CN115784970A

CN115784970A - Pyrene organic compound, mixture, composition and organic electronic device

Info

Publication number: CN115784970A
Application number: CN202111055692.6A
Authority: CN
Inventors: 宋鑫龙; 肖志华; 何锐锋; 宋晶尧
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2021-09-09
Filing date: 2021-09-09
Publication date: 2023-03-14

Abstract

The invention relates to a pyrene organic compound, a mixture, a composition and an organic electronic device. The pyrene organic compound has a structure represented by formula (I), and has fluorescence emission with a short wavelength, and exhibits deep blue fluorescenceAnd (4) shooting. The pyrene organic compound provided by the invention is used as an object luminescent material in a luminescent layer of an organic electronic device, so that the luminescent efficiency and the service life of the organic electronic device can be effectively improved.

Description

Pyrene organic compound, mixture, composition and organic electronic device

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to a pyrene organic compound, a mixture, a composition and an organic electronic device.

Background

Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the synthetic versatility of organic semiconductor materials, relatively low manufacturing costs, and excellent optical and electrical properties.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.

In order to improve the light emitting efficiency of the organic electroluminescent device, various fluorescent and phosphorescent light emitting material systems have been developed, and the development of excellent blue light emitting materials, whether fluorescent materials or phosphorescent materials, is a great challenge, and in general, the reliability of the currently used blue light emitting materials of the organic light emitting diode is higher. However, most of the blue fluorescent materials have too wide emission spectrum, poor color purity, and are not suitable for high-end display, and the synthesis of such fluorescent materials is complicated, which is not suitable for mass production, and the OLED stability of such blue fluorescent materials needs to be further improved. Therefore, the development of the blue fluorescent material with narrow-band emission spectrum and good stability is beneficial to obtaining a blue light device with longer service life and higher efficiency on the one hand, and is beneficial to improving the color gamut on the other hand, thereby improving the display effect.

The luminescent layer of the blue organic electroluminescent element in the prior art adopts a host-guest doped structure. As for the prior blue light host material, anthracene-based fused ring derivatives are disclosed in patent nos. CN1914293B, CN102448945B, US2015287928A1, etc., however, these compounds have problems of insufficient luminous efficiency and brightness, and poor device lifetime. As blue-light-emitting guest compounds of the prior art, aryl vinyl amine compounds are used (WO 04/013073A1, WO04/016575A1, WO04/018587A 1). However, these compounds have poor thermal stability and are easily decomposed, resulting in a short device life, which is the most important drawback in the industry at present. Further, these compounds have poor color purity, and it is difficult to realize deep blue light emission. Further, although patents such as US7233019B2 and KR20060006760A disclose organic electroluminescent elements using pyrene-based compounds having arylamine substituents, they have a problem in full-color displays that exhibit natural colors because deep blue light emission is difficult to achieve due to low color purity of blue light.

Therefore, there is still a need for further improvement of materials, in particular light-emitting compounds, especially blue light-emitting compounds. Blue light emitting materials are enabled to have deep blue light emission, and they are thermally stable, have good efficiency and life in organic electroluminescent elements, are easily repeated in the manufacture and operation of devices, and are simple in material synthesis.

Disclosure of Invention

Based on this, the invention aims to provide a pyrene organic compound, a mixture, a composition and an organic electronic device, which can improve the efficiency and the service life of the device.

The technical scheme is as follows:

a pyrene organic compound has a structure represented by the general formula (I):

wherein:

Ar ₁ -Ar ₄ each occurrence is independently selected from a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms;

and Ar ₁ -Ar ₄ At least one of which is selected from formula (II):

w is independently selected from O, S, CR for each occurrence ₁₂ R ₁₃ Or NR ₁₄ ；

* Represents a linking site;

R ₁₀ ，R ₁₁ each occurrence is independently selected from a straight chain alkyl group having 1 to 20C atoms, or a branched chain alkyl group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms;

l is selected from a single bond, or a substituted or unsubstituted aromatic group with 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group with 5 to 30 ring atoms;

R ₁ -R ₉ ，R ₁₂ -R ₁₄ each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 20C atoms, a straight chain alkoxy group having 1 to 20C atoms, a straight chain thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, a branched alkoxy group having 3 to 20C atoms, a branched thioalkoxy group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, aRadicals, isocyano, isocyanato, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, -CF ₃ -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

n is selected from 0,1,2,3 or 4.

The invention also provides a mixture which comprises the pyrene organic compound and an organic functional material, wherein the organic functional material is at least one selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.

The invention also provides a composition which comprises the pyrene organic compound or the mixture and at least one organic solvent.

The invention also provides an organic electronic device, which comprises a first electrode, a second electrode and one or more organic functional layers positioned between the first electrode and the second electrode, wherein the organic functional layers comprise the pyrene organic compound or the mixture or are prepared from the composition.

The invention has the following beneficial effects:

the pyrene organic compound provided by the invention has deep blue fluorescence emission. The pyrene organic compound provided by the invention is used as an object luminescent material, is matched with a host material, and is used in a luminescent layer of an organic electronic device together, so that the luminescent efficiency and the service life of the organic electronic device can be effectively improved.

Drawings

FIG. 1 is a schematic diagram of an OLED structure according to one embodiment of the present invention;

FIG. 2 is a mass spectrum of Compound 3;

FIG. 3 is a mass spectrum of Compound 8.

Detailed Description

The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the present invention, the term "comprising" means "including but not limited to". The term "plurality" means "two or more". Various embodiments of the invention may exist in a range of forms; it should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the application; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range of numbers, such as 1,2,3,4,5, and 6, for example, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated. Any integer between 0 and 8, including 0,1,2,3,4,5,6,7, and 8.

In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.

In the present invention, the aromatic groups, aromatic groups and aromatic ring systems have the same meaning and are interchangeable.

In the context of the present invention, heteroaromatic groups, heteroaromatic and heteroaromatic ring systems have the same meaning and are interchangeable.

In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1 to 20C atoms, heterocyclic group containing 3 to 20 ring atoms, aromatic group containing 6 to 20 ring atoms, heteroaromatic group containing 5 to 20 ring atoms, -NR' R ", silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted with art-acceptable substituents; understandably, -NR 'R "wherein R' and R" are each independently selected from, but not limited to: H. deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1 to 10C atoms, heterocyclic group containing 3 to 20 ring atoms, aromatic group containing 6 to 20 ring atoms, heteroaromatic group containing 5 to 20 ring atoms.

In the present invention, halogen means fluorine F, chlorine Cl, bromine Br or iodine I.

In the present invention, the "number of ring atoms" represents the number of atoms among the atoms constituting the ring itself of a structural compound (for example, monocyclic compound, condensed ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound) in which the atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

In the present application, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1-20,1-10, or 1-6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the like.

"aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aromatic group, or a fused ring aromatic group, or a polycyclic aromatic group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "a substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, fluoranthenyl, phenanthrenyl, benzophenanthrenyl, perylenyl, tetracenyl, pyrenyl, benzopyrenyl, acenaphthenyl, fluorenyl and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as in particular acenaphthene, fluorene, or 9, 9-diarylfluorene, triarylamine, diarylether systems should also be included in the definition of aryl groups.

"heteroaryl or heteroaromatic group" means that on the basis of an aryl group at least one carbon atom is replaced by a non-carbon atom which may be a N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" means heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted, suitable examples include, but are not limited to: triazinyl, pyridyl, pyrimidinyl, imidazolyl, furyl, thienyl, benzofuryl, benzothienyl, indolyl, carbazolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furopyrrolyl, furofuryl, thienofuryl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, phenanthridinyl, primidinyl, quinazolinyl, dibenzothienyl, dibenzofuryl, carbazolyl, and derivatives thereof.

The term "alkoxy" refers to a group having an-O-alkyl group, i.e., an alkyl group as defined above attached to the parent core structure via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH) ₃ Or OMe), ethoxy (-O-CH) ₂ CH ₃ or-OEt) and t-butoxy (-O-C (CH) ₃ ) ₃ or-OtBu).

In the present invention, the abbreviations for the substituents correspond to: n-, sec-, i-iso-, t-tert-, o-, m-, p-, me methyl-, et ethyl-, pr propyl-, bu-butyl-, am-n-pentyl-, hxhexyl-, cy-cyclohexyl-.

In the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site.

In the present invention, when the fusion site is not specified in the group, it means that an optionally annealable site in the group is a fusion site, and preferably two or more sites in the ortho-position in the group are fusion sites.

In the present invention, when a plurality of substituents of the same symbol are contained on the same group, the substituents may be the same as or different from each other, for example

6R on the benzene ring ¹ May be the same as or different from each other.

In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position of the ring, for example

Wherein R is attached to any substitutable site of the phenyl ring.

In the present invention, cyclic alkyl groups and cycloalkyl groups have the same meaning and may be interchanged with one another.

The expression that two adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring; preferably a 5 or 6 membered ring, such as cyclohexane or adamantane.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy level ET, HOMO, and LUMO play a key role. The determination of these energy levels is described below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

The triplet energy level ET1 of the organic material can be measured by low temperature Time resolved luminescence spectroscopy or can be obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian09W (Gaussian inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

It should be noted that the absolute values of HOMO, LUMO, ET1 depend on the measurement or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiment of the present invention, the values of HOMO, LUMO, and ET1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (LUMO + 1) is defined as the second lowest unoccupied orbital level, (LUMO + 2) is the third lowest occupied orbital level, and so on.

The invention aims to provide a pyrene organic compound and application thereof, which can improve the color purity and the luminous efficiency of a blue luminous body.

The technical scheme is as follows:

wherein:

Ar ₁ -Ar ₄ independently for each occurrence, is selected from a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms;

and Ar ₁ -Ar ₄ At least one of which is selected from formula (II):

* Represents a linking site;

R ₁₀ ，R ₁₁ each timeEach independently selected from a straight chain alkyl group having 1 to 20C atoms, or a branched chain alkyl group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms;

R ₁ -R ₉ ，R ₁₂ -R ₁₄ each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 20C atoms, a straight chain alkoxy group having 1 to 20C atoms, a straight chain thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, a branched alkoxy group having 3 to 20C atoms, a branched thioalkoxy group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amine group, -CF ₃ -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

n is selected from 0,1,2,3 or 4.

In one embodiment, R ₁ -R ₉ ，R ₁₂ -R ₁₄ Each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 10C atoms, a straight chain alkoxy group having 1 to 10C atoms, a straight chain thioalkoxy group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, a branched alkoxy group having 3 to 10C atoms, a branched thioalkoxy group havingA cyclic alkyl group of 3 to 10C atoms, a cyclic alkoxy group of 3 to 10C atoms, or a cyclic thioalkoxy group of 3 to 10C atoms, or a silyl group, or a keto group of 1 to 10C atoms, or an alkoxycarbonyl group of 2 to 10C atoms, or an aryloxycarbonyl group of 7 to 10C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amine group, a CF group ₃ -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups.

In one embodiment, R ₃ And R ₇ Each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 10C atoms, or a branched chain alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms; further, R ₃ And R ₇ Each occurrence is independently selected from-H, -D, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl or 2- (2-methyl) butyl. Further, R ₃ And R ₇ Selected from the same group. Further, R ₁ -R ₂ And R ₄ -R ₆ And R ₈ -R ₉ Is selected from-H or-D.

In one embodiment, R ₁₂ -R ₁₃ Each timeEach independently selected from-H, -D, a straight chain alkyl group having 1 to 10C atoms, or a branched chain alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or phenyl; further, R ₁₂ -R ₁₃ Each occurrence is independently selected from-H, -D, or methyl, ethyl, or isopropyl, or phenyl.

In one embodiment, R ₁₄ Each occurrence is independently selected from-H, -D, a straight chain alkyl group having from 1 to 10C atoms, or a branched alkyl group having from 3 to 10C atoms, or a cyclic alkyl group having from 3 to 10C atoms, or a substituted or unsubstituted aromatic group having from 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 13 ring atoms; further, R ₁₄ Each occurrence is independently selected from-H, -D, or methyl, ethyl, or isopropyl, or tert-butyl, or phenyl, or pyridyl, or pyrimidinyl, or triazinyl, or naphthyl, or biphenyl, or terphenyl.

In one embodiment, the pyrene-based organic compound is selected from formula (III):

wherein:

Ar ₂ -Ar ₄ each occurrence is independently selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.

In one embodiment, the substituent R in the "substituted or unsubstituted" described herein may be mono-or poly-substituted, preferably selected from a deuterium atom, a cyano group, an isocyano group, a nitro group, a halogen atom, a straight chain alkyl group having 1 to 10C atoms, a branched alkyl group having 1 to 10C atoms, a cycloalkyl group having 1 to 10C atoms, an aromatic group having 6 to 20 ring atoms, or a heteroaromatic group having 6 to 20 ring atoms, or a combination thereof.

In one embodiment, ar in formula (III) ₂ -Ar ₄ Each independently selected from any one of (A-1) to (A-6)The method comprises the following steps:

wherein:

x is selected from N or CR ₁₀₁ ；

Y is selected from O, S = O, SO ₂ 、NR ₁₀₂ 、PR ₁₀₂ 、CR ₁₀₂ R ₁₀₃ Or SiR ₁₀₂ R ₁₀₃ ；

R ₁₀₁ -R ₁₀₃ Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, a keto group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, -CF ₃ -Cl, -Br, -F, or an alkenyl group having 2 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

adjacent R ₁₀₁ Are connected with each other to form a ring or not to form a ring; adjacent R ₁₀₂ And R ₁₀₃ With or without a ring of interconnects.

When X is a linking site, X is selected from C.

In one embodiment, the pyrene-based organic compound is selected from formula (IV):

preferably, ar in formula (IV) ₂ -Ar ₃ Each independently selected from any one of (A-1) to (A-6).

In one embodiment, L is selected from a single bond, or a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms; further, L is selected from a single bond, or phenyl, or biphenyl, or terphenyl, or naphthyl; in one embodiment, L is selected from the same group at multiple occurrences.

In one embodiment, formula (IV) is selected from any one of structures (V-1) to (V-4):

in one embodiment, R ₁₀ ，R ₁₁ Each occurrence is independently selected from a straight chain alkyl group having 1 to 10C atoms, or a branched chain alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms; further, R ₁₀ ，R ₁₁ Each occurrence is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl.

In one embodiment, R ₁₀ ，R ₁₁ Each occurrence is selected from the same group.

In one embodiment, ar in formula (III) ₂ -Ar ₄ And Ar in formula (IV) ₂ -Ar ₃ Each independently selected from the group consisting of:

wherein: r is ₁₀₁ Each occurrence independentlySelected from a linear alkyl group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms;

m1 is selected from 0,1,2,3,4 or 5; m2 is selected from 0,1,2,3 or 4; m3 is selected from 0,1,2 or 3; m4 is selected from 0,1 or 2.

* Indicates the attachment site.

Further, R ₁₀₁ Each occurrence is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl.

In one embodiment, (A-3) is selected from the following structures:

further, (A-3) is selected from the following structures

Wherein: y and R ₁₀₁ As defined above. The possible reasons are: the molecular conjugation is enhanced, so that the whole molecular planarity is better, and the luminous chromaticity of the device is further improved, namely the device is more biased to deep blue light.

In one embodiment of the method of manufacturing the optical fiber,

is selected from

In one embodiment, the compounds of formulae (IV) and (V-1) to (V-4): ar (Ar) ₂ And Ar ₃ Are the same group.

The pyrene organic compound according to the present invention is preferably selected from, but not limited to, the following structures, and the ring hydrogen may be further substituted:

wherein t-Bu is tert-butyl, tAm is tert-amyl, ph is phenyl, iPr is isopropyl, and Et is ethyl.

The pyrene organic compound provided by the invention can be used as an organic functional material to be applied to organic electronic devices, in particular to OLED devices. The organic functional material may be selected from at least one of a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), an Emitter (Emitter), a Host material (Host), and an organic dye.

In one embodiment, the pyrene organic compound according to the present invention is used in a light-emitting layer, and preferably, can be used as a guest material of the light-emitting layer.

The invention further relates to a mixture comprising at least one pyrene-like organic compound as described above and at least one further organic functional material selected from the group consisting of Hole Injection Materials (HIM), hole Transport Materials (HTM), electron Transport Materials (ETM), electron Injection Materials (EIM), electron Blocking Materials (EBM), hole Blocking Materials (HBM), light emitting materials (Emitter), host materials (Host) and organic dyes. Detailed descriptions of various organic functional materials are found in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of this 3 patent document being hereby incorporated by reference.

In one embodiment, the other organic functional material is selected from a host material; further, the other organic functional material is selected from blue light host materials.

The invention also relates to a composition comprising at least one organic compound or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents.

Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, alpha, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like.

Examples of solvents based on aromatic ketones suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like.

Examples of solvents based on aromatic ethers suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylbenylether, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.

Suitable aliphatic ketone-based solvents for the present invention are, but not limited to: 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

Examples of ester-based solvents suitable for the present invention are, but not limited to: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Methyl benzoate, octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The solvents mentioned may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention comprises at least one pyrene-based organic compound, or mixture thereof, as described above, and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

δ d (dispersion force) is in the range of 17.0 to 23.2mpa1/2, especially in the range of 18.5 to 21.0mpa1/2;

δ p (polar power) is in the range of 0.2 to 12.5MPa1/2, particularly in the range of 2.0 to 6.0 MPa1/2;

delta h (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, particularly in the range of 2.0 to 6.0 MPa1/2.

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably more than or equal to 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The compositions of the embodiments of the present invention may comprise from 0.01wt% to 10wt% of a compound or mixture according to the present invention, preferably from 0.1wt% to 5wt%, more preferably from 0.2wt% to 5wt%, and most preferably from 0.25wt% to 3wt%.

The invention also relates to the use of said composition as a coating or printing ink for producing organic electronic components, particularly preferably by printing or coating.

Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like.

The invention also provides application of the pyrene organic compound, the mixture or the composition in an organic electronic device. The technical scheme is as follows:

an organic electronic device comprises a first electrode, a second electrode, and one or more organic functional layers positioned between the first electrode and the second electrode, wherein the organic functional layers comprise the pyrene organic compounds, the mixture or the composition.

Further, the organic electronic device comprises a cathode, an anode and at least one functional layer, wherein the functional layer comprises the pyrene organic compound or the mixture thereof, or is prepared from the composition. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL) and a Hole Blocking Layer (HBL); preferably, the functional layer is selected from a light emitting layer.

The Organic electronic device can be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor (fet), an Organic laser, an Organic spintronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode), and the like, and particularly preferred is an Organic electroluminescent device such as an OLED, an Organic light Emitting field effect transistor (OLED). OLEDs are particularly preferred.

In the above-mentioned light emitting device, especially an OLED, comprises a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al appl. Phys. Lett.1996,68, p2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents being hereby incorporated by reference.

In the embodiment of the present invention, it is preferable that the pyrene-based organic compound be used for a light-emitting layer of an OLED device.

In a preferred embodiment, the pyrene-based organic compound is preferably used as a blue guest material, together with a blue host material, in a light-emitting layer of an OLED device. Further, the blue-light host material is selected from anthracene-based derivatives.

In a preferred embodiment, the light-emitting layer in the light-emitting device of the present invention is prepared using the composition of the present invention.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.

The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

1. Synthesis of Compounds

EXAMPLE 1 Synthesis of Compound 1

Synthesis of intermediates 1 to 3:

compound 1-1 (10 mmol) and compound 1-2 (20 mmol) were dissolved in dichloromethane and stirred at room temperature under nitrogen atmosphere for 6 hours. And (3) after cooling, removing the solvent by rotary evaporation, extracting, washing liquid, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 1-3 with the molar weight of 9.17mmol, and the yield: 91.7 percent. MS (ASAP) =338.

Synthesis of intermediates 1 to 5:

the intermediate 1-3 (10 mmol) and the compound 1-4 (20 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added ₃ ) ₄ (0.1) and potassium carbonate (30 mmol). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, then liquid is extracted and washed by water, an organic phase is collected, and the intermediate 1-5 is obtained after drying, decompression concentration and column chromatography recrystallization, wherein the molar weight is 7.84mmol, and the yield is as follows: 78.4 percent. MS (ASAP) =211.

Synthesis of intermediates 1 to 7:

mixing the intermediates 1-5 (10 mmol), the compounds 1-6 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 1-7 with the molar weight of 7.05mmol, yield: 70.5 percent. MS (ASAP) =287.

Synthesis of Compound (1):

mixing the intermediate 1-7 (20 mmol), the compound 1-8 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 1, wherein the yield is as follows: 76.8 percent. MS (ASAP) =772.

Example 2

Synthesis of intermediates 2 to 3:

compound 2-1 (10 mmol) and compound 1-2 (20 mmol) were dissolved in dichloromethane and stirred at room temperature under nitrogen atmosphere for 6 hours. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 2-3, wherein the molar weight is 8.64mmol, the yield is as follows: 86.4 percent. MS (ASAP) =354.

Synthesis of intermediates 2 to 5:

the intermediate 2-3 (10 mmol) and the compound 1-4 (20 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added ₃ ) ₄ (0.1) and potassium carbonate (30 mmol). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, then liquid is extracted and washed by water, an organic phase is collected, and the intermediate 2-5 is obtained after drying, decompression concentration and column chromatography recrystallization, wherein the molar weight is 7.35mmol, and the yield is as follows: 73.5 percent. MS (ASAP) =227.

Synthesis of intermediates 2 to 7:

mixing the intermediate 2-5 (10 mmol), the compound 1-6 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 2-7 with the molar weight of 5.63mmol, yield: 56.3 percent. MS (ASAP) =303.

Synthesis of Compound (2):

mixing the intermediates 2-7 (20 mmol), the compounds 1-8 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 2, wherein the yield is as follows: 45.9 percent. MS (ASAP) =804.

Example 3

Synthesis of intermediate 3-3:

compound 3-1 (10 mmol) and compound 1-2 (20 mmol) were dissolved in dichloromethane and stirred at room temperature under nitrogen atmosphere for 6 hours. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 3-3, wherein the molar weight is 8.15mmol, the yield is as follows: 81.5 percent. MS (ASAP) =413.

Synthesis of intermediates 3 to 5:

the intermediate 3-3 (10 mmol) and the compound 1-4 (20 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added ₃ ) ₄ (0.1) and potassium carbonate (30 mmol). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, then liquid is extracted and washed by water, an organic phase is collected, and the intermediate 3-5 is obtained after drying, decompression concentration and column chromatography recrystallization, wherein the molar weight is 7.18mmol, and the yield is as follows: 71.8 percent. MS (ASAP) =286.

Synthesis of intermediates 3-7:

mixing the intermediate 3-5 (10 mmol), the compound 1-6 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 3-7 with the molar weight of 5.45mmol, yield: 54.5 percent. MS (ASAP) =362.

Synthesis of Compound (3):

mixing the intermediate 3-7 (20 mmol), the compound 1-8 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the liquid, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 3, wherein the yield is as follows: 43.2 percent. MS (ASAP) =922.

Example 4

Synthesis of Compound (4):

mixing the intermediates 1-7 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. Cooling, rotary evaporating to remove solvent, extracting, and washing with waterSeparating, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain a compound 4, wherein the yield is as follows: 52.3 percent. MS (ASAP) =856.

Example 5

Synthesis of Compound (5):

mixing the intermediate 2-7 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 5, wherein the yield is as follows: 67.3 percent. MS (ASAP) =888.

Example 6

Synthesis of Compound (6):

mixing the intermediate 3-7 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the liquid, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 6, wherein the yield is as follows: 32.7 percent. MS (ASAP) =1006.

Example 7

Synthesis of intermediate 7-2:

mixing the intermediate 1-5 (10 mmol), the compound 7-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. Cooling, removing solvent by rotary evaporation, extracting, washing, collecting organic phase, drying, and reducingPressure concentration and column chromatography are carried out to obtain an intermediate 7-2, the molar weight is 6.82mmol, and the yield is: 68.2 percent. MS (ASAP) =377.

Synthesis of Compound (7):

mixing the intermediate 7-2 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 7, wherein the yield is as follows: and (5) 55.6%. MS (ASAP) =1036.

Example 8

Synthesis of intermediate 8-2:

mixing the intermediate 1-5 (10 mmol), the compound 8-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, removing the solvent by rotary evaporation, extracting, washing the separated liquid with water, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 8-2 with the molar weight of 5.96mmol, and the yield: and (5) 59.6%. MS (ASAP) =329.

Synthesis of Compound (8):

mixing the intermediate 8-2 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the liquid, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 8, wherein the yield is as follows: 70.3 percent. MS (ASAP) =940.

Example 9

Synthesis of intermediate 9-2:

mixing the intermediate 1-5 (10 mmol), the compound 9-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 9-2 with the molar weight of 8.16mmol, yield: 81.6 percent. MS (ASAP) =377.

Synthesis of Compound (9):

mixing the intermediate 9-2 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the liquid, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 9, wherein the yield is as follows: 84.6 percent. MS (ASAP) =1036.

Example 10

Synthesis of intermediate 10-1:

mixing the intermediate 2-5 (10 mmol), the compound 7-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, removing the solvent by rotary evaporation, extracting, washing liquid, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 10-1, wherein the molar weight of the intermediate is 6.71mmol, and the yield is as follows: 67.1 percent. MS (ASAP) =393.

Synthesis of Compound (10):

mixing the intermediate 10-1 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 10, wherein the yield is as follows: 68.3 percent. MS (ASAP) =1068.

Example 11

Synthesis of intermediate 11-1:

mixing the intermediate 2-5 (10 mmol), the compound 8-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 11-1, wherein the molar weight is 7.84mmol, the yield is as follows: 78.4 percent. MS (ASAP) =345.

Synthesis of Compound (11):

mixing the intermediate 11-1 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the liquid, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 11, wherein the yield is as follows: 78.6 percent. MS (ASAP) =972.

Example 12

Synthesis of intermediates 2 to 5:

mixing the intermediate 2-5 (10 mmol), the compound 9-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 12-1, wherein the molar weight is 7.49mmol, the yield is as follows: 74.9 percent. MS (ASAP) =393.

Synthesis of Compound (12):

mixing the intermediate 12-1 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the liquid, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 12, wherein the yield is as follows: 79.3％。MS(ASAP)＝1068。

Example 13

Synthesis of intermediate 13-2:

mixing the intermediate 1-5 (10 mmol), the compound 13-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, removing the solvent by rotary evaporation, extracting, washing the separated liquid with water, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 13-2 with the molar weight of 5.69mmol, and the yield: 56.9 percent. MS (ASAP) =433.

Synthesis of Compound (13):

mixing the intermediate 13-2 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 13, wherein the yield is as follows: 68.7 percent. MS (ASAP) =1148.

Example 14

Synthesis of intermediate 14-1:

mixing the intermediate 2-5 (10 mmol), the compound 13-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting and washing liquid, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 14-1 with the molar weight of 7.62mmol, yield: 76.2 percent. MS (ASAP) =449.

Synthesis of Compound (14):

mixing intermediate 14-1 (20 mmol), compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) andsodium tert-butoxide (30 mmol) was dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. After cooling, the solvent was removed by rotary evaporation, the liquid was extracted and washed with water, the organic phase was collected and subjected to drying, concentration under reduced pressure and column chromatography to give compound 14, yield: 70.5 percent. MS (ASAP) =1180.

Example 15

Synthesis of intermediate 15-2:

mixing the intermediate 1-5 (10 mmol), the compound 15-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 15-2, wherein the molar weight is 6.89mmol, the yield is as follows: 68.9 percent. MS (ASAP) =449.

Synthesis of Compound (15):

mixing the intermediate 15-2 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 15, wherein the yield is as follows: 70.4 percent. MS (ASAP) =1180.

Example 16

Synthesis of intermediate 16-3:

the intermediate 1-3 (10 mmol) and the compound 16-2 (20 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added ₃ ) ₄ (0.1) and potassium carbonate (30 mmol). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. Cooling, rotary evaporating to remove most solvent, extracting, washing, collecting organic phase, drying, concentrating under reduced pressure, performing column chromatography, and collecting the organic phaseRecrystallization afforded intermediate 16-3, molar 7.59mmol, yield: 75.9 percent. MS (ASAP) =239.

Synthesis of intermediate 16-5:

mixing the intermediate 16-3 (10 mmol), the compound 16-4 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 16-5 with the molar weight of 8.34mmol, yield: 83.4 percent. MS (ASAP) =365.

Synthesis of intermediates 16-6:

mixing the intermediate 16-5 (10 mmol), the compound 1-8 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 16-6 with the molar weight of 8.59mmol, yield: 85.9 percent. MS (ASAP) =643.

Synthesis of intermediates 16-7:

compound 1-1 (10 mmol) and compound 1-2 (10 mmol) were dissolved in dichloromethane and stirred at room temperature under nitrogen atmosphere for 6 hours. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 16-7 with the molar weight of 8.07mmol, yield: 80.7 percent. MS (ASAP) =260.

Synthesis of intermediates 16-8:

intermediate 16-7 (10 mmol) and compound 16-2 (10 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added ₃ ) ₄ (0.1) and potassium carbonate (30 mmol). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, and then liquid is extracted and washed by water, an organic phase is collected, and the intermediate 16-8 is obtained after drying, decompression concentration and column chromatography recrystallization, wherein the molar weight is 7.23mmol, and the yield is as follows: 72.3 percent. MS (ASAP) =211.

Synthesis of intermediates 16-9:

intermediate 16-8 (10 mmol), compound 16-4 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 16-9 with the molar weight of 5.93mmol and the yield: and (4) 59.3%. MS (ASAP) =337.

Synthesis of Compound (16):

mixing the intermediate 16-9 (10 mmol), the compound 16-6 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 16, wherein the yield is as follows: 42.8 percent. MS (ASAP) =900.

Example 17

Synthesis of intermediate 17-1:

the intermediate 1-5 (10 mmol), tert-butyl nitrite (30 mmol) and cuprous bromide (30 mmol) were dissolved in acetonitrile and stirred at 60 ℃ for 3h under nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 17-1, wherein the molar weight is 7.33mmol, the yield is as follows: 73.3 percent. MS (ASAP) =273.

Synthesis of intermediate 17-3:

the intermediate 17-1 (10 mmol) and the compound 17-2 (10 mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (21/2 ml), and Pd (PPh) was added ₃ ) ₄ (0.1) and potassium carbonate (30 mmol). Stirring was carried out at 100 ℃ for 6h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, then the liquid is extracted and washed by water, the organic phase is collected, and the intermediate 17-3 is obtained after drying, decompression concentration and column chromatography recrystallization, the molar weight is 8.22mmol, and the yield is as follows: 82.2 percent. MS (ASAP) =287.

Synthesis of intermediate 17-4:

mixing the intermediate 17-3 (10 mmol), the compound 9-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, removing the solvent by rotary evaporation, extracting, washing the separated liquid with water, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 17-4 with the molar weight of 8.39mmol, and the yield: 83.9 percent. MS (ASAP) =453.

Synthesis of Compound (17):

mixing intermediate 17-4 (20 mmol), compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 17 with yield: 76.3 percent. MS (ASAP) =1188.

Example 18

Synthesis of intermediate 18-2:

mixing the intermediate 1-5 (10 mmol), the compound 18-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain an intermediate 18-2 with the molar weight of 5.33mmol, yield: 53.3 percent. MS (ASAP) =315.

Synthesis of Compound (18):

mixing the intermediate 18-2 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ for 6h under a nitrogen atmosphere. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 18 with yield: and 64.2 percent. MS (ASAP) =912.

Example 19

Synthesis of intermediate 19-2:

mixing the intermediate 1-5 (10 mmol), the compound 19-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) cooling, performing rotary evaporation to remove the solvent, extracting, washing the separated liquid with water, collecting an organic phase, drying, concentrating under reduced pressure and performing column chromatography to obtain an intermediate 19-2 with the molar weight of 7.59mmol, yield: 75.9 percent. MS (ASAP) =363.

Synthesis of Compound (19):

mixing the intermediate 19-2 (20 mmol), the compound 4-1 (10 mmol), pd (dba) ₂ (0.1 mmol), TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 100 ℃ under a nitrogen atmosphere for 6h. And (3) after cooling, removing the solvent by rotary evaporation, extracting and washing liquid, collecting an organic phase, and performing drying, reduced pressure concentration and column chromatography to obtain a compound 19, wherein the yield is as follows: 78.7 percent. MS (ASAP) =1008.

2. Testing of

The structure of the partial functional materials involved in the test section is as follows:

(1) Energy level of compound

The energy level of the organic compound material can be obtained by quantum calculation, for example, by Gaussian09W (Gaussian inc.) by using TD-DFT (including time density functional theory), and a specific simulation method can be found in WO2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecule is calculated into 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet) by a TD-DFT (including time density functional theory) method. The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1, T1 and the resonance factor f (S1) are used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO, LUMO, T1 and S1 are the direct results of Gaussian09W in Hartree. The results are shown in table 1 below:

TABLE 1

(2) Preparation and characterization of OLED device

The following describes in detail the preparation process of the OLED device using the above compound by using specific device embodiments, and the structure of the OLED device is: substrate/ITO anode/HIL/HTL/EML/ETL/cathode, see fig. 1, where 101 is the substrate, 102 is the ITO anode, 103 is the Hole Injection Layer (HIL), 104 is the Hole Transport Layer (HTL), 105 is the light emitting layer, 106 is the Electron Transport Layer (ETL), and 107 is the cathode.

The preparation of OLDE-1 comprises the following steps:

a. cleaning an ITO (indium tin oxide) conductive glass substrate: washing with chloroform, and then performing ultraviolet ozone treatment;

b. HIL (hole injection layer, 40 nm) preparation of 60nm PEDOT (polyethylenedioxythiophene, clevios) on ITO by spin coating in an ultraclean room environment ^TM AI 4083) as HIL and treated on a hot plate at 180 ℃ for 10 minutes;

c. HTL (hole transport layer, 20 nm) 20nm of PVK (Sigma Aldrich, average Mn 25,000-50,000) prepared by spin-coating a toluene solution of PVK on HIL in a nitrogen glove box, with a solution solubility of 5mg/ml, followed by treatment on a hotplate at 180 ℃ for 60 minutes;

d. EML (organic light emitting layer, 40 nm) a solution of methyl benzoate (the weight ratio of host to guest is 95.

e. Electron transport layer and cathode the heat-treated substrate was transferred to a vacuum chamber, then ET and Liq were co-deposited in a high vacuum (1 x 10-6 mbar) in a ratio of 50 wt% each in a different evaporation unit to form a 20nm electron transport layer on the light-emitting layer, followed by deposition of a 100nm thick Al cathode.

f. Encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

The preparation steps of OLDE-2 to OLDE-Ref are substantially the same as those of OLDE-1, except that the guest material is replaced from compound 1 to the guest material shown in table 2.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus while recording important parameters such as efficiency, lifetime, and external quantum efficiency, with the results shown in table 2.

