CN111362861A - Compound containing dibenzosuberene and application thereof in organic electroluminescent device - Google Patents

Compound containing dibenzosuberene and application thereof in organic electroluminescent device Download PDF

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CN111362861A
CN111362861A CN201811598386.5A CN201811598386A CN111362861A CN 111362861 A CN111362861 A CN 111362861A CN 201811598386 A CN201811598386 A CN 201811598386A CN 111362861 A CN111362861 A CN 111362861A
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李崇
庞羽佳
王芳
谢丹丹
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention relates to a compound containing dibenzosuberene and application thereof in an organic electroluminescent device, wherein the structure of the compound is connected with a six-membered ring parallel-ring branched chain structure by using a dibenzosuberene derivative, and the whole molecule is a larger rigid structure and has a high triplet state energy level; 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.

Description

Compound containing dibenzosuberene and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound with a structure that a dibenzosuberene derivative is connected with a multi-membered ring and a ring, and an application of the organic compound in an organic electroluminescent device.
Background
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 present applicant provides a dibenzosuberene-containing compound and its application in organic electroluminescent devices. The compound contains dibenzo cycloheptene derivatives and a multi-membered ring fused ring structure, has higher glass transition temperature, higher molecular thermal stability and proper HOMO energy level, and can effectively improve the photoelectric performance of an OLED device and the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows: a dibenzosuberene-containing compound has a structure shown in a general formula (1):
Figure BDA0001921859020000021
in the general formula (1), - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
m, n, p and q are respectively and independently 0 or 1;
h. each k independently represents 0 or 1, and h + k is 1;
the R is5、R6Each independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen, C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms;
when R is1、R2、R3、R4When connected in a substituted manner to the general formula (1), R1、R2、R3、R4Each independently represents protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 30 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; when R is1、R2、R3、R4When connected in a substituted manner to the general formula (1), R1、R2、R3、R4Each independently is represented by the general formula(2) Or a structure represented by the general formula (3); and R is1、R2、R3、R4At least one of the structures is represented by a general formula (2) or a general formula (3);
Figure BDA0001921859020000022
in the general formula (2), X is1、X2Each independently represents an oxygen atom, a sulfur atom, -C (R)7)(R8)-、-N(R9) -or-Si (R)10)(R11) -, and X1May also represent a single bond;
R7～R11are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is7And R8、R10And R11Can also be connected with each other to form a ring;
the general formula (2) and the general formula (3) are connected in a fused manner with the two adjacent positions marked with the symbol in the general formula (1) through the two adjacent positions marked with the symbol;
the R isa、RbEach independently represents a structure represented by general formula (4) or general formula (5);
Figure BDA0001921859020000031
in the general formula (4) and the general formula (5), R is12、R13Each independently represents a structure represented by general formula (6), general formula (7) or general formula (8);
s and t are respectively and independently 0 or 1;
z represents a nitrogen atom or C (R)14) (ii) a And Z at the attachment site is represented as a carbon atom;
Figure BDA0001921859020000032
the general formula (6) and the general formula (7) are connected by fusing of two adjacent positions marked with x with two adjacent positions marked with x in the general formula (4) and the general formula (5);
in the general formulae (4), (5) and (7), X3、X4、X5、X6、X7Each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)15)(R16) -or-N (R)17) -, and X3And X4、X6And X7May not be simultaneously represented as a single bond;
R15～R17each independently is represented by1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is15And R16Can be connected with each other to form a ring;
the R is14Represented by hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, C1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted;
each occurrence of L, which is the same or different, is represented by a single bond, substituted or unsubstituted C6-30One of arylene, substituted or unsubstituted 5 to 30 membered heteroarylene;
in the general formula (8), Ar1、Ar2Each independently represents substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted;
the substituents of said substitutable groups are optionally selected from protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl radical, C6-30One or more of aryl, 5-to 50-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, characterized in that R is14Represented by hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenylyl group, substituted or unsubstituted terpinyl group, substituted or unsubstituted naphthyl groupUnsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted benzophenanthrenyl, substituted or unsubstituted azabenzophenanthrenyl, a structure of formula (9) or formula (10);
Figure BDA0001921859020000041
said L1、L2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group;
z is1Represented by nitrogen atom or C (R)18) (ii) a And Z at the connection site1Represented as a carbon atom;
X8、X9、X10each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)19)(R20) -or-N (R)21) -, and X8And X9May not be simultaneously represented as a single bond;
R19～R20each independently is represented by1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is19And R20Can be connected with each other to form a ring;
the R is18Represented by hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, C1-10Alkyl radical, C1-10Alkylene, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; two adjacent R18Can be connected with each other to form a ring;
the substituents of said substitutable groups are optionally selected from protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl radical, C6-30One or more of aryl, 5-to 50-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, Ar is1、Ar2Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted azabenzophenanthrenyl group, a structure represented by general formula (9) or general formula (10);
Figure BDA0001921859020000051
said L1、L2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group;
z is1Represented by nitrogen atom or C (R)18)；
X8、X9、X10Each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)19)(R20) -or-N (R)21) -, and X8And X9May not be simultaneously represented as a single bond;
R19～R20each independently is represented by1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is19And R20Can be connected with each other to form a ring;
the R is18Represented by hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, C1-10Alkyl radical, C1-10Alkylene, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; two adjacent R18Can be connected with each other to form a ring;
the substituents of said substitutable groups are optionally selected from protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl radical, C6-30One or more of aryl, 5-to 50-membered heteroaryl containing one or more heteroatoms;
as a further improvement of the invention, R is5、R6Each independently represents one of a hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted pyridyl group, and substituted or unsubstituted furyl group;
the R is7～R11、R15～R17、R19～R20Each independently represents one of methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl and substituted or unsubstituted furyl;
the L represents one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted pyridylene and a substituted or unsubstituted dibenzofuranylene;
the R is18Represented by one of hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted pyridyl group, and substituted or unsubstituted furyl group;
the substituent of the substitutable group is one or more selected from protium, deuterium, tritium, cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, naphthyridinyl, biphenylyl, terphenylyl, furyl, pyridyl, carbazolyl and dibenzofuryl.
As a further improvement of the present invention, the compound structure is represented by any one of general formulae (II-1) to (II-8):
Figure BDA0001921859020000061
Figure BDA0001921859020000071
preferably, the exact preferred examples of the compounds of general formula (1) according to the invention are described below:
Figure BDA0001921859020000072
Figure BDA0001921859020000081
Figure BDA0001921859020000091
Figure BDA0001921859020000101
Figure BDA0001921859020000111
Figure BDA0001921859020000121
Figure BDA0001921859020000131
Figure BDA0001921859020000141
Figure BDA0001921859020000142
one kind of (1).
