CN113698360A

CN113698360A - Oxazole or thiazole compound and organic electroluminescent device thereof

Info

Publication number: CN113698360A
Application number: CN202111125115.XA
Authority: CN
Inventors: 孙月; 苗玉鹤; 陆影; 刘小婷
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2021-09-25
Filing date: 2021-09-25
Publication date: 2021-11-26
Anticipated expiration: 2041-09-25
Also published as: CN113698360B

Abstract

The invention provides an oxazole or thiazole compound and an organic electroluminescent device thereof, belonging to the technical field of organic electroluminescence. The oxazole or thiazole compound provided by the invention has a proper HOMO energy level, effectively blocks holes in a light-emitting layer, avoids efficiency reduction caused by partial holes passing through the light-emitting layer, improves the recombination rate of electrons and holes in the light-emitting layer, is applied to a hole blocking/electron transmission layer of an organic electroluminescent device, and can greatly improve the light-emitting efficiency and prolong the service life of the organic electroluminescent device. Meanwhile, the compound has a high refractive index, and when the compound is used as a covering layer, the total reflection of light in the device can be effectively reduced, and the light extraction efficiency of the device is improved. The oxazole or thiazole compound and the organic electroluminescent device thereof have good application effect and industrialization prospect.

Description

Oxazole or thiazole compound and organic electroluminescent device thereof

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an oxazole or thiazole compound and an organic electroluminescent device thereof.

Background

Organic Light Emitting Diode (OLED) is developed in the eighties of the twentieth century, is a novel device different from the traditional LCD and LED display, has the characteristics of all solid state, lightness, thinness, wide viewing angle, low energy consumption, high response speed, good anti-seismic performance, high luminous efficiency, high contrast, softness and the like, and is widely applied to the fields of display, illumination and the like.

After a certain direct current voltage is applied to the organic electroluminescent device, holes are injected into the hole transport layer from the transparent anode, electrons are injected into the electron transport layer from the metal cathode, two carriers migrate to the light emitting layer and are combined to form excitons, the excitons jump to the anode side, and then the excitons emit light through radiation recombination. Organic electroluminescent devices are typically classic sandwich structures consisting of a cathode, an anode and organic functional layers, wherein the organic functional layers mainly comprise: a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, and the like.

In terms of development requirements of the current OLED industry, materials need to have characteristics of high brightness and long service life, but development of current organic electroluminescent materials is far from enough, electron mobility of an electron transport material in a device is generally far smaller than hole mobility of a hole transport material, carrier injection in the device is unbalanced, improvement of device performance is limited, and most of the electron transport materials have no hole blocking effect. In addition, the research on the coating material is relatively small at home and abroad, and the performance of most coating materials is poor, so that the light extraction efficiency cannot be improved well. Therefore, it is important to develop an organic functional material that can effectively block holes by improving electron mobility and light extraction efficiency.

Disclosure of Invention

The invention provides an oxazole or thiazole compound and an organic electroluminescent device thereof, aiming at the defects of the current organic electroluminescent materials.

The invention provides an oxazole or thiazole compound having a structure represented by chemical formula 1,

in chemical formula 1, Ar₁The same or different structures are selected from the structures shown below,

said X₁Selected from O or S;

said Y are the same or different and are selected from C (Rx) or N; the Rx is same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx can be connected to form a substituted or unsubstituted ring;

the R is₀、R₅The same or different is selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroarylWherein m is selected from 0,1, 2 or 3; when m is greater than 1, two or more R₀Are the same or different from each other;

k is₁Selected from 2,3, 4 or 5;

the R is₁～R₄The same or different compounds are selected from any one of hydrogen, deuterium, halogen, cyano, C1-C12 alkyl and substituted or unsubstituted C3-C12 cycloalkyl; a is a₁Selected from 0,1, 2 or 3; a is a₂、a₃、a₄The same or different is selected from 0,1, 2,3 or 4; when a is₁、a₂、a₃、a₄Greater than 1, two or more R₁、R₂、R₃、R₄R being identical or different from each other, or adjacent to each other₁Adjacent to each other₂Adjacent to each other₃Adjacent to each other₄Can be connected to form an alicyclic ring;

n is₁、n₂The same or different is selected from 0,1 or 2;

said L₁The same or different one selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C2-C30.

The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, and is characterized in that the organic layer contains any one or the combination of at least two of the oxazole or thiazole compounds.

The invention has the beneficial effects that: the oxazole or thiazole compound provided by the invention has a proper HOMO energy level, effectively blocks holes in a light-emitting layer, avoids the phenomenon that partial holes pass through the light-emitting layer to cause efficiency reduction, and improves the recombination rate of electrons and holes in the light-emitting layer. Meanwhile, the oxazole or thiazole compound has high refractive index, and when the oxazole or thiazole compound is used as a covering layer, the total reflection of light in the device can be effectively reduced, and the light extraction efficiency of the device is improved.

Drawings

Fig. 1 is a current-voltage plot of different single-carrier devices.

Detailed Description

The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.

In the context of the present specification,

means a moiety attached to another substituent.

In the present specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example,

can represent

And so on.

The halogen in the invention refers to fluorine, chlorine, bromine and iodine.

The alkyl group in the present invention refers to a hydrocarbon group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, and examples may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, and the like, but are not limited thereto.

The cycloalkyl group in the present invention means a hydrocarbon group obtained by removing one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 6 carbon atoms, and examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like. The alkyl group is preferably a cyclopentyl group, a cyclohexyl group, an adamantyl group or a norbornyl group.

The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from the aromatic nucleus carbon of the aromatic hydrocarbon molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 60 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, most preferably 6 to 12 carbon atoms, and examples may include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylene group, perylenyl group, etc., but are not limited thereto.

The heteroaryl group in the present invention is a general term for a monovalent group obtained by removing a hydrogen atom from a nuclear atom of an aromatic heterocyclic ring composed of carbon and a hetero atom. The hetero atom may be one or more of N, O, S, Si, P, may be a monocyclic heteroaryl group or a fused ring heteroaryl group, preferably having 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, most preferably 3 to 8 carbon atoms, and examples may include a pyrrolyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a thienyl group, a furyl group, an indolyl group, a quinolyl group, an isoquinolyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group, a pyridooxazolyl group, a pyridothiazolyl group, a pyridoimidazolyl group, a pyrimidooxazolyl group, a pyrimido thiazolyl group, a pyrimidooimidazolyl group, a dibenzofuryl group, a dibenzothienyl group, a carbazolyl group, a phenazinyl group, a quinoxalinyl group, a quinazolino oxazolyl group, a quinoxalinyl group, a, Quinolinothiazolyl, quinolinoimidazolyl, purinyl, 2-purinyl, N-imidazolyl, and the like, but is not limited thereto.

The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from an aromatic nucleus of an aromatic hydrocarbon molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring arylene group, preferably having 6 to 60 carbon atoms, preferably 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, pyrenylene, triphenylene, peryleneene, and the like, but are not limited thereto.

