TW201240976A - 1,3,5-triazine compound, method of producing same, and organic electroluminescent device containing same as structural component - Google Patents

Abstract

A 1, 3, 5-triazine compound represented by general formula (1) shown below. In the formula, each of Ar1 and Ar2 represents an aromatic hydrocarbon group that may be substituted with an alkyl group of 1 to 4 carbon atoms or a fluorine atom, and Ar3 represents a nitrogen-containing heterocyclic group that may be substituted with an alkyl group of 1 to 4 carbon atoms or a fluorine atom. An organic electroluminescent device containing this 1, 3, 5-triazine compound as a structural component can be driven at low voltage and exhibits highly efficient light emission.

Description

201240976 #, invention description: [Technical field of the invention] It is useful as a constituent component of an organic electroluminescence tree; (2) a read compound having a nitrogen-containing heterosexual _ three-stretched silk and its preparation is good = good [Characteristics of charge transport] [Previous technique] The light-emitting element of the light-emitting element is sandwiched between the light-emitting layer containing the light-emitting material: the same as the electron transport layer of the transport layer, and further infused with the light-emitting layer. Holes and electrons ί:; ^ pole 'use Α π / υ π ΤΜ dry, applied to the display and so on. According to the invention, the element of the 3,5_triterpene compound, the benzene (four)==== (fluorescent or phosphorescent) element, is applied to the display y/. When the stalk is inactivated, it emits light having an aromatic hydrocarbon group having an err phenyl group or a di-extended group. The w compound of the present invention differs only in the phenyl group having a fluorene-based electroluminescent element. The substituent of the 2,4,6 heterocyclic aromatic group of the Mitre ring is rr-extension, and the butyl group is contained in the 2, 4 position. The structure of the substituted aryl group is completely different from the 1,3,5-three liter compound of the present invention of (^) 4 201240976 aromatic hydrocarbon group.士. ΐ ΐ 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人The construct of the aryl group, 1, 3, 5 - 2 of the present invention having a triaryl group at the 2, 4 positions. The tablet compounds are completely different. [Prior Art Document] [Patent Document 1] US Patent No. 6057048 (Patent Document 2) US Patent No. 6229012 [Patent Document 3] US Patent No. 6225467 [Patent Document 4] Japanese Laid-Open Patent Publication No. 2004-134829 (Patent Document No. 2007-137829) [Patent Document 7] Japanese Patent Laid-Open Publication No. 2010-155826 (Invention) Contents] [Problems to be Solved by the Invention] There are various light-emitting elements used in various display devices, and the mobile device is made of '''' Electricity. In particular, regarding electron transport materials, excellent charge input and transport characteristics prevent excitons from leaking from adjacent light-emitting layers.

5 201240976 materials, I hope to have new materials. [Technical means for solving the problem] In order to achieve the above object, the inventors of the present invention worked hard to use the electron transport layer, and it was able to drive and improve the luminous efficiency compared to the compound of the general organic compound. In the case of the completion of the Xiao Xiaolong, the present invention provides a compound of the following formula (1), which is a compound of the following formula (1).

(1) Stinky. S is an aromatic hydrocarbon group which may be substituted by a filament or a gas having a carbon number of 1 to 4: an aromatic hydrocarbon group which may be substituted with a carbon group of 1 to 4 or a fluorine. Ar3 represents a nitrogen-containing heterocyclic group which may also be substituted with a decyl group or a fluorine group of the number 1 to 4. ). In the present invention, another type, 1, 3, 5_3 is provided. A method for producing a chelating compound, which is characterized in that a compound represented by the following formula (7) and a compound represented by the following formula (3) are produced in the presence or absence of a base in the presence of a catalyst, and the following reaction is carried out. Formula 1, (1), 1,3,5-triterpene compound; ~ Formula (2)

X1 ν^ν Ar1 (2) (wherein Ar1 represents an aromatic hydrocarbon group which may also be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine. Ar2 represents an alkyl group or a fluorine group which may be substituted by a carbon number of 丨4 or 4 Aromatic hydrocarbon group. χ1 represents a leaving group) Formula (3)

Ar3-Μ (3) 8 6 201240976 US H may also be substituted by a carbon number of 1 to 4 or a substituted nitrogen-containing heterocyclic ring.

base. Μ 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含 不含An alkyl group or a substituted aromatic hydrocarbon group of 4; = a nitrogen-containing heterocyclic group which may also be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine. Further, the present invention provides a method for producing a 1,3,5-membered chelate compound, which is characterized in that a compound represented by the following formula (4) and a compound of the following formula are used. The coupling reaction is carried out in the presence of a surface to produce a 1,3,5-triple compound represented by the formula (1); and the formula (4)

(Formula, Ar represents an aromatic fluorene group which may be substituted by an alkyl group having a carbon number of i to 4 or fluorine, and an aromatic hydrocarbon group which may be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine. Rr , an alkyl group having a carbon number of 44 or a phenyl group, and two r4^_ of b(〇r4)2. Further, '2 like 4 can also be a body and contain an oxygen atom phase and a general formula (5) (5) )

Ar3—X2 (wherein Ar3 represents a nitrogen-containing hybrid which may also be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine (1) 201240976, and X2 represents a leaving group) (1)

Ar2 Ar2

(In the formula 2, Ατ1 represents an aromatic furnace Ar which may be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine, and represents an aromatic smoky group which may be substituted with a carbon group or a fluorine group. a nitrogen-containing heterocyclic ring substituted with a carbon number of 1 to 4 or a gas.

^, the present invention in another aspect, provides an organic luminescence system with the following shots (1) "(3). Three liters of compound as a structure (1) [effect of the invention] hybrid (hereinafter sometimes referred to as It is used as an organic electroluminescence element, etc., for crystal, heat resistance, surface smoothness, non-water resistance, oxygen resistance, electric power capability, redox resistance, and materials. Organic electroluminescence as an electron transport material, a hole "=optical element. _ electric length" [Embodiment] 8 201240976 The following is a detailed description of the present invention. It is a 1,3,5-triterpene compound (1) In the general formula (1), Arl represents an aromatic 庐f such as a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group or a bis-phenylene group (8). The phenotype can also be obtained by an alkyl group having a carbon number. Or a fluorine substitution. Examples of carbon number: thiol, ethyl, propyl, isopropyl, butyl, tert-butyl, etc., etc., such as <, linear, branched or cyclic, It can be further replaced by one or more dentate or the like. "There is a good performance as a material for an organic electroluminescence device." A phenyl group substituted with a carbon group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a carbon group having 1 to 4 carbon atoms, preferably an unsubstituted phenyl group. etc. The following is a list of aromatics represented by Ar1. Specific examples of the hydrocarbon group, but the present invention is not limited to the phenyl group which may be substituted with a carbon number of 1 to 4 or fluorine, and in addition to the phenyl group, it is also a tolyl group, an m-tolyl group, an o-tolyl group. , 4-trifluoromethylphenyl, 3- ΐ 26 Λιί gas methylphenyl, m-silyl, 3,5-dimethylbenzene = 2,6-methyl group, certain group, 2-ethyl Phenyl, 3-ethylphenyl, 4-ethylethenylphenyl, 3,5-diethylphenyl, 2-propylphenyl, 3-propyl phenyl, propylenedipropyl phenyl , 3,5·dipropyl*yl, 2_isopropylphenyl, 3_Λ 2 ΐί莫ί fyl/yl, 2,4-diisopropylphenyl, 3,5-diisopropylbenzene ^丁2^^本2基:3_丁^Phenyl, phenyl, 2,4-dibutylphenyl, 3,5_2~4_二土_第^丁苯苯二3_ Tertiary butylphenyl, 4-tert-butylphenyl, 4: fluorobenzene, 2, 5_2t-butylphenyl, 2-d-phenyl, 3-oxyphenyl, Q, F Fluorine, 9-back-:, 0-mouse-based, 2,3,4-di- benzene , 2,3,5-trifluorobenzene, 9,5-trifluorophenyl, 2,4,6-trifluorophenyl, fluoroyl, etc., '^^ base, 2, 3, 4,6, Phenyl phenyl, 2,3,5,6, fluorophenyl, phenyl ketone of the five-materials as a material from the organic electro-luminous component 2, 6 A month, point / Phenyl group, p-tolyl group, m-tolyl 'o-phenylene group, 2,6-monomethyl group, and 4-tert-butylbutyl group are preferred. From the viewpoint of easy synthesis, benzene 201240976 is more preferable. The naphthyl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, in addition to the 1-naphthyl group or the 2-naphthyl group, may also be, for example, 4-nonylnaphthalen-1-yl or 4-trifluorodecylnaphthalene. -1_yl, 4-ethylnaphthalen-1-yl, 4-propylnaphthalen-1-yl, 4-butylnaphthalene small group, 4-tert-butylnaphthalene small group, 5-nonylnaphthalene-1 -yl, 5-trifluoromethylnaphthalene, 5-ethylnaphthalen-1-yl, 5-propylnaphthalen-1-yl, 5-butylnaphthalen-1-yl, 5-tert-butylnaphthalene _1_yl, 6-methylnaphthalen-2-yl, 6-trifluorodecylnaphthalen-2-yl, 6-ethylnaphthalen-2-yl, 6-propylnaphthalen-2-yl, 6-butyl Naphthyl, 6-t-butylnaphthalen-2-yl, 7-methylnaphthalene-2-yl, 7-trifluorodecylnaphthalen-2-yl, 7-ethylnaphthalen-2-yl, 7 -propylnaphthalen-2-yl, 7-butyl _2_ group, 7-tert-butyl-2-yl and the like. Among the above-mentioned substituted naphthyl groups, from the viewpoint of good performance as a material for an organic electroluminescence device, 丨-naphthyl group, 4-methylnaphthalene small group, 4-t-butylnaphthalene-based group, 5-methylnaphthalen-1-yl, 5-t-butylnaphthalene small group, 2-naphthyl, 6-nonylnaphthalen-2-yl, 6-second butylnaphthalene-2-yl, 7-fluorene Preferably, the naphthyl-2-yl or 7-t-butylnaphthalene-2-yl group is preferred. a mercapto group substituted with an alkyl group having 1 to 4 carbon atoms, a phenanthryl group substituted with an alkyl group having 1 to 4 carbon atoms, a mercapto group which may be substituted with an alkyl group having a carbon number, and a carbon number Alkyl-substituted triphenylene substituted by alkyl group, for example: 丨_蒽 group, 2-valent group, 9-fluorenyl group, 9-phenanthryl group, 1-fluorenyl group, 2-mercapto group and i_linked three-strand Phenyl and the like.