A method for preparing the organic compound, wherein the reaction equation in the preparation method is as follows:
when L represents a single bond, RaOr RbWhen linked to other groups by C-N bonds:
Figure BDA0001921859020000143
reaction equation 1-1
In the above formula, the amino compound is selected from Ra-H or Rb-H；
The specific process of the reaction formula 1-1 is as follows: weighing the intermediate I and the amino compound, and dissolving the intermediate I and the amino compound by using toluene; then adding Pd2(dba)3、P(t-Bu)3Sodium tert-butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain the target product; the molar ratio of the intermediate I to the amino compound is 1:1.2-3.0, and Pd2(dba)3The molar ratio of the intermediate I to the tri-tert-butylphosphine is 0.006-0.02:1, the molar ratio of the tri-tert-butylphosphine to the intermediate I is (0.006-0.02):1, and the molar ratio of the sodium tert-butoxide to the intermediate I is (1.0-3.0): 1;
when L-RaOr L-RbWhen linked to other groups by C-C bonds:
Figure BDA0001921859020000151
reaction equation 1-2
In the above formula, the boric acid compound is selected from Ra-L-B(OH)2Or Rb-L-B(OH)2；
The specific process of the reaction formula 1-2 is as follows: weighing the intermediate I and a boric acid compound, and dissolving the intermediate I and the boric acid compound by using a mixed solvent of toluene and ethanol in a volume ratio of 2: 1; adding Na under inert atmosphere2CO3Aqueous solution, Pd (PPh)3)4(ii) a Mixing the above reactant solution in the reactionReacting at 95-110 ℃ for 10-24 hours, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product; the molar ratio of the intermediate I to the boric acid compound is 1: 1.0-2.0; na (Na)2CO3The mol ratio of the intermediate I to the intermediate I is 1.0-3.0: 1; pd (PPh)3)4The molar ratio of the intermediate I to the intermediate I is 0.006-0.02: 1.
An organic electroluminescent device in which at least one functional layer contains said dibenzocycloheptene-containing compound.
As a further development of the invention, the functional layer is a hole transport layer and/or an electron blocking layer and/or a light-emitting layer.
A lighting or display element comprising the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
(1) the compounds of the invention all take dibenzosuberene as a center and are connected with aromatic ring fused ring structure derivatives, and the structures have stronger rigidity, large steric hindrance and difficult rotation, so that the three-dimensional structures of the compounds of the invention are 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 structure of the compound enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the proper HOMO energy level, the hole injection and transmission performance is improved; when the material is used as a light-emitting functional layer material of an OLED light-emitting device, the mother nucleus containing the dibenzo seven-membered ring and the branched chain in the range of the invention can effectively improve the exciton utilization rate and the high fluorescence radiation efficiency, reduce the efficiency roll-off under the 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 I-1
Figure BDA0001921859020000161
(1) Adding 0.02mol of a raw material A-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 raw material A-1, stirring at room temperature for 5 hours, and sampling a sample point plate to show that no raw material A-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 Q-1-1; HPLC purity 97.6%, yield 64.1%;
elemental analysis Structure (molecular formula C)28H17Br): theoretical value C, 77.61; h, 3.95; br, 18.44; test values are: c, 77.62; h, 3.94; br, 18.44. ESI-MS (M/z) (M +): theoretical value is 432.05, found 432.12.
(2) In a 250mL three-necked flask, 0.01mol of intermediate Q-1-1 and 0.015mol of raw material B-1 were added under nitrogen protection, and the mixture was dissolved in a mixed solvent of toluene and ethanol (wherein the volume of toluene is 90mL, and the volume of ethanol45mL of alcohol) and then 0.03mol of Na was added2CO3Na of (2)2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through silica gel column to obtain intermediate Q-2-1; HPLC purity 97.8%, yield 88.5%;
elemental analysis Structure (molecular formula C)34H22O): theoretical value C, 91.45; h, 4.97; n, 3.58; test values are: c, 91.45; h, 4.98; and N, 3.57. ESI-MS (M/z) (M +): theoretical value is 446.17, found 446.03.
(3) A 250mL three-neck flask, under the protection of nitrogen, adding 0.01mol of intermediate Q-2-1 and 0.0005mol of palladium acetate, adding 0.02mol of PhCO3Bu-t, dissolving with 100ml dimethyl ether, heating to 150 ℃ under microwave, and reacting for 0.5 hour; sampling a spot plate, and displaying that no intermediate Q-2-1 remains and the reaction is complete; extracting with ethyl acetate, separating, drying the organic phase with anhydrous sodium sulfate, vacuum rotary distilling to remove distillate, and passing the obtained crude product through neutral silica gel column to obtain intermediate Q-3-1 with HPLC purity of 97.2% and yield of 82.9%.
Elemental analysis Structure (molecular formula C)34H20O): theoretical value C, 91.87; h, 4.54; o, 3.60; test values are: c, 91.86; h, 4.53; and O, 3.62. ESI-MS (M/z) (M +): theoretical value is 444.15, found 444.28.
(4) Adding 0.02mol of intermediate Q-3-1 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 Q-3-1, stirring at room temperature for 5 hours, sampling a sample point plate, and indicating that no intermediate Q-3-1 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 I-1; HPLC purity 96.2%, yield 77.8%;
elemental analysis Structure (molecular formula C)34H19BrO): theoretical value C, 78.02; h, 3.66; br, 15.27; o, 3.06; test values are: c, 78.01; h,366; br, 15.27; and O, 3.07. ESI-MS (M/z) (M +): theoretical value is 522.06, found 522.13.
The synthesis of the intermediate I-1 comprises four steps: brominating raw material A-1 to form intermediate Q-1-1; synthesizing an intermediate Q-2-1 by the intermediate Q-1-1 and the raw material B-1; the intermediate Q-2-1 is subjected to cyclization reaction to form an intermediate Q-3-1; finally, the intermediate Q-3-1 is brominated to form the intermediate I-1. Other intermediates I were prepared in a similar manner to intermediate I-1, and the specific structure of intermediate I used in the present invention is shown in Table 1.
TABLE 1
Figure BDA0001921859020000171
Figure BDA0001921859020000181
Preparation of intermediate II-1
Figure BDA0001921859020000182
(1) Weighing 0.01mol of the raw material A-1, dissolving in 100ml of acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing 0.012mol of liquid bromine, dissolving in 50ml of glacial acetic acid, slowly dropwise adding into an acetic acid solution of the intermediate raw material A-1, stirring at room temperature for 5h, sampling a point plate, and displaying that no raw material A-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 R-1-1; HPLC purity 98.4%, yield 69.9%; elemental analysis Structure (molecular formula C)28H17Br): theoretical value C, 77.61; h, 3.95; br, 18.44; test values are: c, 77.60; h, 3.95; br, 18.45. ESI-MS (M/z) (M)+): theoretical value is 432.05, found 432.22.
(2) Weighing 0.01mol of intermediate R-1-1 and 0.02mol of raw material C-1, and dissolving by using a toluene-ethanol mixed solvent with a volume ratio of 1.5-3.0: 1; then 0.01mL of 2mol/mLNa is added2CO3Aqueous solution, 0.01mol Pd (PPh)3)4(ii) a Under the protection of nitrogen, stirring the mixed solution at 95-100 ℃ for reaction for 10-24 hours, then cooling to room temperature, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate R-2-1; HPLC purity 98.5%, yield 88.3%; elemental analysis Structure (molecular formula C)36H24O2): theoretical value C, 88.50; h, 4.95; o, 6.55; test values are: c, 88.51; h, 4.95; and O, 6.54. ESI-MS (M/z) (M)+): theoretical value is 488.18, found 488.05.
(3) Weighing 0.01mol of intermediate R-2-1 under the protection of nitrogen, and stirring and dissolving the intermediate R-2-1 by tetrahydrofuran; cooling the mixed solution to 0 ℃ by using an ice salt bath, slowly dropwise adding 0.03mol of a newly prepared tetrahydrofuran solution corresponding to the Grignard reagent raw material D-1, reacting at room temperature for 6-12 hours, and sampling a sample point plate to show that no intermediate R-2-1 remains and the reaction is complete; naturally standing to room temperature, filtering, performing reduced pressure rotary distillation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate R-3-1; HPLC purity 97.2%, yield 87.6%; elemental analysis Structure (molecular formula C)37H28O): theoretical value C, 90.95; h, 5.78; o, 3.27; test values are: c, 90.94; h, 5.79; and O, 3.27. ESI-MS (M/z) (M)+): theoretical value is 488.21, found 488.08.
