Compound with spirofluorene anthrone as core and application thereof in organic electroluminescent device
阅读说明：本技术 一种以螺芴蒽酮为核心的化合物及其在有机电致发光器件上的应用 (Compound with spirofluorene anthrone as core and application thereof in organic electroluminescent device ) 是由 李崇 吴秀芹 王芳 徐浩杰 于 2018-08-21 设计创作，主要内容包括：本发明涉及一种以螺芴蒽酮为核心的化合物及其制备方法与应用,所述化合物的结构以螺芴蒽酮与五元环并环结构相连,整个分子是一个较大的刚性结构,具有高的三线态能级(T1)；结构立体性强,空间位阻大,不易转动,提高了材料化学稳定性,而且使化合物具有较高的玻璃化温度和分子热稳定性；另外,本发明化合物的HOMO和LUMO分布位置相互分开,使其具有了合适的HOMO和LUMO能级；因此,本发明化合物应用于OLED器件后,可有效提升器件的发光效率及使用寿命。(The invention relates to a compound taking spirofluorene anthrone as a core and a preparation method and application thereof, the structure of the compound is that spirofluorene anthrone is connected with a five-membered ring parallel structure, the whole molecule is a larger rigid structure and has a high triplet state energy level (T1); the structure has strong stereospecificity, large steric hindrance and difficult rotation, improves the chemical stability of the material, and ensures that the compound has higher glass transition temperature and molecular thermal stability; in addition, the HOMO and LUMO distribution positions of the compound are separated from each other, so that the compound has proper HOMO and LUMO energy levels; therefore, after the compound is applied to an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.)
1. A compound taking spirofluorene anthrone as a core is characterized in that the structure of the compound is shown as a general formula (1):
in the general formula (1), m, n, p and q are respectively and independently 0 or 1, and m + n + p + q is more than or equal to 1; l represents, identically or differently on each occurrence, a single bond, substituted or unsubstituted C6-30Arylene, substituted or notOne of substituted 5-to 30-membered heteroarylene;
z, identically or differently on each occurrence, being represented by a nitrogen atom or C-R5Z represents a number of nitrogen atoms less than 3, R5Each occurrence, identically or differently, being represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; and the group Z to which the group L is bonded represents a carbon atom;
the R is1、R2、R3、R4Each independently represents a structure represented by general formula (2) or general formula (3);
the R is6、R7、R8、R9Each independently represents a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, or C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, or an arylamine group; r6、R7、R8、R9The connection mode with the general formula (2) or the general formula (3) can be single bond substitution or ring combination connection; r6、R7The same or different; r8、R9The same or different;
in the general formula (3), X1Represented by oxygen atom, sulfur atom, -C (R)10)(R11) -or-N (R)12)-；
The Y represents a nitrogen atom or C-H; and R is6、R7、R8、R9Y at the junction with the general formula (2) or the general formula (3) represents a carbon atom;
R10～R12are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl, 5-30 membered hetero substituted or unsubstituted with one or more hetero atomsOne of aryl groups; wherein R is10And R11Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from cyano, halogen and C1-20Alkyl of (C)6-30One or more of an aryl group, a 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the hetero atom of the heteroaryl is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. A compound of claim 1, wherein R is6、R7、R8、R9Each independently represents a hydrogen atom, a structure represented by the general formula (4), the general formula (5) or the general formula (6)
The general formula (4) and the general formula (5) are connected with the general formula (2) or the general formula (3) in a fused mode through two adjacent positions marked by the symbol;
in the general formula (6), L1Represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group and a substituted or unsubstituted pyridylene group; ar (Ar)1、Ar2Each independently represents substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms;
in the general formula (4) or the general formula (5), Y1Each occurrence, identically or differently, being represented by a nitrogen atom or C-R13；
R13Represented by hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, C1-20Alkyl radical, C6-30Aryl of (a), 5-to 30-membered heteroaryl containing one or more heteroatoms;
in the general formula (4), X2、X3Each independently represents a single bond, -O-, -S-, -C (R)14)(R15) -or-N (R)16) -; and X2、X3May not be simultaneously represented as a single bond;
the R is14～R16Are respectively and independently shown as table C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms; and R is14And R15Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from halogen atom, cyano, C1-20Alkyl of (C)6-30One or more of an aryl group, a 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the hetero atom of the heteroaryl is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
3. A compound of claim 1, wherein R is5Each occurrence, identically or differently, is represented by one of a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, and a substituted or unsubstituted furyl group;
the L represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group;
the R is6、R7、R8、R9Each independently represents one of a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted benzofuryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group;
the R is10～R12、R14～R16Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, biphenyl, or pyridyl;
the R is13Represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phenyl group, a naphthyl group, a biphenyl group, a furyl group or a pyridyl group;
ar is1、Ar2Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirofluorenyl group;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano, phenyl, naphthyl, biphenyl, furyl, pyridyl, carbazolyl, furyl, benzofuryl or benzothienyl.