The aromatic hydrocarbon group which is not represented by Ar may be substituted with a group such as an aromatic hydrocarbon group represented by the above Afl, or may be substituted with a carbon group having 1 to 4 carbon atoms or a gas. From the viewpoint of easy synthesis and good performance of the material for the luminescent element, Ar2 is preferably substituted by a carbon n- phenyl group or a naphthyl group which may also be substituted with a carbon number of 1 to 4 groups. The phenyl group is better.伸如 i: ίίΓίΛ3,5-Mitsui Chemicals (1), characterized by the joints of Mitsui

ί base: The second is taken from the nitrogen heterocyclic group of S porphyrin, and for example, hydrazine. Fixed base, ♦ fixed base, More than 汫基, the county _ replaced. The compound (1) of the u(d) compound of the present invention is characterized in that the Mitsui bond 201240976 is a nitrogen-containing heterocyclic ring of a monocyclic or condensed ring. The aromatic hydrocarbon filaments such as a fixed group are supported by nitrogen, and the nitrogen heterocyclic group has a ternary aryl group, and Ar3 is as defined above, and does not contain a phenyl substituent. Ratio substituted nitrogen-containing heterocyclic group.

Ar is preferably unsubstituted or substituted by methyl or gas. From the viewpoint of easy synthesis and good performance of materials for electroluminescent elements, pyridyl groups, ruthenium groups, and ruthenium are used. Silk, different t-based,.丫, benzyl, benzyl or benzo[%] These may be unsubstituted or may be substituted by fluorenyl or fluoro. Soil ^ The following is a specific example of Ar3', but the present invention is not limited to these. It can also be substituted with a decyl group or a fluorine-substituted fluorenyl group of 1 to 4, except for 2 吼. Set it, 3-. The pyridyl group and the 4-pyridyl group are, for example, 3-methyl-2-pyridyl group and 4_曱^^_. N-decyl, 5-mercapto-2-acridinyl, 6-methyl-2-pyridyl, 2-indenyl-3-yl, 4-methyl-3-pyridyl, 5-methyl-3 』Biridinyl, 6-mercapto_3-. Bipyridyl, 2_mercapto_4_. More than 11 base, 3-mercapto-4-. Bipyridyl, 3,4-dimethyl-2-pyridyl, 3,5-dimethylheptyl, 3,6-dimercapto-2-«pyridinyl, 2,4-diindole Base_3-pyridyl, 2,5_two$yl_3_. Specific ratio, 2,6-dimethyl-3-° ratio, 4,5-dimercapto-3-. Specific bite, 4,6-dimercapto-3_acridinyl, 5,6-dimethyl-3-pyridyl, 2,3-dimercapto-4-pyridyl: 2,5-di & Base ice pyridyl, 2,6-diamidino-4-pyridyl, 3,5-diindolylpiperidinyl, '3,6-di-yl-4-yl ratio bite base, 3-fluoro- 2-° ratio to thiol, thiol, 5-fluoro-based, & Base group, 2-fluoro-3-σϋσ group, 4-oxo-3-π ratio π group, 5-fluoro-3-π[^π group, 6_ gas-3-° ratio. Stationary, 2-fluoro-4-t-based, 3-fluoranthene-11, 3,4-difluoropyrene π-group, 3.5--rat-2-° ratio, 3,6--one gas-2- σ is greater than σ 疋, 2,4-digas-3-0 ratio. Determine its ^, 2 5 difluoro-3-nh group, 2,6-difluoro-3-° ratio °, 4,5-dioxin-3-n ratio α-based, 4 6_二气-3- Acridinyl, 5,6-difluoro-3-pyridyl, 2,3-difluoro-4-pyridyl, 2,5-di'-like _4_n-pyridyl, 2,6-difluoro-4- . Than base, 3,5-difluoro-4-° ratio bite base, 3,6-difluoro hail. Stationary, 3.4.5-trifluoro-2-pyridyl, 3,4,6-trifluoro-2-pyridyl, 3,5,6-tri-following, lowering, lowering, 4.5.6-trifluoro- 2-σΐ^ group, tetrafluoro-2-. Specific ratio, 2,4,5-trifluoro-3-t» ratio π group, 2 4 6_ two 1-3 ° ° ° base, 2,5,6-trifluoro-3-° ratio. Stationary, 4,5,6-trifluoro-3-. ^定定,四败 -3-η ratio π定基, 2,3,5-trifluoro-4-ρΛσ定基, 2,3,6-trifluoro-4-° ratio η-based, tetrafluoro-ice. More than pyridine. The pyrimidinyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine may be, for example, 2-carolina 11 201240976, a pyridyl group, a 5-pyridyl group or a 4-methyl-2-pyrimidinyl group 5-曱基-2-. Methylene, 2-methyl-4-pyrimidinyl, 5-mercapto-4-pyrimidinyl, 6-mercapto-4-pyrimidinyl, 2-mercapto-5-pyrimidinyl, 4-methyl-5 - Pyrimidinyl and the like. ... pyridinyl group which may also be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine, for example, pyrenyl group, 2-mercapto, and 4-mercaptopyridyl. Well base, 5-methylpyridinyl, 2-fluoropyridinyl, fluoropyrazine, 5-fluoroindole λ well base, and the like. It may also be substituted with a carbon number of 1 to 4 or a fluorine. Lin, for example: 2 linalyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl, 6-quinolinyl, 7-quinolinyl, 8-quinolinyl, 3-methyl Benz-2-quinolyl, 4-mercapto-2-quinolyl, 5-mercapto-2-indolyl, 6-methyl-2-sialolinyl, 7-mercapto-2-quinoline Base, 8-mercapto-2-quinolyl, 2-methyl-3-indole. Lin, 4-mercapto-3-indolyl, 5-methyl-3-quinolyl, 6-fluorenyl-3-indolyl, 7-fluorenyl-3-tenylene, 8-methyl 3-quinolinyl, 2-mercapto-4-quinolyl, 3-methylbromoporphyrin, 5-methyl-4-quinolinyl, 6-methyl-4-quinolinyl, 7-Mercapto-4-quinolyl, 8-mercapto-4-indolyl, 2-methyl-5-carbolinyl, 3-methyl-5-quinolinyl, 4-methyl-5 - Porphyrin 1, 6-methyl-5-quinolyl, 7-methyl-5-quinolyl, 8-mercapto-5-quinolyl, 2-mercapto-6-quinolinyl, 3 -mercapto-6-quinolyl, 4-mercapto-6-quinolyl, 5-methyl-6-quinolyl, 7-methyl-6-quinolinyl, 8-mercapto-6- Quinolinyl, 2-mercapto-7-quinolyl, 3-mercapto-7-quinolyl, 4-methyl-7-quinolyl, 5-indolyl-7-quinolinyl, 6_ Indenyl-7-quinolinyl, 8-methyl-7-quinolinyl, 2-methyl-8-quinolinyl, 3-methyl-8-quinolinyl, 4-mercapto-8-quina Polinyl, 5-methyl-8-carbolinyl, 6-fluorenyl-8-quinolyl, 7-methyl-8-carbolinyl, 3-fluoro-2-indole. Linji, 4-fluoro-2-indolyl, 5-fluoro-2-indole. Lin, 6-oxo-2-indolyl, 7-,-2-quinolinyl, 8-fluoro-2-quinolinyl, 2-fluoro-3-quinolinyl, 4-fluoro-3-quino Phytyl, 5-fluoro-3-indolyl, 6-fluoro-3-ringinyl, 7-single-3-indenyl, 8-in-3-indolyl, 2-fluoro-4-quino Phytyl, 3-fluoro-4-ylquinolinyl, 5-fluoro-4-ylquinolinyl, 6-fluoro-4-ylquinolinyl, 7-fluoro-4-indolyl, 8-fluoro-4-indole Lyophilized and so on. An isoquinolyl group which may also be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine, for example, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-Isoquinolyl, 7-isoquinolinyl, 8-isoindole. Linji, 3-mercapto-1-isoindole, and sulfhydryl. Lin,5-methyl-1-isoindolyl, 6-mercapto-1-isoquinolinyl, 7-methylisoisoquinolyl, 8-methyl-1-isoindolyl, 1- Methyl-3-isoquinolyl, 4-methylisoquinolyl, 5-mercapto-3- 12 8 201240976 isoI, 6-methyl-3-isoquinolinyl, 7-methyl _3-Isoquinolyl, 8-mercapto-3-iso-f' lysyl, 1-methyl-4-isoquinolyl, 3-methylisoquinolinyl, 5-fluorenyl-4- Isoquinolyl, methyl-4-isoquinolyl, 7-fluorenyl-4-isoquinolyl, 8-methyl-4-isohexyl, 3-fluoro-1-isoindolyl, 4_fluoroisoisoquinolyl, 5n-isoquinolyl, 6-small isoquinolinyl, 7-fluoro-1-isoquinolinyl, 8-fluoroisoquinolinyl, fluoro--iso-quinoline Phytyl, 4-fluoro-3-isoquinolyl, 5-fluoro-3-isohexyl, 6-fluoro-3-isohydrophenyl, 7-fluoro-3-iso-isolinyl, 8-fluoro -3-isoindole. Linji, 1_Fluorine_4_isoindolinyl, 3_ defeat_4_isoindolyl, 5-fluoro-4-isoquinolinyl, 6-fluoro-4-isoxolinyl, 7-fluoro _4_Isoquinolyl, 8-fluoro-4-isohydroquinolinyl and the like. It is also possible to use a pyridyl group having a carbon number of 1 to 4 or a fluoro-substituted sulfhydryl group, for example, 2_^β-based group, 4-°-zezolyl group, 5-. Sezazolyl and the like. It may also be a benzopyrene-based group substituted with a carbon number of 1 to 4 or a fluorine group, for example, 2_benzoxemyl, 4-benzoxazolyl, 5-benzoxanthyl, 6 - Benzothiazolidine, 7-benzo. Plug σ sit base and so on. Further, it may be substituted with a carbon group having 1 to 4 carbon atoms or fluorine. Hey. The base may also be substituted with a pyridyl group substituted with an alkyl group or a fluorine having 1 to 4 carbon atoms, or an alkyl group having a carbon number of 丨4 or a fluorine atom, or may be burned by a carbon number of 1 to 4. a base or a yttrium-substituted sulfonyl group, which may also be substituted with a carbon number of 1 to 4, or a sulfhydryl group substituted with a carbon number of 1 to 4; Specific examples are, for example, 9-acridinyl, 1,6-pyrimidin-2-yl, iota, 8-returned-n-butyl-2-yl, 2-indole-based, 4-indolyl-based , 2-嘻喔琳基, 2-called 卜巾 base, σ米唾和[l,2-a] acridine-2-yl and the like. Any hydrogen atom in the compound (1) of the 1,3,5-three well can also be substituted with a halogen atom. Next, a description will be given of a method for producing the 1,3,5-tris-sigma well compound (1) of the present invention. The 1,3,5-trianthracene compound (1) can be produced according to the method comprising the step 1 represented by the following reaction formula.

