WO2012091026A1 - Composé de 1,3,5-triazine, son procédé de préparation et élément électroluminescent organique l'utilisant - Google Patents

Composé de 1,3,5-triazine, son procédé de préparation et élément électroluminescent organique l'utilisant Download PDF

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WO2012091026A1
WO2012091026A1 PCT/JP2011/080242 JP2011080242W WO2012091026A1 WO 2012091026 A1 WO2012091026 A1 WO 2012091026A1 JP 2011080242 W JP2011080242 W JP 2011080242W WO 2012091026 A1 WO2012091026 A1 WO 2012091026A1
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秀典 相原
田中　剛
内田　直樹
真由美 阿部
尚志 飯田
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東ソー株式会社
公益財団法人相模中央化学研究所
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    • H05B33/00—Electroluminescent light sources
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Definitions

  • the present invention relates to a 1,3,5-triazine compound having a terarenyl group containing a nitrogen-containing heterocyclic group, which is useful as a component of an organic electroluminescence device, and a method for producing the same.
  • the 1,3,5-triazine compound of the present invention is useful as a component of an organic electroluminescent device because it has good charge transport properties.
  • the present invention further relates to an organic electroluminescence device having at least one layer containing the 1,3,5-triazine compound and excellent in driving performance and durability.
  • An organic electroluminescent element is formed by sandwiching a light-emitting layer containing a light-emitting material between a hole transport layer and an electron transport layer, and further attaching an anode and a cathode to the outside, and recombination of holes and electrons injected into the light-emitting layer. It is an element that utilizes light emission (fluorescence or phosphorescence) when the generated excitons are deactivated, and is applied to displays and the like.
  • the 1,3,5-triazine compound of the present invention has a phenyl group substituted with a nitrogen-containing heterocyclic group and an aromatic hydrocarbon group at the 2- and 4-positions of the triazine ring, and at the 6-position. It has an aromatic hydrocarbon group.
  • 1,3,5-triazine derivatives in organic electroluminescent devices (see, for example, Patent Documents 1 to 4), and these triazine derivatives are in the 2,4,6 positions of the triazine ring.
  • 1,3,5-triazine compound of the present invention having a terarylenyl group only at the 2- and 4-positions in that it has a 2,4-disubstituted phenyl group or a 3,4-disubstituted phenyl group. Is.
  • 1,3,5-triazine derivatives in organic electroluminescent devices (see, for example, Patent Documents 5 and 6).
  • the 2,4,6 positions of the triazine ring are proposed.
  • the position of the substituent on the phenyl group is not limited, and the 1,3,5-triazine compound of the present invention characterized by having a terarylenyl group containing a heterocyclic aromatic group at the 2,4-positions It is not specifically shown.
  • triazine derivatives having a terarylenyl group containing a heterocyclic aromatic group in a triazine ring used in an organic electroluminescence device have been proposed (see, for example, Patent Document 5).
  • 1, 3, 5 of the present invention having a structure having an aromatic hydrocarbon group substituted with an aromatic group at the 6-position and an aromatic hydrocarbon group not substituted with another aromatic group at the 6-position -Completely different from triazine compounds.
  • 1,3,5-triazine derivatives in organic electroluminescent devices (see, for example, Patent Document 7).
  • These 1,3,5-triazine derivatives are 2,4 of the triazine ring. It has a structure having a quateraryl group at the position and is completely different from the 1,3,5-triazine compound of the present invention having a teraryl group at the 2,4 position.
  • Organic electroluminescent elements are used in various display devices, but the use of organic electroluminescent elements in portable devices with limited power supply is required to further reduce power consumption.
  • the device can be driven at a low voltage due to excellent charge injection and transport characteristics, and the consumption output can be reduced by preventing the leakage of excitons from the adjacent light emitting layer and increasing the light emission efficiency.
  • Such materials cannot be found in conventional compounds, and new materials are desired.
  • the present inventors have used a 1,3,5-triazine compound having a specific terarylenyl group only at the 2,4-position of the triazine ring as an electron transport layer. As a result, it has been found that driving at a lower voltage and improvement in luminous efficiency can be achieved as compared with general-purpose organic electroluminescent elements, and the present invention has been completed.
  • the present invention provides the following general formula (1): (In the formula, Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group optionally substituted with fluorine. Ar 2 is substituted with an alkyl group having 1 to 4 carbon atoms or fluorine. Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group optionally substituted with fluorine) 1,3,5-triazine compound I will provide a.