Heteroarylene as used herein refers to a general term in which two hydrogen atoms are removed from the core carbon of an aromatic heterocyclic ring composed of carbon and hetero atoms, which may be one or more of N, O, S, Si, P, a monocyclic heteroarylene group or a fused-ring heteroarylene group, preferably having 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, most preferably 3 to 8 carbon atoms, and examples may include pyrrolylene, pyridylene, pyrimidylene, triazinylene, thienylene, furylene, indolyl, quinolylene, isoquinolylene, oxazolylene, thiazolyl, imidazolyl, benzothienyl, benzofuranylene, benzoxazylene, benzothiazylene, benzimidazolylene, pyridooxazolylene, pyridothiazolyl, pyridinothiazole, or the like, Pyridinylimidazolylides, pyrimidinyoxazolyl, pyrimidinylthiozolyl, pyrimidinylimidazolylides, dibenzofuranylidene, dibenzothiophenyl, carbazolyl, phenazinylene, quinoxalinyl, quinazolinylene, quinoxalinyl, quinolinoyloxazolylene, quinolinoylthiazole, quinolinoylimidazolyl, purinylene and the like, but are not limited thereto.

The "substitution" as referred to herein means that a hydrogen atom in a compound group is replaced with another atom or group, and the position of substitution is not limited.

The "substituted or unsubstituted" as referred to herein means not substituted or substituted with one or more substituents selected from the group consisting of: deuterium, halogen atom, amino group, cyano group, nitro group, alkyl group having from C1 to C30, cycloalkyl group having from C3 to C20, aryl group having from C6 to C60, heteroaryl group having from C2 to C60, arylamine group having from C6 to C60, aryloxy group having from C6 to C60, preferably deuterium, halogen atom, cyano group, alkyl group having from C1 to C12, aryl group having from C6 to C30, heteroaryl group having from C2 to C30, more preferably deuterium, halogen atom, cyano group, aryl group having from C1 to C12, heteroaryl group having from C6 to C30, and more preferably deuterium, halogen atom, cyano group, heteroaryl group, nitro group, aryl group having from C2 to C30Examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclohexyl, adamantyl, norbornyl, phenyl, tolyl, mesityl, pentadeuterated phenyl, biphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, pyrenyl, triphenylenyl, and the like,

A group, a perylene group, a fluoranthenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a 9-methyl-9-phenylfluorenyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a spirobifluorenyl group, a carbazoloindolyl group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzotriazolyl group, a benzimidazolyl group, a pyridooxazolyl group, a pyridothiazolyl group, a pyridoimidazolyl group, a pyrimidooxazolyl group, a pyrimido thiazolyl group, a pyrimido imidazolyl group, a quinolyl group, an isoquinolyl group, a quinooxazolyl group, a quinolothiazolyl group, a phenothiazinyl group, a phenoxazinyl group, Acridinyl, and the like, but are not limited thereto. Or when the substituent is plural, adjacent substituents may be bonded to form a ring; when the substituent is plural, plural substituents are the same as or different from each other.

The linking to form a substituted or unsubstituted ring according to the present invention means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:

in the present invention, the ring formed by the linkage may be an alicyclic ring or an aromatic ring, and the alicyclic ring may be classified into cycloalkane, cycloalkene and cycloalkyne, and examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclopentene, cyclohexene, but not limited thereto; the aromatic ring may be classified into a five-membered ring or a six-membered ring or a fused ring, and examples may include benzene, pyridine, pyrimidine, naphthalene, quinoline, isoquinoline, dibenzothiophene, phenanthrene, or pyrene, but are not limited thereto.

said X₁Selected from O or S;

the R is₀、R₅The same or different compounds are selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl, and m is selected from 0,1, 2 or 3; when m is greater than 1, two or more R₀Are the same or different from each other;

k is₁Selected from 2,3, 4 or 5;

the R is₁～R₄The same or different compounds are selected from any one of hydrogen, deuterium, halogen, cyano, C1-C12 alkyl and substituted or unsubstituted C3-C12 cycloalkyl; a is a₁Selected from 0,1, 2 or 3; a is a₂、a₃、a₄The same or different are selected from 0,1.2, 3 or 4; when a is₁、a₂、a₃、a₄Greater than 1, two or more R₁、R₂、R₃、R₄R being identical or different from each other, or adjacent to each other₁Adjacent to each other₂Adjacent to each other₃Adjacent to each other₄Can be connected to form an alicyclic ring;

n is₁、n₂The same or different is selected from 0,1 or 2;

Preferably, the oxazole or thiazole compound has a structure represented by chemical formula 1-1 to 1-4,

the R is₀Any one selected from the group consisting of hydrogen, deuterium, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, and substituted or unsubstituted triazinyl;

m is₁Selected from 0,1, 2 or 3; m is₂Selected from 0,1 or 2; m is₃Is selected from 0 or 1. When m is₁、m₂Greater than 1, two or more R₀The same or different from each other.

Preferably, the oxazole or thiazole compound has any one of the structures shown in the following,

preferably, the

Having any one of the structures shown below,

the R is₁～R₄Any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl and adamantyl, which are the same or different; a is a₁Selected from 0,1, 2 or 3; a is a₂、a₃、a₄The same or different is selected from 0,1, 2,3 or 4; when a is₁、a₂、a₃、a₄Greater than 1, two or more R₁、R₂、R₃、R₄R being identical or different from each other, or adjacent to each other₁Adjacent to each other₂Adjacent to each other₃Adjacent to each other₄May be bonded to form an alicyclic ring.

Preferably, said "adjacent R" s₁Adjacent to each other₂Adjacent to each other₃Adjacent to each other₄The alicyclic ring in which an alicyclic ring can be bonded "has a structure shown below,

the "") means a position bonded to another substituent.

Preferably, Ar is₁、Ar₂The same or different structures are selected from the structures shown below,

the R is₅Any one of the same or different groups selected from methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted pyrimidyl;

said Y are the same or different and are selected from C (Rx) or N; the Rx are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl and substituted or unsubstituted triazinyl, or adjacent two Rx can be connected to form a substituted or unsubstituted ring.

Preferably, Ar is₁、Ar₂The same or different is selected from any one of the structures shown below,

preferably, said L₁The same or different is selected from any one of the structures shown below,

wherein, R is₇The same or different is selected from any one of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C2-C12 heteroarylSeed growing;

the R is₆Any one of the same or different hydrogen, deuterium, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C2-C12 heteroaryl;

b is₁Identical or different integers from 0,1, 2,3 or 4, b₂Identical or different integers from 0,1, 2,3, 4,5 or 6, b₃Identical or different integers from 0,1, 2,3, 4,5, 6,7 or 8, b₄Identical or different integers from 0,1, 2 or 3, b₅Identical or different integers from 0,1 or 2, b₆Identical or different integers from 0,1, 2,3, 4 or 5, when b₁、b₂、b₃、b₄、b₅、b₆Greater than 1, two or more R₆The same or different from each other.

Preferably, the oxazole or thiazole compound is selected from any one of the structures shown in the following,

the invention also provides a preparation method of the oxazole or thiazole compound,

Ar₁、L₁、k₁、m、R₀、a₁、a₂、a₃、a₄、R₁、R₂、R₃、R₄、n₁、n₂the definitions are the same as above;

xa is selected from any one of I, Br and Cl;

the reaction type related to the oxazole or thiazole compound is Suziki reaction.

The present invention may be bonded to the above-mentioned substituents through a method known in the art, and the kind and position of the substituents or the number of the substituents may be changed according to the technique known in the art.

The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises the oxazole or thiazole compound.