201240976 $Formula (1), (2) and φ 'Ar1 denotes an aromatic hydrocarbon group which may also be substituted by carbon number 4 or substituted. Af silk can also be substituted with a carbon number of 44 or a fluorine-substituted aromatic base.表示 represents a nitrogen-containing heterocyclic group which may also be substituted by the carbon tU~4. Specific examples of & Ar and Ar3 are as described above. X1 represents a leaving group. X1 represents a depilation such as a chlorine atom, a desert atom or a substitution atom. From the viewpoint of a good reaction rate, a bromine atom or a chlorine atom is preferred. The M table contains no metal or hetero atom groups. Specific examples thereof will be described with respect to the compound (3) described later. The compound represented by the formula ($) (hereinafter sometimes referred to as "r compound (2)") can be produced, for example, by the method shown in the following phase _1. Any hydrogen atom of the compound (2) can also be substituted with a halogen atom. The compound represented by the formula (3) (hereinafter sometimes referred to as "compound (3)") can be used, for example, J. Tsuji, "palladium Reagents - Catalysts" JJohn Wiley & 2004, journa] 〇f. Chemistry, 60, 7508-7510, 1995, Journai of Organic Chemistry, Vol. 65, 164-168, 2000,

Organic Letters '10 Volume ' 941-944, 2008, or chemistry of Materials, 5951-5953, manufactured by the method disclosed in 2008. Any hydrogen atom in the compound (3) may be substituted with a halogen atom. Preferable examples of the diatom compound (3) include, for example, the following 3-1 to 3-24 (wherein Μ represents a group containing a & or a hetero atom group), but the present invention is not limited thereto. 201240976 3-1 3-2 3-3 {>- c>^ 3-7 3-8 3-9

M

3-16 3-5

Me. Μ N, ^~M 3-6 Me Me 3-12 3-11

3-17 3-18

-N 3-13 N N

•M 3-19 3-14 3-15

i [Vm 〇C^m 3-22 3-23 3-24 M represents a metal-containing group, and examples thereof include Li, Na, MgChMgBr, MgI, CuC, CuBr, Cul, A1C12, AlBr2, and Al(Me). 2. Al(Et)2, ΑΐόΒιιΧ, Sn(Me)3, Sn(Bu)3, SnF3, ZnR3 (in the formula, a halogen atom), and the like, and ZnR3 may, for example, be fnCl, ZnBr, Znl or the like. From the viewpoint of good yield, the metal-containing group, fnCl is more preferable, and ZnC1 (TMEDA) having tetramethylethylenediamine coordination is more preferable. Again, . The metal-containing group such as the genus may also have a ligand such as an ether or an amine, and the type of the ligand is not limited as long as it does not interfere with the step 1. , oh. The two original f groups may be, for example, three R4 hydrogen atoms, a carbon number of 1 to 4 or a phenyl group, and a b (〇R4)2 shoulder different from the first, the third, the first, and the B (〇R4)2. . Also, '2 r4 can also be a body and contain oxygen B (〇M^ B(JC B(〇R4) 2 , B(〇H) 2 ' oxygen atom and er, 3, B (°Ph4) 2 #. 2 R4 are 'is-body and show the base. Among these, 'B(0R)2 can be, for example, the following (1) to (VI) table, the yield of the product is good, to (11) ) indicates that the basis is 15 201240976

"Step 1" is a method in which the compound (2) is reacted with the compound (3) in the presence or absence of a catalyst in the presence of a catalyst to produce the three-well compound (1) of the present invention. The reaction conditions of a general coupling reaction such as a Suzuki-Miyaura reaction, a root-bank reaction, a Yuwei_Kumian reaction, and a Stille reaction are obtained in good yield. The "palladium catalyst" which can be used in "Step 1" is, for example, palladium chloride, palladium acetate, trifluoroacetic acid or nitric acid. Furthermore, for example: π-allyl chlorinated dimer, acetoxyacetone, bis(monohexylidene) bis-bar, ginseng (di-mercaptoacetone) dioxime, dichlorobis ( Tris, phosphine) palladium, ruthenium (triphenylphosphine) palladium and di-gas (15; 1, bis (diphenylphosphino) ferrocene) palladium and other compounds. Among them, a complex having a tertiary phosphine as a ligand is preferred from the viewpoint of a good reaction yield, and from the viewpoint of easy availability, a compound having triphenylphosphine as a ligand is further good. The amount of the palladium catalyst used in the "Step 1" is not particularly limited as long as it is a so-called catalyst amount, and the molar ratio of the palladium catalyst to the compound (7) is 1:50 to 1:10 from the viewpoint of good yield. good. , </ br> A palladium complex with a tertiary phosphine as a ligand, or a palladium-substituted compound added to the reaction system. Can be added to the palladium salt or the distorted secondary phosphine, for example: triphenylphosphine, tridecylphosphine, tributylphosphine, tris(t-butylphosphine, tricyclohexylphosphine, tert-butyldiphenyl Phosphine, 9,9-dimethyl-4 (diyl)+ star, 2-(diphenylphosphino)_2,_(N,N-dimethylamino)biphenyl,} (two_third) Phosphonyl)biphenyl, 2 Cyclohexylphosphino)biphenyl, bis(diphenyl fluorenyl), 2,diphenylphosphino), 1,3 bis (diphenylphosphino) ), M• bis (diphenylphosphinopyrene, 1,1 - bis(diphenylphosphino)ferrocene, tris(2_indolyl), tris(phosphine, ginseng (2,5-) Xylyl phosphine, (±&gt;252, _bis(diphenyl aryl&gt;1,1: cleavage, 2 =, phosphine^2', 4',6'-triisopropylbiphenyl Etc. From the easy and anti-"good rate, diphenyl fine, two (t-butyl na or 2 - dicyclohexyl group 2,4,6, · tripropylene propyl biphenyl is preferred. The molar ratio of the phosphine contact salt or the wrong compound is u〇~^ 8 16 201240976 . Preferably, from the viewpoint of good yield, it is preferably 1:4 to 5:1. In "Step 1", M is used. b(〇r4 should be implemented from the viewpoint of good yield, in the presence of inspection ^ ^ Suzuki-Miyaura anti-use test, for example: sodium hydroxide, hydrogen and oxygen: At this time, acid clock, 铯: acetic acid unloading, sodium acetate, Wei unloading, stone f potassium, It hammer Etc., from the viewpoint of good yield, the molar ratio of the chlorine oxide and the fluorine compound to the compound (3) is not particularly limited, and is preferably 2: 1. The good viewpoint is 1:1~3.·1 is even better. From the good yield, the molar ratio is not particularly limited to the factory. It is better to produce a good point of 2:1~3:1. "The reaction of bovine 1 ^, from the viewpoint of good yield, In the solvent, 鲈# L acupoints, benzene, diethyl _, 1 4-tower ^ ^ butanol or xylene, etc., may also be used as a mixed solvent of ethanol, a mixture and a mixture of four winds and seven souths.二 醇 醇 ί ί 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于2 steps to create.)" then u