  • the following general formula (2) (In the formula, Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group optionally substituted with fluorine. Ar 2 is substituted with an alkyl group having 1 to 4 carbon atoms or fluorine. And a compound represented by the following general formula (3): X 1 represents a leaving group. (Wherein Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group which may be substituted with fluorine; M represents a metal-containing group or a heteroatom group); Is subjected to a coupling reaction in the presence or absence of a base and in the presence of a palladium catalyst.
  • Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group optionally substituted with fluorine.
  • Ar 2 is substituted with an alkyl group having 1 to 4 carbon atoms or fluorine.
  • Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group optionally substituted with fluorine) 1,3,5-triazine compound A manufacturing method is provided.
  • Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group optionally substituted with fluorine.
  • Ar 2 is substituted with an alkyl group having 1 to 4 carbon atoms or fluorine.
  • .R 4 is hydrogen atom may denote an aromatic hydrocarbon group, an alkyl group or a phenyl group having 1 to 4 carbon atoms, B (oR 4) 2 two R 4 2 may be the same or different.
  • R 4s can be combined to form an oxygen atom and a boron atom to form a ring.
  • a compound represented by the following general formula (5) (Wherein Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group which may be substituted with fluorine.
  • X 2 represents a leaving group)
  • a coupling reaction in the presence of a palladium catalyst the following general formula (1)
  • Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group optionally substituted with fluorine.
  • Ar 2 is substituted with an alkyl group having 1 to 4 carbon atoms or fluorine.
  • Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group optionally substituted with fluorine) 1,3,5-triazine compound A manufacturing method is provided.
  • Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group optionally substituted with fluorine.
  • Ar 2 is substituted with an alkyl group having 1 to 4 carbon atoms or fluorine.
  • Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group optionally substituted with fluorine) 1,3,5-triazine compound
  • An organic electroluminescent device comprising a component as a component.
  • a thin film comprising the 1,3,5-triazine compound of the present invention represented by the general formula (1) (hereinafter sometimes referred to as “1,3,5-triazine compound (1)”) has high surface smoothness. Since it has amorphous properties, heat resistance, electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection properties, etc., it is useful as a material for organic electroluminescent elements, especially an electron transport material, It can be used as a hole blocking material, a light emitting host material, or the like.
  • the thin film containing the 1,3,5-triazine compound (1) can be driven at a low voltage, exhibits high luminous efficiency, and thus provides an organic electroluminescence device having characteristics of low power consumption and long life. .
  • FIG. 1 Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. Light emitting layer 5. Hole blocking layer 6. 6. Electron transport layer Cathode layer
  • FIG. 1 Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. Light emitting layer 5. Electron transport layer 6. Cathode layer
  • the aromatic hydrocarbon group represented by Ar 1 includes a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a perylenyl group, or a triphenylenyl group. And monocyclic hydrocarbon groups such as a group and condensed polycyclic hydrocarbon groups. These groups may be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine.
  • Ar 1 does not include an aryl group having an aryl substituent such as a ring assembly hydrocarbon group, for example, a biphenylyl group.
  • alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group. These alkyl groups may be linear, branched or cyclic. Further, one or more halogen atoms or the like may be substituted.
  • Ar 1 is substituted with a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group with 1 to 4 carbon atoms from the viewpoint of easy synthesis and good performance as a material for an organic electroluminescent device.
  • a naphthyl group which may be present is preferred.
  • Particularly preferred is an unsubstituted phenyl group.
  • phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine
  • examples of the phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include p-tolyl group, m-tolyl group, o-tolyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3 -Ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-di Propylphenyl group, 3,5-
  • a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, and 2,6-dimethyl are preferable in terms of performance as an organic electroluminescent element material.
  • a phenyl group and a 4-tert-butylphenyl group are preferred.
  • a phenyl group is more preferable in terms of easy synthesis.
  • naphthyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms
  • Examples of the naphthyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include 1-naphthyl group and 2-naphthyl group, 4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalene-1 -Yl group, 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalene -1-yl group, 5-trifluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5- tert-butylnaphthalen-1-y
  • a 1-naphthyl group, a 4-methylnaphthalen-1-yl group, and a 4-tert-butylnaphthalene-1 are preferable in terms of performance as a material for an organic electroluminescence device.
  • An yl group, a 7-methylnaphthalen-2-yl group or a 7-tert-butylnaphthalen-2-yl group is preferred.
