CN111943956A - Compound with dibenzo six-membered ring as core, preparation method and application thereof - Google Patents

Compound with dibenzo six-membered ring as core, preparation method and application thereof Download PDF

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CN111943956A
CN111943956A CN201910399156.4A CN201910399156A CN111943956A CN 111943956 A CN111943956 A CN 111943956A CN 201910399156 A CN201910399156 A CN 201910399156A CN 111943956 A CN111943956 A CN 111943956A
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group
substituted
unsubstituted
compound
membered ring
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CN111943956B (en
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张宇阳
李崇
张兆超
吴秀芹
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention discloses a compound taking a dibenzo six-membered ring as a core, a preparation method and application thereof, belonging to the technical field of semiconductors. The structure of the compound provided by the invention is shown as a general formula (1):
Figure DDA0002059162900000011
the compound provided by the invention contains a dibenzo six-membered ring structure, has strong rigidity, and has the characteristics of difficult intermolecular crystallization, difficult aggregation and good film forming property after connecting a five-membered ring union ring or a six-membered ring union ring or a seven-membered ring union ring; the compound has different electron-donating abilities of the branched chain structures, so that the HOMO energy levels of the material are different, and the material can be used as materials of different functional layers; in addition, the compound has higher triplet state energy level, can effectively block energy loss and is beneficial to energy transfer. Therefore, after the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the efficiency and the service life of the device are greatly improved.

Description

Compound with dibenzo six-membered ring as core, preparation method and application thereof
Technical Field
The invention relates to a compound taking a dibenzo six-membered ring as a core, a preparation method and application thereof, belonging to the technical field of semiconductors.
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 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
One of the objects of the present invention is to provide a compound having a dibenzo six-membered ring as a core. The compound takes a dibenzo six-membered ring as a core, has higher glass transition temperature, higher molecular thermal stability, proper HOMO and LUMO energy levels and higher Eg, and can be used as a hole transport layer/electron barrier layer material or a luminescent layer material of an organic electroluminescent device through device structure optimization, so that the photoelectric property of the OLED device is effectively improved, and the service life of the OLED device is prolonged.
The technical scheme for solving the technical problems is as follows: a compound with a dibenzo six-membered ring as a core,
Figure BDA0002059162880000021
in the general formula (1), L represents substituted or unsubstituted C6-C30One of arylene, 5 to 30 membered heteroarylene substituted or unsubstituted with one or more heteroatoms;
L1、L2each independently represents a single bond, substituted or unsubstituted C6-C30One of arylene, 5 to 30 membered heteroarylene substituted or unsubstituted with one or more heteroatoms;
x represents an oxygen atom, a sulfur atom, -CR4＝CR5-、-C(R6)(R7)-、-Si(R8)(R9) -or-N (R)10) -one of the above;
R4to R10Each independently is represented by C1-C20Straight or branched alkyl, substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r6And R7、R8And R9May be bonded to each other to form a 5-to 30-membered aliphatic, aromatic or heteroaromatic ring; r4、R5May also be represented as a hydrogen atom;
R1、R2each independently represents substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms;
in the general formula (1), R3Represented by the structure represented by the general formula (2):
Figure BDA0002059162880000022
in the general formula (2), X1、X2Each independently represents a single bond, an oxygen atom, a sulfur atom, -CR11＝CR12-、-C(R13)(R14)-、-Si(R15)(R16) -or-N (R)17) -one of (A) and X1、X2Not simultaneously represent a single bond;
R11to R17Each independently is represented by C1-C20Straight or branched alkyl, substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r11And R12、R13And R14、R15And R16May be bonded to each other to form a 5-to 30-membered aliphatic, aromatic or heteroaromatic ring;
formula (2) is connected by fusing two adjacent positions of the label with two adjacent positions of the label in formula (1);
the substituent for substituting the above-mentioned substitutable group is selected from the group consisting of halogen, cyano, C1-C20Alkyl radical, C6-C30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is selected from one or more of oxygen atom, sulfur atom or nitrogen atom.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in the general formula (1), L represents one of a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted benzofuranyl group, and a substituted or unsubstituted benzothiophenyl group;
said L1、L2Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted benzofuranylene group and a substituted or unsubstituted benzothiophenylene group;
the R is1、R2Each independently represents one of phenyl, naphthyl, biphenyl, pyridyl, furyl and fluorenyl;
the R is4To R17Each independently represents one of methyl, ethyl, propyl, isopropyl, tertiary butyl, amyl, phenyl, naphthyl, biphenyl, pyridyl, furyl and fluorenyl; r4、R5May also be represented as a hydrogen atom;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, amyl group, phenyl group, naphthyl group, biphenyl group, fluorenyl group, pyridyl group or furyl group.