B(0R4)2

ΑΘ—χ2 (5) Γ5^3 Step 2 W, Ar2 and Ar3 are replaced by the second f, which means that the argon-fluorine can also be taken through the carbon number 1~4. The aryl group of 1 to 4 or the aromatic α 取代 substituted with a hydrazone represents a nitrogen-containing heterocyclic group which may also be substituted with an alkyl group having a carbon number of 4 to 4 or a fluorine. Specifically, for example, the above-mentioned 17 201240976 σ R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and the two R 4 units of B(OR4) 2 may be the same. Further, two r4 may be a body and contain an oxygen atom and a stone atom to form a ring. Specific examples of B(OR4) 2 are, for example, the same as those enumerated for the compound (3). X represents a leaving group. X2 represents a leaving group such as a chlorine atom, a bromine atom or a touch. From the viewpoint of good yield, a bromine atom is preferred. The compound represented by the formula (4) (hereinafter sometimes referred to as "the compound (4) is produced by the method of Reference Example 2. Further, any one atom of the compound (4) towel may be substituted with hydrazine. The compound represented by the formula (5) (hereinafter sometimes referred to as the r compound (5)") can be produced, for example, by the method disclosed in JOrg. Chem., Vol. 48, 1064-1069, 1983. Further, the compound ( Any of the hydrogen atoms in 5) may be substituted with a ruthenium atom. A preferred example of the substance (5) is, for example, the following ～5_24 (wherein χ2 represents a leaving group), but the present invention is not limited thereto.

Me 5-1 5-2 5-3 5-4 5-5 5-6 ^ ^ Γ&gt;&gt;_^χ2 5-7 5.8 Me Me 5-9 5-10 5-11 5-12 -X2

A A

Me 'χ2 N^x2 O-x2 ν}~χ2 5·13 5-14 5-15 5-16 5-17 ft

5-18

X2 [household 2 C〇-x2〇5-21 5-22 5-23 5-24 step 2"' is the compound (4) in the presence of palladium catalyst and base with compound (3) ν^Λ-χ2 ^x2 5- 19 5-20 5-21 18 8 201240976 气, method of Mitsui compound (1). The object can be obtained in good yield by applying the reaction conditions of a general Suzuki-Lupu reaction. The palladium catalyst which can be used in the "Step 2" is, for example, "palladium _ exemplified in the step i, a wrong compound. Among them, a tertiary phosphine is used as a coordination base complex, and it is preferable from the viewpoint of J ^. Achieve easy and good yields,

It is especially good for the complex of the ligand. The "step 2" used is not specifically limited, but from the viewpoint of good yield, the molar ratio of the mordant compound (4) is preferably 1:100 to 1:1. . The hand-receiving compound as a ligand can also be prepared by using a salt or a misclassification system. A tertiary phosphine exemplified in the step 丨 can be added to a salt or a wrong compound. It is preferred that the shot is easy to obtain and that hexyl/lacquer 2', especially 6,-triisopropylbiphenyl is preferred. The tertiary phosphine point r2 ^ is ^, which is preferably 1:1Q~, and is carried out in the presence of a good yield. Can use " ^ . 氕 氕 potassium, carbon _, potassium carbonate, carbon two = from the production of reed two v (four) 夂 unloading, sodium silicate, sodium fluoride, I unloading, fluoride recording, etc., ear ratio 'carbon _, It is ideal for the acidification of the dish. The Mosquito mosquito of the compound (4) is 1 domain: 1 is preferred, from the viewpoint of good yield, 3:1~3ΐ "Step f Hi reaction, from the viewpoint of good yield, in the solvent Preferably, the solvent to be used is not particularly limited, and for example, water, dimethyl sulphur, dimethyl sulphate, and ytb can also be used in combination as appropriate. 3 si It is ideal for mixing and mixing of water and water. The treatment can be carried out by "step 2" and after the end. For the first step, the raw material compound (4) of the "Step 2" of the compound (1) may be recrystallized, column chromatography or sublimation, for example, 201240976 may be included in the following reaction formula. The method of step 3 is shown.

Palladium catalyst base ^ ^ H - called 0 (9) or . (R40) 2B-~B(OR4)2 (7)

'~~' (R40>2B Step 3 Stupid (6) and (27) Μ indicates that it can also pass through a carbon number of 1 to 4 or

Hr ί fragrance base. ^ represents a nitrogen-containing heterocyclic ring which may also be substituted with a carbon number or a fluorine group by a group having a carbon number of 1 to 4 or a group substituted by a compound: 4, and a hydrogen atom from f ' R An alkyl group having 1 to 4 carbon atoms or a phenyl group, and Λ may be the same or different. Further, two R4 may be integrated and contain an oxygen atom and a butterfly atom to form a ring. "Step 3" is a compound (2) which is used in the presence of a base and a catalyst, and a compound represented by the formula or the formula (7): which compound (4) is reacted, ^, 2" The steps. This step can be obtained in a good yield by the reaction iW disclosed in the application of ^. The Journal of Organic Chemistry. 60 4 7750-7510 &gt; 1995 = nal of Organic Chemistry '65, i64_168, 2_. . μ for two ill·, a 1 bar catalyst can be used, for example, the same as the “step exemplified seam or the second Γ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 具有 具有 具有 具有 具有 具有 具有 具有 具有The viewpoint is better, and from the viewpoint of easy availability and good yield, there are three-port ί Sint, and the complex compound is particularly preferable. The amount of the silk medium used in "Step 3", the molar ratio of the medium to the compound (2) is 1:50. ~1:1 is better. The human t has a palladium complex which has a secondary phosphine as a ligand. It can also be prepared by substituting palladium salt with f-scale and in the reaction system. It can be added to the third-order lining exemplified in the first step lj of the slit or the wrong compound. Among them, it is preferable to obtain an easy basis. The molar ratio of the tertiary phosphine to the m or the wrong compound is 1:10 to 1 "〇: 1 is preferred, and from the viewpoint of good yield, 1:2 to 5:1 is more preferable. It must be implemented in the presence of the test. The base which can be used in "Step 3" can be, for example, sodium hydroxide, sulphuric acid, carbonic acid steel, carbonic acid unloading, carbonic acid clock, 8 20 201240976 &quot;-color μ 知 知 'Unloading, sodium acetate, scalar clock, stone Calcium acetate, copper fluoride, fluorination, ruthenium, etc., from the viewpoint of good yield, potassium acetate is preferred. The alkali-fishing human ear ratio is not particularly limited, and is preferably 1:2 to 10:1, and is preferably from a good yield of ‘(,) 1:1 to 3:1. The borane compound (6) or the diboron compound (7) used in the "Step 3" is not particularly limited, and is preferably 1:1 to 5:1, from the point of good yield, 丄~·3: 1 is even better. The reaction of 'Step 3' can also be carried out in a solvent. "Step 3 S special: 匕卿:: water, dimethyl, wind, dimethyl ketone = appropriate combination. From the point of view of good yield, use; A or 1,4-dioxane is more desirable. The compound (4) may also be isolated after the reaction, but may not be separated from the * - 1, 3, 5 - 3 compound (1), and may be used for the production of at least one of the organic electro-structures. The film manufacturing method is not limited to the film 'can be used in the general use of the real turn. In the straight (four) (four) short, the manufacturing cost is advantageous, it should be the same as the ordinary day and the thirsty wheel molecular pump &gt; t, cryopump The material can be __ lxlG_2 = two steaming bonds ΐ ί = the thickness of the formed film, the organic electroluminescent element _ film composed of two seconds. For example, soluble in chloroform, methylene chloride, m-rail compound (1) Hydrogen humming and other money, and the film formation is carried out by using a general-purpose acid=or four-casting method or a dipping method. Main method, Hemo method, [Examples] These examples and reference examples are - The steps are illustrative of the invention, but the invention is not limited to 21 201240976

