Patent ID: 12221430

MODE(S) FOR CARRYING OUT THE INVENTION

The “aromatic heterocyclic group” in the “substituted or unsubstituted aromatic heterocyclic group” represented by A1to A5in the general formulae (1) to (5) is selected from, specifically, the group consisting of a heteroaryl group having 2 to 20 carbon atoms in addition to a pyridyl group, a pyrimidinyl group, a triazinyl group, a furil group, a pyrrolyl group, an imidazolyl group, a thienyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzothiazolyl group, an azafluorenyl group, a diazafluorenyl group, an azaspirobifluorenyl group, a diazaspirobifluorenyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthyridinyl group, a phenanthrolinyl group, an acridinyl group, and a carbolinyl group.

The “aromatic hydrocarbon group”, “aromatic heterocyclic group”, or “fused polycyclic aromatic group” in the “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group”, or “substituted or unsubstituted fused polycyclic aromatic group” represented by Ar1to Ar13in the general formulae (1) to (5) is selected from, specifically, the group consisting of an aryl group having 6 to 30 carbon atoms and a heteroaryl group having 2 to 20 carbon atoms in addition to a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a spirobifluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a furil group, a pyrrolyl group, a thienyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzothiazolyl group, an azafluorenyl group, a diazafluorenyl group, an azaspirobifluorenyl group, a diazaspirobifluorenyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthyridinyl group, a phenanthrolinyl group, an acridinyl group, and a carbolinyl group.

Examples of the “substituted group” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group”, or “substituted fused polycyclic aromatic group” represented by A1to A5and Ar1to Ar13in the general formulae (1) to (5) include, specifically, a deuterium atom, a cyano group, and a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a silyl group such as a trimethylsilyl group and a triphenylsilyl group; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a linear or branched alkyloxy group having 1 to 6 carbon atoms such as a methyloxy group, an ethyloxy group, and a propyloxy group; an alkenyl group such as a vinyl group and an allyl group; an aryloxy group such as a phenyloxy group and a tolyloxy group; an arylalkyloxy group such as a benzyloxy group and a phenethyloxy group; an aromatic hydrocarbon group or fused polycyclic aromatic group such as a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a spirobifluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, and a triphenylenyl group; and an aromatic heterocyclic group such as a pyridyl group, a thienyl group, a furil group, a pyrrolyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, and a carbolinyl group, and these substituted groups may be further substituted with the exemplified substituted groups. Further, benzene rings substituted with these substituted groups or a plurality of substituted groups substituted on the same benzene ring may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

A compound having a pyrimidine ring structure represented by the above-mentioned formula (1), which is suitably used for an organic EL device according to the present invention, can be used as a constituent material of an electron injection layer, an electron transport layer, or a hole blocking layer in an organic EL device. This compound is favorable as a material of an electron injection layer or an electron transport layer because it has high mobility of electrons.

Since the organic EL device according to the present invention uses a material for an organic EL device having excellent electron injection/transport performance, stability in a thin film state, and durability, the electron transport efficiency from an electron transport layer to a light-emitting layer is improved, the light emission efficiency is improved, and a drive voltage is reduced as compared with the existing organic EL device, which makes it possible to improve the durability of the organic EL device and realize an organic EL device having high efficiency, a low drive voltage, and a long lifetime.

A compound having a pyrimidine ring structure according to the present invention has characteristics such as (1) having favorable electron injection property, (2) having high mobility of electrons, (3) having excellent hole blocking performance, (4) being stable in a thin film state, and (5) having excellent heat resistance, and an organic EL device according to the present invention has characteristics such as (6) having high light emission efficiency, (7) having a low light emission start voltage, (8) having a low practical driving voltage, and (9) having a long lifetime.

The compound having a pyrimidine ring structure according to the present invention has high electron injection/mobility. Therefore, an organic EL device including an electron injection layer and/or an electron transport layer prepared by using the compound as an electron injection material and/or an electron transport material, the electron transport efficiency to the light-emitting layer is improved, the light emission efficiency is improved, and the drive voltage is reduced, thereby improving the durability of the organic EL device.

The compound having a pyrimidine ring structure according to the present invention is excellent in hole blocking performance and an electron transport property and stable also in a thin film state, and has a feature of confining the excitons generated in the light-emitting layer. Therefore, in an organic EL device including a hole blocking layer prepared by using the compound as a hole blocking property material, the maximum light emission luminance is improved because the probability of recombination of holes and electrons is improved, heat deactivation is suppressed, high light emission efficiency is provided, the drive voltage is reduced, and the current resistance is improved.

The compound having a pyrimidine ring structure according to the present invention has an excellent electron transport property and a wide band gap. Therefore, in an organic EL device including a light-emitting layer prepared by using the compound as a host material, the drive voltage is reduced and the light emission efficiency is improved by forming the light-emitting layer so as to carry a fluorescent material, a phosphorescent material, and a delayed fluorescent material called dopants.

Therefore, the compound having a pyrimidine ring structure according to the present invention is useful as a material of an electron injection layer, an electron transport layer, a hole blocking layer, or a light-emitting layer in an organic EL device, and the light emission efficiency, the drive voltage, and the durability of the existing organic EL device can be improved.

The compound having a pyrimidine ring structure according to the present invention is a novel compound but can be synthesized in accordance with a method well-known per se (see, for example, patent Literature 5, and Non-Patent Literature 6).

As favorable specific examples of a pyrimidine compound represented by the above-mentioned general formula (1) suitably used for the organic EL device according to the present invention, a compound-1 to a compound-160 are shown inFIG.1toFIG.11. However, the present invention is not limited to these compounds.