4. The compound of claim 1, wherein the compound has a structure represented by any one of general formulae (II-1) to (II-8):
5. the compound of claim 1, wherein the specific structure of the compound is:
6. An organic electroluminescent device comprising at least one functional layer containing the spirofluorene anthrone-based compound according to any one of claims 1 to 5.
7. The organic electroluminescent device according to claim 6, comprising a hole transport layer/electron blocking layer, wherein the hole transport layer/electron blocking layer contains the spirofluorene anthracenone cored compound according to any one of claims 1 to 5.
8. The organic electroluminescent device according to claim 6, comprising a light-emitting layer, wherein the light-emitting layer contains the spirofluorene anthracenone-based compound according to any one of claims 1 to 5.
9. A lighting or display element, characterized in that the element comprises an organic electroluminescent device according to any one of claims 6 to 8.
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound which takes a spirofluorene anthrone structure as a core and contains a five-membered ring and ring structure and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) 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 a very wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved. Current research into improving the performance of OLED light emitting devices 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 the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
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, etc. are required, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission 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 transmission material, a light emitting material, an electron transmission 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 material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher 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 lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the applicant of the present invention provides a compound with spirofluorene anthrone as a core and an application thereof in an organic electroluminescent device. The compound contains spirofluorene anthrone and a five-membered ring fused ring structure, has higher glass transition temperature, higher molecular thermal stability, proper HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and prolong the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows:
a compound taking spirofluorene anthrone as a core has a structure shown as a general formula (1):
in the general formula (1), m, n, p and q are respectively and independently 0 or 1, and m + n + p + q is more than or equal to 1; l represents, identically or differently on each occurrence, a single bond, substituted or unsubstituted C6-30One of arylene and substituted or unsubstituted 5-to 30-membered heteroarylene;
z, identically or differently on each occurrence, being represented by a nitrogen atom or C-R5Z represents a number of nitrogen atoms less than 3, R5Each occurrence, identically or differently, being represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; and the group Z to which the group L is bonded represents a carbon atom;
the R is1、R2、R3、R4Each independently represents a structure represented by general formula (2) or general formula (3);
the R is6、R7、R8、R9Each independently represents a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, or C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, or an arylamine group; r6、R7、R8、R9The connection mode with the general formula (2) or the general formula (3) can be single bond substitution or ring combination connection; r6、R7The same or different; r8、R9The same or different;
in the general formula (3), X1Represented by oxygen atom, sulfur atom, -C (R)10)(R11) -or-N (R)12)-；
The Y represents a nitrogen atom or C-H; and R is6、R7、R8、R9Y at the junction with the general formula (2) or the general formula (3) represents a carbon atom;
R10～R12are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; wherein R is10And R11Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from cyano, halogen and C1-20Alkyl of (C)6-30One or more of an aryl group, a 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the hetero atom of the heteroaryl is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
Preferred embodiment, R6、R7、R8、R9Are respectively independentThe structure represented by the formula (4), the formula (5) or the formula (6)
The general formula (4) and the general formula (5) are connected with the general formula (2) or the general formula (3) in a fused mode through two adjacent positions marked by the symbol;
in the general formula (6), L1Is one of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene and substituted or unsubstituted pyridylene; ar (Ar)1、Ar2Each independently represents substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms;