Further, the structure of the compound is shown as any one of general formula (3) to general formula (5):
Figure BDA0002059162880000031
further, the specific structure of the compound of the general formula (1) is any one of the following structures:
Figure BDA0002059162880000032
Figure BDA0002059162880000041
Figure BDA0002059162880000051
Figure BDA0002059162880000061
Figure BDA0002059162880000071
Figure BDA0002059162880000081
Figure BDA0002059162880000091
Figure BDA0002059162880000101
Figure BDA0002059162880000111
it should be noted that the above-described structure is only for illustrating the present invention, and is not intended to limit the present invention.
The second object of the present invention is to provide a process for producing the organic compound having a dibenzo six-membered ring as a core. The compound disclosed by the invention is simple in preparation method, wide in market prospect and suitable for large-scale popularization and application.
The technical scheme for solving the technical problems is as follows: a process for the preparation of a compound having a core of a dibenzo-six membered ring, said process involving the reaction equation:
Figure BDA0002059162880000121
the preparation method comprises the following steps:
under the protection of nitrogen, sequentially weighing the intermediate D, the raw material F, sodium tert-butoxide and Pd2(dba)3Adding toluene into tri-tert-butylphosphine, stirring and mixing, heating to 100-120 ℃, carrying out reflux reaction for 12-24 hours, sampling a sample point plate, and indicating that no intermediate D remains and the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain a target product; the molar ratio of the intermediate D to the raw material F is 1 (1-2); the Pd2(dba)3The molar ratio of the tri-tert-butylphosphine to the intermediate D is (0.006-0.02):1, and the molar ratio of the tri-tert-butylphosphine to the intermediate D is (0.006-0.02): 1; the molar ratio of the sodium tert-butoxide to the intermediate D is (2.0-3.0): 1; the amount of toluene used was 0.01mol of intermediate D to 150ml of toluene.
It is a further object of the present invention to provide an organic electroluminescent device. When the compound is applied to an OLED device, the structure of the device is optimized, so that high film stability can be kept, the photoelectric property of the OLED device can be effectively improved, and the service life of the OLED device can be effectively prolonged.
The technical scheme for solving the technical problems is as follows: at least one functional layer of the organic electroluminescent element contains the compound with the dibenzo six-membered ring as the core.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the functional layer is a hole transport layer and/or an electron blocking layer, and the hole transport layer or the electron blocking layer is made of a compound with the dibenzo six-membered ring as a core.
The fourth objective of the present invention is to provide an illumination or display device. The organic electroluminescent device can be applied to display elements, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
The technical scheme for solving the technical problems is as follows: a lighting or display element comprising an organic electroluminescent device as described above.
The invention has the beneficial effects that:
1. the compound contains a dibenzo six-membered ring structure, has strong rigidity, and has the characteristics of difficult crystallization and aggregation among molecules and good film forming property after connecting a five-membered ring or a six-membered ring or a seven-membered ring; the compound parent nucleus has bipolarity, the branched chain is an electron-donating group, and because the electron-donating capability of the group is different, the HOMO energy levels of the material are different, and the material can be used as materials of different functional layers; in addition, the compound has high triplet state energy level, can effectively block energy loss and is beneficial to energy transfer. Therefore, after the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged.
2. When the compound is applied to an OLED device, the structure of the device is optimized, so that high film stability can be kept, the photoelectric property of the OLED device can be effectively improved, and the service life of the OLED device can be effectively prolonged.
3. The organic electroluminescent device can be applied to illumination or display elements, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
Drawings
FIG. 1 is a schematic diagram of a device structure to which the compound of the present invention is applied, wherein the components represented by the respective reference numerals are as follows:
1. transparent substrate layer, 2, anode layer, 3, hole injection layer, 4, hole transport layer, 5, electron blocking layer, 6, light emitting layer, 7, hole blocking/electron transport layer, 8, electron injection layer, 9, cathode layer, 10, CPL layer.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
The detection method used herein is as follows:
the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of mol/L;
glass transition temperature Tg: measured by differential scanning calorimetry (DSC, DSC204F1 DSC, German Nasicon company), the rate of temperature rise was 10 ℃/min.