The organic layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a covering layer. However, the structure of the organic electroluminescent device of the present invention is not limited to the above structure, and multiple organic layers may be omitted or simultaneously provided, if necessary. For example, an electron blocking layer may be further provided between the hole transport layer and the light emitting layer, and a hole blocking layer may be further provided between the electron transport layer and the light emitting layer; the organic layers having the same function may be formed in a stacked structure of two or more layers.

The light-emitting layer of the present invention may include a host material, a dopant material, and the like, and may be formed of a single-layer structure or a multilayer structure in which layers above each other are stacked.

The organic electroluminescent device of the present invention preferably has the following structure:

substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer;

substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

substrate/anode/hole injection layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

substrate/anode/hole injection layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer;

substrate/anode/hole injection layer/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

substrate/anode/hole injection layer/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer;

however, the structure of the organic electroluminescent device is not limited thereto. The organic electroluminescent device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, part of organic layers can be added or omitted, and the organic layers with the same function can be made into a laminated structure with more than two layers.

The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like.

In the organic electroluminescent device according to the present invention, it is preferable to use a high work function material capable of promoting hole injection into the organic layer as the anode material. Specific examples of the anode material usable in the present invention may include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO); combinations of metals and oxides, such as ITO-Ag-ITO; and conductive polymers such as poly (3-methylthiophene), polypyrrole, polyaniline, poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDT), and the like, but not limited thereto. Preferably, the anode material is selected from ITO, ITO-Ag-ITO and the like.

In the organic electroluminescent device according to the present invention, the hole injection material is preferably a material having a good hole accepting ability. Specific examples of the hole injection material that can be used in the present invention may include: metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, phthalocyanine compound, benzidine compound, phenazine compound, and the like, for example, copper phthalocyanine (CuPc), titanyl phthalocyanine, N, N ' -diphenyl-N, N ' -di- [4- (N, N-diphenylamine) phenyl ] benzidine (NPNPNPNPB), N, N, N ', N ' -tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), bisquinoxalino [2,3-a:2',3' -c ] phenazine (HATNA), 4' -tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN), 4,4' -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but is not limited thereto. Preferably, the hole injection material of the present invention is selected from copper phthalocyanine (CuPc), 4',4 ″ -tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like.

In the organic electroluminescent device of the present invention, the hole transport material is preferably a material having an excellent hole transport property and a HOMO level matched with a corresponding anode material. Specific examples of the hole transporting material usable in the present invention may include diphenylamines, triphenylamines, fluorenes and carbazoles, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -di (naphthalen-1-yl) -N, N ' -di (phenyl) -2,2' -dimethylbenzidine (. alpha. -NPD), N ' -diphenyl-N, N ' -di (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4- [1- [4- [ di (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), and the like, but is not limited thereto. Preferably, the hole transport material of the present invention is selected from N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-di (naphthalen-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (α -NPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (TAPC), and the like.

In the organic electroluminescent device, the light-emitting layer material comprises a light-emitting layer host material and a light-emitting layer doping material, the light-emitting layer host material can be selected from 4,4' -bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4' -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (alpha-ADN), N ' -bis- (1-naphthyl) -N, N ' -diphenyl- [1,1':4', 1':4'1' -quaterphenyl]-4,4' -diamino (4PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like, but is not limited thereto. Preferably, the light-emitting layer host material of the present invention is selected from 9, 10-bis (2-naphthyl) Anthracene (ADN), 9'- (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), AND the like. The luminescent layer doping material can be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -bis [4- (diphenylamino) styryl]Biphenyl (BDAVBi), 4' -bis [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp2), bis (4, 6-difluorophenylpyridine-C2, N) picolinyliridium (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy)₃) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy)₂(acac)), 9, 10-bis [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq)₃) Bis (1-phenylisoquinoline) (acetylacetonato) iridium (Ir (piq))₂(acac)), etc., but is not limited thereto. Preferably, the light emitting layer guest of the present invention is selected from 4,4' -bis [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 9, 10-di [ N- (p-tolyl) anilino group]Anthracene (TPA), and the like.

The doping ratio of the host material for the light-emitting layer and the dopant material for the light-emitting layer is preferably different depending on the materials used, and is usually 0.01% to 20%, preferably 0.1% to 15%, more preferably 1% to 10%.

In the organic electroluminescent device according to the present invention, the hole blocking material has a strong hole blocking ability and suitable HOMO and LUMO energy levels, and specific examples of the hole blocking material that may be used in the present invention, in addition to the oxazole or thiazole compound according to the present invention, may include imidazoles, triazoles, phenanthroline derivatives, quinolines, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like, but are not limited thereto. Preferably, the hole blocking material of the present invention is selected from the oxazole or thiazole compounds of the present invention.

In the organic electroluminescent device according to the present invention, the electron transport material is preferably a material having a strong electron withdrawing ability and low HOMO and LUMO energy levels, and specific examples of the electron transport material that may be used in the present invention, in addition to the oxazole or thiazole compound according to the present invention, may include imidazoles, triazoles, phenanthroline derivatives, quinolines, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] phenanthrene]Benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalen-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (HNBphen), 8-hydroxyquinoline-Lithium (LiQ), and the like, but are not limited thereto. Preferably, the electron transport material of the present invention is selected from 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), tris (8-hydroxyquinoline) aluminum (III) (Alq)₃) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), and the like, but not limited thereto, it is preferable that the electron transport material of the present invention is selected from the heterocyclic ring-containing compounds of the present invention.

In the organic electroluminescent device according to the present invention, the electron injection material is preferably a material having a small difference in potential barrier with an adjacent organic transport material or host material, and has an effect of injecting electrons from the cathode. Examples of the electron injecting material that can be used in the present invention include: alkali metal salts (such as LiF, CsF), alkaline earth metal salts (such as MgF)₂) Metal oxides (e.g. Al)₂O₃、MoO₃) But is not limited thereto. Preferably, the electron injection material of the present invention is selected from lithium fluoride (LiF), 8-hydroxyquinoline-lithium (Liq), and the like.

In the organic electroluminescent device according to the present invention, a low work function material capable of promoting electron injection into the organic layer is preferably used as the cathode material. Specific examples of the cathode material that can be used in the present invention may include: metals such as aluminum, magnesium, silver, indium, tin,Titanium and the like and alloys thereof; multilayer metallic materials, e.g. LiF/Al, Mg/Ag, Li/Al, LiO₂/Al、BaF₂Al, etc., but are not limited thereto. Preferably, the cathode according to the invention is selected from semi-transparent cathodes, such as Ag or Mg-Ag alloys or thin Al.

In the organic electroluminescent device according to the present invention, a material for improving optical coupling is preferably used as the material for the cover layer. Specific examples of the coating material that may be used in the present invention may include, but are not limited to, arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, etc., in addition to the oxazole or thiazole compounds described in the present invention, and preferably, the coating material in the present invention is selected from the oxazole or thiazole compounds described in the present invention. The coating layer may be formed on both the outer side of the anode and the outer side of the cathode, or may be disposed on the outer side of the anode or the outer side of the cathode, and preferably, the coating layer according to the present invention is disposed on the outer side of the cathode.

The present invention is not particularly limited to the thickness of each organic layer of the organic electroluminescent device, and may be any thickness commonly used in the art.

The organic electroluminescent device of the present invention may employ any one of vacuum evaporation, spin coating, vapor deposition, knife coating, laser thermal transfer, electrospray coating, slit coating, and dip coating, and in the present invention, vacuum evaporation is preferably employed.