Purification of compounds represented by the general formulae (1) to (5) each having a pyrimidine ring structure was carried out by purification by column chromatography, adsorption purification with silica gel, activated carbon, activated clay, or the like, recrystallization with a solvent, a crystallization method, a sublimation purification method, or the like. Identification of the compounds was performed by NMR analysis. As physical property values, a melting point, a glass transition point (Tg), and a work function were measured. The melting point is an index of vapor deposition property. The glass transition point (Tg) is an index of stability in a thin film state. The work function is an index of a hole transport property and a hole blocking property.

The melting point and the glass transition point (Tg) were measured with a powder using a high sensitivity differential scanning calorimeter (DSC3100SA manufactured by Bruker AXS GmbH).

The work function was obtained by preparing a thin film of 100 nm on an ITO substrate and using an ionization potential measuring apparatus (PYS-202 manufactured by Sumitomo Heavy Industries, Ltd.).

Examples of the structure of the organic EL device according to the present invention include those including an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode in the stated order on a substrate, those including an electron blocking layer between the hole transport layer and the light-emitting layer, and those including a hole blocking layer between the light-emitting layer and the electron transport layer. In the multilayer structures, several organic layers can be omitted or combined. For example, the hole injection layer and the hole transport layer may be combined or the electron injection layer and the electron transport layer may be combined. Further, two or more organic layers having the same function can be stacked. For example, two hole transport layers may be stacked, two light-emitting layers may be stacked, or two electron transport layers may be stacked.

For the anode of the organic EL device according to the present invention, an electrode material having a large work function such as ITO and gold is used. As the hole injection layer of the organic EL device according to the present invention, a starburst type triphenylamine derivative, an arylamine compound having two or more triphenylamine or carbazolyl structures in the molecule, each of which is bonded via a single bond or a divalent group containing no hetero atom, an acceptor heterocyclic compound such as hexacyanoazatriphenylene, a coating type polymer material, or the like in addition to a porphyrin compound typified by copper phthalocyanine can be used. These materials can be formed into a thin film by a known method such as a spin coat method and an ink jet method in addition to a vapor deposition method.

For the hole transport layer of the organic EL device according to the present invention, a benzidine derivative such as N,N′-diphenyl-N,N′-di(m-tolyl)-benzidine (hereinafter, referred to as TPD), N,N′-diphenyl-N,N′-di(a-naphthyl)-benzidine (hereinafter, referred to as NPD), and N,N,N′,N′-tetrabiphenylylbenzidine, 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (hereinafter, referred to as TAPC), an arylamine compound having two or more triphenylamine or carbazolyl structures in the molecule, each of which is bonded via a single bond or a divalent group containing no hetero atom, or the like can be used. These materials may be deposited alone. However, any of the materials may be mixed with another material and used as a single deposited layer. Further, a stacked structure may be achieved by depositing layers of the plurality of materials alone, or mixing the plurality of materials and depositing layers thereof. Alternatively, a stacked structure of at least one layer of any of the plurality of materials deposited alone and at least one layer obtained by mixing the plurality of materials and depositing at least one layer thereof may be achieved. Further, as a hole injection/transport layer, a coating polymer material such as poly(3,4-ethylenedioxythiophene) (hereinafter, referred to as PEDOT)/poly(styrene sulfonate) (hereinafter, referred to as PSS) can be used. These materials can be formed into a thin film by a known method such as a spin coat method and an ink jet method in addition to a vapor deposition method.

Further, for the hole injection layer or hole transport layer, those obtained by P-doping the material typically used for the layer with trisbromophenylamine hexachloroantimony or a radialene derivative (see, for example, Patent Literature 7), a polymer compound having, as a partial structure, the structure of a benzidine derivative such as TPD, or the like can be used.

For the electron blocking layer of the organic EL device according to the present invention, a compound having an electron blocking property, such as a carbazol derivative such as 4,4′,4″-tri(N-carbazolyl) triphenylamine (hereinafter, referred to as TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (hereinafter, referred to as mCP), and 2,2-bis(4-carbazol-9-ylphenyl)adamantane (hereinafter, referred to as Ad-Cz), and a compound having a triphenylsilyl group and a triarylamine structure typified by 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene can be used. These materials may be deposited alone. However, any of the materials may be mixed with another material and used as a single deposited layer. Further, a stacked structure may be achieved by depositing layers of the plurality of materials alone, or mixing the plurality of materials and depositing layers thereof. Alternatively, a stacked structure of at least one layer of any of the plurality of materials deposited alone and at least one layer obtained by mixing the plurality of materials and depositing at least one layer thereof may be achieved. These materials can be formed into a thin film by a known method such as a spin coat method and an ink jet method in addition to a vapor deposition method.

For the light-emitting layer of the organic EL device according to the present invention, a metal complex of a quinolinol derivative including Alq3, various metal complexes, an anthracene derivative a bis-styryl benzene derivative, a pyrene derivative, an oxazole derivative, a poly(p-phenylene vinylene) derivative, or the like in addition to the compound having a pyrimidine ring structure according to the present invention can be used. Further, the light-emitting layer may be formed of a host material and a dopant material. As the host material, an anthracene derivative is favorably used. In addition, not only the above-mentioned light-emitting material including the compound having a pyrimidine ring structure according to the present invention but also a heterocyclic compound having an indole ring as a partial structure of the fused ring, a heterocyclic compound having a carbazol ring as a partial structure of the fused ring, a carbazol derivative, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or the like can be used. Further, as the dopant material, quinacridone, coumarin, rubrene, perylene, and derivatives thereof, a benzopyran derivative, a rhodamine derivative, an aminostyryl derivative, or the like can be used. These materials may be deposited alone. However, any of the materials may be mixed with another material and used as a single deposited layer. Further, a stacked structure may be achieved by depositing layers of the plurality of materials alone, or mixing the plurality of materials and depositing layers thereof. Alternatively, a stacked structure of at least one layer of any of the plurality of materials deposited alone and at least one layer obtained by mixing the plurality of materials and depositing at least one layer thereof may be achieved.