Thermal weight loss temperature Td: the weight loss was 0.5% in a nitrogen atmosphere, and the nitrogen flow rate was 20mL/min as measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan.
Highest occupied molecular orbital HOMO energy level: is tested by an ionization energy testing system (IPS3) in an atmospheric environment.
Cyclic voltammetric stability: the redox characteristics of the material are observed through cyclic voltammetry to identify, and the test conditions are as follows: dissolving a test sample in a mixed solvent of dichloromethane and acetonitrile at a volume ratio of 2:1, wherein the concentration is 1mg/mL, the electrolyte is 0.1M organic solution of tetrabutylammonium tetrafluoroborate, and the reference electrode is Ag/Ag+The electrode, the counter electrode is a titanium plate, the working electrode is an ITO electrode, and the cycle time is 20 times.
Hole mobility: the material was fabricated into single charge devices and tested by the SCLC method.
Synthesis of intermediate D
Figure BDA0002059162880000131
The specific preparation method of the reaction comprises the following steps:
(1) weighing raw materials 1 and 2, and dissolving with toluene; then adding Pd2(dba)3、P(t-Bu)3And sodium 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 an intermediate B; the molar ratio of the raw material 1 to the raw material 2 is 1 (1.2-3.0), and Pd2(dba)3The molar ratio of the raw material to the raw material 1 is (0.006-0.02):1, P (t-Bu)3The molar ratio of the sodium tert-butoxide to the raw material 1 is (0.006-0.02) to 1, and the molar ratio of the sodium tert-butoxide to the raw material 1 is (1.0-3.0) to 1;
(2) weighing intermediate B and raw material 3, dissolving with toluene, and adding Pd2(dba)3、P(t-Bu)3And sodium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 90-110 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate D; the molar ratio of the intermediate B to the raw material 3 is 1 (1.2-3.0); pd2(dba)3The molar ratio of the intermediate B to the intermediate B is (0.006-0.02) to 1, and the molar ratio of the sodium tert-butoxide to the intermediate B is (1.0-3.0) to 1; p (t-Bu)3The molar ratio of the intermediate B to the intermediate B is (0.006-0.02): 1.
This is exemplified by the synthesis of intermediate D-1:
Figure BDA0002059162880000132
Figure BDA0002059162880000141
(1) adding 0.01mol of raw material 1-1, 0.012mol of raw material 2-1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10-5mol Pd2(dba)3、5×10-5mol P(t-Bu)3And 0.03mol of sodium tert-butoxide, heating to 105 ℃, 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, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product intermediate B-1; HPLC purity 99.41%, yield 76.2％；
Elemental analysis Structure (molecular formula C)24H19N): theoretical value C, 89.68; h, 5.96; n, 4.36; test values are: 89.70, respectively; h, 5.95; and N, 4.35. ESI-MS (M/z) (M)+): theoretical value is 321.15, found 321.31.
(2) Adding 0.005mol of intermediate B-1, 0.006mol of raw material 3-1 and 150ml of toluene into a 250ml three-necked flask under the protection of nitrogen, stirring, mixing, and adding 2.5X 10-5mol Pd2(dba)3，2.5×10-5mol P(t-Bu)3And 0.015mol of sodium tert-butoxide, heating to 105 ℃, 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, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product intermediate D-1; HPLC purity 99.24%, yield 78.6%;
elemental analysis Structure (molecular formula C)30H22BrN): theoretical value C, 75.63; h, 4.65; br, 16.77; n, 2.94; test values are: c, 75.60; h, 4.64; br, 16.79; and N, 2.96. ESI-MS (M/z) (M)+): theoretical value is 475.09, found 475.28.
Intermediate D was synthesized according to the preparation method of intermediate D-1, and the specific structure is shown in Table 1.