(4) Under the protection of nitrogen, 0.01mol of intermediate R-3-1 is weighed, and concentrated H containing 0.05mol of phosphoric acid and having the volume ratio of 1: 2.0-4.0 is used3PO4Dissolving the mixed solution of the intermediate and water as a solvent, reacting at room temperature for 6-12 hours, sampling a sample point plate, and displaying that no intermediate R-3-1 remains and the reaction is complete; adding NaOH aqueous solution to neutralize until pH is 7, adding dichloromethane to extract, layering, taking an organic phase to filter, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain an intermediate R-4-1; HPLC purity 98.1%, yield 88.6%; elemental analysis Structure (molecular formula C)37H26): theoretical value C, 94.43; h, 5.57; test values are: c, 94.43; h, 5.57. ESI-MS (M/z) (M)+): theoretical value is 470.20, found 470.22.
(5) Weighing 0.01mol of intermediate R-4-1, dissolving in 100ml of acetic acid, and cooling to 0 ℃ by using an ice salt bath; 0.012mol of liquid bromine is weighed and dissolved in 50ml of glacial acetic acid, and is slowly dripped into the ethyl of the intermediate R-4-1Stirring for 5 hours at room temperature in an acid solution, sampling a sample point plate, and displaying that the intermediate R-4-1 is not remained 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 II-1; HPLC purity 98.4%, yield 86.7%; elemental analysis Structure (molecular formula C)37H25Br): theoretical value C, 80.87; h, 4.59; br, 14.54; test values are: c, 80.87; h, 4.58; br, 14.55. ESI-MS (M/z) (M)+): theoretical value is 548.11, found 548.26.
The synthesis of the intermediate II-1 comprises five steps: brominating raw material A-1 to form intermediate R-1-1; synthesizing an intermediate R-2-1 by the intermediate R-1-1 and the raw material C-1; the intermediate R-2-1 reacts with the Grignard reagent raw material D-1 to form an intermediate R-3-1; the intermediate R-3-1 is subjected to cyclization reaction to form an intermediate R-4-1; finally, the intermediate R-4-1 is brominated to form an intermediate II-1. The preparation method of other intermediate II is similar to that of intermediate II-1, and the specific structure of the intermediate II used in the invention is shown in Table 2.
TABLE 2
Figure BDA0001921859020000201
Figure BDA0001921859020000211
Preparation of intermediate III-1
Figure BDA0001921859020000212
(1) Adding 0.02mol of a raw material A-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 raw material A-1, stirring at room temperature for 5 hours, and sampling a sample point plate to show that no raw material A-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 S-1-1; HPLC purity 98.0%, yield 67.5%;
elemental analysis Structure (molecular formula C)28H17Br): theoretical value C, 77.61; h, 3.95; br, 18.44; test values are: c, 77.61; h, 3.94; br, 18.45. ESI-MS (M/z) (M +): theoretical value is 432.05, found 432.23.
(2) In a 250mL three-necked flask, 0.01mol of intermediate S-1-1, 0.015mol of raw material E-1 was added under nitrogen protection, dissolved in a mixed solvent of toluene and ethanol (wherein the mixed solvent is 90mL of toluene and 45mL of ethanol), and then 0.03mol of Na was added2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through silica gel column to obtain intermediate S-2-1; HPLC purity 98.3%, yield 85.6%;
elemental analysis Structure (molecular formula C)34H21NO2): theoretical value C, 85.87; h, 4.45; n, 2.95; o, 6.73; test values are: c, 85.88; h, 4.45; n, 2.95; and O, 6.72. ESI-MS (M/z) (M +): theoretical value is 475.16, found 475.03.
(3) Adding 0.02mol of intermediate S-2-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 100mL of o-dichlorobenzene, adding 0.03mol of triphenylphosphine, stirring at 170-190 ℃ for reaction for 12-16 h, cooling to room temperature after the reaction is finished, filtering, decompressing and rotary-steaming filtrate, and passing through a neutral silica gel column to obtain an intermediate S-3-1; HPLC purity 98.0%, yield 88.6%;
elemental analysis Structure (molecular formula C)34H21N): theoretical value C, 92.07; h, 4.77; n, 3.16; test values are: c, 92.07; h, 4.76; and N, 3.17. ESI-MS (M/z) (M +): theoretical value is 443.17, found 443.29.
(4) In a 250mL three-neck flask, under the protection of nitrogen, 0.02mol of intermediate S-3-1, 0.03mol of bromobenzene, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd are added2(dba)30.2mmol of tri-tert-butylphosphine, stirring and mixing with 150mL of toluene, heating to 110-120 ℃, refluxing and reacting for 12-24 hours, sampling a sample point plate, showing that no intermediate S-3-1 remains, and reactingShould be complete; naturally cooling to room temperature, filtering, carrying out reduced pressure rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate S-4-1; HPLC purity 97.2%, yield 82.6%;
elemental analysis Structure (molecular formula C)40H25N): theoretical value C, 92.46; h, 4.85; n, 2.70; test values are: c, 92.46; h, 4.84; n, 2.71. ESI-MS (M/z) (M +): theoretical value is 519.20, found 519.33.
(5) Adding 0.02mol of intermediate S-4-1 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 S-4-1, stirring at room temperature for 5 hours, sampling a sample point plate, and indicating that no intermediate S-4-1 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 III-1; HPLC purity 98.4%, yield 69.5%;
elemental analysis Structure (molecular formula C)40H24BrN): theoretical value C, 80.27; h, 4.04; br, 13.35; n, 2.34; test values are: c, 80.27; h, 4.05; br, 13.34; and N, 2.34. ESI-MS (M/z) (M +): theoretical value is 597.11, found 596.94.
The synthesis of the intermediate III-1 comprises five steps: brominating raw material A-1 to form intermediate S-1-1; synthesizing the intermediate S-2-1 by the intermediate S-1-1 and the raw material E-1; the intermediate S-2-1 is subjected to cyclization reaction to form an intermediate S-3-1; the intermediate S-3-1 reacts with bromobenzene to form an intermediate S-4-1; finally, the intermediate S-4-1 is brominated to form an intermediate III-1. The preparation of the other intermediate III is similar to that of the intermediate III-1, and the specific structure of the intermediate III used in the present invention is shown in Table 3.
TABLE 3
Figure BDA0001921859020000221
Figure BDA0001921859020000231
Preparation of intermediate IV-1
Figure BDA0001921859020000241
(1) In a 250mL three-necked flask, 0.01mol of F-1 as a starting material and 0.015mol of G-1 as a starting material were added under nitrogen protection, and the mixture was dissolved in a mixed solvent of toluene and ethanol (90 mL of toluene and 45mL of ethanol), followed by addition of Na containing 0.03mol of Na2CO3Na of (2)2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through silica gel column to obtain intermediate T-1-1; HPLC purity 97.8%, yield 86.9%;
elemental analysis Structure (molecular formula C)21H17NO2): theoretical value C, 79.98; h, 5.43; n, 4.44; o, 10.15; test values are: c, 79.97; h, 5.43; n, 4.45; o, 10.15. ESI-MS (M/z) (M +): theoretical value is 315.13, found 315.29.
(2) Adding 0.02mol of intermediate T-1-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 100mL of o-dichlorobenzene, adding 0.03mol of triphenylphosphine, stirring at 170-190 ℃ for reaction for 12-16 h, cooling to room temperature after the reaction is finished, filtering, decompressing and rotary-steaming filtrate, and passing through a neutral silica gel column to obtain intermediate T-2-1; HPLC purity 96.2%, yield 79.4%;
elemental analysis Structure (molecular formula C)21H17N): theoretical value C, 89.01; h, 6.05; n, 4.94; test values are: c, 89.01; h, 6.04; and N, 4.95. ESI-MS (M/z) (M +): theoretical value is 283.14, found 283.28.