Further, as the light-emitting material, a phosphorescent material can be used. As the phosphorescent material, a phosphorescent material of a metal complex such as iridium and platinum can be used. A green phosphorescent material such as Ir(ppy)3, a blue phosphorescent material such as FIrpic and FIr6, a red phosphorescent material such as Btp2Ir (acac), or the like is used. As the host material (having a hole injection/transporting property) at this time, the compound having a pyrimidine ring structure according to the present invention in addition to 4,4′-di(N-carbazolyl) biphenyl (hereinafter, referred to as CBP) and a carbazol derivative such as TCTA and mCP can be used. As a host material having an electron transportability, p-bis(triphenylsilyl)benzene (hereinafter, referred to as UGH2), 2,2′,2″-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (hereinafter, referred to as, TPBI), or the like can be used, and an organic EL device having high performance can be prepared.

In order to avoid concentration quenching, it is favorable to dope the host material with the phosphorescent material by co-deposition in the range of 1 to 30 weight percent with respect to the entire light-emitting layer.

Further, as the light-emitting material, a material emitting delayed fluorescence such as a CDCB derivative including PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN can be used (see, for example, Non-Patent Literature 3). These materials can be formed into a thin film by a known method such as a spin coat method and an ink jet method in addition to a vapor deposition method.

For the hole blocking layer of the organic EL device according to the present invention, a phenanthroline derivative such as bathocuproin (hereinafter, abbreviated as BCP), a compound having a hole blocking effect, such as a metal complex of a quinolinol derivative such as BAlq, various rare earth complexes, an oxazole derivative, a triazole derivative, and a triazine derivative, in addition to the compound having a pyrimidine ring structure according to the present invention, can be used. These materials may double as the material of the electron transport layer. These materials may be deposited alone. However, any of the materials may be mixed with another material and used as a single deposited layer. Further, a stacked structure may be achieved by depositing layers of the plurality of materials alone, or mixing the plurality of materials and depositing layers thereof. Alternatively, a stacked structure of at least one layer of any of the plurality of materials deposited alone and at least one layer obtained by mixing the plurality of materials and depositing at least one layer thereof may be achieved. These materials can be formed into a thin film by a known method such as a spin coat method and an ink jet method in addition to a vapor deposition method.

For the electron transport layer of the organic EL device according to the present invention, a metal complex of a quinolinol derivative including Alq3and BAlq, various metal complexes, a triazole derivative, a triazine derivative, an oxadiazole derivative, a pyridine derivative, a benzimidazole derivative, a thiadiazole derivative, an anthracene derivative, a carbodiimide derivative, a quinoxaline derivative, a pyridoindole derivative, a phenanthroline derivative, a silole derivative, or the like in addition to the compound having a pyrimidine ring structure according to the present invention can be used. These materials may be deposited alone. However, any of the materials may be mixed with another material and used as a single deposited layer. Further, a stacked structure may be achieved by depositing layers of the plurality of materials alone, or mixing the plurality of materials and depositing layers thereof. Alternatively, a stacked structure of at least one layer of any of the plurality of materials deposited alone and at least one layer obtained by mixing the plurality of materials and depositing at least one layer thereof may be achieved. These materials can be formed into a thin film by a known method such as a spin coat method and an ink jet method in addition to a vapor deposition method.

For the electron injection layer of the organic EL device according to the present invention, an alkali metal salt such as lithium fluoride and cesium fluoride, an alkaline earth metal salt such as magnesium fluoride, a metal complex of a quinolinol derivative such as lithiumquinolinol, a metal oxide such as an aluminum oxide, a metal such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), and cesium (Cs), or the like in addition to the compound having a pyrimidine ring structure according to the present invention can be used. However, this can be omitted in the favorable selection of the electron transport layer and the cathode.

Further, for the electron injection layer or electron transport layer, those obtained by N-doping the material typically used for the layer with a metal such as cesium can be used.

In the cathode of the organic EL device according to the present invention, an electrode material having a low work function, such as aluminum, an alloy having a lower work function, such as a magnesium silver alloy, a magnesium indium alloy, and an aluminum magnesium alloy, or the like is used as the electrode material.

Hereinafter, the embodiment of the present invention will be specifically described by way of Examples. However, the present technology is not limited to the following Examples as long as the essence of the present invention is not exceeded.

Example 1

Synthesis of 6-(biphenyl-4-yl)-2-{4-(phenanthren-9-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine (Compound-17)

6-(biphenyl-4-yl)-2-chloro-4-(pyridin-3-yl)-pyrimidine: 7.5 g, 4-(phenanthren-9-yl)-phenylboronic acid: 7.2 g, tetrakis (triphenylphosphine) palladium (0): 0.5 g, and potassium carbonate: 6.0 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, an organic layer was extracted by liquid separation and then the extract was concentrated under reduced pressure. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: toluene/ethyl acetate), and thus, a white powder of 6-(biphenyl-4-yl)-2-{4-(phenanthren-9-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine (Compound-17): 1.5 g (yield of 12%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 27 hydrogen signals were detected by 1H-NMR (CDCl3).

δ(ppm)=9.55 (1H), 8.90 (2H), 8.85 (1H), 8.82 (1H), 8.78 (1H), 8.70 (1H), 8.46 (2H), 8.15 (1H), 8.04 (1H), 7.97 (1H), 7.86 (2H), 7.80 (2H), 7.78-7.49 (10H), 7.44 (1H).