3-bromo-5-cyanobiphenyl (2. 〇g), benzoquinone chloride (〇.45 mL) was dissolved in chloroform (10 mL) under argon&gt; and cooled to dryness. Five gasified hydrazine (〇49 mL), the mixture was heated under reflux with heating and heated for 20 hours. After cooling to room temperature, the mixture was added to aqueous ammonia (40 mL) and the solid was filtered. After the solid was filtered with chloroform, the obtained solution was concentrated to obtain the desired 2,4-bis(5-bromobiphenyl-3-yl)-6-phenyl-1,3,5-three well White solid (yield i.7 g, yield 7%). (1H-NMR (CDCl3): 57.48-7.66 (m, 9H), 7.75 (d, J = 7.0 Hz, 4H), 8.01 (s, 2H), 8.80 (d, J = 8.0 Hz, 2H), 8.87 ( s, 2H), 8.93 (s, 2H) Reference Example-2

2,4-bis(5-bromobiphenyl-3-yl)-6-phenyl-1,3,5-tris under a stream of argon. Well (3.00 layer), double-linked pinacol bismuth (bispinac〇iate (jib〇r〇n) (27 g), potassium acetate (2.09 g), bistriphenylphosphine palladium dichloride ( 136 mg) was suspended in tetrahydrofuran (100 mL) and refluxed for 21 hours. After cooling to room temperature, the low-boiling component was removed under reduced pressure, and a gas mixture (1 mL) was added to the obtained solid, and the organic layer was taken with water. (1 〇〇mL) = After 'Using sulphur_drying. Separating sulphur sulphide', chloroform was decompressed, and the obtained crude product was purified by cerium oxide gel chromatography (developing solvent chloroform) to obtain 22 8 201240976 . 2-Phenyl-4,6·bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaorganostone _2_)) -Based -1,3,5-three-well yellow solid (yield 2.77 g 'yield 8 %).

1H-NMR (CDC13): δ 1.49 (s, 24H), 7.3 3 (tt, J = 7.3, 1.4 Hz, 2H), 7.44 (t, J = 7.3 Hz, 4H), 7.51-7.57 (m, 3H) , 7.74 (brdd, J = 7.3, 1.4 Hz, 4H), 8.23 (dd, J = 1.8, 1.2 Hz, 2H), 8.77 (brdd, J = 7.3, 1.4 Hz, 2H), 9.06 (t, J = 1.8) Hz, 2H), 9.11 (brdd, J = 1.8, 1.2 Hz, 2H) 'Example-1

Ο cat [Pd]

ZnCI(tmeda)

A solution of 1.58 M-t-butyllithium pentane (iimL) was dissolved in tetrahydroanion (10 mL) under argon flow and cooled to _78. Hey. 2_Bromopyridine (〇86 mL) was added dropwise thereto, and the mixture was stirred for 0.5 hour, then (tetrakisylethylenediamine) was added to be gasified (5. (8) g), and the mixture was warmed to room temperature and stirred for further hr. To the mixture, 2, bis-bis(5-&gt; odorant ☆ phenyl-3-yl)-6-phenyl^^, ternary and triphenylphosphine* (69 mg) were suspended in tetrahydrofuran (2). 〇mL), stirred under reflux for 72 hours. The cold part of the mixture was taken at room temperature and then added (5 〇 mL), and the crude product was taken. Will get doubt = column chromatography (expanding solvent / chloroform: hexane = 4: ι ~ ^) and again: day (曱本一)! Clothing 'obtained the purpose of 2_phenyl _4,6_ double [5_ (2♦ fixed base) combined with a white solid of 乂, 3,-dimorph (yield 1.30 g, yield 69%). H-NMR (CDCl3): 67.32-7.38 (m, 2H), 7.42-7.48 (m, 3H), 7.84-7.9U m 56H), 8.00 (d5J=8.0H252H), 8.57 (U=1.8Hz, 2H), 8.81 (d, J = 4.8 Hz 2 Η), 8.8_, (4) · 8, 8 positions 2H), 9 qing = 丨 8 Hz, 2H), 9 34 (u =, 1 · 8 Ηζ, 2 Η) Example _2 23 201240976

3-Pyridylboronic acid (U2g), 2,4-bis(5-bromobiphenyl-3-yl)-6-bens-1,3,5-di under a stream of argon. Well (2.17笆), 4M-aqueous sodium hydroxide solution (gjmL), acetic acid (16mg), 1M-di-p-butyl butyl sulfonate solution (〇.2imL) suspended in tetrazole (40mL) and ethanol (20mL) The solvent was mixed and refluxed for 15 hours. After the reaction mixture was allowed to cool, the low-dot point component was depressurized, and the precipitated solid was washed with water, methanol and hexane. Thereafter, recrystallization is carried out in o-xylene to obtain the desired 2_phenyl_4,6_bis[5-(3-° ratio)-biphenyl-3-yl]-1,3,5_three wells White powder (yield 6 mg, yield 28%).

Br H-NMR (CDCl3): 57.49 (t, J = 7.4 Hz, 2H), 7.53-7.7i (m, 9H), 8.14 (d, J-7.0 Hz, 4H), 8.05 (s, 2H), 8.16 (d, J = 7.9 Hz, 2H), 8.73 (d J = 4 9 Hz 2H), 8.82 (d, J = 8.3, 2H), 8.97 (s, 2H), 9.06 (s, 2H), 9.09 (s 2H) 5 'Example-3 ' '

In the rolling, Guab 'book of tetradecyl-1Λ2_dioxane 67mg), 2,4-bis(tetra)biphenylyl cold phenyl) cesium carbonate (8471^ and bis(triphenyl) Phosphine (4) This secret floats in a mixed solvent of tetranitrogen (10mL), ethanol (2mL) and water (2mL), and refluxed for 12Q hours. After the reaction mixture is allowed to cool, 'the low-boiling component is left and the sterol is added. The precipitated solid was subjected to silica gel column chromatography (developing solution 24 201240976 bp)-1,3,5_triter white powder (yield 49 mg, yield 16%). 1H-NMR (CDCl3) : 67.47-7.56 (m, 13H), 7.65 (d, J = 6.8 Hz, 4H), 7.88 (s, 2H), 8.60 (d, J = 7.6 Hz 52H), 8.70 (m, 4H), 8.77 (s, 2H), 8.85 (s, 2H) Example-4

Combining 2-phenyl-4,6-bis[5-(4,4,5,5-tetradecyl-1,3,2-dioxaorganoborane-2-yl) under argon flow Benzene-3-yl]-1,3,5-triazine (1.31g), 2-bromopyrimidine (760mg) and hydrazine (triphenylphosphine)palladium (170mg) were dissolved in 2M sodium carbonate aqueous solution (20mL) and A mixed solution of toluene (100 mL) was refluxed for 25 hours. After the reaction mixture was allowed to cool, the low-boiling component was depressurized, and water was added. The precipitated solid is separated by washing with water, methanol, hexane, and then recrystallized from o-xylene to obtain the desired 2-phenyl-4,6-bis[5-(2-ye'. White powder of benzene-3-yl]-l,3,5-tris-sodium well (yield 898 mg, yield 79%). 1H-NMR (CDCl3): 67.32 (t, J = 4.9 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H)

7.59 (tJ = 7.4 Hz, 4H), 7.64 - 7.67 (m, 3H), 7.93 (d, J = 8.4 Hz, 4H), 8.93 (d, J = -6.9 Hz, 2H), 8.96 (d, J = 4.8 Hz, 4H), 9.01 (s, 2H), 9.23 (s, 2H), 9.88 (s, 2H) Example-5

2,4-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaorganoboropyrene~2-yl)biphenyl-3-yl under argon ]-6-phenyl-1,3,5-three well (1.6〇8), chlorine °° well (67〇11^), ginseng (dibenzylideneacetone) dipalladium (41mg) and 2- Dicyclohexylphosphino-2',4',6'-triisopropyl linkage 25 201240976 Benzene (85 mg) suspended in a mixed solution of 2M sodium carbonate aqueous solution (5.8 mL) and terpene (29 mL) for 90 hours Reflux. After the reaction mixture was allowed to cool, the low-boiling component was distilled off under reduced pressure and water was added. The precipitated solid was separated by washing with water, methanol and hexane, dissolved in hot o-diphenylbenzene, and the insoluble material was filtered. The o-diphenylbenzene is distilled off under reduced pressure, and then cooled, and the resulting solid is separated to give the desired 2-phenyl-4,6-bis[5-(2-pyrazinyl)biphenyl- White powder of 3-base]-1,3,5-three wells (yield 960 mg, yield 70%). 1H-NMR (CDCl3): 57.49 (U = 7.4 Hz, 2H), 7.59 (t5J = 7.3 Hz, 4H), 7.63-7.70 (m, 3H), 7.87 (d, J = 7.1 Hz, 4H), 8.58 ( s, 2H), 8.65 (s, 2H), 8.78 (s, 2H), 8.87 (d, J = 6.4 Hz, 2H), 9_163 (s, 2H), 9.32 (s, 2H), 9.42 (s, 2H) ) Example -6