(3) In a 250mL three-neck flask, 0.02mol of intermediate T-2-1, 0.03mol of bromobenzene, 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 T-2-1 remains and the reaction is complete; naturally cooling to room temperature, filtering, and rotary steaming the filtrate under reduced pressure to obtain the final productPassing through a neutral silica gel column without fractions to obtain an intermediate T-3-1; HPLC purity 94.8%, yield 85.2%;
elemental analysis Structure (molecular formula C)27H21N): theoretical value C, 90.21; h, 5.89; n, 3.90; test values are: c, 90.21; h, 5.88; and N, 3.91. ESI-MS (M/z) (M +): theoretical value is 359.17, found 359.26.
(4) Adding 0.02mol of intermediate T-3-1 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 T-3-1, stirring at room temperature for 5 hours, sampling a sample point plate, and indicating that no intermediate T-3-1 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 T-4-1; HPLC purity 97.9%, yield 82.7%;
elemental analysis Structure (molecular formula C)27H20BrN): theoretical value C, 73.98; h, 4.60; br, 18.23; n, 3.20; test values are: c, 73.97; h, 4.60; br, 18.23; and N, 3.21. ESI-MS (M/z) (M +): theoretical value is 437.08, found 437.14.
(5) Adding 0.02mol of intermediate T-4-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 40mL tetrahydrofuran, cooling to-78 ℃, then adding 15mL tetrahydrofuran solution of 1.6mol/L n-butyllithium into the reaction system, reacting for 3h at-78 ℃, adding 0.024mol triisopropyl borate, reacting for 2h, then raising the temperature of the reaction system to 0 ℃, adding 50mL 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into the extract, drying, rotary steaming, and recrystallizing with ethanol solvent to obtain the intermediate IV-1. HPLC purity 98.3%, yield 73.4%;
elemental analysis Structure (molecular formula C)27H22BNO2): theoretical value C, 80.41; h, 5.50; b, 2.68; n, 3.47; o, 7.93; test values are: c, 80.41; h, 5.50; b, 2.69; n, 3.46; and O, 7.93. ESI-MS (M/z) (M +): theoretical value is 403.17, found 403.25.
The synthesis of the intermediate IV-1 comprises five steps: synthesizing an intermediate T-1-1 from the raw material F-1 and the raw material G-1; the intermediate T-1-1 is subjected to cyclization reaction to form an intermediate T-2-1; synthesizing an intermediate T-3-1 by the intermediate T-2-1 and bromobenzene; brominating the intermediate T-3-1 to form an intermediate T-4-1; and finally synthesizing an intermediate IV-1 by using the intermediate T-4-1 and triisopropyl borate. 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
Figure BDA0001921859020000251
Figure BDA0001921859020000261
Preparation of intermediate V-1
Figure BDA0001921859020000262
(1) In a 250mL three-necked flask, 0.01mol of F-4 as a starting material and 0.015mol of G-4 as a starting material were added under nitrogen protection, and the mixture was dissolved in a mixed solvent of toluene and ethanol (90 mL of toluene and 45mL of ethanol), followed by addition of Na containing 0.03mol of Na2CO3Na of (2)2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through a silica gel column to obtain an intermediate U-1; HPLC purity 96.7%, yield 89.6%;
elemental analysis Structure (molecular formula C)18H11NO3): theoretical value C, 74.73; h, 3.83; n, 4.84; o, 16.59; test values are: c, 74.73; h, 3.84; n, 4.84; and O, 16.58. ESI-MS (M/z) (M +): theoretical value is 289.07, found 289.12.
(2) Adding 0.02mol of an intermediate U-1 into a 250mL three-neck flask under the protection of nitrogen, dissolving with 100mL of o-dichlorobenzene, adding 0.03mol of triphenylphosphine, stirring at 170-190 ℃ for reaction for 12-16 h, cooling to room temperature after the reaction is finished, filtering, decompressing and rotary-steaming the filtrate, and passing through a neutral silica gel column to obtain an intermediate V-1; HPLC purity 94.8%, yield 82.8%;
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, 84.03; h, 4.32; n, 5.44; and O, 6.23. ESI-MS (M/z) (M +): theoretical value is 257.08, found 257.24.
The synthesis of the intermediate V-1 comprises two steps: synthesizing an intermediate U-1 from a raw material F-4 and a raw material G-4; intermediate U-1 is subjected to cyclization reaction to form intermediate V-1. The preparation of the other intermediate V is similar to that of the intermediate V-1, and the specific structure of the intermediate V used in the present invention is shown in Table 5.
TABLE 5
Figure BDA0001921859020000263
Figure BDA0001921859020000271
Preparation of intermediate VI-1
Figure BDA0001921859020000272
(1) Weighing 0.01mol of raw material H-1 and 0.02mol of raw material J-1, and dissolving by using a toluene-ethanol mixed solvent with a volume ratio of 1.5-3.0: 1; then, 0.01mL of 2mol/mL of Na was added2CO3Aqueous solution, 0.01mol Pd (PPh)3)4(ii) a Under the protection of nitrogen, stirring the mixed solution at 95-100 ℃ for reaction for 10-24 hours, then cooling to room temperature, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate W-1-1; HPLC purity 97.5%, yield 87.4%; elemental analysis Structure (molecular formula C)20H14O2S): theoretical value C, 75.45; h, 4.43; o, 10.05; s, 10.07; test values are: c, 75.45; h, 4.42; o, 10.05; and S, 10.08. ESI-MS (M/z) (M)+): theoretical value is 318.07, found 318.25.
(2) Weighing 0.01mol of intermediate W-1-1 under the protection of nitrogen, and stirring and dissolving the intermediate W-1-1 with tetrahydrofuran; cooling the mixed solution to 0 ℃ by using an ice salt bath, slowly dropwise adding 0.03mol of a newly prepared tetrahydrofuran solution corresponding to the Grignard reagent raw material D-1, reacting at room temperature for 6-12 hours, and sampling a sample point plate to show that no intermediate W-1-1 remains and the reaction is complete; naturally standing 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 W-2-1; HPLC purity 94.9%, yield 79.9%; elemental analysis Structure (molecular formula C)21H18OS): theoretical value C, 79.21; h, 5.70; o, 5.02; s, 10.07; test values are: c, 79.22; h, 5.70; o, 5.02; s, 10.06. ESI-MS (M/z) (M)+): theoretical value is 318.11, found 318.04.
(3) Under the protection of nitrogen, 0.01mol of intermediate W-2-1 is weighed, and concentrated H containing 0.05mol of phosphoric acid and having the volume ratio of 1: 2.0-4.0 is used3PO4Dissolving the mixed solution of the intermediate and water as a solvent, reacting at room temperature for 6-12 hours, sampling a sample point plate, and indicating that no intermediate W-2-1 is left and the reaction is complete; adding NaOH aqueous solution to neutralize until pH is 7, adding dichloromethane to extract, demixing, taking an organic phase to filter, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain an intermediate W-3-1; HPLC purity 94.8%, yield 85.9%; elemental analysis Structure (molecular formula C)21H16S): theoretical value C, 83.96; h, 5.37; s, 10.67; test values are: c, 83.95; h, 5.38; s, 10.67. ESI-MS (M/z) (M)+): theoretical value is 300.10, found 299.98.