The organic electroluminescent device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.

Preparation and characterization of the Compounds

Description of raw materials, reagents and characterization equipment:

the present invention is not particularly limited to the starting materials and sources of reagents used in the following examples, and they may be commercially available products or prepared by methods known to those skilled in the art.

The mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;

the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;

synthesis example 1 Synthesis of Compound 1

Preparation of b-1

A-1(120.00mmol, 30.97g) and B₂Pin₂(132.00mmol, 33.52g), dissolved well in DMF (600mL), followed by the addition of Pd (PPh)₃)₄(3.60mmol, 4.16g) and Na₂CO₃(360.00mmol, 38.16g), the reaction system was replaced with nitrogen, the reaction was stopped after heating and stirring for 3 hours, the reaction mixture was cooled to room temperature, 900mL of water was added thereto, the mixture was extracted with dichloromethane, and the organic layer was separated with anhydrous MgSO₄Drying, concentration, and recrystallization from ethyl acetate afforded b-1(32.23g, 88% yield); HPLC purity is more than or equal to 99.74 percent. Mass spectrum m/z: 305.1595 (theoretical value: 305.1587).

Preparation of d-1

Mixing b-1(101.00mmol, 30.82g), c-1(100.00mmol, 19.15g), Pd (PPh)₃)₄(2.00mmol, 2.31g) and K₂CO₃(200.00mmol, 27.64g) and 300mL of toluene, 100mL of ethanol and 100mL of water are mixed and added into a reaction bottle, the reaction system is replaced by nitrogen, the reaction is stopped after reacting for 2h under the reflux condition, the reaction is cooled to room temperature, a filter cake is obtained by suction filtration, and the filter cake is treated by using ABenzene/ethanol ═ 10: 3 recrystallization to give d-1(24.63g, 85% yield); the HPLC purity is more than or equal to 99.71 percent. Mass spectrum m/z: 289.0669 (theoretical value: 289.0658).

Preparation of e-1

D-1(80.00mmol, 23.18g) and B₂Pin₂(88.00mmol, 22.35g) was dissolved in anhydrous dioxane (750mL) and Pd (dppf) Cl was added thereto₂(2.40mmol, 1.76g) and KOAc (240.00mmol, 23.55g), the reaction system was replaced with nitrogen, the reaction was stirred for 3.5 hours while heating, the reaction was stopped, the mixture was cooled to room temperature, 800mL of water was added thereto, the mixture was extracted with dichloromethane, and the organic layer was separated with anhydrous MgSO₄Drying, concentration, and recrystallization from ethyl acetate afforded e-1(25.32g, 83% yield); the HPLC purity is more than or equal to 99.65 percent. Mass spectrum m/z: 381.1915 (theoretical value: 381.1900).

Preparation of g-1

E-1(60.60mmol, 23.11g), f-1(60.00mmol, 13.55g), Pd (dppf) Cl₂(1.20mmol, 0.88g) and KOAc (120.00mmol, 11.78g) were mixed with 180mL of toluene, 75mL of ethanol and 75mL of water, the mixture was charged into a reaction flask, the reaction system was replaced with nitrogen, the reaction was stopped after 3 hours of reaction under reflux, the reaction was cooled to room temperature, a cake was obtained by suction filtration, the cake was washed with ethanol, and the cake was dried with toluene/ethanol (5: 1 recrystallization to give g-1(19.69g, 82% yield); the HPLC purity is more than or equal to 99.57 percent. Mass spectrum m/z: 399.0598 (theoretical value: 399.0582).

Preparation of h-1

Mixing g-1(40.00mmol, 16.01g) with B₂Pin₂(88.00mmol, 22.35g), dissolved well in DMF (400mL), followed by the addition of Pd (dppf) Cl₂(2.40mmol, 1.76g) and KOAc (240.00mmol, 23.55g), the reaction system was replaced with nitrogen, the reaction was stirred for 4 hours while heating, the reaction was stopped, the mixture was cooled to room temperature, water was added to the reaction mixture, the mixture was extracted with dichloromethane, and the organic layer was separated with anhydrous MgSO₄Drying, concentration, and recrystallization from ethyl acetate afforded h-1(18.43g, 79% yield); the HPLC purity is more than or equal to 99.51 percent. Mass spectrum m/z: 583.3081 (theoretical value: 583.3065).

Preparation of Compound 1

H-1(20.00mmol, 11.67g), i-1(40.40mmol, 9.2)8g)，Pd₂(dba)₃(0.40mmol，0.37g)，P(t-Bu)₃(3.20mmol，0.65g)，K₂CO₃(80.00mmol, 11.06g) and THF (100mL), the reaction was replaced with nitrogen, the reaction was stopped after 4h under reflux, cooled to room temperature, filtered to give a cake, the cake was washed with ethanol, and finally the cake was washed with toluene/ethanol ═ 10: 1 recrystallization to give compound 1(11.05g, 77% yield); the HPLC purity is more than or equal to 99.46 percent. Mass spectrum m/z: 717.2431 (theoretical value: 717.2416). Theoretical element content (%) C₅₁H₃₁N₃O₂: c, 85.34; h, 4.35; and N, 5.85. Measured elemental content (%): c, 85.29; h, 4.40; n, 5.79.

Synthesis example 2 Synthesis of Compound 38

The same preparation as in Synthesis example 1 was carried out except for replacing a-1 in Synthesis example 1 with the equimolar of a-38 and replacing i-1 with the equimolar of i-38 to give compound 38(10.36g, yield 84%); the HPLC purity is more than or equal to 99.75 percent. Mass spectrum m/z: 616.2162 (theoretical value: 616.2151). Theoretical element content (%) C₄₄H₂₈N₂O₂: c, 85.69; h, 4.58; n, 4.54. Measured elemental content (%): c, 85.72; h, 4.63; and N, 4.49.

Synthesis example 3 Synthesis of Compound 44

Compound 44(11.09g, yield 80%) was obtained according to the same preparation method as synthetic example 1, substituting a-1 for equimolar a-38, substituting c-1 for equimolar c-44, and substituting i-1 for equimolar i-38 in synthetic example 1; the HPLC purity is more than or equal to 99.63 percent. Mass spectrum m/z: 692.2475 (theoretical value: 692.2464). Theoretical element content (%) C₅₀H₃₂N₂O₂: c, 86.68; h, 4.66; and N, 4.04. Measured elemental content (%)：C,86.73；H,4.70；N,3.99。

Synthesis example 4 Synthesis of Compound 60

Compound 60(10.93g, yield 81%) was obtained according to the same preparation method as synthetic example 1 by substituting a-1 in synthetic example 1 with equimolar a-60, substituting c-1 with equimolar c-44, and substituting i-1 with equimolar i-38; the HPLC purity is more than or equal to 99.69 percent. Mass spectrum m/z: 674.2949 (theoretical value: 674.2933). Theoretical element content (%) C₄₈H₃₈N₂O₂: c, 85.43; h, 5.68; and N, 4.15. Measured elemental content (%): c, 85.38; h, 5.72; n, 4.21.