Example 2

Synthesis of 6-(biphenyl-4-yl)-2-(9,9-diphenyl [9H] fluoren-2-yl)-4-(pyridin-3-yl)-pyrimidine (Compound-26)

6-(biphenyl-4-yl)-2-chloro-4-(pyridin-3-yl)-pyrimidine: 5.0 g, 2-(9,9-diphenyl [9H] fluorene) boronic acid: 6.8 g, tetrakis (triphenylphosphine) palladium (0): 0.3 g, and potassium carbonate: 2.4 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, an organic layer was extracted by liquid separation and then the extract was concentrated under reduced pressure. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: toluene/ethyl acetate), and thus, a light-gray brown powder of 6-(biphenyl-4-yl)-2-(9,9-diphenyl [9H]fluoren-2-yl)-4-(pyridin-3-yl)-pyrimidine (Compound-26): 6.6 g (yield of 73%) was obtained.

The structure of the obtained light-gray brown powder was identified using NMR.

The following 31 hydrogen signals were detected by1H-NMR (DMSO-d6).

δ(ppm)=9.63 (1H), 8.81 (2H), 8.77 (1H), 8.69 (2H), 8.58 (2H), 8.19 (1H), 8.08 (1H), 7.96 (2H), 7.84 (2H), 7.68 (1H), 7.54 (3H), 7.45 (3H), 7.39-7.21 (10H).

Example 3

<Synthesis of 6-(biphenyl-4-yl)-4-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluoren-2-yl)-pyrimidine (Compound-27)

6-(biphenyl-4-yl)-2-chloro-4-(pyridin-3-yl)-pyrimidine: 7.0 g, 2-(9,9′-spirobi [9H] fluorene) boronic acid: 8.1 g, tetrakis (triphenylphosphine) palladium (0): 0.5 g, and potassium carbonate: 3.4 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, an organic layer was extracted by liquid separation and then the extract was concentrated under reduced pressure. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate), and thus, a white powder of 6-(biphenyl-4-yl)-4-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluoren-2-yl)-pyrimidine (Compound-27): 5.5 g (yield of 43%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 29 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=9.37 (1H), 8.85 (1H), 8.75 (1H), 8.46 (1H), 8.26 (2H), 8.06 (1H), 8.05 (1H), 7.94 (4H), 7.77 (2H), 7.69 (2H), 7.55-7.37 (7H), 7.16 (3H), 6.83 (2H), 6.75 (1H).

Example 4

Synthesis of 6-(biphenyl-4-yl)-4-(pyridin-3-yl)-2-{4-(9,9′-spirobi [9H] fluoren-2-yl)-phenyl}-pyrimidine (Compound-36)

By using 4-(9,9′-spirobi [9H] fluoren-2-yl)-phenylboronic acid instead of 2-(9,9′-spirobi [9H]fluorene) boronic acid in Example 3 and performing the reaction under the same conditions, a white powder of 6-(biphenyl-4-yl)-4-(pyridin-3-yl)-2-{4-(9,9′-spirobi [9H] fluoren-2-yl)-phenyl}-pyrimidine (Compound-36): 6.4 g (yield of 45%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 33 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=9.48 (1H), 8.80 (1H), 8.69 (2H), 8.60 (1H), 8.38 (2H), 8.06 (1H), 7.98 (1H), 7.91 (1H), 7.90 (2H), 7.82 (2H), 7.76 (1H), 7.71 (2H), 7.64 (2H), 7.52 (3H), 7.46-7.37 (4H), 7.16 (3H), 7.09 (1H), 6.84 (2H), 6.78 (1H).

Example 5

Synthesis of 2,6-bis{4-(naphthalen-1-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine (Compound-43)

2-chloro-6-{4-(naphthalen-1-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine: 8.0 g, 4-(naphthalen-1-yl)-phenylboronic acid: 5.5 g, tetrakis (triphenylphosphine) palladium (0): 0.5 g, and potassium carbonate: 3.4 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, methanol was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by recrystallization using a monochlorobenzene solvent, and thus, a white powder of 2,6-bis{4-(naphthalen-1-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine (Compound-43): 6.8 g (yield of 60%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 27 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=9.57 (1H), 8.91 (2H), 8.84 (1H), 8.71 (1H), 8.50 (2H), 8.19 (1H), 8.07-7.90 (6H), 7.76 (4H), 7.64-7.45 (9H).

Example 6

Synthesis of 6-{4-(naphthalen-1-yl)-phenyl}-4-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluoren-2-yl)-pyrimidine (Compound-46)

2-chloro-6-{4-(naphthalen-1-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine: 8.0 g, 2-(9,9′-spirobi [9H]fluorene) boronic acid: 8.1 g, tetrakis (triphenylphosphine) palladium (0): 0.5 g, and potassium carbonate: 3.4 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, methanol was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by crystallization using a monochlorobenzene/acetone mixed solvent, and thus, a white powder of 6-{4-(naphthalen-1-yl)-phenyl}-4-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluoren-2-yl)-pyrimidine (Compound-46): 6.2 g (yield of 45%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 31 hydrogen signals were detected by 1H-NMR (CDCl3).

δ(ppm)=9.40 (1H), 8.88 (1H), 8.77 (1H), 8.48 (1H), 8.31 (2H), 8.12-7.87 (9H), 7.68 (2H), 7.57 (2H), 7.53-7.36 (6H), 7.16 (3H), 6.84 (2H), 6.76 (1H).