  • Examples of a good perylenyl group and a triphenylenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 9-phenanthryl group, and a 1-perylenyl group. 2-perylenyl group, 1-triphenylenyl group and the like.
  • Examples of the aromatic hydrocarbon group represented by Ar 2 include the same aromatic hydrocarbon groups represented by Ar 1 described above, and these groups are alkyl groups having 1 to 4 carbon atoms or It may be substituted with fluorine.
  • Ar 2 is substituted with a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group with 1 to 4 carbon atoms from the viewpoint of easy synthesis and good performance as a material for an organic electroluminescent device.
  • An naphthyl group which may be present is preferable, and an unsubstituted phenyl group is more preferable.
  • the 1,3,5-triazine compound (1) of the present invention is characterized in that a terarylenyl group is bonded to triazine, and Ar 1 and Ar 2 are substituted with an aryl group such as a biphenylyl group. Does not contain aryl groups.
  • the 1,3,5-triazine compound (1) of the present invention is characterized in that a terarylenyl group is bonded to triazine, and Ar 3 is a nitrogen-containing heterocyclic group substituted with an aryl group, for example, phenylpyridyl Does not contain groups. Ar 3 does not contain a ring assembly nitrogen-containing heterocyclic group such as a bipyridyl group.
  • Ar 3 is preferably unsubstituted or substituted with a methyl group or fluorine.
  • a pyridyl group, a quinolyl group, a pyrimidyl group, a pyrazyl group, an isoquinolyl group, an acridyl group, a thiazolyl group, or a benzothiazolyl group is more preferable because they are easy to synthesize and have good performance as a material for an organic electroluminescent device. Alternatively, it may be substituted with a methyl group or fluorine.
  • Ar 3 specific examples of Ar 3 will be given, but the present invention is not limited thereto.
  • Examples of the pyridyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 3-methyl-2-pyridyl group, 4- Methyl-2-pyridyl group, 5-methyl-2-pyridyl group, 6-methyl-2-pyridyl group, 2-methyl-3-pyridyl group, 4-methyl-3-pyridyl group, 5-methyl-3-pyridyl group Group, 6-methyl-3-pyridyl group, 2-methyl-4-pyridyl group, 3-methyl-4-pyridyl group, 3,4-dimethyl-2-pyridyl group, 3,5-dimethyl-2-pyridyl group 3,6-dimethyl-2-pyridyl group, 2,4-dimethyl-3-pyridyl group, 2,5-dimethyl-3-pyridyl group, 2,6-dimethyl-3-pyri
  • Examples of the pyrimidyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 4-methyl-2-pyrimidyl group, 5-methyl- 2-pyrimidyl group, 2-methyl-4-pyrimidyl group, 5-methyl-4-pyrimidyl group, 6-methyl-4-pyrimidyl group, 2-methyl-5-pyrimidyl group, 4-methyl-5-pyrimidyl group, etc. Can give.
  • Examples of the pyrazyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include pyrazyl group, 2-methylpyrazyl group, 4-methylpyrazyl group, 5-methylpyrazyl group, 2-fluoropyrazyl group, 4-fluoropyrazyl group Examples thereof include a pyrazyl group and a 5-fluoropyrazyl group.
  • Examples of the quinolyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include a 2-quinolyl group, a 3-quinolyl group, a 4-quinolyl group, a 5-quinolyl group, a 6-quinolyl group, and a 7-quinolyl group.
  • Examples of the isoquinolyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group.
  • Examples of the thiazolyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group and the like.
  • benzothiazolyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine
  • examples of the benzothiazolyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, etc. Can do.
  • Specific examples of the group and an azaindolidyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or fluorine include 9-acridyl group, 1,6-naphthyridin-2-yl group, 1,8-naphthyridine -2-yl group, 2-quinazolyl group, 4-quinazolyl group
  • Any hydrogen atom in the 1,3,5-triazine compound (1) may be replaced with a deuterium atom.
  • the 1,3,5-triazine compound (1) can be produced by a method including Step 1 represented by the following reaction formula.
  • Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group which may be substituted with fluorine.
  • Ar 2 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group which may be substituted with fluorine.
  • Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group which may be substituted with fluorine. Specific examples of Ar 1 , Ar 2 and Ar 3 are as described above.
  • X 1 represents a leaving group.
  • Examples of the leaving group represented by X 1 include a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of good reaction yield, a bromine atom or a chlorine atom is preferred.
  • M represents a metal-containing group or a heteroatom group. Specific examples thereof will be described for the compound (3) described later.