Synthesis example 5 Synthesis of Compound 90

The same preparation method as in Synthesis example 1 was repeated except for replacing a-1 in Synthesis example 1 with an equimolar amount of a-90 to give compound 90(11.34g, yield 79%); the HPLC purity is more than or equal to 99.57 percent. Mass spectrum m/z: 717.2425 (theoretical value: 717.2416). Theoretical element content (%) C₅₁H₃₁N₃O₂: c, 85.34; h, 4.35; and N, 5.85. Measured elemental content (%): c, 85.29; h, 4.41; n, 5.79.

Synthesis example 6 Synthesis of Compound 99

The same preparation method as in Synthesis example 1 was repeated except for replacing a-1 in Synthesis example 1 with an equimolar amount of a-99 to give compound 99(10.87g, yield 81%); the HPLC purity is more than or equal to 99.68 percent. Mass spectrum m/z: 670.2638 (theoretical value: 670.2620). Theoretical element content (%) C₄₈H₃₄N₂O₂: c, 85.94; h, 5.11; and N, 4.18. Measured elemental content (%): c, 85.88; h, 5.09; and N, 4.24.

Synthesis example 7 Synthesis of Compound 105

The same preparation as in Synthesis example 1 was carried out except for replacing d-1 in Synthesis example 1 with d-105 in an equimolar amount to give compound 105(10.36g, yield 84%); the HPLC purity is more than or equal to 99.77 percent. Mass spectrum m/z: 616.2142 (theoretical value: 616.2151). Theoretical element content (%) C₄₄H₂₈N₂O₂: c, 85.69; h, 4.58; n, 4.54. Measured elemental content (%): c, 85.74; h, 4.61; and N, 4.49.

Synthesis example 8 Synthesis of Compound 116

The same preparation as in Synthesis example 1 was carried out except for replacing e-1 with equimolar b-90 and replacing i-1 with equimolar i-116 in Synthesis example 1 to give compound 116(11.72g, yield 79%); the HPLC purity is more than or equal to 99.54 percent. Mass spectrum m/z: 741.2411 (theoretical value: 741.2416). Theoretical element content (%) C₅₃H₃₁N₃O₂: c, 85.81; h, 4.21; and N, 5.66. Measured elemental content (%): c, 85.78; h, 4.19; n, 5.71.

Synthesis example 9 Synthesis of Compound 133

The same preparation as in Synthesis example 1 was carried out except for replacing d-1 with equimolar d-133 and replacing i-1 with equimolar i-133 in Synthesis example 1 to give compound 133(10.39g, yield 84%); the HPLC purity is more than or equal to 99.76 percent. Mass spectrum m/z: 618.2072 (theoretical value: 618.2056). Theoretical element content(％)C₄₂H₂₆N₄O₂: c, 81.54; h, 4.24; and N, 9.06. Measured elemental content (%): c, 81.49; h, 4.18; and N, 9.12.

Synthesis example 10 Synthesis of Compound 150

The same preparation as in Synthesis example 1 was carried out except that a-1 in Synthesis example 1 was replaced with equimolar a-150 and i-1 was replaced with equimolar i-133 to give compound 150(11.20g, yield 80%); the HPLC purity is more than or equal to 99.61 percent. Mass spectrum m/z: 699.2696 (theoretical value: 699.2683). Theoretical element content (%) C₄₈H₂₅D₅N₄O₂: c, 82.38; h, 5.04; and N, 8.01. Measured elemental content (%): c, 82.43; h, 4.98; and N, 7.99.

Synthesis example 11 Synthesis of Compound 156

Compound 156 was obtained (12.15g, yield 78%) by the same preparation method as in Synthesis example 1 except that a-1 in Synthesis example 1 was replaced with equimolar a-156, c-1 was replaced with equimolar c-156, and i-1 was replaced with equimolar i-156; the HPLC purity is more than or equal to 99.46 percent. Mass spectrum m/z: 778.3056 (theoretical value: 778.3056). Theoretical element content (%) C₅₂H₃₈N₆O₂: c, 80.18; h, 4.92; n, 10.79. Measured elemental content (%): c, 80.23; h, 4.87; n, 10.83.

Synthesis example 12 Synthesis of Compound 185

Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-38 and i-1 was replaced with equimolar i-185, and the same procedure as in Synthesis example 1 was repeatedPreparation gave compound 185(10.39g, 84% yield); the HPLC purity is more than or equal to 99.78 percent. Mass spectrum m/z: 618.2041 (theoretical value: 618.2056). Theoretical element content (%) C₄₂H₂₆N₄O₂: c, 81.54; h, 4.24; and N, 9.06. Measured elemental content (%): c, 81.49; h, 4.18; and N, 9.12.

Synthesis example 13 Synthesis of Compound 219

The same preparation as in Synthesis example 1 was carried out except for replacing a-1 in Synthesis example 1 with an equimolar of a-38 and replacing i-1 with an equimolar of i-219, to give compound 219(12.18g, yield 79%); the HPLC purity is more than or equal to 99.48 percent. Mass spectrum m/z: 770.2695 (theoretical value: 770.2682). Theoretical element content (%) C₅₄H₃₄N₄O₂: c, 84.14; h, 4.45; and N, 7.27. Measured elemental content (%): c, 84.09; h, 4.39; n, 7.33.

Synthesis example 14 Synthesis of Compound 227

The same preparation as in Synthesis example 1 was carried out except for replacing a-1 in Synthesis example 1 with an equimolar a-90 and replacing i-1 with an equimolar i-227 to give 227(11.08g, yield 77%); the HPLC purity is more than or equal to 99.54 percent. Mass spectrum m/z: 719.2337 (theoretical value: 719.2321). Theoretical element content (%) C₄₉H₂₉N₅O₂: c, 81.76; h, 4.06; n, 9.73. Measured elemental content (%): c, 81.81; h, 4.10; and N, 9.68.

Synthesis example 15 Synthesis of Compound 237

D-1 in Synthesis example 1 was substitutedThe same preparation as in synthetic example 1 was carried out for the same moles of d-237 instead of i-1 for the same moles of i-237, to give 237 compound (11.26g, yield 81%); the HPLC purity is more than or equal to 99.64 percent. Mass spectrum m/z: 694.2352 (theoretical value: 694.2369). Theoretical element content (%) C₄₈H₃₀N₄O₂: c, 82.98; h, 4.35; and N, 8.06. Measured elemental content (%): c, 83.02; h, 4.29; n, 8.11.

Synthesis example 16 Synthesis of Compound 239

Compound 239(11.12g, yield 80%) was obtained according to the same preparation method as in synthesis example 1, substituting d-1 for equimolar d-239 and substituting i-1 for equimolar i-239 in synthesis example 1; the HPLC purity is more than or equal to 99.65 percent. Mass spectrum m/z: 694.2356 (theoretical value: 694.2369). Theoretical element content (%) C₄₈H₃₀N₄O₂: c, 82.98; h, 4.35; and N, 8.06. Measured elemental content (%): c, 83.03; h, 4.40; and N, 8.01.

Synthesis example 17 Synthesis of Compound 260

Preparation of i' -260

J-260(101.00mmol, 15.89g), i-260(100.00mmol, 19.90g), Pd (PPh)₃)₄(2.00mmol, 2.31g) and K₂CO₃(200.00mmol, 27.64g) and 300mL of toluene, 100mL of ethanol, 100mL of water were mixed and charged into a reaction flask, the reaction system was replaced with nitrogen, the reaction was stopped after 2 hours of reaction under reflux, the reaction was cooled to room temperature, and a cake was obtained by suction filtration, and the cake was cooled with a toluene/ethanol ratio of 5: 1 recrystallization to give i' -260(19.69g, 85% yield); the HPLC purity is more than or equal to 99.77 percent. Mass spectrum m/z: 231.0212 (theoretical value: 231.0199).