Example 7

Synthesis of 6-(biphenyl-4-yl)-2-{3-(10-phenyl-anthracen-9-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine (Compound-149)

6-(biphenyl-4-yl)-2-chloro-4-(pyridin-3-yl)-pyrimidine: 6.0 g, 3-(10-phenyl-anthracen-9-yl) phenylboronic acid: 7.8 g, tetrakis (triphenylphosphine) palladium (0): 0.4 g, and potassium carbonate: 4.8 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, H2O was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by recrystallization using a monochlorobenzene solvent, and thus, a white powder of 6-(biphenyl-4-yl)-2-{3-(10-phenyl-anthracen-9-yl)-phenyl}-4-(pyridin-3-yl)-pyrimidine (Compound-149): 6.2 g (yield of 56%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 31 hydrogen signals were detected by 1H-NMR (CDCl3).

δ(ppm)=9.47 (1H), 8.98 (1H), 8.88 (1H), 8.77 (1H), 8.62 (1H), 8.39 (2H), 8.13 (1H), 7.89-7.73 (8H), 7.71-7.34 (15H).

Example 8

Synthesis of 6-(biphenyl-4-yl)-4-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluorene-4-yl)-pyrimidine (Compound-151)

6-(biphenyl-4-yl)-2-chloro-4-(pyridin-3-yl)-pyrimidine: 5.0 g, 4-(9,9′-spirobi [9H] fluorene) boronic acid: 5.8 g, tetrakis (triphenylphosphine) palladium (0): 0.3 g, and potassium carbonate: 2.4 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, an organic layer was extracted by liquid separation and then the extract was concentrated under reduced pressure. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: toluene), and thus, a light-gray brown powder of 6-(biphenyl-4-yl)-4-(pyridin-3-yl)-2-(9,9′-spirobi [9H]fluorene-4-yl)-pyrimidine (Compound-151): 4.0 g (yield of 44%) was obtained.

The structure of the obtained light-gray brown powder was identified using NMR.

The following 29 hydrogen signals were detected by1H-NMR (DMSO-d6).

δ(ppm)=9.75 (1H), 8.97 (1H), 8.87 (1H), 8.82 (1H), 8.65 (2H), 8.07 (2H), 7.92 (2H), 7.84 (3H), 7.68 (1H), 7.64 (1H), 7.54 (2H), 7.45 (3H), 7.33 (1H), 7.20 (2H), 7.13 (2H), 6.77 (1H), 6.76 (2H), 6.65 (1H).

Example 9

Synthesis of 6-(biphenyl-4-yl)-4-(quinolin-8-yl)-2-(9,9′-spirobi [9H] fluoren-2-yl)-pyrimidine (Compound-152)

6-(biphenyl-4-yl)-2-chloro-4-(quinolin-8-yl)-pyrimidine: 6.0 g, 2-(9,9′-spirobi [9H] fluorene) boronic acid: 6.0 g, tetrakis (triphenylphosphine) palladium (0): 0.4 g, and potassium carbonate: 2.5 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, methanol was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by recrystallization using a monochlorobenzene solvent, and thus, a white powder of 6-(biphenyl-4-yl)-4-(quinolin-8-yl)-2-(9,9′-spirobi [9H] fluoren-2-yl)-pyrimidine (Compound-152): 6.5 g (yield of 63%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 31 hydrogen signals were detected by 1H-NMR (DMSO-d6).

δ(ppm)=8.94 (1H), 8.80 (1H), 8.55 (1H), 8.52 (1H), 8.32 (2H), 8.27 (1H), 8.18 (2H), 8.14 (1H), 8.07 (2H), 7.88 (2H), 7.78 (4H), 7.63 (1H), 7.51 (3H), 7.43 (3H), 7.18 (3H), 6.72 (2H), 6.63 (1H).

Example 10

Synthesis of 6-(biphenyl-4-yl)-2-(9,9-diphenyl [9H] fluoren-2-yl)-4-(quinolin-8-yl)-pyrimidine (Compound-153)

6-(biphenyl-4-yl)-2-chloro-4-(quinolin-8-yl)-pyrimidine: 6.0 g, 2-(9,9-diphenyl [9H] fluorene) boronic acid: 7.2 g, tetrakis (triphenylphosphine) palladium (0): 0.4 g, and potassium carbonate: 2.5 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, an organic layer was extracted by liquid separation and then the extract was concentrated under reduced pressure. The crude product thus obtained was purified by recrystallization using an acetone solvent, and thus, a white powder of 6-(biphenyl-4-yl)-2-(9,9-diphenyl [9H] fluoren-2-yl)-4-(quinolin-8-yl)-pyrimidine (Compound-153): 8.5 g (yield of 83%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 33 hydrogen signals were detected by 1H-NMR (CDCl3).

δ(ppm)=9.04 (1H), 8.76 (1H), 8.73 (1H), 8.66 (1H), 8.56 (1H), 8.42 (3H), 8.23 (1H), 8.17 (1H), 8.06 (1H), 7.94 (2H), 7.87 (1H), 7.81 (2H), 7.68 (1H), 7.54 (3H), 7.46 (2H), 7.41 (1H), 7.38-7.19 (10H).

Example 11

Synthesis of 2-(9,9-diphenyl [9H] fluoren-2-yl)-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-154)

2-chloro-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine: 8.0 g, 2-(9,9-diphenyl [9H] fluorene) boronic acid: 7.6 g, tetrakis (triphenylphosphine) palladium (0): 0.4 g, and potassium carbonate: 5.4 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, methanol was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate), and thus, a white powder of 2-(9,9-diphenyl [9H] fluoren-2-yl)-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-154): 3.9 g (yield of 29%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 35 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=9.47 (1H), 8.81 (1H), 8.80 (2H), 8.57 (1H), 8.37 (2H), 8.05 (1H), 7.96 (1H), 7.88 (3H), 7.78 (4H), 7.68 (2H), 7.56-7.23 (17H).