'6-Bromo-3-methylpyridine (I57mg), 2,4-bis[5-(4,4,5,5-tetradecyl-1,3,2-dioxa organic) under argon flow Borane-2-yl)biphenylyl]_6_phenyl 4,3,5_tri^(250mg) and hydrazine (diphenylphosphine) (23mg) was suspended in 2M sodium carbonate aqueous solution (2mL) and A mixed solution of toluene (8 mL) was refluxed for 9 hours. After the reaction mixture was allowed to cool, the low-boiling component was depressurized and water was added. The precipitated solid was separated by washing with water, decyl alcohol and hexane to produce the desired 2,4_bis[(4)-fluorenyl. A white powder of each phenyl-1,3,5-three a well (yield 2 〇〇mg, yield 89%). (s, 2H) 1H-NMR (CDCl3): 52.47 (s, 6H) J7.46 (tJ = 7.3 Hz, 2H), 7.55 aJ = 7.3 Hz, 4H), 7.62-7.70 (m, 5H), 7.88 ( d, J = 7.0 Hz, 4H), 7.91 ((U = 8.1 Hz 5 2H), 8.55 (s, 2H), 8.65 (s, 2H), 8.87 (d, J = 7.7 Hz, 2H), 9.09 (s 2H) ) 9 32 Example-7 26 8 201240976

5-Bromo-2-methylpyridine (157 mg), 2,4-bis[5-(4,4,5,5-tetradecyl-1,3,2-dioxa organic) under a stream of argon Borane-2-yl)biphenyl-3-yl]-6-phenyl-1,3,5-trimorphine (250 mg), potassium phosphate (386 mg) and hydrazine (triphenylphosphine)palladium (32 mg) suspended A mixed solvent of 1,4-two-port (8 mL) and water (2 mL) was refluxed for 4 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated to give the desired 2,4-bis[5-(2-methylpyridin-5-yl)biphenyl-3-yl]-6-phenyl-1,3,5-trimium White powder (yield 215 mg, yield 95%). ^-1^^1(00013): 62.75 (8,6H), 7.42 (d, J = 8.0 Hz, 2H), 7.49 (t, J = 7.4 Hz, 2H), 7.56-7.68 (m, 7H), 7.81 (d, J = 7.1 Hz, 4H), 8.03 (s, 2H), 8.08 (d, J = 8.0 Hz, 2H), 8.82 (d, J = 6.6 Hz, 2H), 8.95 (s, 2H), 8.97 (s, 2H), 9.04 (s, 2H) Example-8

-1,3,2-dioxaborolan-2-yl)biphenyl-3-yl]-6-phenyl-1,3,5-trisole (1.Olg), 3M-potassium potassium phosphate solution (1.4 mL) and hydrazine (triphenylphosphine) palladium (32.4 mg) were suspended in 1,4-dioxane (10 mL) and refluxed for 3 hours. The reaction mixture was allowed to cool and water was added. Separating the precipitated solid to obtain the desired white powder of 2,4-bis[5-(isoquinolinyl)biphenyl-3-yl]-6-phenyl-1,3,5-triazine (yield 948 mg, yield 94%).

^-^^(00013): 67.45 (1, J = 7.3 Hz, 2H), 7.51 - 7.65 (m, 9H), 7.73 (d, J = 8.2 Hz, 2H), 7.76 (d > J = 5.2 Hz, 2H), 7.84 (cU = 7.1 Hz, 4H), 7.97 (d, J 27 201240976 = 8.2 Hz, 2H), 8.21 (s, 2H), 8.26 (d, J = 8.5 Hz, 2H), 8.71 (d, J-5.7Hz, 2H), 8.81 (d, J=6.8Hz, 2H), 9.11 (s, 2H), 9.17(s, 2H)

2-Chloroquinoline (596 mg), 2,4-bis[5-(4,4,5,5-tetradecyl-1,3,2-dioxaorganoborane-2_) under a stream of argon Biphenyl-3-yl]-6-phenyl-1,3,5_tri. Well (1. Olg), 3M aqueous potassium phosphate solution (L4 mL) and hydrazine (triphenylphosphine) palladium (32.4 mg) were suspended in 1,4-dioxane (10 mL) and refluxed for 5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration and dried. The obtained solid was recrystallized from o-diphenylbenzene (3.5 mL) to give the desired 2-phenyl-4,6-bis[5-(quinolin-2-yl)biphenyl-3-yl]-l, White powder of 3,5-three wells (yield 913 mg, yield 90%). 1H-NMR (CDCl3): 57.48 (t, J = 7.2 Hz, 2H), 7.55-7.64 (m, 9H), 7.78 (t, J = 7.6 Hz, 2H), 7.88 (m, 6H), 8.08 (d) , J = 8.4 Hz, 2H), 8.26 (d, J = 8.0 Hz, 4H), 8.68 (s, 2H), 8.83 (d, J = 5.2 Hz, 2H), 9.11 (s, 2H), 9.54 (s , 2H) Example-10

3-bromoquinoline (757 mg), 2,4-bis[5-(4,4,5,5-tetradecyl-1,3,2-dioxaorganoborane_2) under a stream of argon _ base)biphenyl_3_yl]_6_phenyl-1,3,5-triazine (l.Og), 3M-carbonate planing aqueous solution (i.9mL) and bis(triphenylphosphine) dichlorination Palladium (19.7 mg) was suspended in 1,4-dioxane (10 mL) and refluxed for 3 hours. The reaction mixture was allowed to cool and water was added. Separating the precipitated solid to obtain a white powder of the desired 2-phenyl-4,6-bis[5-(quinolin-3-yl)biphenyl-3-yl]-1,3,5-triplate (yield 949mg, yield 95%) 〇8 201240976 ,H&quot;N^(CDC1^:s7.49(t,J-7.mz,2H), 7.56-7.66(m,9H),7.8〇(t5j = 7.0 Hz, 2H), 7.84 (d, J &gt; 7 〇 Hz, 4H), 7 97 (d, J = 8 〇Ηζ, 2 Ή), 8 17 (s, 2h), 8.22 (d, J = 8.4 Hz, 2H), 8.52 (s52H), 8.83 (s52H), 9.08 (s, 2H), 9.12 (s, 2H) 9.41 (s, 2H), Example-11

'8-Bromo-2-methylquinoline (808 mg), 2,4-bis[5-(4,4,5,5-tetradecyl-l,3,2-dioxa) under argon flow Organoborane-2-yl)biphenyl_3_yl]_6_phenyl_1,3,5_trioxane (1.0 g), aqueous solution of 3M-potassium phosphate (i/rnL) and palladium acetate (6. ; 3 mg), bis(diphenylphosphino)ferrocene (15.5 mg) was suspended in DMF (10 mL) and refluxed for 3 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated to give the desired 2,4-bis[5-(2-methylquinolin-8-yl)biphenyl-3-yl]-6-phenyl-1,3,5-triazine White powder (yield 949 mg, yield 91%). 1H-NMR (CDCl3): 52.65 (s, 6H), 7.28 (d, J-8.4 Hz, 2H), 7.48 (t, J = 7.3 Hz, 2H), 7.55-7.67 (m, 9H), 7.84 (d) , J = 8.1 Hz, 2H), 7_98 (d, J = 7.2 Hz, 4H), 7.94 (d, J-7.1 Hz, 2H), 8.12 (d, J = 8.4 Hz, 2H), 8.33 (s, 2H) ), 8.91 (d, J: 7.6 Hz, 2H), 9.12 (s, 2H), 9.34 (s, 2H) Experimental Example-12

-1,3,2-dioxaorganoboran-2-yl)biphenyl-3-yl]-6-phenyl-l,3,5-triazine (0.50 g), aqueous 3M-potassium phosphate solution ( 〇.7 mL) and hydrazine (triphenylphosphine) palladium (16.2 mg) were suspended in 29 201240976 and floated on 1,4-yakisaki (5 mL) and refluxed for 2 hours. The reaction mixture was allowed to cool and water was added. Separation of precipitated solids to obtain the desired white yellow powder of 2,4-bis[5-(9-acridinyl)biphenyl-3-yl]-6-phenyl-1,3,5-three well (yield 49811^, yield 87°/〇). 1H-NMR (CDCl3): 67.44-7.53 (m, 13H), 7.79-7.88 (m, 12H), 7.95 (s, 2 H), 8.34 (d, J = 8.8 Hz, 4H), 8.74 (d, J) =4.2 Hz, 2H), 8.82 (s, 2H), 9.22 (s, 2H) Example-13