  • compound (2) The compound represented by the general formula (2) (hereinafter sometimes referred to as “compound (2)”) can be produced, for example, using the method shown in Reference Example-1 described later. Arbitrary hydrogen atoms in compound (2) may be substituted with deuterium atoms.
  • the compound represented by the general formula (3) (hereinafter sometimes referred to as “compound (3)”) is, for example, Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal 16: Journal of Japan. 10, 941-944, 2008, or Chemistry of Materials, 20, 595-15953, 2008. Any hydrogen atom in the compound (3) may be substituted with a deuterium atom.
  • Preferred examples of the compound (3) include the following 3-1 to 3-24 (wherein M represents a metal-containing group or a heteroatom group), but the present invention is limited to this. It is not a thing.
  • ZnR 3 include ZnCl, ZnBr, ZnI, and the like. It can be illustrated.
  • the metal-containing group is preferably ZnCl, and more preferably ZnCl (TMEDA) coordinated with tetramethylethylenediamine.
  • ligands such as ethers and amines may be coordinated with these metal-containing groups, and the type of the ligand is not limited as long as it does not inhibit step 1.
  • Examples of the heteroatom group represented by M include SiMe 3 , SiPh 3 , SiF 3 , B (OR 4 ) 2 and the like.
  • R 4 represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms
  • B (OR 4) 2 two R 4 2 may be the same or different. Further, two R 4 may form a ring containing an oxygen atom and a boron atom together.
  • Specific examples of B (OR 4 ) 2 include B (OH) 2 , B (OMe) 2 , B (O i Pr) 2 , B (OBu) 2 , and B (OPh) 2 .
  • Examples of B (OR 4 ) 2 when two R 4 are combined to form a ring containing an oxygen atom and a boron atom include the groups represented by the following (I) to (VI). Among these, the group represented by (II) is preferable in that the yield is good.
  • Step 1 the compound (2) is reacted with the compound (3) in the presence or absence of a base in the presence of a palladium catalyst to give the 1,3,5-triazine compound (1) of the present invention.
  • reaction conditions for general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc.
  • the target product can be obtained in high yield. .
  • Examples of the palladium catalyst that can be used in “Step 1” include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. Further, ⁇ -allyl palladium chloride dimer, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro (1 , 1'-bis (diphenylphosphino) ferrocene) palladium and the like.
  • a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good yield, and a palladium complex having triphenylphosphine as a ligand is more preferable in terms of easy availability.
  • the amount of the palladium catalyst used in “Step 1” is not particularly limited as long as it is a so-called catalyst amount. However, the molar ratio of the palladium catalyst to the compound (2) is 1:50 to 1: 10 is preferred.
  • the palladium complex which has these tertiary phosphines as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound.
  • the tertiary phosphine that can be added to the palladium salt or complex compound includes triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4 , 5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 ′-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphine) Fino) biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (dipheny
  • Triphenylphosphine tri (tert-butyl) phosphine or 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred because it is readily available and yields are good.
  • the molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 4 to 5: 1 in terms of good yield.
  • the reaction in the “step 1”, in the case of the Suzuki-Miyaura reaction using the compound (3) in which M is B (OR 4 ) 2 , it is preferable to carry out the reaction in the presence of a base in terms of good yield.
  • the bases that can be used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride, fluoride. Examples thereof include potassium chloride and cesium fluoride, and cesium carbonate or sodium hydroxide is preferable in terms of a good yield.
  • the molar ratio of the base and the compound (3) is not particularly limited, but is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of good yield.
  • the molar ratio of the compound (2) and the compound (3) used in “Step 1” is not particularly limited, but is preferably 1: 1 to 5: 1, and 2: 1 to 3: 1 is preferable in terms of a good yield. Further preferred.
  • the reaction of “Step 1” is preferably carried out in a solvent in terms of good yield.
  • the solvent that can be used in “Step 1” is not particularly limited, but examples include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, and xylene. These may be used in appropriate combination. From the viewpoint of good yield, it is preferable to use tetrahydrofuran or a mixed solvent of ethanol and tetrahydrofuran or a mixed solvent of 1,4-dioxane and butanol.
  • Compound (1) can be obtained by performing a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.
  • the 1,3,5-triazine compound (1) of the present invention can also be produced by a process including the process 2 represented by the following reaction formula.
  • Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group which may be substituted with fluorine.
  • Ar 2 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group which may be substituted with fluorine.
  • Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group which may be substituted with fluorine. Specific examples of Ar 1 , Ar 2 and Ar 3 are as described above.
  • R 4 represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms
  • B (OR 4) 2 two R 4 2 may be the same or different. Further, two R 4 may form a ring containing an oxygen atom and a boron atom together. Specific examples of B (OR 4 ) 2 include the same as those mentioned for compound (3).
  • X 2 represents a leaving group.
  • Examples of the leaving group represented by X 2 include a chlorine atom, a bromine atom, and an iodine atom.
  • a bromine atom is preferable in terms of a good yield.
  • compound (4) The compound represented by the general formula (4) (hereinafter sometimes referred to as “compound (4)”) can be produced, for example, according to the method shown in Reference Example-2 described later.
  • any hydrogen atom in the compound (4) may be substituted with a deuterium atom.
  • compound (5) The compound represented by the general formula (5) (hereinafter sometimes referred to as “compound (5)”) is, for example, Org. Chem. 48, 1064-1069, 1983.
  • any hydrogen atom in compound (5) may be substituted with a deuterium atom.
  • Preferred examples of compound (5) include the following 5-1 to 5-24 (wherein X 2 represents a leaving group), but the present invention is not limited thereto. Absent.
  • Step 2 is a method in which compound (4) is reacted with compound (5) in the presence of a palladium catalyst and a base to obtain 1,3,5-triazine compound (1).
  • reaction conditions of general Suzuki-Miyaura reaction the desired product can be obtained in high yield.
  • Examples of the palladium catalyst that can be used in “Step 2” include the palladium salts and complex compounds exemplified in “Step 1”. Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is particularly preferable in terms of a good yield.
  • the amount of the palladium catalyst used in “Step 2” is not particularly limited as long as it is a so-called catalyst amount. However, the molar ratio of the palladium catalyst to the compound (4) is 1: 100 to 1: 10 is preferred.
  • a palladium complex having tertiary phosphine as a ligand can also be prepared in a reaction system by adding tertiary phosphine to a palladium salt or complex compound.
  • the tertiary phosphine that can be added to the palladium salt or complex compound include the tertiary phosphine exemplified in “Step 1”. Among them, triphenylphosphine, bis (diphenylphosphino) ferrocene, bis (diphenylphosphino) binaphthyl or 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropyl is easy to obtain and has a good yield. Biphenyl is preferred.
  • the molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of a good yield
  • Step 2 must be carried out in the presence of a base.
  • the base that can be used in “Step 2” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride. , Potassium fluoride, cesium fluoride, and the like, and sodium carbonate and potassium phosphate are desirable in terms of good yield.
  • the molar ratio of base to compound (4) is not particularly limited, but is preferably 1: 2 to 10: 1, and more preferably 3: 1 to 3: 1 in terms of good yield.
  • the reaction in “Step 2” is preferably carried out in a solvent in terms of good yield.
  • the solvent that can be used in “Step 2” is not particularly limited, but examples thereof include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, ethanol, methanol, butanol, 1,4-dioxane, and xylene. These may be used in appropriate combination. It is desirable to use a mixed solvent of toluene and water or a mixed solvent of 1,4-dioxane and water in terms of a good yield.
  • the 1,3,5-triazine compound (1) can be obtained by performing a normal treatment after completion of “Step 2”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.
  • Compound (4) which is a raw material of “Step 2” for producing 1,3,5-triazine compound (1), can be produced, for example, by a method including Step 3 shown by the following reaction formula.
  • Ar 1 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group which may be substituted with fluorine.
  • Ar 2 represents an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group which may be substituted with fluorine.
  • Ar 3 represents an alkyl group having 1 to 4 carbon atoms or a nitrogen-containing heterocyclic group which may be substituted with fluorine.
  • X 1 represents a leaving group.
  • R 4 represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms, B (OR 4) 2 two R 4 2 may be the same or different. Further, two R 4 may form a ring containing an oxygen atom and a boron atom together.
  • Step 3 is a reaction of reacting compound (2) with a borane compound represented by general formula (6) or a diboron compound represented by general formula (7) in the presence of a base and a palladium catalyst.
  • the compound (4) used in 2) is produced.
  • this step for example, by applying the reaction conditions disclosed in The Journal of Organic Chemistry, 60, 7508-7510, 1995 or Journal of Organic Chemistry, 65, 164-168, 2000. The object can be obtained efficiently.
  • Examples of the palladium catalyst that can be used in “Step 3” include those similar to the palladium salts or complex compounds exemplified in “Step 1”. Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is particularly preferable in terms of a good yield.