Example 12

Synthesis of 4-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluoren-2-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-155)

2-chloro-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine: 8.0 g, 2-(9,9′-spirobi [9H] fluorene) boronic acid: 6.9 g, tetrakis (triphenylphosphine) palladium (0): 0.4 g, and potassium carbonate: 3.2 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, H2O was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate), and thus, a white powder of 4-(pyridin-3-yl)-2-(9,9′-spirobi [9H]fluoren-2-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-155): 4.2 g (yield of 32%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 33 hydrogen signals were detected by 1H-NMR (CDCl3).

δ(ppm)=9.38 (1H), 8.86 (1H), 8.76 (1H), 8.47 (1H), 8.28 (2H), 8.07 (1H), 8.05 (1H), 7.95 (4H), 7.82 (2H), 7.76 (4H), 7.69 (2H), 7.51 (3H), 7.42 (4H), 7.16 (3H), 6.83 (2H), 6.76 (1H).

Example 13

Synthesis of 2-(9,9-diphenyl [9H] fluorene-3-yl)-4-(pyridin-3-yl)-6-([1,1′;4′,1‘ ’ ]terphenyl-4-yl)-pyrimidine (Compound-156)

2-chloro-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine: 8.0 g, 3-(9,9-diphenyl [9H] fluorene) boronic acid: 7.6 g, tetrakis (triphenylphosphine) palladium (0): 0.4 g, and potassium carbonate: 5.3 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, H2O was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate), and thus, a white powder of 2-(9,9-diphenyl [9H] fluorene-3-yl)-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-156): 3.4 g (yield of 25%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 35 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=9.54 (1H), 9.10 (1H), 8.83 (1H), 8.67 (2H), 8.45 (2H), 8.12 (1H), 8.03 (1H), 7.90 (2H), 7.79 (4H), 7.70 (2H), 7.62 (1H), 7.56 (2H), 7.54-7.23 (15H).

Example 14

Synthesis of 2-(9,9-diphenyl [9H] fluorene-4-yl)-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-157)

2-chloro-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine: 5.5 g, 4-(9,9-diphenyl [9H] fluorene) boronic acid: 4.7 g, tetrakis (triphenylphosphine) palladium (0): 0.3 g, and potassium carbonate: 3.6 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, H2O was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate), and thus, a white powder of 2-(9,9-diphenyl [9H] fluorene-4-yl)-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-157): 3.2 g (yield of 35%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 35 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=9.50 (1H), 8.81 (1H), 8.64 (1H), 8.43 (2H), 8.30 (1H), 7.86 (3H), 7.77 (4H), 7.68 (2H), 7.60 (1H), 7.58 (1H), 7.54-7.21 (17H), 7.10 (1H).

Example 15

Synthesis of 4-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluorene-4-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine (Compound-158)

2-chloro-4-(pyridin-3-yl)-6-([1,1′;4′,1″]terphenyl-4-yl)-pyrimidine: 8.0 g, 4-(9,9′-spirobi [9H] fluorene) boronic acid: 6.9 g, tetrakis (triphenylphosphine) palladium (0): 0.4 g, and potassium carbonate: 5.3 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of toluene, ethanol and H2O. After the mixture was allowed to cool, H2O was added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate), and thus, a white powder of 4-(pyridin-3-yl)-2-(9,9′-spirobi [9H]fluorene-4-yl)-6-([1,1′;4′,1″] terphenyl-4-yl)-pyrimidine (Compound-158): 3.7 g (yield of 28%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 33 hydrogen signals were detected by 1H-NMR (CDCl3).

δ(ppm)=9.55 (1H), 8.83 (1H), 8.70 (1H), 8.48 (2H), 8.33 (1H), 7.90 (5H), 7.79 (4H), 7.75 (1H), 7.69 (2H), 7.54 (1H), 7.51 (2H), 7.43 (3H), 7.28 (1H), 7.18 (2H), 7.11 (2H), 6.91 (2H), 6.88 (1H), 6.78 (1H).

Example 16

Synthesis of 4-(phenanthren-9-yl)-5-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluorene-4-yl)-pyrimidine (Compound-159)

5-chloro-4-(phenanthren-9-yl)-2-(9,9′-spirobi [9H]fluorene-4-yl)-pyrimidine: 5.0 g, 3-pyridylboronic acid: 1.2 g, tris(dibenzylideneacetone)dipalladium (0): 0.4 g, tricyclohexylphosphine: 0.5 g, and tripotassium phosphate: 5.3 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of 1,4-dioxane and H2O. After the mixture was allowed to cool, H2O was added to the system, an organic layer was extracted by liquid separation, and then the extract was concentrated under reduced pressure. The crude product thus obtained was purified by column chromatography (carrier: silica gel, eluent: dichloromethane/ethyl acetate), and thus, a white powder of 4-(phenanthren-9-yl)-5-(pyridin-3-yl)-2-(9,9′-spirobi [9H] fluorene-4-yl)-pyrimidine (Compound-159): 1.7 g (yield of 32%) was obtained.

The structure of the obtained white powder was identified using NMR.

The following 29 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=δ (ppm)=8.84 (1H), 8.70 (2H), 8.67 (1H), 8.47 (1H), 8.33 (1H), 7.98 (1H), 7.96 (1H), 7.91 (1H), 7.87 (2H), 7.78 (1H), 7.70 (1H), 7.61 (4H), 7.46-7.26 (5H), 7.14 (3H), 6.94 (1H), 6.80 (2H), 6.75 (1H).