The 2-gas-3-fluoroπ ratio was obtained under a stream of argon. (479mg), 2,4-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaorganoboran-2-yl)biphenyl-3-yl] -6-phenyl-1,3,5-three well (1.4 g), 3M-potassium potassium phosphate solution (1.4 mL) and hydrazine (triphenylphosphine) palladium (32.4 mg) were suspended in M-dioxane ( 10 mL) and reflux for 16 hours. The reaction mixture was allowed to cool and water was added. Separating the precipitated solid to obtain the desired 2,4-bis[5-(3-fluoropyridin-2-yl)biphenyl-3-yl]-6-phenyl-1,3,5-three-well Yellow-white powder (yield 87,211^, yield 68%). lH-NMR (CDCl3): 57.35-7.40 (m, 2H), 7.46 (t, J = 7.4 Hz, 2H), 7.54-7.67 (m, 9H), 7.87 (d, J = 7.1 Hz, 4H), 8.51 (s, 2H), 8.64 (dJ = 4.6 Hz, 2H), 8.86 (d, J = 7.9 Hz, 2H), 9.14 (s52H), 9.42 (s, 2H) Example-14

Cat.[Pd], K2C03

'2-Chlorobenzothiazole (618mS), 2,4-bis[5-(4,4,5,5-tetradecyl-1,3,2-dioxaorganoborane) under argon flow 2-yl)biphenyl-3-yl]-6-phenyl-1,3,5-three well (1.0 g), 3M-potassium carbonate aqueous solution (1.4 mL) and hydrazine (triphenylphosphine) (32.4 mg) was suspended in 1,4-dione (10 mL) and refluxed for 21 hours. The reaction mixture was allowed to cool and water was added. 30 8 201240976 The solid precipitated by filtration was recrystallized from 20 mL of o-xylene. The solid obtained was separated by filtration to obtain the desired 2,4-bis(2-benzothiazolyl)biphenyl; a white powder of the base of -6 (yield: 300 mg, yield 29%). 1H-NMR (CDCl3): 57.44-7.49 (m, 5H), 7.54-7.61 (m, 8H), 7.86 (d, J = 7.6 Hz, 4H), 7.96 (d, J = 7.7 Hz, 2H), 8.16 (d, J =: 8.0 Hz, 2H), 8.60 (s, 2H), 8.81 (d, J = 7.6 Hz, 2H), 9.12 (s, 2H), 9.41 (s, 2H) Example-15

Under the argon gas flow, 'will be 2 - saliva (597 mg), 2,4-bis[5-(4,4,5,5-tetradecyl-1,3,2-dioxaorganoborane_2 _ base)biphenyl-3-yl]-6-phenyl-1,3,5-trix (l.〇g), 3M-potassium potassium carbonate solution (1.4mL), bis(dibenzylideneacetone (161 mg) and bis(diphenylphosphino)binaphthalene (34-9 mg) were suspended in dimethyl sulfoxide (10 mL) and refluxed for 21 hours. The reaction mixture was allowed to cool and then water was added. The o-diphenylbenzene of mL is recrystallized. The solid obtained by fractionation is obtained to obtain the desired 2,4_bis[5_(2_thiazolyl)biphenyl-3-ylι]-6-phenyl_1,3,5 - Triterpenoid lavender powder (yield 2 〇〇mg, yield 23%). 1H-NMR (CDCl3): 57.32-7.36 (m, 3H), 7.42-7.46 (m, 6H), 7.54-7 56 ( m54H) 57.74 (d, J = 8.4 Hz, 4H), 8.23 (s, 2H), 8.76-8.79 (m, 2H) 59.06 (s, 2H), 9.11 (s, 2H) Test Example-1 Organic electroluminescence Element fabrication and performance evaluation The substrate was a glass substrate with a transparent electrode patterned in a strip shape of 2 mm indium tin-tin (11 Å) film. The substrate was washed with isopropyl alcohol. Line washing: ^ line surface treatment. For the secret substrate, the real vacuum method 'The organic electroluminescence element having the multi-layered luminescent surface 2 as shown in Fig. 。. 201240976 First, the glass substrate is introduced into a vacuum deposition tank, and the pressure is reduced to 1 〇 xl 〇 _4 Pa. FIG. 1 shows that the hole injection layer 2, the hole transport layer 3, the light-emitting layer 4, the hole-blocking sound 5, and the electron transport layer 6' which are formed as an organic compound layer on the glass substrate are sequentially formed. The cathode layer 7 is formed into a film. S 'Electrical hole into the layer 2, which is obtained by sublimating the refined sassafras bronze (Liao) by vacuum evaporation of a film thickness of 10 nm. The hole transport layer 3 'system will wind · gt; ,-bis(naphthalene-phenylbenzidine (NPD) vacuum evaporation is formed to a film thickness of 30 nm. The light-emitting layer 4) is 4·4′_bis(sit-winter)biphenyl (CBp) and ginseng (2) _Phenylpyridinium is formed by vacuum evaporation at a ratio of 94:6 (% by mass) to a film thickness of 30 nm. The hole blocking layer 5 is a double (2-methyl-8-pyridyl) Base)_(〇,__Biphenyl_4_olyl) Ming (BAlq) (bisP-methyl-S-quninoiinato^!, seven-mail _4_〇aluminum) vacuum steamed money for the thickness of 5 jobs Electron transport layer 6, which is a 2-phenyl-4,6 synthesized in Example 2. - Bis[5-(3-acridinyl)biphenylyl]]3 5_: σ well straight* The vapor deposition is a film thickness of 45 nm. Then, the film was formed by a fine resistance heating method, and the pure compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm/second. Finally, the configuration gold = straight to the ITO strip and the cathode layer 6 is thin. The cathode layer 6 was vacuum-steamed with a film thickness of 1.0 side and 100 legs to form a two-layer structure: The material was measured by a stylus type film thickness meter (DEKTAK). Further, the element 2 and the nitrogen gas atmosphere having a water concentration of 1 ppm or less were placed in a glove box. Sealing system (na〇!s^^