(4) Weighing 0.01mol of intermediate W-3-1, dissolving in 100ml of acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing 0.012mol of liquid bromine, dissolving in 50ml of glacial acetic acid, slowly dropwise adding into an acetic acid solution of the intermediate W-3-1, stirring at room temperature for 5h, sampling a point plate, and displaying that the intermediate W-3-1 has no residue 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 W-4-1; HPLC purity 97.3%, yield 82.1%; elemental analysis Structure (molecular formula C)21H15BrS): theoretical value C, 66.50; h, 3.99; br, 21.07; s, 8.45; test values are: c, 66.50; h, 3.98;Br,21.07；S,8.46。ESI-MS(m/z)(M+): theoretical value is 378.01, found 378.24.
(5) Adding 0.02mol of intermediate W-4-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 40mL tetrahydrofuran, cooling to-78 ℃, then adding 15mL tetrahydrofuran solution of 1.6mol/L n-butyllithium into the reaction system, reacting for 3h at-78 ℃, then adding 0.024mol triisopropyl borate, reacting for 2h, then raising the temperature of the reaction system to 0 ℃, adding 50mL 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into the extract, drying, carrying out rotary evaporation, and recrystallizing with an ethanol solvent to obtain the intermediate VI-1. HPLC purity 96.4%, yield 78.4%;
elemental analysis Structure (molecular formula C)21H17BO2S): theoretical value C, 73.27; h, 4.98; b, 3.14; o, 9.30; s, 9.31; test values are: c, 73.26; h, 4.98; b, 3.14; o, 9.31; s, 9.31. ESI-MS (M/z) (M +): theoretical value is 344.10, found 344.23.
The synthesis of the intermediate VI-1 comprises five steps: reacting a raw material H-1 with a raw material J-1 to generate an intermediate W-1-1; synthesizing an intermediate W-2-1 by the intermediate W-1-1 and a Grignard reagent raw material D-1; the intermediate W-2-1 is subjected to cyclization reaction to form an intermediate W-3-1; carrying out bromination reaction on the intermediate W-3-1 to form an intermediate W-4-1; finally, the intermediate W-4-1 reacts to generate a boric acid compound intermediate VI-1. The preparation method of other intermediate VI is similar to that of intermediate VI-1, and the specific structure of the intermediate VI used in the invention is shown in Table 6.
TABLE 6
Figure BDA0001921859020000291
EXAMPLE 1 preparation of Compound 8
Figure BDA0001921859020000292
In a 250mL three-necked flask, nitrogen gas was introduced, 0.01mol of the starting material X-1, 0.015mol of the intermediate IV-1 were added, and the mixture was dissolved in a mixed solvent of toluene and ethanol (wherein toluene was used90mL of ethanol, 45mL) and then 0.03mol of Na is added2CO3Na of (2)2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through a silica gel column to obtain a target product with HPLC purity of 96.4% and yield of 87.6%;
elemental analysis Structure (molecular formula C)59H39N): theoretical value C, 93.00; h, 5.16; n, 1.84; test values are: c, 93.00; h, 5.15; n, 1.85. HPLC-MS: the molecular weight of the material is 761.31, and the measured molecular weight is 761.24.
EXAMPLE 2 preparation of Compound 13
Figure BDA0001921859020000301
Adding 0.01mol of raw material X-2, 0.012mol of intermediate V-1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, then adding 0.03mol of sodium tert-butoxide, 5 × 10-5molPd2(dba)3，5×10-5Heating the mol tri-tert-butylphosphine to 105 ℃, carrying out reflux reaction for 24 hours, sampling a point plate, and indicating 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 through a neutral silica gel column to obtain a target product, wherein the HPLC purity is 97.8%, and the yield is 88.1%;
elemental analysis Structure (molecular formula C)50H31NO): theoretical value C, 90.74; h, 4.72; n, 2.12; o, 2.42; test values are: c, 90.74; h, 4.71; n, 2.12; o, 2.43. HPLC-MS: the molecular weight of the material is 661.24, and the measured molecular weight is 661.29.
EXAMPLE 3 preparation of Compound 22
Figure BDA0001921859020000302
Compound 22 is prepared as in example 2, except that intermediate I-1 is used instead of starting material X-2 and intermediate V-2 is used instead of intermediate V-1.
Elemental analysis Structure (molecular formula C)52H29NO2): theoretical value C, 89.25; h, 4.18; n, 2.00; o, 4.57; test values are: c, 89.25; h, 4.17; n, 2.01; and O, 4.57. HPLC-MS: the molecular weight of the material is 699.22, and the measured molecular weight is 699.32.
EXAMPLE 4 preparation of Compound 31
Figure BDA0001921859020000303
Compound 31 is prepared as in example 2, except that intermediate I-2 is used instead of starting material X-2 and intermediate V-3 is used instead of intermediate V-1.
Elemental analysis Structure (molecular formula C)58H36N2O): theoretical value C, 89.66; h, 4.67; n, 3.61; o, 2.06; test values are: c, 89.66; h, 4.68; n, 3.60; and O, 2.06. HPLC-MS: the molecular weight of the material is 776.28, and the measured molecular weight is 776.31.
EXAMPLE 5 preparation of Compound 45
Figure BDA0001921859020000311
Compound 45 was prepared as in example 2, except that intermediate I-3 was used instead of starting material X-2 and intermediate V-3 was used instead of intermediate V-1.
Elemental analysis Structure (molecular formula C)58H34N2O): theoretical value C, 89.90; h, 4.42; n, 3.62; o, 2.06; test values are: c, 89.91; h, 4.41; n, 3.62; and O, 2.06. HPLC-MS: the molecular weight of the material is 774.27, and the measured molecular weight is 774.35.
EXAMPLE 6 preparation of Compound 67
Figure BDA0001921859020000312
Compound 67 was prepared as in example 2, except that intermediate II-1 was used in place of starting material X-2 and intermediate V-4 was used in place of intermediate V-1.
Element classificationStructure (molecular formula C)58H41NO): theoretical value C, 90.71; h, 5.38; n, 1.82; o, 2.08; test values are: c, 90.70; h, 5.38; n, 1.82; and O, 2.09. HPLC-MS: the molecular weight of the material is 767.32, and the measured molecular weight is 767.40.
EXAMPLE 7 preparation of Compound 73
Figure BDA0001921859020000313
Compound 73 was prepared as in example 1, except that intermediate II-2 was used in place of starting material X-1 and intermediate VI-1 was used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)58H40S): theoretical value C, 90.59; h, 5.24; s, 4.17; test values are: c, 90.58; h, 5.24; and S, 4.18. HPLC-MS: the molecular weight of the material is 768.29, and the measured molecular weight is 768.31.
EXAMPLE 8 preparation of Compound 87
Figure BDA0001921859020000321
Compound 87 was prepared as in example 2, except that intermediate II-3 was used in place of starting material X-2 and starting material Y-1 was used in place of intermediate V-1.
Elemental analysis Structure (molecular formula C)57H37N): theoretical value C, 93.03; h, 5.07; n, 1.90; test values are: c, 93.02; h, 5.07; and N, 1.91. HPLC-MS: the molecular weight of the material is 735.29, and the measured molecular weight is 735.42.
EXAMPLE 9 preparation of Compound 104
Figure BDA0001921859020000322
Compound 104 was prepared as in example 1, except that intermediate III-1 was used in place of starting material X-1 and starting material Y-2 was used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)69H43N): theoretical value C, 93.53; h, 4.89; n, 1.58; test values are: c,93.54(ii) a H, 4.90; n, 1.56. HPLC-MS: the molecular weight of the material is 885.34, and the measured molecular weight is 885.24.