Example 17

Synthesis of 4-(biphenyl-4-yl)-2-(10-phenyl-anthracen-9-yl)-5-(quinolin-8-yl)-pyrimidine (Compound-160)

4-(biphenyl-4-yl)-5-chloro-2-(10-phenyl-anthracen-9-yl)-pyrimidine: 5.0 g, 8-quinolineboronic acid: 2.0 g, tris(dibenzylideneacetone)dipalladium (0): 0.4 g, tricyclohexylphosphine: 0.5 g, and tripotassium phosphate: 6.1 g were charged into a reaction vessel, and stirred under reflux overnight in a mixed solvent of 1,4-dioxane and H2O. After the mixture was allowed to cool, H2O and methanol were added to the system, and the precipitated solid was filtered to obtain a crude product. The crude product thus obtained was purified by crystallization using a toluene/acetone mixed solvent, and thus, a pale yellow powder of 4-(biphenyl-4-yl)-2-(10-phenyl-anthracen-9-yl)-5-(quinolin-8-yl)-pyrimidine (Compound-160): 3.0 g (yield of 51%) was obtained.

The structure of the obtained pale yellow powder was identified using NMR.

The following 29 hydrogen signals were detected by1H-NMR (CDCl3).

δ(ppm)=9.42 (1H), 9.15 (1H), 8.70 (1H), 8.14 (1H), 7.90 (2H), 7.88-7.59 (10H), 7.55-7.30 (13H).

Example 18

The melting point and the glass transition point of the pyrimidine compound represented by the general formula (1) were measured using a high sensitivity differential scanning calorimeter (DSC3100SA manufactured by Bruker AXS GmbH).

Melting Point Glass Transition Point

Compound of Example 1236° C.115° C.Compound of Example 2267° C.135° C.Compound of Example 3Not observed146° C.Compound of Example 4331° C.164° C.Compound of Example 5257° C.103° C.Compound of Example 6306° C.157° C.Compound of Example 7303° C.144° C.Compound of Example 8Not observed148° C.Compound of Example 9306° C.151° C.Compound of Example 10Not observed137° C.Compound of Example 11282° C.147° C.Compound of Example 12274° C.159° C.Compound of Example 13326° C.149° C.Compound of Example 14275° C.148° C.Compound of Example 15Not observed161° C.Compound of Example 16Not observed164° C.Compound of Example 17Not observed141° C.

The compound having a pyrimidine ring structure represented by the general formula (1) has the glass transition point of 100° C. or more, which shows that the thin film state is stable.

Example 19

The compound having a pyrimidine ring structure represented by the general formula (1) was used to prepare a vapor deposition film having a film thickness of 100 nm on an ITO substrate, and the work function thereof was measured by an ionization potential measuring apparatus (PYS-202 manufactured by Sumitomo Heavy Industries, Ltd.).

Work Function

Compound of Example 16.53 eVCompound of Example 26.57 eVCompound of Example 36.52 eVCompound of Example 46.40 eVCompound of Example 56.49 eVCompound of Example 66.53 eVCompound of Example 75.97 eVCompound of Example 86.43 eVCompound of Example 96.51 eVCompound of Example 106.51 eVCompound of Example 116.59 eVCompound of Example 126.58 eVCompound of Example 136.58 eVCompound of Example 146.51 eVCompound of Example 156.56 eVCompound of Example 166.59 eVCompound of Example 176.07 eV

The compound having a pyrimidine ring structure represented by the general formula (1) has a value of work function larger than 5.5 eV that is a value of work function of a general hole transport material such as NPD and TPD and has large hole blocking performance.

Example 20

The organic EL device was prepared by depositing a hole injection layer3, a hole transport layer4, a light-emitting layer5, a hole blocking layer6, an electron transport layer7, an electron injection layer8, and a cathode (aluminum electrode)9in the stated order on a transparent anode2, which has been formed on a glass substrate1as an ITO electrode in advance, as shown inFIG.12.

Specifically, after performing, in isopropyl alcohol for 20 minutes, ultrasonic cleaning on the glass substrate1on which ITO having a film thickness of 50 nm was formed, the glass substrate1was dried for 10 minutes on a hot plate heated to 200° C. After that, UV ozone treatment was performed for 15 minutes, and then, the ITO-attached glass substrate was mounted in a vacuum deposition machine. The pressure in the vacuum deposition machine was reduced to 0.001 Pa or less. Subsequently, a film of an electron acceptor (Acceptor-1) having the following structural formula and a compound (HTM-1) having the following structural formula was formed, as the hole injection layer3, to have a film thickness of 10 nm and cover the transparent anode2by binary deposition at a deposition rate in which the ratio of the deposition rates of Acceptor-1 and the compound (HTM-1) was 3:97. As the hole transport layer4, a film of the compound (HTM-1) having the following structural formula was formed on the hole injection layer3to have a film thickness of 60 nm. A film of a compound (EMD-1) having the following structural formula and a compound (EMH-1) having the following structural formula was formed, as the light-emitting layer5, on the hole transport layer4to have a film thickness of 20 nm by binary deposition at a deposition rate in which the ratio of the deposition rates of EMD-1 and EMH-1 was 5:95. A film of the compound (Compound-17) according to Example 1 of the present invention and a compound (ETM-1) having the following structural formula was formed on the light-emitting layer5, as the hole blocking layer and electron transport layer6and7to have a film thickness of 30 nm by binary deposition at a deposition rate in which the ratio of the deposition rates of the compound (Compound-17) and the compound (ETM-1) was 50:50. A film of lithium fluoride was formed, as the electron injection layer8, on the hole blocking layer and electron transport layer6and7to have a film thickness of 1 nm. Finally, aluminum was deposited to have a thickness of 100 nm to form the cathode9. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 21