  • the amount of the palladium catalyst used in “Step 3” is not particularly limited as long as it is a so-called catalyst amount. However, the molar ratio of the palladium catalyst to the compound (2) is 1:50 to 1: 10 is preferred.
  • a palladium complex having tertiary phosphine as a ligand can also be prepared in a reaction system by adding tertiary phosphine to a palladium salt or complex compound.
  • tertiary phosphine examples include the tertiary phosphine exemplified in “Step 1”. Among them, triphenylphosphine is preferable because it is easily available.
  • the molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of a good yield.
  • the base that can be used in “Step 3” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride. , Potassium fluoride, cesium fluoride, and the like, and potassium acetate is desirable in terms of good yield.
  • the molar ratio of the base and the compound (2) is not particularly limited, but is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of a good yield.
  • the molar ratio of the borane compound (6) or diboron compound (7) and the compound (2) used in “Step 3” is not particularly limited, but is preferably 1: 1 to 5: 1 and 2 in terms of good yield. 1 to 3: 1 is more preferable.
  • the reaction of “Step 3” may be carried out in a solvent.
  • the solvent that can be used in “Step 3” is not particularly limited, and examples thereof include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, methanol, and xylene. You may use combining these suitably. It is desirable to use tetrahydrofuran, toluene or 1,4-dioxane in terms of a good yield.
  • Compound (4) obtained in this step may be isolated after the reaction, but may be subjected to “Step 2” without isolation.
  • the 1,3,5-triazine compound (1) of the present invention is used for producing at least one of thin films forming a multilayer structure of an organic electroluminescence device.
  • the film-forming by a vacuum evaporation method can be mentioned as a preferable example.
  • 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 such that the production tact time for producing the organic electroluminescent element is short and the production cost is superior, so that commonly used diffusion pumps, turbo molecular pumps, cryogenic pumps are used. It is preferably about 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 6 Pa that can be reached by a pump or the like.
  • the deposition rate is preferably 0.005 to 10 nm / second, depending on the thickness of the film to be formed.
  • a thin film for an organic electroluminescence device comprising the 1,3,5-triazine compound (1) can also be produced by a solution coating method.
  • a spin coating method using a general-purpose apparatus by dissolving a 1,3,5-triazine compound (1) in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, or tetrahydrofuran.
  • Film formation by an ink jet method, a cast method, a dip method, or the like is possible.
  • 3-pyridylboronic acid (1.12 g), 2,4-bis (5-bromobiphenyl-3-yl) -6-phenyl-1,3,5-triazine (2.17 g), 4M- Aqueous sodium hydroxide (3.5 mL), palladium acetate (16 mg), 1M-tri-tert-butylphosphine toluene solution (0.21 mL) are suspended in a mixed solvent of tetrahydrofuran (40 mL) and ethanol (20 mL) for 15 hours. Refluxed.
  • a white powder of biphenyl-3-yl] -1,3,5-triazine (yield 49 mg, yield 16%) was obtained.
  • 6-bromo-3-picoline 157 mg
  • 2,4-bis [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl-3 -Yl] -6-phenyl-1,3,5-triazine 250 mg
  • tetrakis (triphenylphosphine) palladium 23 mg
  • 2M aqueous sodium carbonate 2 mL
  • toluene 8 mL
  • 3-bromoquinoline (757 mg), 2,4-bis [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl-3-yl] -6-phenyl-1,3,5-triazine (1.0 g), 3M-aqueous cesium carbonate solution (1.9 mL) and bis (triphenylphosphine) palladium dichloride (19.7 mg) were added to 1,4-dioxane ( 10 mL) and refluxed for 3 hours. The reaction mixture was allowed to cool, and water was added.
  • 2-bromothiazole (597 mg), 2,4-bis [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl-3-yl] -6-phenyl-1,3,5-triazine (1.0 g), 3M aqueous potassium phosphate (1.4 mL), bis (dibenzylideneacetone) palladium (16.1 mg) and bis (diphenylphosphino) binaphthyl (34.9 mg) was suspended in dimethyl sulfoxide (10 mL) and refluxed for 21 hours. The reaction mixture was allowed to cool, and water was added.
  • Test example-1 Production and Performance Evaluation of Organic Electroluminescent Device
  • a glass substrate with an ITO transparent electrode in which a 2 mm-wide indium-tin oxide (ITO) film was patterned in a stripe shape was used as a substrate.