in the general formula (4) or the general formula (5), Y1Each occurrence, identically or differently, being represented by a nitrogen atom or C-R13；
R13Represented by hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, C1-20Alkyl radical, C6-30Aryl of (a), 5-to 30-membered heteroaryl containing one or more heteroatoms;
in the general formula (4), X2、X3Each independently represents a single bond, -O-, -S-, -C (R)14)(R15) -or-N (R)16) -; and X2、X3May not be simultaneously represented as a single bond;
the R is14～R16Are respectively and independently shown as table C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms; and R is14And R15Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from halogen atom, cyano, C1-20Alkyl of (C)6-30One or more of an aryl group, a 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the hetero atom of the heteroaryl is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
In a further preferred embodiment, R is5Each occurrence, identically or differently, is represented by one of a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, and a substituted or unsubstituted furyl group;
the L represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group;
the R is6、R7、R8、R9Each independently represents one of a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted benzofuryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group;
the R is10～R12、R14～R16Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, biphenyl, or pyridyl;
the R is13Represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a phenyl group, a naphthyl group, a biphenyl group, a furyl group or a pyridyl group;
ar to1、Ar2Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl groupSubstituted or unsubstituted fluorenyl group, substituted or unsubstituted spirofluorenyl group;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano, phenyl, naphthyl, biphenyl, furyl, pyridyl, carbazolyl, furyl, benzofuryl or benzothienyl.
Preferably, the structure of the compound is represented by any one of general formulas (II-1) to (II-8):
each group in the general formula (1) may be represented by the following symbol;
wherein A represents a substituted or unsubstituted spirofluorene anthrone derivative, and B represents R1、R2、R3、R4。
A is preferably of the structure:
b is preferably of the structure:
preferably, table 1 below gives preferred combinations of (a) and (B), but is not limited thereto:
TABLE 1
Rx is selected from R1、R2、R3、R4、R5(ii) a Preferably, the compound of the present invention is selected from one of compounds 1 to 237.
In one embodiment, the compound of the invention is selected from one of the following compounds:
compound 1-237;
compound 238-474, in turn, having the same structure as compound 1-237, except that A-1 is replaced with A-2;
compound 475-711, which in turn has the same structure as compound 1-237, except that A-1 is replaced with A-3;
compound 712-948, which in turn has the same structure as compound 1-237, except that A-1 is replaced with A-4;
compound 949-11850, which in turn has the same structure as compound 1-237, except that a-1 is replaced with a-5 to a-50, respectively;
further, the compound taking spirofluorene anthrone as a core is preferably of the following specific structure:
any one of the above.
The invention also provides an organic electroluminescent device which comprises at least one functional layer containing the compound taking spirofluorene anthrone as the core.
The organic electroluminescent device comprises a hole transport layer/an electron blocking layer, wherein the hole transport layer/the electron blocking layer contains the compound taking spirofluorene anthrone as a core.
The organic electroluminescent device comprises a light-emitting layer, wherein the light-emitting layer contains the compound taking spirofluorene anthrone as a core.
A lighting or display element comprising the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
(1) the compound is connected with a carbazole derivative by taking spirofluorene anthrone as a framework, and the structure is a large-pi-bond conjugated rigid structure, has large steric hindrance and is not easy to rotate, so that the three-dimensional structure of the compound material is more stable. When the compound is used as a hole transport layer/electron blocking material of an OLED, the appropriate HOMO energy level can effectively realize hole transport; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, improves the recombination efficiency of excitons in the luminescent layer, reduces energy loss, and enables the energy of the main material of the luminescent layer to be fully transferred to the doping material, thereby improving the luminous efficiency of the material after being applied to a device.