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 26) according to Example 2 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-26) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 22

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 27) according to Example 3 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-27) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 23

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 36) according to Example 4 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-36) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 24

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 43) according to Example 5 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-43) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 25

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 46) according to Example 6 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-46) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 26

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 149) according to Example 7 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-149) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 27

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 151) according to Example 8 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-151) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 28

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 152) according to Example 9 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-152) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 29

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 153) according to Example 10 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-153) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 30

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 154) according to Example 11 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-154) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 31

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 155) according to Example 12 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-155) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 32

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 156) according to Example 13 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-156) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 33

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 157) according to Example 14 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-157) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 34

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 158) according to Example 15 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-158) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 35

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 159) according to Example 16 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-159) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Example 36

An organic EL device was prepared in similar conditions to Example 20 except that the compound (Compound 160) according to Example 17 was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (Compound-160) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Comparative Example 1

For comparison, an organic EL device was prepared in similar conditions to Example 20 except that a compound (ETM-2) (see, for example, Patent Literature 6) having the following structural formula was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (ETM-2) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

Comparative Example 2

For comparison, an organic EL device was prepared in similar conditions to Example 20 except that a compound (ETM-3) (see, for example, Patent Literature 8) having the following structural formula was used as the material of the hole blocking layer and electron transport layer6and7instead of the compound (Compound 17) according to Example 1 of the present invention and binary deposition was performed at a deposition rate in which the ratio of the deposition rates of the compound (ETM-3) and the compound (ETM-1) was 50:50. The characteristics of the prepared organic EL device were measured at room temperature in the atmosphere. The measurement results of the light-emitting characteristics when a direct current voltage was applied to the prepared organic EL device were collectively shown in Table 1.

The device lifetime was measured using each of the organic EL devices prepared in Examples 20 to 36 and Comparative Examples 1 and 2, and the results were collectively shown in Table 1. The device lifetime was measured as the time until the light emission luminance attenuated to 1900 cd/m2(corresponding to 95% in the case where the initial luminance was 100%: 95% attenuation) when constant current driving was performed with the light emission luminance (initial luminance) at the start of light emission set to 2000 cd/m2.

TABLE 1Light emissionVoltageLuminanceefficiencyPower efficiencyElementHole blocking[V][cd/m2][cd/A][lm/W]lifetimelayer and electron(@10(@10(@10(@1095%transport layermA/cm2)mA/cm2)mA/cm2)mA/cm2)attenuatedExample 20Compound-17/3.678238.247.06244 hoursETM- 1Example 21Compound-26/3.568958.957.89231 hoursETM- 1Example 22Compound-27/3.498998.998.11257 hoursETM-1Example 23Compound-36/3.608878.877.74307 hoursETM-1Example 24Compound-43/3.528638.647.73261 hoursETM-1Example 25Compound-46/3.498878.888.00287 hoursETM-1Example 26Compound-149/3.708718.737.43248 hoursETM-1Example 27Compound-151/3.428618.617.90252 hoursETM-1Example 28Compound-152/3.558958.967.94296 hoursETM-1Example 29Compound-153/3.568738.747.73283 hoursETM-1Example 30Compound-154/3.458938.948.13316 hoursETM-1Example 31Compound-155/3.458878.888.09259 hoursETM-1Example 32Compound-156/3.578758.767.71323 hoursETM-1Example 33Compound-157/3.728738.757.40271 hoursETM-1Example 34Compound-158/3.678808.827.55275 hoursETM-1Example 35Compound-159/3.449239.248.43233 hoursETM-1Example 36Compound-160/3.489099.098.22267 hoursETM-1ComparativeETM-2/3.828058.05S.62165 hoursExample 1ETM-1ComparativeETM-3/4.016596.595.16203 hoursExample 2ETM-1

As shown in Table 1, the drive voltage when a current having a current density of 10 mA/cm2was caused to flow was lowered to 3.42 to 3.72 V in the organic EL devices according to Examples 20 to 36 as compared with the 3.82 to 4.01 V of the organic EL devices according to Comparative Examples 1 and 2 using the compounds (ETM-2 and 3) having the above-mentioned structural formulae. Further, the light emission efficiency was improved to 8.24 to 9.24 cd/A in the organic EL devices according to Examples 20 to 36 as compared with 6.59 to 8.05 cd/A of the organic EL devices according to Comparative Examples 1 and 2. Also the power efficiency of the organic EL devices according to Examples 20 to 36 was largely improved to 7.06 to 8.43 lm/W as compared with 5.16 to 6.62 lm/W of the organic EL devices according to Comparative Examples 1 and 2. In particular, the device lifetime (95% attenuation) was largely extended to 231 to 323 hours in the organic EL devices according to Examples 20 to 36 as compared with 165 to 203 hours of the organic EL devices according to Comparative Examples 1 and 2.

As described above, the organic EL device according to the present invention is excellent in the light emission efficiency and power efficiency as compared with the devices using the compounds (ETM-2 and 3) having the above-mentioned structural formulae, and it has been found that it is possible to realize an organic EL device having a long lifetime.

INDUSTRIAL APPLICABILITY

The compound having a specific pyrimidine ring structure according to the present invention is excellent in electron injection property and hole blocking performance and is stable in a thin film state, and thus is suitably used as a compound for organic EL device. By preparing an organic EL device using the compound, it is possible to achieve high efficiency, reduce the drive voltage, and improve the durability. For example, it has become possible to expand to home appliances and lighting applications.

REFERENCE SIGNS LIST

1glass substrate2transparent anode3hole injection layer4hole transport layer5light-emitting layer6hole blocking layer7electron transport layer8electron injection layer9cathode