminescent element used is shown in FIG. The substrate 1 was a glass substrate with an ITO transparent electrode in which a 2 mm wide ITO (indium tin oxide) film was patterned in a stripe shape. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. The substrate 1 is introduced into a vacuum deposition tank and the pressure is reduced to 1.0 × 10 ⁻⁴ Pa, and the hole injection layer 2, the hole transport layer 3, the light emitting layer 4, and the electron transport layer 5 are sequentially vacuumed on the substrate. A film was formed by vapor deposition, and a cathode layer 6 was further formed.

As the hole injection layer 2, sublimation-purified copper phthalocyanine was vacuum deposited at 25 nm. As the hole transport layer 3, NPD (N, N′-di (naphthalen-1-yl) -N, N′-diphenyl) benzidine was vacuum-deposited at 45 nm. Subsequently, the light emitting layer 4 was vacuum-deposited by 40 nm. Further, Alq was vacuum deposited as the electron transport layer 5 by 20 nm. Each layer was vacuum deposited by a resistance heating method at a film forming rate of 0.3 to 0.5 nm / second. Next, a cathode layer 6 was formed by arranging a metal mask so as to be orthogonal to the ITO stripe on the substrate thus laminated. The cathode layer 6 was vacuum-deposited with a thickness of 0.5 nm and 100 nm using a two-layer structure of LiF and Al, respectively. Each film thickness was measured with a stylus type film thickness meter (DEKTAK). Through the above operation, an organic electroluminescent element having a light emitting area of 4 mm ² was produced.

  Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen / water concentration of 1 ppm or less. For the sealing, a glass sealing cap and an 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 color purity of light emission was measured with a spectroscope USB-2000 manufactured by Ocean Photonics Co., Ltd.

Example 8 Light emission of 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3,5-triazine Measurement of Color Purity of Organic Electroluminescent Element as Material 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4 synthesized in Example 1 -A device having yl-1,3,5-triazine as a light emitting layer was prepared according to Reference Example 7, and when a direct current voltage was applied, it was confirmed to emit blue light. It became clear that the chromaticity coordinates of the emission color were (0.16, 0.13), which is close to pure blue. The color purity of the obtained device was 2,4-bis (4-tert-butylphenyl) -6- [1,1 ′: 4 ′, 1 ″] terphenyl-4-yl-1,3. , 5-triazine was well-corresponding to the chromaticity coordinates (0.15, 0.07) of the emission color of the fluorescence spectrum of the thin film deposited by vacuum evaporation, and it was confirmed that it was derived from the triazine derivative.

FIG. 6 is a diagram showing a configuration of an organic electroluminescent element described in Reference Example 5. FIG. 10 is a diagram showing a configuration of an organic electroluminescent element described in Reference Example 7.

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. Electron injection layer 7. Cathode layer 8. 8. Glass substrate with ITO transparent electrode Hole injection layer 10. Hole transport layer 11. Light emitting layer 12. Electron transport layer 13. Cathode layer

Claims (8)

General formula (1)

[Wherein Ar ¹ and Ar ² represent the same or different phenyl group or naphthyl group, and these may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. ] The 1,3,5-triazine derivative characterized by the above-mentioned. The 1,3,5-triazine derivative according to claim 1, wherein Ar ¹ and Ar ² are a phenyl group, a 4-tert-butylphenyl group or a 1-naphthyl group. General formula (2)

[In the formula, M ¹ represents —ZnR ¹ group, —MgR ¹ group, —Sn (R ² ) ₃ group, —B (OH) ₂ group, —BR ³ group, —BF ₃ ^— (Z ¹ ) ⁺ group or —Si (R ⁴ ) ₃ groups are shown. Where R ¹ represents a chlorine atom, a bromine atom or an iodine atom, R ² is the same or different and represents an alkyl group having 1 to 4 carbon atoms, and R ³ represents 2,3-dimethylbutane-2,3-dioxy. Group, an ethylenedioxy group or a 1,3-propanedioxy group, (Z ¹ ) ⁺ represents an alkali metal ion or a quaternary ammonium ion, and R ⁴ is the same or different and is a methyl group, an ethyl group, a methoxy group, A group, an ethoxy group or a chlorine atom; A substituted biphenyl compound represented by:
General formula (3)

[Wherein Ar ¹ and Ar ² represent the same or different phenyl group or naphthyl group, and these may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. Y ¹ represents a leaving group. And a 1,3,5-triazine compound represented by general formula (1), wherein a coupling reaction is performed in the presence of a metal catalyst.

[Wherein, Ar ¹ and Ar ² represent the same or different phenyl group or naphthyl group, and these may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. ] The manufacturing method of the 1,3,5-triazine derivative represented by this. General formula (4)

[Wherein Ar ¹ and Ar ² represent the same or different phenyl group or naphthyl group, and these may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. M ² represents —ZnR ⁵ group, —MgR ⁵ group, —Sn (R ⁶ ) ₃ group, —B (OH) ₂ group, —BR ⁷ group, —BF ₃ — (Z ² ) ⁺ group or —Si (R ⁸ ) ₃ groups are shown. However, R5 is a chlorine atom, a bromine atom or an iodine atom, ^{R 6} are the same or different and represents an alkyl group having 1 to 4 carbon atoms, ^{R 7} is 2,3-dimethylbutane-2,3-dioxy group Represents an ethylenedioxy group or a 1,3-propanedioxy group, (Z ² ) ⁺ represents an alkali metal ion or a quaternary ammonium ion, and R ⁸ is the same or different and is a methyl group, an ethyl group or a methoxy group. Represents an ethoxy group or a chlorine atom. A substituted 1,3,5-triazine compound represented by the general formula (5)

[Wherein Y ² represents a leaving group. And a biphenyl compound represented by the general formula (1), wherein a coupling reaction is performed in the presence of a metal catalyst.

[Wherein, Ar ¹ and Ar ² represent the same or different phenyl group or naphthyl group, and these may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. ] The manufacturing method of the 1,3,5-triazine derivative represented by this. The production method according to claim 3 or 4, wherein the metal catalyst is a palladium catalyst, a nickel catalyst or an iron catalyst. The production method according to any one of claims 3 to 5, wherein the metal catalyst is a palladium catalyst. General formula (1)

[Wherein, Ar ¹ and Ar ² represent the same or different phenyl group or naphthyl group, and these may be substituted with one or more alkyl groups having 1 to 4 carbon atoms. An organic electroluminescent device comprising a 1,3,5-triazine derivative represented by the formula: The organic electroluminescent element according to claim 7, wherein Ar ¹ and Ar ² are a phenyl group, a 4-tert-butylphenyl group, or a 1-naphthyl group.

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