EXAMPLE 10 preparation of Compound 115
Figure BDA0001921859020000323
Compound 115 is prepared as in example 1, except that intermediate III-2 is used in place of starting material X-1 and intermediate IV-2 is used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)77H50N2): theoretical value C, 92.18; h, 5.02; n, 2.79; test values are: c, 92.18; h, 5.03; n, 2.78. HPLC-MS: the molecular weight of the material is 1002.40, and the measured molecular weight is 1002.46.
EXAMPLE 11 preparation of Compound 136
Figure BDA0001921859020000331
Compound 136 was prepared as in example 2, except that intermediate III-3 was used in place of starting material X-2.
Elemental analysis Structure (molecular formula C)58H36N2O): theoretical value C, 89.66; h, 4.67; n, 3.61; o, 2.06; test values are: c, 89.65; h, 4.67; n, 3.61; and O, 2.07. HPLC-MS: the molecular weight of the material is 776.28, and the measured molecular weight is 776.43.
EXAMPLE 12 preparation of Compound 145
Figure BDA0001921859020000332
Compound 145 was prepared as in example 2, except that intermediate II-4 was used in place of starting material X-2.
Elemental analysis Structure (molecular formula C)65H39NO): theoretical value C, 91.85; h, 4.62; n, 1.65; o, 1.88; test values are: c, 91.84; h, 4.62; n, 1.65; o, 1.89. HPLC-MS: the molecular weight of the material is 849.30, and the measured molecular weight is 849.46.
EXAMPLE 13 preparation of Compound 159
Figure BDA0001921859020000333
Compound 159 was prepared as in example 1, except that intermediate II-5 was used in place of starting material X-1 and intermediate IV-3 was used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)84H53N): theoretical value C, 93.74; h, 4.96; n, 1.30; test values are: c, 93.74; h, 4.95; n, 1.31. HPLC-MS: the molecular weight of the material is 1075.42, and the measured molecular weight is 1075.51.
EXAMPLE 14 preparation of Compound 187
Figure BDA0001921859020000334
Compound 187 can be prepared as in example 1, except that intermediate III-4 is used in place of starting material X-1 and starting material Y-3 is used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)72H51N): theoretical value C, 92.97; h, 5.53; n, 1.51; test values are: c, 92.96; h, 5.53; n, 1.52. HPLC-MS: the molecular weight of the material is 929.40, and the measured molecular weight is 929.46.
EXAMPLE 15 preparation of Compound 201
Figure BDA0001921859020000341
The preparation method of the compound 201 is the same as that of example 1, except that the intermediate III-5 is used instead of the raw material X-1, and the raw material VI-2 is used instead of the intermediate IV-1.
Elemental analysis Structure (molecular formula C)87H59N): theoretical value C, 93.43; h, 5.32; n, 1.25; test values are: c, 93.43; h, 5.33; and N, 1.24. HPLC-MS: the molecular weight of the material is 1117.46, and the measured molecular weight is 1117.30.
EXAMPLE 16 preparation of Compound 214
Figure BDA0001921859020000342
Compound 214 is prepared as in example 1, except that intermediate I-4 is used in place of starting material X-1 and intermediate VI-3 is used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)58H40OS): theoretical value C, 88.74; h, 5.14; o, 2.04; s, 4.08; test values are: c, 88.73; h, 5.15; o, 2.04; and S, 4.08. HPLC-MS: the molecular weight of the material is 784.28, and the measured molecular weight is 784.09.
EXAMPLE 17 preparation of Compound 230
Figure BDA0001921859020000343
The preparation of compound 230 was carried out as in example 1 except that intermediate III-6 was used in place of starting material X-1 and intermediate IV-1 was used in place of starting material VI-4.
Elemental analysis Structure (molecular formula C)61H39NO2): theoretical value C, 89.57; h, 4.81; n, 1.71; o, 3.91; test values are: c, 89.57; h, 4.80; n, 1.71; and O, 3.92. HPLC-MS: the molecular weight of the material is 817.30, and the measured molecular weight is 817.18.
EXAMPLE 18 preparation of Compound 243
Figure BDA0001921859020000351
Compound 243 is prepared as in example 2, except that intermediate III-7 is used instead of starting material X-2 and intermediate V-5 is used instead of intermediate V-1.
Elemental analysis Structure (molecular formula C)67H47N3): theoretical value C, 90.00; h, 5.30; n, 4.70; test values are: c, 89.99; h, 5.30; n, 4.71. HPLC-MS: the molecular weight of the material is 893.38, and the measured molecular weight is 893.46.
EXAMPLE 19 preparation of Compound 247
Figure BDA0001921859020000352
Compound 247 was prepared as in example 2, except that intermediate I-5 was used instead of starting material X-2 and intermediate V-6 was used instead of intermediate V-1.
Elemental analysis Structure (molecular formula C)60H32N4O): theoretical value C, 87.36; h, 3.91; n, 6.79; o, 1.94; test values are: c, 87.35; h, 3.91; n, 6.79; o, 1.95. HPLC-MS: the molecular weight of the material is 824.26, and the measured molecular weight is 824.32.
EXAMPLE 20 preparation of Compound 248
Figure BDA0001921859020000353
Compound 248 is prepared as in example 2, except that intermediate II-6 is used in place of starting material X-2 and starting material Y-4 is used in place of intermediate V-1.
Elemental analysis Structure (molecular formula C)53H33Br2N): theoretical value C, 75.45; h, 3.94; br, 18.94; n, 1.66; test values are: c, 75.46; h, 3.94; br, 18.93; n, 1.66. HPLC-MS: the molecular weight of the material is 841.10, and the measured molecular weight is 841.03.
EXAMPLE 21 preparation of Compound 249
Figure BDA0001921859020000361
Compound 249 is prepared as in example 1, except that intermediate I-6 is used in place of starting material X-1 and intermediate IV-4 is used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)69H55NO): theoretical value C, 90.65; h, 6.06; n, 1.53; o, 1.75; test values are: c, 90.65; h, 6.06; n, 1.52; o, 1.76. HPLC-MS: the molecular weight of the material is 913.43, and the measured molecular weight is 913.49.
EXAMPLE 22 preparation of Compound 257
Figure BDA0001921859020000362
Compound 257 was prepared as in example 1, except that intermediate I-7 was used in place of starting material X-1 and starting material Y-5 was used in place of intermediate IV-1.
Elemental analysis Structure (molecular formula C)75H48O): theoretical value C, 93.33; h, 5.01; o, 1.66; test values are: c, 93.32; h, 5.01; o, 1.67. HPLC-MS: the molecular weight of the material is 964.37, and the measured molecular weight is 964.28.
EXAMPLE 23 preparation of Compound 258
Figure BDA0001921859020000363
Compound 258 is prepared as in example 2, except that intermediate II-7 is used in place of starting material X-2 and intermediate V-7 is used in place of intermediate V-1.
Elemental analysis Structure (molecular formula C)71H48N4): theoretical value C, 89.09; h, 5.05; n, 5.85; test values are: c, 89.09; h, 5.04; and N, 5.86. HPLC-MS: the molecular weight of the material is 956.39, and the measured molecular weight is 956.36.
The compound is used in a light-emitting device, has high glass transition temperature (Tg) and triplet state energy level (T1), and suitable HOMO and LUMO energy levels, and can be used as hole transport, electron blocking and light-emitting layer materials. The compounds prepared in the above examples of the present invention were tested for thermal properties, T1 energy level, and HOMO energy level, respectively, and the results are shown in table 7.