The TopSimi organic electroluminescent device is applied with a direct current f-flow and is evaluated by a luminance meter using the LUMNANCE __9). The t-light characteristic is a voltage (v) and time when the flow density is measured. Subtraction: _d/A), power efficiency (lm/w), and measurement of the differential light rate component is: voltage 6·9ν, luminance 5490cd/m2, current effect noon/.5cd/A, power efficiency i2 .61m/W. έ型验例-2 8 32 201240976 5, 2 • Phenyl ♦ bis [5_(2__ yl) biphenyl each well money is 45mn film thickness 'to replace the electron transport layer 6 of Test Example-1, made Organic electroluminescent element. The rate element t was measured as: voltage 7.6 V, luminance 5 〇 8 〇 cd/m 2 , current efficiency 25.4 cd/A, and power efficiency 1 〇. Comparative Example-1 A general-purpose electron transporting material Alq3 was vacuum-distilled to a film thickness of 45 nm to replace the electron transporting layer 6' of the test example-1 with the weave. , Brightness 5200cd/m2, current efficiency The measured components are: voltage 9.0V rate 26.0cd/A, power efficiency 9.llnVW. Test Example-3 A glass substrate having a transparent electrode of a strip shape having a width of 2 mm of indium oxide TQ was attached. The substrate was washed with isopropyl alcohol and surface-treated with ozone wilt line washing. The organic electroluminescence element of the light-emitting area bucket surface 2 having a multilayer structure was prepared by vacuum-plating the substrates of the blanks by the true transfer plating method. First, the glass substrate is introduced into the real steaming tank, and the pressure is reduced to 1.〇χΐ〇_4ρ&amp;. $ ' as shown in Figure 2' on the aforementioned glass substrate! The film formation is sequentially performed as the hole injection layer 2, the hole transport layer 3, the light-emitting layer 4, and the electron transport sound 5 of the organic compound, and then the cathode layer 6 is formed into a film. The hole injection layer 2 is a sublimation-purified silk flower bronze (the melon straight to the lining shout. The hole is 3, Weng N, N, · diphenyl phthalonitrile (NPD) is vacuum evaporated to a film of 30 nm. Thick layer. The luminescent layer 4 is composed of 2 —-butyl _9,1 〇 _ (2_Qinyl) 'UBADN) and 4,4' _ double [4_(di-p- 曱 胺 amine) stupid The vinylidene-1-yl]biphenyl (DPAVBi) was formed by a film thickness of 40 nm at a ratio of 95:5 (% by mass). / '' Electron transport layer 5, which is a 2-phenyl- 4,6-bis[5-(2-n ratio.-fixed)biphenyl-3-yl]-1,3,5 synthesized in Example-1 -three. The well vacuum evaporation is formed into a film thickness of 20 nm. Further, each of the organic materials was formed by resistance heating, and the heated compound was vacuum-deposited at a deposition rate of 33 201240976 〇 3 to 0.5 nm / sec. The mask is placed perpendicular to the IT0 strip and the cathode layer 6 is filmed. ^β曰’, the word I and the clock are all made with the film thickness of l.〇nm and i〇〇nm. Each film thickness system _ needle-type measuring instrument (dektak ^ 卷 ϋ ϋ ϋ ϋ ϋ ϋ ϋ 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件 元件Hardened resin (manufactured by NAGASECHEMTEX Co., Ltd.) ', A DC current was applied to the produced organic electroluminescence device, and the luminescence property was evaluated using a TOK: (10) A LUMINANCE METER (BM-9) luminance meter. The luminescence property was measured by flowing current. The voltage at a density of 2 〇 mA/cm 2 (x, luminance (cd/m2), current efficiency (Cd/A), power efficiency (lm/w), and the luminance half-decrement time at the time of measurement. The measured enthalpy was: voltage 6.1 ν, luminance l8 〇 4 cd/m 2 , current efficiency 9.02 cd/A, and electric power efficiency 4.621 m/W. Test Example-4 The 2-phenyl-4,6- synthesized in Example 4 Bis[5-(2.pyrimidinyl)biphenylyl]-1,3,5-three vacuum evaporation to a film thickness of 2 〇nm, in place of the electron transport layer 5' of the vacuum evaporation test The light-emitting element: The measured voltage of the fabricated device is: voltage 6.5V, luminance 1875cd/m2, current efficiency 9.38cd/A, and power efficiency 4.78m/W. Example-5 The 2,4-biguanide (isoquinolin-1-yl)biphenyl_3_yl-phenyl--1,3,5-three well synthesized in Example 8 was vacuum-evaporated to a film thickness of 2 〇 nm. An organic electroluminescence device was produced instead of the electron transport layer 5' of Test Example_3. The measured dimensions of the fabricated device were: 64 V, luminance 1891 cd/m2, current efficiency 9.468 cd/A, and power efficiency 4.611 m/VV. Test Example -6 The 2-phenyl-4,6-bis[5-(quinolin-2-yl)biphenyl_3_ group H,3,5-three well synthesized in Example 9 was vacuum-deposited to 20 nm. The film thickness was replaced by the electron transport layer 5 of Test Example _3 to prepare an organic electroluminescence device. The measurement of the fabricated device was: electricity 8 34 201240976 Pressure tear cdW, current efficiency 9.96·, power efficiency 4 83斯型例例-7 The 2_phenyl ♦ double compounded in Example 10 [Base H, 3, 5 - Mitsui vacuum distillation is the film thickness of m, to: 25 hui 3 乍 76 into 3: 2Electric light, the measurement of the fabricated components is: electric house 6.4 = degree brain d / m, current efficiency 8.82 Wei, power sector. Comparative example - 2 general use of electronic transport material Alq3 vacuum distillation of 2 〇 The film thickness of nm is in lieu of ίίί « 6.6V . 1768cd/m2 . t flow efficiency 8.84cd/A, The efficiency is 4.291 m/W. [Industrial Applicability] The film composed of the 1,3,5-three-bell compound (1) of the present invention is slippery, amorphous, and Xie Sheng, electron transporting ability, and electrowetting resistance. ^ At least ^ of the multi-layer structure of the machine light-emitting element. In particular, the electronic component of the optical component and the hole resistance are required to be used in addition to the flat panel display. Fig. 1 is a cross-sectional view showing an example of a layer structure of an electroluminescent device of the invention. Fig. 2 is a cross-sectional view showing another embodiment of the layer structure of the organic electroluminescence device of the present invention. [Main element symbol description] 35 201240976 1 1 Glass substrate with ITO transparent electrode 2 Hole injection layer 3 Hole transport layer 4 Light-emitting layer 5 Hole stop layer 6 Electron transport layer 7 Cathode layer Figure 2 1 Glass substrate with ΙΤΟ transparent electrode 2 Hole injection Layer 3 hole transport layer 4 light-emitting layer 5 electron transport layer 6 cathode layer 8

Claims (1)

201240976 VII. Patent application scope: 1. A type 1,3,5-three. Well compound, represented by the following general formula (1), general formula (1) Ar2 (1) (wherein Ar1 represents an aromatic furnace group which may be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine, and Ar represents an aromatic hydrocarbon group which may also be substituted with a carbon group having 1 to 4 carbon atoms or fluorine.仏3 Table factory, nitrogen-containing heterocyclic group which may also be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine. 2. A compound of claim 1, wherein the Ari is a phenyl group which may also be substituted with a carbon number of 1 to 4 or an alkane having a carbon number of 1 to 4. Base 3. 3. For the 1,3,5-trisole compound of claim 1 or 2, δ1 is phenyl.八丁Ar 4. For example, please refer to any of the items i to 3 of the patent range, 3,5_three compounds, wherein Ar2 is a phenyl group which may also be substituted with an alkyl group having a carbon number of 4~4 or An alkyl substituted naphthyl group of 1. 4 5·If, please patent scope! 153, 5_Sanchajing, which is any one of the four items, wherein Ar2 is a phenyl group. 6. The compound of any one of items 1 to 5 of the monthly patent range of 1, 3, 5 - 3 liters, wherein Ar is a nitrogen-containing heterocyclic group which may also be substituted with a methyl group or a fluorine. 7.·If, please patent the scope! a Mitsui compound of any one of the six, /, 'Ar' is unsubstituted or substituted by methyl or fluoro, cyclyl, livure, yiji, y, y, y, or Shot base. a method for producing a compound of the following formula (7)/23, which is characterized in that a compound represented by the following formula (3) of the following formula is subjected to a coupling reaction in the presence of a test or in a non-existent state; 1,3,5-triphthyl compound; 37 201240976 (wherein Ar1 represents an aromatic radical which may also be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine; and Ar2 represents an aromatic hydrocarbon group which may also be substituted with an alkyl group having a carbon number of 44 or fluorine; χ1 is detached Base) ^' (In the formula, 'Ar3 denotes a nitrogen-containing heterocyclic group which may be substituted by a carbon number of 1 to 4 or a fluorine; Μ means a metal group or a hetero atom group) (wherein 'Ar1 means a carbon number 1) a halogenated or fluorine-substituted aromatic hydrocarbon group of 1-4; Ar2 represents an aromatic hydrocarbon group which may also be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine; and Ar3 represents an alkyl group or a fluorine atom which may also be substituted with a carbon number of 1 to 4; a nitrogen-containing heterocyclic group). 9. The method for producing a triterpenoid compound according to the eighth aspect of the patent application, wherein 'M is Ζη^3 (wherein R3 represents a halogen atom) or B(OR4)2 (wherein R4 A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and two R4 of b(OR4)2 may be the same or different; and two R4 may be integrated and contain an oxygen atom and a boron atom. Form the ring) the base of the representation. 10. A method of producing a 1,3,5-triazine compound according to claim 8 or 9, wherein the palladium catalyst has a tertiary phosphine as a ligand. 11. The method for producing a compound of 1, 3, 5 and 2d, wherein the third-stage phosphine is a tri-phenylphosphine or a tri(tert-butyl)phosphine. 12. A method for producing a 1,3,5-three liter compound, which comprises subjecting a compound represented by the following formula (4) to a compound represented by the following formula (5) in the presence of a base and a palladium catalyst Coupling reaction to produce a compound represented by the following formula (1); 38 201240976 (R40) 2B B(〇R4)2 (4) (In the formula, Ar1 represents an aromatic hydrocarbon group which may also be substituted with an alkyl group having a carbon number of 44 or fluorine; and Ar2 represents an aromatic group which may be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine. a hydrocarbon group; R4 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 4 or a phenyl group; and two R4 of B(OR4)2 may be the same or different; in addition, two R4 may be integrated and contain an oxygen atom. And a boron atom to form Ar3—X2 (5) J (wherein Ar3 represents a nitrogen-containing hetero group which may also be substituted with an alkyl group having a carbon number of 44 or fluorine; X is a 7F-free group) (1) In the formula (2), Ar1 represents an aromatic hydrocarbon group which may also be substituted with an alkyl group or a hydrocarbon having a carbon number of 44; and the core _ represents an aromatic hydrocarbon group which may also be substituted with an alkyl group having a carbon number of 44 or fluorine. Ar3 represents a nitrogen-containing heterocyclic group which may also be substituted with a carbon number of 1 to 4 or a fluorine group. 13. A method for producing a compound according to claim 12, wherein the palladium catalyst is a palladium complex having a tertiary phosphine as a ligand. Method for producing U,5-trimeric compound of the 13th item of the genus Ganzi, Fuiji scale, bis(diphenylphosphino)ferrocene, bis(diphenylphosphino)1⁄2 or 2 - monohexylphosphino 2,4,6,_triisopropylbiphenyl. A J electroluminescent device comprising a 1,3,5-three-bell compound represented by the following formula (1) as a constituent component; 39 1 201240976 (wherein Ar1 represents an aromatic hydrocarbon group which may be substituted by an alkyl group having 1 to 4 carbon atoms or fluorine; and Ar2 represents an aromatic hydrocarbon group which may also be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine; Ar3; A nitrogen-containing heterocyclic group which may also be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine.