阅读说明：本技术 一种用于oled的稠环化合物及其应用 (Condensed ring compound for OLED and application thereof ) 是由 李崇 谢丹丹 王芳 叶中华 于 2018-08-27 设计创作，主要内容包括：本发明公开了一种用于OLED的稠环化合物及其应用,该化合物的结构如通式(A)所示,本发明化合物以在芘或氮杂芘的环上进一步增加芳环或杂芳环所形成的稠环化合物为骨架,并引入其他芳香基团,从而使得本发明的稠环化合物具有深的HOMO能级和较高载流子迁移率,通过其他取代基团的修饰,对HOMO能级进一步进行调整,使得本发明的稠环化合物具有较高的单线态能级和合适的三线态能级,以及良好的可逆氧化还原特性,能够和EB、ET材料进行良好的器件能级匹配,降低器件驱动电压。本发明的稠环化合物其具有较高的S1单线态能级,并且T1≥0.5S1,具有良好的TTA作用,能够充分利用三线态能量,提高器件的外量子效率。(The invention discloses a condensed ring compound for OLED and application thereof, the structure of the compound is shown in a general formula (A), the condensed ring compound formed by further adding an aromatic ring or a heteroaromatic ring on a pyrene or aza-pyrene ring is taken as a framework, and other aromatic groups are introduced, so that the condensed ring compound has deep HOMO energy level and higher carrier mobility, the HOMO energy level is further adjusted through modification of other substituent groups, the condensed ring compound has higher singlet state energy level, proper triplet state energy level and good reversible redox property, and can be well matched with EB and ET materials in device energy level, and the driving voltage of the device is reduced. The fused ring compound has higher S1 singlet state energy level, T1 is more than or equal to 0.5S1, has good TTA effect, can fully utilize triplet state energy, and improves the external quantum efficiency of devices.)

1. A fused ring compound for an OLED, wherein the fused ring compound has a structure represented by general formula (A):

in the general formula (A), Z₁～Z₁₃Each independently represents a nitrogen atom or C-R, R represents, identically or differently at each occurrence, a hydrogen atom, a cyano group, a fluorine atom, C_1-20Alkyl of (C)_1-20Alkyl-substituted silyl group of (A), substituted or unsubstituted C_6-60Substituted or unsubstituted 5-60 membered heteroaryl;

Ar₁is a single bond, substituted or unsubstituted C_6-60Substituted or unsubstituted 5-60 membered heteroarylene;

Ar₂is represented by substituted or unsubstituted C_6-60Substituted or unsubstituted 5-60 membered heteroaryl;

m represents 0, 1 or 2; when Ar is₁When represents a single bond, Ar₂Can not be represented by phenyl, methyl substituted phenyl, methoxy substituted phenyl, fluorine atom substituted phenyl; when m represents 0, Ar₁Can not represent a single bond, phenyl, methyl-substituted phenyl, methoxy-substituted phenyl, fluorine atom-substituted phenyl;

said substituted C_6-60The substituents of aryl and substituted 5-60 membered heteroaryl of (A) are optionally selected from halogen atom, cyano, C_1-20Alkyl of (C)_6-30One or more of aryl, 5-30 membered heteroaryl containing one or more heteroatoms;

the hetero atom in the heteroaryl and the heteroarylene is selected from one or more of N, O or S.

2. The fused ring compound of claim 1, wherein R, Ar is present₂Represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzisofuryl group, a substituted or unsubstituted isobenzothienyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted pyrenyl group, a general formula (B), a general formula (C), a general formula (D) or a general formula (E):

wherein said Z, which may be the same or different, represent a nitrogen atom or C-R₁(ii) a Z at the bonding site is represented as a carbon atom;

said X₁、X₂、X₃Each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)₂)(R₃)-、-Si(R₄)(R₅)-、or-N (R)₆) -one of the above; and X₁、X₂Not simultaneously represent a single bond;

R₁represented by hydrogen atom, halogen atom, cyano group, C_1-20Alkyl of (C)_2-20Alkenyl of (a), substituted or unsubstituted C_6-60An aryl group of (a), a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more heteroatoms; and two or more adjacent R₁May be bonded to each other to form a 5-to 30-membered aliphatic or aromatic ring;

R₂to R₆Are each independently represented by C_1-20Alkyl, substituted or unsubstituted C_6-60An aryl group of (a), a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more heteroatoms; and R is₂And R₃、R₄And R₅Can be bonded to each other to form a ring;

the substituent of the substitutable group is selected from halogen atom, cyano, C_1-20Alkyl of (C)_6-30One or more of aryl, 5-30 membered heteroaryl containing one or more heteroatoms;

the heteroatom in the heteroaryl group is selected from an oxygen atom, a sulfur atom or a nitrogen atom.

3. The fused ring compound of claim 1, wherein the fused ring compound is structurally represented by formula (F):

4. the fused ring compound of claim 1, wherein the fused ring compound is structurally represented by formula (G):

5. the fused ring compound of claim 2, wherein Ar is₁Represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted phenanthrylene groupSubstituted anthracenylene, substituted or unsubstituted benzisothiofuranylene, substituted or unsubstituted isobenzothiophenylene, substituted or unsubstituted quinolylene, substituted or unsubstituted isoquinolylene, substituted or unsubstituted pyrenylene;

the R is₁Represented by a hydrogen atom, a cyano group, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, a furyl group, a pyrimidinyl group, a benzofuryl group, a carbazolyl group or a benzothienyl group;

the R is₂To R₆Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl or pyridyl;

the substituent of the above-mentioned substitutable group is selected from one or more of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or pyrimidyl.

6. The fused ring compound of claim 1, wherein: the fused ring compound structure is represented by any one of general formulas (A-1) to (A-10):

7. the fused ring compound of claim 1, wherein: the fused ring compound has a specific structure:

8. An organic electroluminescent device, characterized in that: at least one functional layer of the organic electroluminescent element contains the condensed cyclic compound for OLED according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, wherein: the functional layer includes a light-emitting layer containing the condensed-cyclic compound for OLED according to any one of claims 1 to 7.

10. A lighting or display element comprising the organic electroluminescent device according to any one of claims 8 to 9.

Technical Field

The invention relates to the technical field of semiconductors, in particular to a compound containing a fused ring structure and application thereof in an OLED device.

Background

The organic electroluminescent device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials sandwiched between the different electrode material film layers, and the different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.

At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the photoelectric functional material of the OLED are required to create a functional material of the higher-performance OLED. The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials. In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, and the like are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, and the like are required.

The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises 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 and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.

Disclosure of Invention

Aiming at the problems in the prior art, the condensed ring compound for the OLED provided by the invention has the advantages of higher glass transition temperature, higher molecular thermal stability, proper HOMO and LUMO energy levels and higher carrier mobility, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.

The technical scheme of the invention is as follows:

a fused ring compound for use in an OLED, the fused ring compound having the structure shown in formula (A):

in the general formula (A), Z₁～Z₁₃Each independently represents a nitrogen atom or C-R, R represents, identically or differently at each occurrence, a hydrogen atom, a cyano group, a fluorine atom, C_1-20Alkyl of (C)_1-20Alkyl-substituted silyl group of (A), substituted or unsubstituted C_6-60Substituted or unsubstituted 5-60 membered heteroaryl;

Ar₁is a single bond, substituted or unsubstituted C_6-60Substituted or unsubstituted 5-60 membered heteroarylene;

Ar₂is represented by substituted or unsubstituted C_6-60Substituted or unsubstituted 5-60 membered heteroaryl;

m represents 0, 1 or 2; when Ar is₁When represents a single bond, Ar₂Not represented by phenyl, methyl-substituted phenyl, methoxyPhenyl substituted by phenyl, phenyl substituted by fluorine atom; when m represents 0, Ar₁Can not represent a single bond, phenyl, methyl-substituted phenyl, methoxy-substituted phenyl, fluorine atom-substituted phenyl;

said substituted C_6-60The substituents of aryl and substituted 5-60 membered heteroaryl of (A) are optionally selected from halogen atom, cyano, C_1-20Alkyl of (C)_6-30One or more of aryl, 5-30 membered heteroaryl containing one or more heteroatoms;

the hetero atom in the heteroaryl and the heteroarylene is selected from one or more of N, O or S.

As a further improvement of the invention, the R, Ar₂Represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzisofuryl group, a substituted or unsubstituted isobenzothienyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted pyrenyl group, a general formula (B), a general formula (C), a general formula (D) or a general formula (E):

wherein said Z, which may be the same or different, represent a nitrogen atom or C-R₁(ii) a Z at the bonding site is represented as a carbon atom;

said X₁、X₂、X₃Each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)₂)(R₃)-、-Si(R₄)(R₅)-、

or-N (R)₆) -one of the above; and X₁、X₂Not simultaneously represent a single bond;

R₁represented by hydrogen atom, halogen atom, cyano group, C_1-20Alkyl of (C)_2-20Alkenyl, substituted orUnsubstituted C_6-60An aryl group of (a), a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more heteroatoms; and two or more adjacent R₁May be bonded to each other to form a 5-to 30-membered aliphatic or aromatic ring;

R₂to R₆Are each independently represented by C_1-20Alkyl, substituted or unsubstituted C_6-60An aryl group of (a), a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more heteroatoms; and R is₂And R₃、R₄And R₅Can be bonded to each other to form a ring;

the substituent of the substitutable group is selected from halogen atom, cyano, C_1-20Alkyl of (C)_6-30One or more of aryl, 5-30 membered heteroaryl containing one or more heteroatoms;

the heteroatom in the heteroaryl group is selected from an oxygen atom, a sulfur atom or a nitrogen atom.

As a further development of the invention, the R is denoted C, identically or differently on each occurrence_1-10Straight chain alkyl group of (1), C_3-10Branched alkyl of C_1-10Alkyl substituted silyl, substituted or unsubstituted C_6-30A substituted or unsubstituted 5-30 membered heteroaryl, wherein the heteroatom in the heteroaryl is one or more of N, O or S;

ar is₁Is represented by substituted or unsubstituted C_6-30Substituted or unsubstituted 5-30 membered heteroarylene;

ar is₂Is represented by substituted or unsubstituted C_6-30Substituted or unsubstituted 5-30 membered heteroaryl;

the substituent of the substitutable group is selected from C_1-10Alkyl radical, C_1-10Alkoxy radical, C_6-20Aryloxy radical, C_1-10Heterocycloalkyl radical, C_4-10Cycloalkenyl radical, C_4-10Heterocycloalkenyl, C_1-10Alkenyl radical, C_1-10Alkyl-substituted amino, C_6-20Any of aryl substituted amine groups.

As a further improvement of the invention, R is₁Represented by hydrogen atom, cyano groupFluorine atom, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, phenyl group, naphthyl group, biphenyl group, pyridyl group, furyl group, pyrimidinyl group, benzofuryl group, carbazolyl group, or benzothienyl group;

the R is₂To R₆Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl or pyridyl;

the substituent of the substituent group is selected from one of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or pyrimidyl.

As a further improvement of the present invention, the fused ring compound has a structure represented by the general formula (F):

as a further development of the invention, Z is₈、Z₉、Z₆、Z₁、Z₃、Z₄、Z₁₁And Z₁₃At least one of which is represented by a nitrogen atom.

As a further development of the invention, Z is₈、Z₉、Z₆、Z₁、Z₃、Z₄、Z₁₁And Z₁₃At least two of which are represented as nitrogen atoms.

As a further improvement of the present invention, the fused ring compound has a structure represented by general formula (G):

as a further development of the invention, Z is₈、Z₉、Z₁、Z₄And Z₁₃At least one of which is represented by a nitrogen atom.

As a further development of the invention, Z is₈、Z₉、Z₁、Z₄And Z₁₃At least two of which are represented as nitrogen atoms.

As a further improvement of the present invention, the condensed ring compound structure is represented by any one of general formulae (A-1) to (A-10):

as a further improvement of the invention, Ar is₂Selected from the group consisting of

As a further improvement of the invention, Ar is₁Represented by a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted 9, 9-spirobifluorenylene group, a substituted or unsubstituted isoindolylene group, a substituted or unsubstituted 9, 9-diphenylfluorenyl group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted triazinylene group, a substituted or unsubstituted benzofuranylene group, a substituted or unsubstituted isobenzofuranylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted benzisothiazolyl group, a substituted or unsubstituted isoquinolinylene group, Substituted or unsubstituted benzothienylene;

the R, Ar₂Independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted 9, 9-spirobifluorenyl group, a substituted or unsubstituted isoindolyl group, a substituted or unsubstituted spirobifluorenyl group

Radical, substitution orUnsubstituted 9, 9-diphenylfluorenyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted isobenzofuranyl group, substituted or unsubstituted quinolyl group, substituted or unsubstituted benzisothiazolyl group, substituted or unsubstituted isoxazolyl group, substituted or unsubstituted isoquinolyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted benzothienyl group, substituted or unsubstituted indazolyl group, substituted or unsubstituted isobenzothienyl group, substituted or unsubstituted indolizinyl group, substituted or unsubstituted benzisoxazolyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothienyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted benzoxazolyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothienyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted benzoxazolyl group, Substituted or unsubstituted xanthenyl, substituted or unsubstituted azacarbazolyl, substituted or unsubstituted azadibenzofuranyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted aza 9, 9' -spirobifluorenyl, substituted or unsubstituted azafluorenyl, substituted or unsubstituted azadiphenylfluorenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted azadibenzothienyl; a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted azulenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylene group, a substituted or unsubstituted phthalazinyl group, a substituted or unsubstituted cinnolinyl group, a substituted or unsubstituted phenanthrolinyl group or a substituted or unsubstituted pteridinyl group.

As a further improvement of the invention, the substituents of the substituted aryl having 6to 30 ring atoms and the substituted heteroaryl having 5 to 30 ring atoms are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, sec-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-ethylhexyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl.

As a further improvement of the invention, the fused ring compound has a specific structure:

any one of the above.

An organic electroluminescent device in which at least one functional layer contains the condensed ring compound for OLED.

As a further improvement of the present invention, the functional layer comprises a light-emitting layer containing the condensed ring compound for OLED.

A lighting or display element comprising the organic electroluminescent device.

The beneficial technical effects of the invention are as follows: according to the invention, a fused ring compound formed by further adding an aromatic ring or a heteroaromatic ring on a pyrene or aza-pyrene ring is taken as a framework, and other aromatic groups are introduced, so that the fused ring compound has higher carrier mobility, the HOMO energy level can be adjusted through modification of other substituent groups, and the fused ring compound has higher singlet state energy level, proper triplet state energy level and good reversible redox property, can be well matched with EB and ET layer materials, and can reduce the driving voltage of a device. The fused ring compound has higher S1 singlet state energy level, T1 is more than or equal to 0.5S1, has good TTA effect, can fully utilize triplet state energy, and improves the external quantum efficiency of devices.

In addition, the aromatic ring or heteroaromatic ring is further added on the pyrene or aza-pyrene ring, so that the molecular symmetry is destroyed, and the intermolecular aggregation effect is avoided.

Drawings

FIG. 1 is a schematic structural view of a fused cyclic compound of the present invention applied to an OLED device;

wherein, 1 is a transparent glass substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a luminescent layer, 7 is a hole blocking layer or an electron transport layer, 8 is an electron injection layer, and 9 is a cathode electrode layer.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings and examples.

Synthesis of intermediate a:

stirring raw materials A, N-bromosuccinimide (NBS), dichloromethane and acetonitrile at normal temperature for reaction, performing reduced pressure suction filtration on a precipitated solid product after the reaction is finished, and washing the obtained solid product with methanol to obtain an intermediate; the molar ratio of the raw material A to the NBS is 1 (2-3), 40-60ml of dichloromethane is added into 0.01mol of dichloromethane solvent, and 40-60ml of acetonitrile is added into 0.01mol of the raw material A.

Preparation of raw material A-1:

(1) a500 ml three-necked flask was prepared, 0.12mol of reactant 1 was added, the temperature was adjusted to 0 ℃, and sulfuric acid: nitric acid: heating the mixed acid with water of 4:2:1 to 30 ℃, stirring for 30 minutes, standing, extracting the upper-layer nitride with ethyl acetate, washing the mixture to be neutral with distilled water, separating liquid, performing rotary evaporation, recrystallizing and filtering to obtain an intermediate 1 with the yield of 85%;

(2) preparing a 500ml three-neck flask, adding 160ml of 0.2mol/L hydrochloric acid aqueous solution, gradually adding 0.1mol of intermediate 1 and 0.5mol of iron powder while stirring, heating and refluxing for 6 hours, cooling, adding saturated sodium carbonate aqueous solution into a reaction system until the reaction system is neutral, extracting with ethyl acetate, separating, rotary steaming, drying, and filtering to obtain an intermediate 2 with the yield of 93%;

(3) 10mmol of intermediate 2 and 4mmol of intermediate 3 were dissolved in 10ml of mesitylene, and 0.4mmol of IrCl was added₃·3H₂O, 0.6mmol BINAP and 0.65mmol sodium carbonate are added into the reaction system, and then the temperature is raised to the temperature under the stirring conditionReacting at 168 ℃ for 18 hours, removing the solvent by rotary evaporation, and passing through a silica gel column to obtain the raw material A-1 with the yield of 75%.

Preparation of raw material A-2:

(1) a500 ml three-necked flask was prepared, 0.12mol of reactant 2 was added, the temperature was adjusted to 0 ℃, and sulfuric acid: nitric acid: heating the mixed acid to 30 ℃ with water, stirring for 30 minutes, standing, extracting the upper-layer nitride with ethyl acetate, washing the mixture to be neutral with distilled water, separating liquid, performing rotary evaporation, recrystallizing and filtering to obtain an intermediate 4 with the yield of 84%.

(2) Preparing a 500ml three-neck flask, adding 160ml of 02mol/L hydrochloric acid aqueous solution, gradually adding 0.1mol of intermediate 4 and 0.5mol of iron powder while stirring, heating and refluxing for 6 hours, cooling, adding saturated sodium carbonate aqueous solution into a reaction system until the reaction system is neutral, extracting with ethyl acetate, separating, rotary steaming, drying, and filtering to obtain an intermediate 5 with the yield of 92%.

(3) 10mmol of intermediate 5 and 4mmol of intermediate 3 are dissolved in 10ml of mesitylene, 0.4mmol of IrCl3 & 3H2O, 0.6mmol of BINAP and 0.65mmol of sodium carbonate are added into the reaction system, then the temperature is raised to 168 ℃ under the stirring condition, the reaction is carried out for 18 hours, the solvent is removed by rotary evaporation, and the raw material A-2 is obtained by passing through a silica gel column with the yield of 78%.

Preparation of raw material A-3:

(1) a500 ml three-necked flask was prepared, 0.12mol of reactant 3 was added, the temperature was adjusted to 0 ℃, and sulfuric acid: nitric acid: heating the mixed acid to 30 ℃ with water, stirring for 30 minutes, standing, extracting the upper-layer nitride with ethyl acetate, washing the mixture to be neutral with distilled water, separating liquid, performing rotary evaporation, recrystallizing and filtering to obtain an intermediate 6 with the yield of 81%.

(2) Preparing a 500ml three-neck flask, adding 160ml of 02mol/L hydrochloric acid aqueous solution, gradually adding 0.1mol of intermediate 4 and 0.5mol of iron powder while stirring, heating and refluxing for 6 hours, cooling, adding saturated sodium carbonate aqueous solution into a reaction system until the reaction system is neutral, extracting with ethyl acetate, separating, rotary-steaming, drying, and filtering to obtain an intermediate 7 with the yield of 91%.

(3) 10mmol of intermediate 7 and 4mmol of intermediate 3 are dissolved in 10ml of mesitylene, 0.4mmol of IrCl3 & 3H2O, 0.6mmol of BINAP and 0.65mmol of sodium carbonate are added into the reaction system, then the temperature is raised to 168 ℃ under the stirring condition, the reaction is carried out for 18 hours, the solvent is removed by rotary evaporation, and the raw material A-3 is obtained by passing through a silica gel column with the yield of 78%.

Preparation of raw material A-4:

dissolving 10mmol of reactant 4 and 4mmol of intermediate 3 in 10ml of mesitylene, adding 0.4mmol of IrCl3.H2O, 0.6mmol of BINAP and 0.65mmol of sodium carbonate into the reaction system, heating to 168 ℃ under the condition of stirring, reacting for 18 hours, and performing rotary evaporation to remove the solvent, and passing through a silica gel column to obtain the raw material A-4 with the yield of 80%.

The preparation method of the raw material A containing nitrogen atoms refers to the following synthesis steps:

synthesis of intermediate a 1:

adding 0.05mol of raw material A, 20.8g of N-bromosuccinimide (NBS), 250ml of dichloromethane and 250ml of acetonitrile into a three-neck flask in sequence, stirring at normal temperature for 24 hours, after the reaction is finished, carrying out vacuum filtration on a precipitated solid product, and washing the obtained solid product with methanol to obtain an intermediate A1, wherein the purity is 96.3%, and the yield is 70.4%; ESI-MS (M/z) (M +): theoretical value is 380.02, found 380.00.

Synthesis of intermediates a2-a12 reference was made to the synthesis of intermediate a 1.

Synthesis of intermediate B:

weighing a reactant C and dissolving the reactant C in tetrahydrofuran under the nitrogen atmosphere, cooling to-78 ℃, slowly dropping a cyclohexane solution containing n-butyllithium, and keeping the temperature and stirring for 30 minutes; slowly dripping tetrahydrofuran solution containing trimethyl borate, slowly heating to room temperature after dripping, and reacting for 10 hours under heat preservation; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; extracting with ethyl acetate, washing with saturated saline solution, drying with anhydrous magnesium sulfate, distilling under reduced pressure, and recrystallizing the obtained solid with mixed solution of toluene and ethanol to obtain intermediate B; the molar ratio of the reactant C to n-butyllithium is 1: 1-2, and the molar ratio of the reactant C to trimethyl borate is 1: 3-6, and the dosage ratio of the reactant C to the THF is 1g: 20-30 ml.

Reactant C was prepared as follows:

weighing 0.01mol of raw material C-1 in a nitrogen atmosphere, dissolving in 45ml of tetrahydrofuran, cooling to-78 ℃, slowly dripping a cyclohexane solution containing 0.02mol of n-butyllithium, and keeping the temperature and stirring for 30 minutes after dripping is finished; slowly dripping tetrahydrofuran solution containing 0.035mol trimethyl borate, after dripping, slowly heating to room temperature, and reacting for 10 hours under the condition of heat preservation; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; the reaction solution was extracted with 150ml of ethyl acetate, the extract was washed with 150ml of saturated brine three times, finally dried over anhydrous magnesium sulfate, the solution was distilled under reduced pressure, and the obtained solid was purified by distillation with 400ml of toluene: recrystallizing the mixed solution of 3:1 ethanol to obtain an intermediate C;

to a 200ml three-necked flask, 0.01mol of intermediate C, 0.011mol of reactant C-2, 0.03mol of potassium carbonate, and 1X 10^-4mol Pd(PPh₃)Cl₂And 1X 10^-4mol of triphenylphosphine, then 120ml of toluene: ethanol: the mixture of water and water at 1:1:1 was heated at 70-110 ℃ under reflux for 24 hours, and the reaction was observed by TLC until the reaction was complete. Naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was purified by silica gel column (dichloromethane: mixed solvent of petroleum ether ═ 1:5 as eluent) to obtain reaction product C.

Synthesis of intermediate B1:

weighing 0.01mol of raw material B1 in a nitrogen atmosphere, dissolving in 45ml of tetrahydrofuran, cooling to-78 ℃, slowly dripping a cyclohexane solution containing 0.02mol of n-butyllithium, and keeping the temperature and stirring for 30 minutes after dripping is finished; slowly dripping tetrahydrofuran solution containing 0.035mol trimethyl borate, after dripping, slowly heating to room temperature, and reacting for 10 hours under the condition of heat preservation; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; the reaction solution was extracted with 150ml of ethyl acetate, the extract was washed with 150ml of saturated brine three times, and finally dried over anhydrous magnesium sulfate, the solution was distilled under reduced pressure, and the obtained solid was recrystallized from 400ml of a mixed solution (toluene: ethanol ═ 3:1) to obtain intermediate B1; purity 95.3% and yield 77.4%. ESI-MS (M/z) (M +): theoretical value is 248.10, found 248.09.

Synthesis of intermediates B2-B12 reference was made to the synthesis of intermediate B1.

And (3) synthesis of a product:

under the protection of nitrogen, adding the intermediate A and the intermediate B, then adding a proper amount of mixed solvent of toluene, ethanol and water in a volume ratio of 1:1:1, then adding triphenylphosphine and dichlorotriphenylphosphine palladium, heating and refluxing at 75-130 ℃ for 24 hours, then cooling to room temperature, filtering the reaction solution, separating the filtrate to remove a water layer, carrying out rotary evaporation on an organic layer, and passing through a silica gel column to obtain a product; the molar ratio of the intermediate A to the intermediate B is 1: 1.05-1: 1.0, the molar ratio of the intermediate A to triphenylphosphine is 1: 0.001-1: 0.01, the molar ratio of the intermediate A to dichlorotriphenylphosphine palladium is 1: 0.001-1: 0.01, and the amount of the mixed solvent is that 100 ml of the intermediate A is added into 0.01mol of the mixed solvent.