  • This substrate was cleaned with isopropyl alcohol, and further subjected to surface treatment by ozone ultraviolet cleaning.
  • Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method to produce an organic electroluminescent device having a light emitting area of 4 mm 2 having a multilayer structure as shown in FIG.
  • the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa. Thereafter, as shown in FIG. 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, a hole blocking layer 5, and an electron transport layer 6 are sequentially formed on the glass substrate 1 as organic compound layers. Then, the cathode layer 7 was formed.
  • hole injection layer 2 sublimation-purified phthalocyanine copper (II) was vacuum-deposited with a thickness of 10 nm.
  • hole transport layer 3 N, N′-di (naphthylene-1-yl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 30 nm.
  • NPD N′-diphenylbenzidine
  • 94 6 (mass%) of 4-4′-bis (carbazol-9-yl) biphenyl (CBP) and tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) The film was vacuum deposited at a thickness of 30 nm.
  • hole blocking layer 5 bis (2-methyl-8-quinolinolate)-(1,1'-biphenyl-4-olate) aluminum (BAlq) was vacuum-deposited with a film thickness of 5 nm.
  • As the electron transport layer 6 2-phenyl-4,6-bis [5- (3-pyridyl) biphenyl-3-yl] -1,3,5-triazine synthesized in Example 2 was formed to a thickness of 45 nm. Vacuum deposited.
  • Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second. Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed.
  • the cathode layer 6 was made into a two-layer structure by vacuum deposition of lithium fluoride and aluminum with a thickness of 1.0 nm and 100 nm, respectively.
  • Each film thickness was measured with a stylus type film thickness meter (DEKTAK). Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.
  • a direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • V voltage
  • cd / m 2 luminance
  • cd / A current efficiency
  • lm / W power efficiency
  • the measured values of the fabricated element were a voltage of 6.9 V, a luminance of 5490 cd / m 2 , a current efficiency of 27.5 cd / A, and a power efficiency of 12.6 lm / W.
  • Test Example-2 instead of the electron transport layer 6 of Test Example 1, 2-phenyl-4,6-bis [5- (2-pyrazinyl) biphenyl-3-yl] -1,3,5-triazine synthesized in Example 5
  • the organic electroluminescent element which vacuum-deposited this with the film thickness of 45 nm was created.
  • the measured values of the fabricated element were a voltage of 7.6 V, a luminance of 5080 cd / m 2 , a current efficiency of 25.4 cd / A, and a power efficiency of 10.6 lm / W.
  • Comparative Example-1 instead of the electron transport layer 6 of Test Example 1, an organic electroluminescent element obtained by vacuum-depositing Alq3, which is a general-purpose electron transport material, with a film thickness of 45 nm was produced in the same manner as Test Example 1.
  • the measured values of the fabricated element were a voltage of 9.0 V, a luminance of 5200 cd / m 2 , a current efficiency of 26.0 cd / A, and a power efficiency of 9.1 lm / W.
  • Test Example-3 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method to produce an organic electroluminescence device having a light-emitting area of 4 mm 2 having a multilayer structure as shown in FIG.
  • ITO indium-tin oxide
  • the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa. Thereafter, as shown in FIG. 2, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, and an electron transport layer 5 are sequentially formed on the glass substrate 1 as an organic compound layer. A film was formed.
  • hole injection layer 2 sublimated and purified phthalocyanine copper (II) was vacuum-deposited with a thickness of 10 nm.
  • hole transport layer 3 N, N'-di (naphthylene-1-yl) -N, N'-diphenylbenzidine (NPD) was vacuum-deposited with a thickness of 30 nm.
  • 2-phenyl-4,6-bis [5- (2-pyridyl) biphenyl-3-yl] -1,3,5-triazine synthesized in Example-1 was formed to a thickness of 20 nm.
  • Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second.
  • the cathode layer 6 was made into a two-layer structure by vacuum deposition of lithium fluoride and aluminum with a thickness of 1.0 nm and 100 nm, respectively. Each film thickness was measured with a stylus type film thickness meter (DEKTAK).
  • this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less.
  • a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin manufactured by Nagase ChemteX Corporation were used.
  • a direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • V voltage
  • cd / m 2 luminance
  • cd / A current efficiency
  • lm / W power efficiency
  • the measured values of the fabricated element were a voltage of 6.1 V, a luminance of 1804 cd / m 2 , a current efficiency of 9.02 cd / A, and a power efficiency of 4.62 lm / W.
  • Test Example-4 instead of the electron transport layer 5 of Test Example 3, 2-phenyl-4,6-bis [5- (2-pyrimidinyl) biphenyl-3-yl] -1,3,5-triazine synthesized in Example 4 was used.
  • the organic electroluminescent element which vacuum-deposited with a film thickness of 20 nm was created.
  • the measured values of the fabricated element were a voltage of 6.5 V, a luminance of 1875 cd / m 2 , a current efficiency of 9.38 cd / A, and a power efficiency of 4.78 lm / W.
  • Test example-5 instead of the electron transport layer 5 in Test Example 3, 2,4-bis [5- (isoquinolin-1-yl) biphenyl-3-yl] -6-phenyl-1,3,5 synthesized in Example 8 was used.
  • An organic electroluminescent device was prepared by vacuum-depositing triazine with a thickness of 20 nm. The measured values of the fabricated element were 6.4 V, luminance 1891 cd / m2, current efficiency 9.468 cd / A, and power efficiency 4.61 lm / W.
  • Test Example-6 instead of the electron transport layer 5 of Test Example 3, 2-phenyl-4,6-bis [5- (quinolin-2-yl) biphenyl-3-yl] -1,3,5 synthesized in Example 9 was used.
  • An organic electroluminescent device was prepared by vacuum-depositing triazine with a thickness of 20 nm. The measured values of the fabricated element were a voltage of 6.5 V, a luminance of 1991 cd / m 2 , a current efficiency of 9.96 cd / A, and a power efficiency of 4.83 lm / W.
  • Test Example-7 instead of the electron transport layer 5 of Test Example 3, 2-phenyl-4,6-bis [5- (quinolin-3-yl) biphenyl-3-yl] -1,3,5 synthesized in Example 10 was used.
  • An organic electroluminescent device was prepared by vacuum-depositing triazine with a thickness of 20 nm. The measured values of the fabricated element were a voltage of 6.4 V, a luminance of 1763 cd / m 2 , a current efficiency of 8.82 cd / A, and a power efficiency of 4.35 lm / W.
  • Comparative Example-2 instead of the electron transport layer 5 of Test Example 3, an organic electroluminescent element obtained by vacuum-depositing Alq3, which is a general-purpose electron transport material, with a film thickness of 20 nm was produced in the same manner as Test Example 1.
  • the measured values of the fabricated element were a voltage of 6.6 V, a luminance of 1768 cd / m 2 , a current efficiency of 8.84 cd / A, and a power efficiency of 4.29 lm / W.
  • the thin film comprising the 1,3,5-triazine compound (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron It has injection characteristics and the like, and can be used to construct at least one layer of a multilayer structure of an organic electroluminescent element.
  • the 1,3,5-triazine compound (1) can be used as an electron transport material, a hole blocking material, a light emitting host material and the like of an organic electroluminescence device.
  • it can be applied to various organic electroluminescent devices using fluorescent materials.
  • the organic electroluminescence device having a thin film made of the 1,3,5-triazine compound (1) has the features that it can be driven at a low voltage, has low power consumption, and has a long life.
  • 1,3,5-triazine compound (1) is useful not only for applications such as flat panel displays but also for illumination applications that require low power consumption.

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Abstract

L'invention concerne un composé de 1,3,5-triazine de formule générale (1). (1) Dans la formule générale (1), Ar1 et Ar2 représentent des groupes alkyle comportant de 1 à 4 atomes de carbone ou des groupes de type hydrocarbure aromatique qui peuvent être substitués par du fluor, et Ar3 représente un groupe alkyle comportant de 1 à 4 atomes de carbone ou un groupe hétérocyclique contenant un atome d'azote qui peut être substitué par du fluor. Un élément électroluminescent comprenant le composé de 1,3,5-triazine en tant que composant constitutif peut fonctionner à basse tension et montrer une efficacité électroluminescente élevée.
PCT/JP2011/080242 2010-12-27 2011-12-27 Composé de 1,3,5-triazine, son procédé de préparation et élément électroluminescent organique l'utilisant WO2012091026A1 (fr)

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WO2018103749A1 (fr) * 2016-12-08 2018-06-14 广州华睿光电材料有限公司 Dérivé cyclique fusionné de triazine et son application dans un dispositif électronique organique
WO2020009519A1 (fr) * 2018-07-05 2020-01-09 주식회사 엘지화학 Composé polycyclique et diode électroluminescente organique le comprenant
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