Preparation of Compound 260

The same preparation as in Synthesis example 1 was carried out except for replacing d-1 with equimolar d-133 and replacing i-1 with equimolar i' -260 to give compound 260(10.43g, yield 84%); HPLC purity is more than or equal to 99.74 percent. Mass spectrum m/z: 620.1979 (theoretical value: 620.1961). Theoretical element content (%) C₄₀H₂₄N₆O₂: c, 77.41; h, 3.90; n, 13.54. Measured elemental content (%): c, 77.36; h, 3.87; and N, 13.60.

Synthesis example 18 Synthesis of Compound 265

Preparation of i' -265

The same preparation method as that for i '-260 in Synthesis example 17 was followed except that j-260 in Synthesis example 17 was replaced with equimolar j-265 and i-260 was replaced with equimolar i-265 to give i' -265(19.92g, yield 86%); the HPLC purity is more than or equal to 99.75 percent. Mass spectrum m/z: 231.0211 (theoretical value: 231.0199).

Preparation of Compound 265

The same preparation as in Synthesis example 1 was carried out except for replacing a-1 in Synthesis example 1 with equimolar a-60 and replacing i-1 with equimolar i' -265 to give 265(11.78g, yield 78%); the HPLC purity is more than or equal to 99.53 percent. Mass spectrum m/z: 754.3067 (theoretical value: 754.3056). Theoretical element content (%) C₅₀H₃₈N₆O₂: c, 79.55; h, 5.07; n, 11.13. Measured elemental content (%): c, 79.60; h, 5.11; n, 11.07.

[ Synthesis example 19] Synthesis of Compound 269

Preparation of i' -269

The same preparation method as that for i '-260 in Synthesis example 17 was followed except that j-260 in Synthesis example 17 was replaced with equimolar j-269 and i-260 was replaced with equimolar i-265 to give i' -269(19.54g, yield 84%); HPLC purity is more than or equal to 99.73 percent. Mass spectrum m/z: 232.0170 (theoretical value: 232.0152).

Preparation of Compound 269

The same preparation as in Synthesis example 1 was carried out except for replacing e-1 by equimolar b-150 and replacing i-1 by equimolar i' -269 in Synthesis example 1 to give compound 269(10.29g, yield 82%); the HPLC purity is more than or equal to 99.70 percent. Mass spectrum m/z: 627.2171 (theoretical value: 627.2180). Theoretical element content (%) C₃₈H₁₇D₅N₈O₂: c, 72.72; h, 4.33; n, 17.85. Measured elemental content (%): c, 72.68; h, 4.29; n, 17.91.

Synthesis example 20 Synthesis of Compound 270

Preparation of i' -270

The same preparation method as that for i '-260 in Synthesis example 17 was followed except that j-260 in Synthesis example 17 was replaced with equimolar j-270 and i-260 was replaced with equimolar i-270, to give i' -270(19.39g, yield 83%); the HPLC purity is more than or equal to 99.70 percent. Mass spectrum m/z: 233.0120 (theoretical value: 233.0104).

Preparation of Compound 270

The same preparation as in Synthesis example 1 was carried out except for replacing d-1 with equimolar d-270 and replacing i-1 with equimolar i' -270 to give compound 270(10.39g, yield 80%); the HPLC purity is more than or equal to 99.68 percent. Mass spectrum m/z: 649.1735 (theoretical value: 649.1723). Theoretical element content (%) C₃₇H₁₉N₁₁O₂: c, 68.41; h, 2.95; n, 23.72. Measured elemental content (%): c, 68.37; h, 3.01; n, 23.68.

[ Synthesis example 21] Synthesis of Compound 283

Preparation of i' -283

The same preparation method as that for i '-260 in Synthesis example 17 was repeated except for replacing j-260 with equimolar j-269 and replacing i-260 with equimolar i-270 to give i' -283(19.62g, yield 84%); the HPLC purity is more than or equal to 99.71 percent. Mass spectrum m/z: 233.0123 (theoretical value: 233.0104).

Preparation of Compound 283

Compound 283(12.37g, yield 79%) was obtained according to the same preparation method as that of Synthesis example 1 except that a-1 in Synthesis example 1 was replaced with equimolar a-156 and i-1 was replaced with equimolar i' -283; the HPLC purity is more than or equal to 99.44 percent. Mass spectrum m/z: 782.2879 (theoretical value: 782.2866). Theoretical element content (%) C₄₈H₃₄N₁₀O₂: c, 73.64; h, 4.38; and N, 17.89. Measured elemental content (%): c, 73.59; h, 4.41; n, 17.93.

Synthesis example 22 Synthesis of Compound 290

Preparation of i' -290

The same preparation method as that for i '-260 in Synthesis example 17 was followed except that j-260 in Synthesis example 17 was replaced with equimolar j-265 and i-260 was replaced with equimolar i-290 to give i' -290(18.53g, yield 80%); HPLC purity is more than or equal to 99.74 percent. Mass spectrum m/z: 231.0214 (theoretical value: 231.0199).

Preparation of Compound 290

Compound 290(12.14g, yield 78%) was obtained according to the same preparation method as in Synthesis example 1, except that a-1 in Synthesis example 1 was replaced with equimolar a-150, c-1 was replaced with equimolar c-44, and i-1 was replaced with equimolar i' -290; the HPLC purity is more than or equal to 99.47 percent. Mass spectrum m/z: 777.2915 (theoretical value: 777.2901). Theoretical element content (%) C₅₂H₂₇D₅N₆O₂: c, 80.29; h, 4.79; n, 10.80. Measured elemental content (%): c, 80.34; h, 4.82; n, 10.76.

Synthesis example 23 Synthesis of Compound 309

The same preparation as in Synthesis example 1 was carried out except for replacing d-1 with equimolar d-309 and replacing i-1 with equimolar i' -290 to give compound 309(11.15g, yield 80%); the HPLC purity is more than or equal to 99.63 percent. Mass spectrum m/z: 696.2263 (theoretical value: 696.2274). Theoretical element content (%) C₄₆H₂₈N₆O₂: c, 79.30; h, 4.05; and N, 12.06. Measured elemental content (%): c, 79.24; h, 4.10; n, 12.11.

Synthesis example 24 Synthesis of Compound 350

The same preparation as in Synthesis example 1 was carried out except for replacing e-1 with equimolar b-150 and replacing i-1 with equimolar i-350 in Synthesis example 1 to give compound 350(10.72g, yield 82%); the HPLC purity is more than or equal to 99.71 percent. Mass spectrum m/z: 653.2023 (theoretical value: 653.2008). Theoretical element content (%) C₄₄H₂₃D₅N₂S₂: c, 80.82; h, 5.09; and N, 4.28. Measured elemental content (%): c, 80.78; h, 5.11; n, 4.34.

[ Synthesis example 25] Synthesis of Compound 386

The same preparation as in Synthesis example 1 was carried out except that a-1 in Synthesis example 1 was replaced with an equimolar of a-38 and i-1 was replaced with an equimolar of i-386 to give a compound 386(10.54g, yield 81%); the HPLC purity is more than or equal to 99.76 percent. Mass spectrum m/z: 650.1612 (theoretical value: 650.1599). Theoretical element content (%) C₄₂H₂₆N₄S₂: c, 77.51; h, 4.03; and N, 8.61. Measured elemental content (%): c, 77.49; h, 3.98; n, 8.67.

[ Synthesis example 26] Synthesis of Compound 399

Compound 399(10.67g, yield 82%) was obtained according to the same preparation method as synthetic example 1, substituting d-1 for equimolar d-399 and i-1 for equimolar i-399 in synthetic example 1; the HPLC purity is more than or equal to 99.72 percent. Mass spectrum m/z: 650.1615 (theoretical value: 650.1599). Theoretical element content (%) C₄₂H₂₆N₄S₂: c, 77.51; h, 4.03; and N, 8.61. Measured elemental content (%): c, 77.47; h, 4.08; and N, 8.58.

Synthesis example 27 Synthesis of Compound 423

Preparation of i' -423

The same preparation method as that for i '-260 in Synthesis example 17 was followed except that i-260 in Synthesis example 17 was replaced with equimolar i-399 to give i' -423(20.31g, yield 82%); HPLC purity is more than or equal to 99.73 percent. Mass spectrum m/z: 246.9982 (theoretical value: 246.9971).

Preparation of Compound 423

Compound 423(12.21g, yield 78%) was obtained according to the same preparation method as Synthesis example 1 except that a-1 in Synthesis example 1 was replaced with equimolar a-423, c-1 was replaced with equimolar c-156, and i-1 was replaced with equimolar i' -423; the HPLC purity is more than or equal to 99.42 percent. Mass spectrum m/z: 782.2297 (theoretical value: 782.2286). Theoretical element content (%) C₅₀H₃₄N₆S₂: c, 76.70; h, 4.38; n, 10.73. Measured elemental content (%): c, 76.68; h, 4.43; n, 10.69.

Synthesis example 28 Synthesis of Compound 449

Compound 449(11.16g, yield 81%) was obtained according to the same preparation method as in synthesis example 1 except that a-1 in synthesis example 1 was replaced with equimolar a-449 and i-1 was replaced with equimolar i-449; HPLC purity is more than or equal to 99.67%. Mass spectrum m/z: 688.1741 (theoretical value: 688.1755). Theoretical element content (%) C₄₅H₂₈N₄S₂: c, 78.46; h, 4.10; and N, 8.13. Measured elemental content (%): c, 78.51; h, 4.07; and N, 8.09.

Synthesis example 29 Synthesis of Compound 450

Preparation of g-450

B-38(60.60mmol, 21.59g), f-450(60.00mmol, 15.62g), Pd (dppf) Cl₂(1.20mmol, 0.88g) and K₂CO₃(120.00mmol, 16.58g), 180mL of toluene, 60mL of ethanol and 60mL of water, and the mixture is added into a reaction bottle, the reaction system is replaced by nitrogen, the mixture reacts for 3 hours under the reflux condition, the reaction is stopped, the reaction mixture is cooled to room temperature and filtered to obtain a filter cake, and the filter cake is filtered by using a toluene/ethanol ratio of 5: 1 recrystallization to give g-450(20.90g, 85% yield); HPLC purity is more than or equal to 98.73 percent. Mass spectrum m/z: 408.0247 (theoretical value: 408.0239).

Preparation of h-450

Mixing g-450(40.00mmol, 16.39g) and B₂Pin₂(132.00mmol, 33.52g) well dissolved in DMF (600mL) was added Pd (dppf) Cl in that order₂(3.60mmol, 2.63g) and KOAc (360.00mmol, 35.33g), the reaction system was replaced with nitrogen, the reaction was stirred for 4 hours while heating, the reaction was stopped, the mixture was cooled to room temperature, 900mL of water was added thereto, the mixture was extracted with dichloromethane, and the organic layer was separated with anhydrous MgSO₄Drying, concentration, and recrystallization from ethyl acetate afforded h-450(22.72g, 83% yield); HPLC purity is more than or equal to 98.69 percent. Mass spectrum m/z: 684.3972 (theoretical value: 684.3965).

Preparation of Compound 450

H-450(20.00mmol, 13.69g), i-38(60.60mmol, 12.00g), Pd₂(dba)₃(0.60mmol，0.55g)，P(t-Bu)₃(4.80mmol，0.97g)，K₂CO₃(120.00mmol, 16.59g) and THF (120mL), wherein a reaction system is replaced by nitrogen, the reaction is stopped after 4.5 hours of reaction under the reflux condition, the reaction is cooled to room temperature, a filter cake is obtained by suction filtration, the filter cake is washed by ethanol, and finally the filter cake is recrystallized by toluene to obtain a compound 450(10.79g, yield 82%); HPLC purity is more than or equal to 99.73 percent. Mass spectrum m/z: 657.2068 (theoretical value: 657.2052). Theoretical element content (%) C₄₅H₂₇N₃O₃: c, 82.18; h, 4.14; and N, 6.39. Measured elemental content (%): c, 82.23; h, 4.09; and N, 6.41.

Synthesis example 30 Synthesis of Compound 458

The same procedures used in Synthesis example 31 were repeated except for replacing b-38 with equivalent mol of e-150 and replacing i-38 with equivalent mol of i-270 to give compound 458(10.83g, yield 81%); the HPLC purity is more than or equal to 99.71 percent. Mass spectrum m/z: 668.2069 (theoretical value: 668.2081). Theoretical element content (%) C₃₉H₁₆D₅N₉O₃: c, 70.05; h, 3.92; n, 18.85. Measured elemental content (%): c, 70.10; h, 3.86; n, 18.91.

[ Synthesis example 31] Synthesis of Compound 459

The same preparation method as in synthetic example 31 was repeated except for replacing i-38 in synthetic example 29 with equimolar i' -290 to give compound 459(13.74g, yield 77%); the HPLC purity is more than or equal to 99.41 percent. Mass spectrum m/z: 891.2718 (theoretical value: 891.2706). Theoretical element content (%)C₅₇H₃₃N₉O₃: c, 76.76; h, 3.73; n, 14.13. Measured elemental content (%): c, 76.81; h, 3.69; n, 14.08.

Device examples 1 to 6

The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. Vacuum evaporation MoO layer by layer on ITO glass substrate₃The evaporation thickness of the compound 219 of the invention is 10nm, the evaporation thickness of the compound is 60nm, and MoO₃The thickness of the vapor deposition is 10nm, the thickness of the vapor deposition is 100 nm.

Device embodiments 2 to 6: a single carrier device was prepared by applying the same procedure as in device example 1 except that the inventive compound 227, 239, 260, 270, 386 was used instead of the inventive compound 219 in device example 1, respectively.

Comparative example 1: a single carrier device was prepared using the same procedure as in device example 1, except that the compound 219 of the present invention in device example 1 was replaced with comparative compound 4.

Fig. 1 is a current-voltage curve diagram of a single-carrier device prepared according to an embodiment of the present invention, and it can be seen from fig. 1 that in a region having a diode effect, the slope of the curve corresponding to the compounds 219, 227, 239, 260, 270, 386 is significantly greater than the slope of the curve corresponding to the comparative compound 4, which proves that the compound of the present invention has high electron mobility and is beneficial to electron injection and transport.