TABLE 2

As can be seen from table 2, on the one hand, the blue light device prepared by using the compounds 1 to 19 as guest materials in the EML layer has better color coordinates than the comparative compound 1, and shows more excellent deep blue light emission. On the other hand, the luminous efficiency of the blue light device prepared by adopting the compounds 1-19 as guest materials in the EML layer luminous layer is in the range of 8-9cd/A, so that the blue light device has more excellent luminous efficiency; this is because introduction of an alkyl group at the ortho position of dibenzofuran (comparative compound 1 is dibenzofuran) in the present invention, as compared to comparative compound 1, increases the solubility of molecules, improves the purification ability of molecules, and further improves the molecular purity, thereby improving the device performance. Further, on the other side of the amine group, an ortho-dibenzofuran derivative or dibenzothiophene derivative (OLED-7, 10,13,14, 15) is introduced, so that the molecular conjugation is improved, and the device performance is improved. In addition, the service life of the blue light device prepared by adopting the compounds 1 to 19 as guest materials in the EML layer luminous layer is better than that of the comparative compound 1.

All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the patent of the present invention shall be subject to the content of the appended claims, and the description and the attached drawings can be used for explaining the content of the claims.

Claims

1. A pyrene organic compound having a structure represented by general formula (I):

wherein:

and Ar ₁ -Ar ₄ At least one of which is selected from formula (II):

* Represents a linking site;

R ₁ -R ₉ ，R ₁₂ -R ₁₄ each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 20C atoms, a straight chain alkoxy group having 1 to 20C atoms, a straight chain thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, a branched alkoxy group having 3 to 20C atoms, a branched thioalkoxy group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amine group, -CF ₃ -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atomsAn oxy group, or a combination of these groups;

n is selected from 0,1,2,3 or 4.

2. The pyrene organic compound according to claim 1, having a structure represented by formula (III) or (VI):

wherein:

ar in the formula (III) ₂ -Ar ₄ Independently for each occurrence, is selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;

ar in formula (IV) ₂ -Ar ₃ Each occurrence is independently selected from a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.

3. The pyrene organic compound according to claim 2, wherein Ar in the formula (III) ₂ -Ar ₄ And Ar in formula (IV) ₂ -Ar ₃ Each independently selected from any one of (A-1) to (A-6):

wherein:

x is selected from N or CR ₁₀₁ ；

R ₁₀₁ -R ₁₀₃ Each occurrence is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20C atoms, a straight-chain alkoxy group having 1 to 20C atoms, a straight-chain thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, -CF ₃ -Cl, -Br, -F, or an alkenyl group having 2 to 20C atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

4. The pyrene organic compound according to claim 3, wherein Ar in the formula (III) ₂ -Ar ₄ And Ar in formula (IV) ₂ -Ar ₃ Each independently selected from the group consisting of:

wherein:

R ₁₀₁ each occurrence is independently selected from a straight chain alkyl group having 1 to 10C atoms, orA branched alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms;

5. The pyrene organic compound according to claim 4, wherein (A-3) has the following structure

6. The pyrene organic compound according to claim 3, having a structure represented by any one of formulas (V-1) to (V-4):

7. the pyrene-based organic compound according to any one of claims 1 to 6, wherein R is ₁ -R ₉ ，R ₁₂ -R ₁₄ Independently at each occurrence, is selected from-H, -D, or a straight chain alkyl group having 1 to 10C atoms, a straight chain alkoxy group having 1 to 10C atoms, a straight chain thioalkoxy group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, a branched alkoxy group having 3 to 10C atoms, a branched thioalkoxy group having 3 to 10C atoms, a cyclic alkyl group having 3 to 10C atoms, a cyclic alkoxy group having 3 to 10C atoms, or a cyclic thioalkoxy group having 3 to 10C atoms, or a silyl group, or a keto group having 1 to 10C atoms, or an alkoxycarbonyl group having 2 to 10C atoms, or an aryloxycarbonyl group having 7 to 10C atoms, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group,hydroxy, nitro, amino, -CF ₃ -Cl, -Br, -F, -I, or an alkenyl group having 2 to 20C atoms, or a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups.

8. The pyrene-based organic compound according to claim 7, wherein R is ₃ And R ₇ Each occurrence is independently selected from-H, -D, or a straight chain alkyl group having 1 to 10C atoms, or a branched chain alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms; and/or

R ₁₀ ，R ₁₁ Each occurrence is independently selected from a straight chain alkyl group having 1 to 10C atoms, or a branched chain alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms; and/or

R ₁₂ -R ₁₃ Each occurrence is independently selected from-H, -D, a straight chain alkyl group having 1 to 10C atoms, or a branched chain alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or a phenyl group; and/or

R ₁₄ Each occurrence is independently selected from-H, -D, a linear alkyl group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a cyclic alkyl group having 3 to 10C atoms, or a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 13 ring atoms.

9. The pyrene-based organic compound according to claim 1, having a structure represented by any one of the following:

10. a mixture comprising one pyrene-based organic compound according to any one of claims 1 to 9 and an organic functional material selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.

11. A composition comprising at least one pyrene organic compound according to any one of claims 1 to 9 or the mixture according to claim 10 and at least one organic solvent.

12. An organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers between the first electrode and the second electrode, wherein the organic functional layers comprise a pyrene-based organic compound according to any one of claims 1 to 9, or a mixture according to claim 10, or are prepared from a composition according to claim 11.