TABLE 7
Compound (I) T1(eV) Tg(℃) HOMO energy level (eV) Functional layer
Compound 8 2.73 159 -5.61 Hole transport/electron blocking layer
Compound 13 2.64 154 -5.48 Hole transport/electron blocking layer
Compound 22 2.77 162 -5.71 Luminescent layer
Compound 31 2.70 158 -5.63 Hole transport/electron blocking layer
Compound 45 2.69 161 -5.65 Hole transport/electron blocking layer
Compound 67 2.62 158 -5.46 Hole transport/electron blocking layer
Compound 73 2.64 156 -5.50 Hole transport/electron blocking layer
Compound 87 2.71 162 -5.64 Hole transport/electron blocking layer
Compound 104 2.73 161 -5.62 Hole transport/electron blocking layer
Compound 115 2.62 158 -5.48 Hole transport/electron blocking layer
Compound 136 2.76 156 -5.69 Luminescent layer
Compound 145 2.69 159 -5.63 Hole transport/electron blocking layer
Compound 159 2.65 158 -5.47 Hole transport/electron blocking layer
Compound 187 2.70 161 -5.61 Hole transport/electron blocking layer
Compound 201 2.71 158 -5.63 Hole transport/electron blocking layer
Compound 214 2.73 160 -5.73 Luminescent layer
Compound 230 2.69 158 -5.64 Hole transport/electron blocking layer
Compound 243 2.71 160 -5.71 Luminescent layer
Compound 247 2.65 158 -5.49 Hole transport/electron blocking layer
Compound 248 2.68 162 -5.62 Luminescent layer
Compound 249 2.70 159 -5.63 Hole transport/electron blocking layer
Compound 257 (Novak) 2.66 162 -5.65 Hole transport/electron blocking layer
Compound 258 2.72 160 -5.47 Hole transportElectron transport/blocking layer
Compound 261 2.69 158 -5.60 Hole transport/electron blocking layer
Compound 264 2.71 161 -5.51 Hole transport/electron blocking layer
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10- 5A toluene solution of mol/L; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy test system (IPS-3), which is an atmospheric environment.
The data in the table show that the compound has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the compound contains an electron donor and an electron acceptor, so that electrons and holes of an OLED device applying the compound reach a balanced state, the recombination rate of the electrons and the holes is ensured, the efficiency and the service life of the OLED device are improved, and the material has a high triplet state energy level, can block energy loss of a light-emitting layer, and improves the light-emitting efficiency of the device. Meanwhile, the material has a proper HOMO energy level, so that the problem of carrier injection can be solved, and the voltage of a device can be reduced; therefore, after the organic material is applied to different functional layers of an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.
The effect of the application of the compounds of the present invention in OLED devices will now be illustrated by device examples 1-25 and device comparative example 1. Device examples 2 to 25 and device comparative example 1 were compared with device example 1, and the manufacturing processes were completely the same, and the same substrate material and electrode material were used, and the film thicknesses of the electrode materials were also kept the same, except that the hole transport/electron blocking layer material or the light emitting layer material in the devices were changed, the composition of each layer of each device is shown in table 8, and the performance test results of each device are shown in tables 9 and 10.
Device example 1
As shown in fig. 1, an electroluminescent device is prepared by the following steps:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes;
b) evaporating HAT-CN as a hole injection layer 3 on the ITO anode layer 2 in a vacuum evaporation mode, wherein the evaporation thickness is 10 nm;
c) evaporating a compound HT-1 on the hole injection layer 3 in a vacuum evaporation mode to form a hole transport layer 4, wherein the evaporation thickness is 60 nm;
d) evaporating the compound 8 of the invention as an electron blocking layer 5 on the hole transport layer 4 in a vacuum evaporation mode, wherein the evaporation thickness is 20 nm;
e) a light-emitting layer 6 is vapor-plated on the electron blocking layer 5, the host materials of the light-emitting layer 6 are GH-1 and GH-2, the doping material is GD-1, the mass ratio of GH-1 to GH-2 to GD-1 is 45:45:10, and the thickness is 30 nm;
f) evaporating ET-1 and Liq as a hole blocking/electron transporting layer 7 on the light-emitting layer 6 in a vacuum evaporation mode, wherein the mass ratio is 1:1, and the evaporation thickness is 35 nm;
g) vacuum evaporation of an electron injection layer LiF serving as an electron injection layer 8 is carried out on the hole blocking/electron transport layer 7, and the evaporation thickness is 1 nm;
h) and vacuum evaporating cathode Al on the electron injection layer 8 to form a cathode reflection electrode layer 9, wherein the evaporation thickness is 100nm, and thus the electroluminescent device is obtained. The composition of each layer of each device is shown in table 8, the performance test results of each device are shown in tables 9 and 10, and the structural formula of the existing material used by each device is as follows:
Figure BDA0001921859020000391
TABLE 8
Figure BDA0001921859020000392
Figure BDA0001921859020000401
Figure BDA0001921859020000411
TABLE 9
Figure BDA0001921859020000421
Figure BDA0001921859020000431
Note: LT97 refers to a current density of 10mA/cm2In the case, the time taken for the luminance of the device to decay to 97%;
the life test system is a Korean pulse science M600 type OLED device life tester.
As can be seen from the results in Table 9, the dibenzosuberene-containing compound prepared by the invention can be applied to the preparation of OLED light-emitting devices, and compared with comparative device examples, the efficiency and the service life of the compound are greatly improved compared with those of known OLED materials, and particularly the service life decay of the device is greatly improved.
In order to compare the efficiency attenuation conditions of different devices under high current density, the efficiency attenuation coefficient of each device is defined
Figure BDA0001921859020000433
Indicates that the drive current is 100mAcm2The ratio between the difference between the maximum efficiency μ 100 of the device and the maximum efficiency μm of the device and the maximum efficiency,
Figure BDA0001921859020000434
the larger the value, the more serious the efficiency roll-off of the device is, and conversely, the problem that the device rapidly decays under high current density is controlled. The efficiency attenuation coefficient of the devices obtained in device examples 1-25 and device comparative example 1 was measured
Figure BDA0001921859020000435
The results are shown in Table 10:
watch 10
Figure BDA0001921859020000432
As can be seen from the data in table 10, the organic light emitting device prepared by using the compound of the present invention has a smaller efficiency roll-off coefficient, which indicates that the organic light emitting device prepared by using the compound of the present invention can effectively reduce the efficiency roll-off.
The efficiency of the OLED device prepared by the compound is stable when the OLED device works at low temperature, the efficiency of the devices obtained in device examples 1, 5 and 9 and device comparative example 1 is tested at the temperature of-10-80 ℃, and the obtained results are shown in a table 11 and a figure 2.