Device examples 7 to 26

The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. HI-1 is evaporated on the ITO glass substrate in vacuum to be used as a hole injection layer, and the evaporation thickness is 15 nm; evaporating HT-1 on the hole injection layer in vacuum to form a hole transport layer, wherein the evaporation thickness is 80 nm; vacuum evaporating RH, RD, 98:2 on the hole transport layer to form a light emitting layer, wherein the evaporation thickness is 20 nm; the compound 1 of the invention is vacuum evaporated on the luminescent layer to be used as an electron transport layer, and the evaporation thickness is 30 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1 nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70 nm.

Device examples 8 to 26: an organic electroluminescent device was produced by using the same procedure as in device example 7 except that compound 38, 60, 90, 99, 116, 133, 156, 219, 227, 239, 265, 269, 270, 309, 350, 386, 449, 450, 467 according to the present invention was used as an electron transporting material in place of compound 1 according to the present invention in device example 7, respectively.

Comparative examples 2 to 5: an organic electroluminescent device was produced by using the same procedure as in device example 7 except that compound 1 of the present invention in device example 7 was replaced with compound 1, compound 2, compound 3 and compound 4 as an electron transport layer, respectively.

The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative materials.

Table 1 test of light emitting characteristics of organic electroluminescent device

As can be seen from the results in Table 1, the organic electroluminescent element of the present invention has advantages of high luminous efficiency and long life as compared with comparative examples 2 to 5.

Device examples 27 to 47

The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. HI-1 is evaporated on the ITO glass substrate in vacuum to be used as a hole injection layer, and the evaporation thickness is 15 nm; evaporating HT-1 on the hole injection layer in vacuum to form a hole transport layer, wherein the evaporation thickness is 80 nm; vacuum evaporating RH, RD, 98:2 on the hole transport layer to form a light emitting layer, wherein the evaporation thickness is 20 nm; the compound 1 of the invention is vacuum evaporated on the luminescent layer to be used as a hole blocking layer, and the evaporation thickness is 10 nm; evaporating ET-1 on the hole blocking layer to form an electron transport layer, wherein the evaporation thickness is 25 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1 nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70 nm.

Device examples 28 to 47: an organic electroluminescent device was produced by using the same procedure as in device example 27 except that compound 44, 60, 90, 105, 116, 150, 185, 219, 227, 239, 260, 265, 269, 270, 283, 290, 350, 386, 423, 459, respectively, of the present invention was used instead of compound 1 of the present invention as a hole blocking material in device example 27.

Comparative examples 6 to 9: an organic electroluminescent device was produced by using the same procedure as in device example 27 except that compound 1 of the present invention in device example 27 was replaced with compound 1, compound 2, compound 3 and compound 4 as a hole-blocking material, respectively.

The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 2. Table 2 shows the results of the test of the light emitting characteristics of the organic electroluminescent devices prepared by the compounds prepared in the inventive examples and the comparative materials.

Table 2 test of light emitting characteristics of organic electroluminescent device

As can be seen from the results in Table 2, the organic electroluminescent device of the present invention exhibits advantages of high luminous efficiency and long life as compared with comparative examples 6 to 9.

Device examples 48 to 53

The glass substrate was ultrasonically cleaned by 5% glass cleaning solution for 2 times, each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times, each for 10 minutes. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. ITO/Ag/ITO is used as an anode on the glass substrate; vacuum evaporating HI-1 on the anode to form a hole injection layer with the thickness of 20 nm; evaporating HT-1 on the hole injection layer in vacuum to form a hole transport layer, wherein the evaporation thickness is 100 nm; vacuum evaporating RH, RD, 98:2 on the hole transport layer to form a light emitting layer, wherein the evaporation thickness is 20 nm; performing vacuum evaporation on the light-emitting layer to form ET-1 as an electron transport layer, wherein the evaporation thickness is 28 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1 nm; vacuum evaporation of Mg on the electron injection layer: ag 1:9 as a cathode, and the thickness was 15 nm. The compound 105 of the present invention was vacuum-evaporated as a capping layer material on the cathode to a thickness of 70 nm.

Device examples 49 to 53: an organic electroluminescent device was produced by using the same procedure as in device example 48 except that the compound of the invention 105 in device example 48 was replaced with the compound of the invention 237, 269, 309, 399, 423 as a capping layer material, respectively.

Comparative example 10: an organic electroluminescent device was produced by using the same procedure as in device example 48 except that comparative compound 3 was used as a covering layer material instead of inventive compound 105 in device example 48.

The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 3. Table 3 shows the results of the test of the light emitting characteristics of the organic electroluminescent devices prepared by the compounds prepared in the inventive examples and the comparative materials.

Table 3 test of light emitting characteristics of organic electroluminescent device

As can be seen from the results of table 3, the organic electroluminescent device of the present invention exhibited an advantage of high luminous efficiency as compared to comparative example 10.

It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims

1. An oxazole or thiazole compound, which has a structure represented by chemical formula 1,

said X₁Selected from O or S;

k is₁Selected from 2,3, 4 or 5;

n is₁、n₂The same or different is selected from 0,1 or 2;

2. An oxazole or thiazole compound according to claim 1, wherein the oxazole or thiazole compound has a structure represented by chemical formula 1-1 to chemical formula 1-4,

m is₁Selected from 0,1, 2 or 3; m is₂Selected from 0,1 or 2; m is₃Is selected from 0 or 1; when m is₁、m₂Greater than 1, two or more R₀The same or different from each other.

3. An oxazole or thiazole compound according to claim 1, wherein said oxazole or thiazole compound is

Having any one of the structures shown below,

4. An oxazole or thiazole compound according to claim 1, wherein said Ar is₁、Ar₂The same or different structures are selected from the structures shown below,

5. An oxazole or thiazole compound according to claim 1, wherein said Ar is₁、Ar₂The same or different is selected from any one of the structures shown below,

6. an oxazole or thiazole compound according to claim 1, wherein said L is₁The same or different is selected from any one of the structures shown below,

wherein, R is₇The same or different one selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C2-C12 heteroaryl;

b is₁Identical or different integers from 0,1, 2,3 or 4, b₂Identical or different integers from 0,1, 2,3, 4,5 or 6, b₃Identical or different integers from 0,1, 2,3, 4,5, 6,7 or 8, b₄The same or different are selected from 0,1.2 or 3, b₅Identical or different integers from 0,1 or 2, b₆Identical or different integers from 0,1, 2,3, 4 or 5, when b₁、b₂、b₃、b₄、b₅、b₆Greater than 1, two or more R₆The same or different from each other.

7. An oxazole or thiazole compound according to claim 1, wherein said oxazole or thiazole compound is selected from any one of the following structures,

8. an organic electroluminescent device comprising an anode, a cathode, and an organic layer, wherein the organic layer comprises at least one of an oxazole or thiazole compound according to any one of claims 1 to 7.

9. An organic electroluminescent device according to claim 8, wherein the organic layer is located between the anode and the cathode, wherein the organic layer comprises at least one of an electron transport layer or a hole blocking layer, and the electron transport layer or the hole blocking layer comprises at least one of an oxazole or thiazole compound according to claims 1 to 7.

10. An organic electroluminescent device according to claim 8, wherein the organic layer is located outside the cathode, and the organic layer comprises a capping layer comprising at least one of an oxazole or thiazole compound according to any one of claims 1 to 7.