(2) The parent nucleus and the branched chain of the compound are connected, so that the distribution of electrons and holes in a light-emitting layer is more balanced, and the hole injection and transmission performance is improved under the proper HOMO energy level; when the spirofluorene anthrone serving as a light-emitting functional layer material of an OLED light-emitting device is used, the spirofluorene anthrone can be matched with the branched chain in the range of the spirofluorene anthrone so as to effectively improve the exciton utilization rate and the high fluorescence radiation efficiency, reduce the efficiency roll-off under high current density, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device.
(3) When the compound is applied to an OLED device, high film stability can be kept through device structure optimization, the photoelectric performance of the OLED device and the service life of the OLED device can be effectively improved, and the compound has good application effect and industrialization prospect.
Drawings
FIG. 1 is a schematic diagram of the application of the compounds of the present invention to an OLED device;
in the figure: 1 is a transparent 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 light emitting layer, 7 is a hole blocking/electron transport layer, 8 is an electron injection layer, and 9 is a cathode reflection electrode layer.
FIG. 2 is a graph of current efficiency measured at different temperatures for OLED devices prepared with the compounds of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Preparation of intermediate II-1
(1) Adding 0.01mol of raw material M1, 0.012mol of raw material N1, 150mL of mixed solvent of toluene and ethanol (wherein the toluene is 100mL, and the ethanol is 50mL) into a 250mL three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 0.02mol K2CO3，1×10-4mol Pd(PPh3)4Heating to 120 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and passing the residue through a neutral silica gel column to obtain an intermediate a 1;
(2) 0.01mol of intermediate a1 was weighed out and dissolved in 100mL of o-dichlorobenzene, and
HPLC purity of intermediate II-1 was 99.82%, yield 76.0%; elemental analysis Structure (molecular formula C)18H11NO): theoretical value: c, 84.03; h, 4.31; n, 5.44; o, 6.22; test values are: c, 84.04; h, 4.31; n, 5.44; o, 6.21. ESI-MS (M/z) (M)+): theoretical value is 257.08, found 257.35.
The synthesis of the intermediate II-1 comprises two steps: synthesizing an intermediate a1 from a raw material M1 and a raw material N1; intermediate a1 undergoes a cyclization reaction to form intermediate II-1. The preparation method of other intermediate II is similar to that of intermediate II-1, and the specific structure of intermediate II used in the invention is shown in Table 2.
TABLE 2
Preparation of intermediate III-1
(1) Adding 0.01mol of raw material M1, 0.012mol of raw material N6, 150mL of mixed solvent of toluene and ethanol (wherein the toluene is 100mL, and the ethanol is 50mL) into a 250mL three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 0.02mol K2CO3，1×10-4mol Pd(PPh3)4Heating to 120 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and passing the residue through a neutral silica gel column to obtain an intermediate a 14;
(2) 0.01mol of intermediate a14 was weighed out and dissolved in 100mL of o-dichlorobenzene, and
(3) In a 250mL three-necked flask, 0.01mol of intermediate II-a, 0.012mol of raw material Z1 and 150mL of toluene were added under nitrogen protection, stirred and mixed, and then
(4) under a nitrogen atmosphere, 0.01mol of intermediate b1, 0.0075mol of bis (pinacolato) diboron, 0.0005mol of Pd (dppf) Cl2Dissolving 0.025mol of potassium acetate in toluene, reacting for 24 hours at 105 ℃, sampling a sample point plate, completely reacting, naturally cooling, filtering, and rotatably steaming filtrate to obtain a crude product, and passing the crude product through a neutral silica gel column to obtain an intermediate III-1.