TABLE 11
Figure BDA0001921859020000441
As can be seen from the data in table 11 and fig. 2, device examples 1, 5 and 9 are device structures in which the compound of the present invention and known materials are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A dibenzosuberene-containing compound is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0001921859010000011
in the general formula (1), - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
m, n, p and q are respectively and independently 0 or 1;
h. each k independently represents 0 or 1, and h + k is 1;
the R is5、R6Each independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen, C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms;
when R is1、R2、R3、R4When connected in a substituted manner to the general formula (1), R1、R2、R3、R4Each independently represents protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 30 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; when R is1、R2、R3、R4When connected in a substituted manner to the general formula (1), R1、R2、R3、R4Each independently represents a structure shown in a general formula (2) or a general formula (3); and R is1、R2、R3、R4At least one of the structures is represented by a general formula (2) or a general formula (3);
Figure FDA0001921859010000012
in the general formula (2), X is1、X2Each independently represents an oxygen atom, a sulfur atom, -C (R)7)(R8)-、-N(R9)-or-Si (R)10)(R11) -, and X1May also represent a single bond;
R7～R11are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is7And R8、R10And R11Can also be connected with each other to form a ring;
the general formula (2) and the general formula (3) are connected in a fused manner with the two adjacent positions marked with the symbol in the general formula (1) through the two adjacent positions marked with the symbol;
the R isa、RbEach independently represents a structure represented by general formula (4) or general formula (5);
Figure FDA0001921859010000021
s and t are respectively and independently 0 or 1;
z represents a nitrogen atom or C (R)14) (ii) a And Z at the attachment site is represented as a carbon atom;
in the general formula (4) and the general formula (5), R is12、R13Each independently represents a structure represented by general formula (6), general formula (7) or general formula (8);
Figure FDA0001921859010000022
the general formula (6) and the general formula (7) are connected by fusing of two adjacent positions marked with x with two adjacent positions marked with x in the general formula (4) and the general formula (5);
in the general formulae (4), (5) and (7), X3、X4、X5、X6、X7Each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)15)(R16) -or-N (R)17) -, and X3And X4、X6And X7May not be simultaneously represented as a single bond;
R15～R17each independently is represented by1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is15And R16Can be connected with each other to form a ring;
the R is14Represented by hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, C1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted;
each occurrence of L, which is the same or different, is represented by a single bond, substituted or unsubstituted C6-30One of arylene, substituted or unsubstituted 5 to 30 membered heteroarylene;
in the general formula (8), Ar1、Ar2Each independently represents substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted;
the substituents of said substitutable groups are optionally selected from protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl radical, C6-30One or more of aryl, 5-to 50-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. The dibenzocycloheptene-containing compound of claim 1, wherein R is selected from the group consisting of14Represented by a hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenylyl group, substituted or unsubstituted terpinyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted azabenzophenanthrenyl group, a structure represented by general formula (9) or general formula (10);
Figure FDA0001921859010000031
said L1、L2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group;
z is1Represented by nitrogen atom or C (R)18) (ii) a And Z at the connection site1Represented as a carbon atom;
X8、X9、X10each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)19)(R20) -or-N (R)21) -, and X8And X9May not be simultaneously represented as a single bond;
R19～R20each independently is represented by1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is19And R20Can be connected with each other to form a ring;
the R is18Represented by hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, C1-10Alkyl radical, C1-10Alkylene, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; two adjacent R18Can be connected with each other to form a ring;
the substituents of said substitutable groups are optionally selected from protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl radical, C6-30One or more of aryl, 5-to 50-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
3. The dibenzocycloheptene-containing compound of claim 1, wherein Ar is Ar1、Ar2Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl groupSubstituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted benzophenanthrenyl, substituted or unsubstituted azabenzophenanthrenyl, a structure of formula (9) or (10);
Figure FDA0001921859010000032
said L1、L2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group;
z is1Represented by nitrogen atom or C (R)18)；
X8、X9、X10Each independently represents a single bond, an oxygen atom, a sulfur atom, -C (R)19)(R20) -or-N (R)21) -, and X8And X9May not be simultaneously represented as a single bond;
R19～R20each independently is represented by1-10Alkyl, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; wherein R is19And R20Can be connected with each other to form a ring;
the R is18Represented by hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, C1-10Alkyl radical, C1-10Alkylene, substituted or unsubstituted C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms substituted or unsubstituted; two adjacent R18Can be connected with each other to form a ring;
the substituents of said substitutable groups are optionally selected from protium, deuterium, tritium, cyano, halogen atom, C1-10Alkyl radical, C6-30Aryl, 5 to 50 membered heteroaryl containing one or more heteroatoms.
4. The dibenzocycloheptene-containing compound of claim 2 wherein R is5、R6Each independently represents one of a hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted pyridyl group, and substituted or unsubstituted furyl group;
the R is7～R11、R15～R17、R19～R20Each independently represents one of methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl and substituted or unsubstituted furyl;
the L represents one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted pyridylene and a substituted or unsubstituted dibenzofuranylene;
the R is18Represented by one of hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted pyridyl group, and substituted or unsubstituted furyl group;
the substituent of the substitutable group is one or more selected from protium, deuterium, tritium, cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, naphthyridinyl, biphenylyl, terphenylyl, furyl, pyridyl, carbazolyl and dibenzofuryl.
5. The compound of claim 1, wherein the compound structure is represented by any one of general formulae (ii-1) to (ii-8):
Figure FDA0001921859010000051
Figure FDA0001921859010000061
6. the dibenzosuberene-cored compound of claim 1, wherein the compound has the following structure:
Figure FDA0001921859010000062
Figure FDA0001921859010000071
Figure FDA0001921859010000081
Figure FDA0001921859010000091
Figure FDA0001921859010000101
Figure FDA0001921859010000111
Figure FDA0001921859010000121
Figure FDA0001921859010000131
Figure FDA0001921859010000132
one kind of (1).
7. A process for the preparation of an organic compound according to any one of claims 1 to 6, wherein the reaction equation in the preparation process is:
when L represents a single bond, RaOr RbWhen linked to other groups by C-N bonds:
Figure FDA0001921859010000133
in the above formula, the amino compound is selected from Ra-H or Rb-H；
The specific process of the reaction formula 1-1 is as follows: weighing the intermediate I and the amino compound, and dissolving the intermediate I and the amino compound by using toluene; then adding Pd2(dba)3、P(t-Bu)3Sodium tert-butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain the target product; the molar ratio of the intermediate I to the amino compound is 1:1.2-3.0, and Pd2(dba)3The molar ratio of the intermediate I to the tri-tert-butylphosphine is 0.006-0.02:1, the molar ratio of the tri-tert-butylphosphine to the intermediate I is (0.006-0.02):1, and the molar ratio of the sodium tert-butoxide to the intermediate I is (1.0-3.0): 1;
when L-RaOr L-RbWhen linked to other groups by C-C bonds:
Figure FDA0001921859010000141
in the above formula, the boric acid compound is selected from Ra-L-B(OH)2Or Rb-L-B(OH)2；
The specific process of the reaction formula 1-2 is as follows: weighing the intermediate I and a boric acid compound, and dissolving the intermediate I and the boric acid compound by using a mixed solvent of toluene and ethanol in a volume ratio of 2: 1; adding Na under inert atmosphere2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product; the molar ratio of the intermediate I to the boric acid compound is 1: 1.0-2.0; na (Na)2CO3The mol ratio of the intermediate I to the intermediate I is 1.0-3.0: 1; pd (PPh)3)4The molar ratio of the intermediate I to the intermediate I is 0.006-0.02: 1.
8. An organic electroluminescent element, wherein at least one functional layer of the organic electroluminescent element comprises the dibenzocycloheptene-containing compound according to any one of claims 1 to 6.
9. An organic electroluminescent device according to claim 8, wherein the functional layer is a hole transport layer and/or an electron blocking layer and/or a light emitting layer.
10. A lighting or display element comprising the organic electroluminescent device according to claim 8 or 9.
CN201811598386.5A 2018-12-26 2018-12-26 Compound containing dibenzosuberene and application thereof in organic electroluminescent device Pending CN111362861A (en)

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CN110655471A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Compound taking spiro dibenzosuberene fluorene as core and application of compound in organic electroluminescent device
WO2024067503A1 (en) * 2022-09-30 2024-04-04 阜阳欣奕华材料科技有限公司 Composition and organic electroluminescent device comprising same

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KR20150104259A (en) * 2014-03-04 2015-09-15 삼성디스플레이 주식회사 Organic light emitting device

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Publication number Priority date Publication date Assignee Title
KR20150104259A (en) * 2014-03-04 2015-09-15 삼성디스플레이 주식회사 Organic light emitting device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655471A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Compound taking spiro dibenzosuberene fluorene as core and application of compound in organic electroluminescent device
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