HPLC purity of intermediate III-1 was 99.80%, yield 74.3%; elemental analysis Structure (molecular formula C)33H32BNO2): theoretical value: c, 81.65; h, 6.64; b, 2.23; n, 2.89; o, 6.59; test values are: c, 81.64; h, 6.65; b, 2.24; n, 2.89; and O, 6.58. ESI-MS (M/z) (M)+): theoretical value is 485.43, found 485.41.
The synthesis of the intermediate III-1 comprises four steps: synthesizing an intermediate a14 from a raw material M1 and a raw material N6; intermediate a14 is subjected to cyclization reaction to form intermediate II-a, intermediate II-a and bis (pinacolato) diboron are synthesized into intermediate III-1, the preparation method of other intermediate III is similar to that of intermediate III-1, and the specific structure of the intermediate III used in the invention is shown in Table 3.
TABLE 3
Preparation of intermediate IV-1
(1) Adding 0.01mol of raw material M1, 0.012mol of raw material N1, 150mL of mixed solvent of toluene and ethanol (wherein the toluene is 100mL, and the ethanol is 50mL) into a 250mL three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 0.02mol K2CO3，1×10-4mol Pd(PPh3)4Heating to 120 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperatureFiltering, and performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and passing the residue through a neutral silica gel column to obtain an intermediate a 1;
(2) 0.01mol of intermediate a1 was weighed out and dissolved in 100mL of o-dichlorobenzene, and
(3) in a 250mL three-necked flask, 0.02mol of intermediate II-1, 0.03mol of raw material E-1, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd are added under the protection of nitrogen2(dba)3Stirring and mixing 0.2mmol of tri-tert-butylphosphine with 150mL of toluene, heating to 110-120 ℃, carrying out reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate II-1 remains and the reaction is complete; naturally cooling to room temperature, filtering, carrying out reduced pressure rotary distillation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate S1-1;
(4) adding 0.02mol of intermediate S1-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 50mL of acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing 0.025mol of liquid bromine, dissolving in 50mL of glacial acetic acid, slowly dropwise adding into an acetic acid solution of the intermediate S1-1, stirring for 5 hours at room temperature, sampling a sample point plate, and indicating that no intermediate S1-1 remains and the reaction is complete; after the reaction is finished, adding alkali liquor into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase for filtration, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate S2-1;
(5) under a nitrogen atmosphere, 0.01mol of intermediate S2-1, 0.0075mol of bis (pinacolato) diboron, and 0.0005mol of Pd (dppf) Cl2Dissolving 0.025mol of potassium acetate in toluene, reacting for 24 hours at 105 ℃, sampling a sample point plate, completely reacting, naturally cooling, filtering, and rotatably steaming filtrate to obtain a crude product, and passing the crude product through a neutral silica gel column to obtain an intermediate IV-1;
the HPLC purity of the intermediate IV-1 is 99.78 percent, and the yield is 75.1 percent; elemental analysis Structure (molecular formula C)36H30BNO3): theoretical value: c, 80.75; h, 5.65; b, 2.02; n, 2.62; o, 8.96; test values are: c, 80.75; h, 5.66; b, 2.02; n, 2.62; and O, 8.95. ESI-MS (M/z) (M)+): theoretical value of 535.45, foundValue 535.43.
The synthesis of the intermediate IV-1 comprises five steps: synthesizing an intermediate a1 from a raw material M1 and a raw material N1; the intermediate a1 is subjected to cyclization reaction to form an intermediate II-1; synthesizing an intermediate S1-1 by the intermediate II-1 and the raw material E-1; bromination of intermediate S1-1 results in intermediate S2-1; finally, intermediate IV-1 is synthesized from intermediate S2-1 and bis (pinacolato) diboron. The preparation method of other intermediate IV is similar to that of intermediate IV-1, and the specific structure of the intermediate IV used in the invention is shown in Table 4.
TABLE 4
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