TABLE 1
Figure BDA0002059162880000142
Figure BDA0002059162880000151
Figure BDA0002059162880000161
Figure BDA0002059162880000171
Example 1: preparation of Compound 15
Figure BDA0002059162880000172
In a 500ml three-necked flask, 0.01mol of intermediate D-1, 0.015mol of starting material 4-1, 0.03mol of sodium tert-butoxide, 5X 10 in a nitrogen atmosphere-5mol Pd2(dba)3And 5X 10-5After the reaction was completed, 150ml of toluene was added to dissolve tri-t-butylphosphine, and the mixture was heated to 100 ℃ and refluxed for 24 hours, and the reaction was observed by TLC. Naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was purified by silica gel column (petroleum ether as eluent) to give the desired product in 99.41% purity and 67.2% yield.
Elemental analysis Structure (molecular formula C)61H42N2O): theoretical value: c, 89.46; h, 5.17; n, 3.42; o, 1.95; test values are: c, 89.47; h, 5.15; n, 3.40; o, 1.98. ESI-MS (M/z) (M)+): theoretical value is 818.33, found 818.57. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H), 7.61-7.52 (m,9H),7.48(td,1H), 7.44-7.31 (m,8H), 7.30-7.15 (m,17H),7.12(td,1H),7.09(s,1H), 7.08-7.03 (m,2H),7.02(td, 2H).
Example 2: preparation of Compound 20
Figure BDA0002059162880000181
Prepared according to the synthesis method of the compound 1, except that the intermediate D-2 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.81 percent, and the yield is 79.3 percent.
Elemental analysis Structure (molecular formula C)67H46N2O): theoretical value: c, 89.90; h, 5.18; n, 3.13; o, 1.79; test values are: c, 89.92; h, 5.19; n, 3.12; o, 1.77. ESI-MS (M/z) (M)+): theoretical value is 894.36, found 894.24. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H),7.60(dt,2H), 7.60-7.54 (m,5H),7.57–7.51(m,3H),7.48(td,1H),7.42–7.31(m,10H),7.32(s,1H),7.31–7.16(m,11H),7.14(dd,4H),7.15–7.06(m,6H),7.02(ddd,2H)。
Example 3: preparation of Compound 33
Figure BDA0002059162880000182
Prepared according to the synthesis method of the compound 1, except that the intermediate D-3 is used for replacing the intermediate D-1, the raw material 4-2 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.32 percent, and the yield is 71.2 percent.
Elemental analysis Structure (molecular formula C)67H46N2O): theoretical value: c, 89.90; h, 5.18; n, 3.13; o, 1.79; test values are: c, 89.91; h, 5.17; n, 3.14; o, 1.78. ESI-MS (M/z) (M)+): theoretical value is 894.36, found 894.51. Nuclear magnetic hydrogen spectrum analysis: 7.93(dd,1H),7.61(t,1H), 7.61-7.49 (m,7H),7.45(td,1H), 7.44-7.36 (m,5H), 7.39-7.33 (m,6H),7.34(d,1H), 7.36-7.30 (m,1H), 7.30-7.17 (m,9H), 7.17-7.10 (m,8H), 7.13-7.00 (m, 6H).
Example 4: preparation of Compound 40
Figure BDA0002059162880000183
Prepared according to the synthesis method of the compound 1, except that the intermediate D-4 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.28 percent, and the yield is 70.9 percent.
Elemental analysis Structure (molecular formula C)67H46N2O): theoretical value: c, 89.90; h, 5.18; n, 3.13; o, 1.79; test values are: c, 89.87; h, 5.16; n, 3.16; o, 1.81. ESI-MS (M/z) (M)+): theoretical value is 894.36, found 894.61. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H),7.59(ddt,7H), 7.56-7.51 (m,3H), 7.51-7.31(m, 12H), 7.30-7.16(m,13H), 7.15-7.06 (m,8H), 7.05-6.99 (m, 2H).
Practice ofExample 5: preparation of Compound 45
Figure BDA0002059162880000191
Prepared according to the synthesis method of the compound 1, except that the intermediate D-5 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.91 percent, and the yield is 76.6 percent.
Elemental analysis Structure (molecular formula C)61H40N2O2): theoretical value: c, 87.96; h, 4.84; n, 3.36; o, 3.84; test values are: c, 87.97; h, 4.83; n, 3.38; and O, 3.82. ESI-MS (M/z) (M)+): theoretical value is 832.31, found 832.39. Nuclear magnetic hydrogen spectrum analysis: 8.01(dt,2H),7.71(dd,1H), 7.61-7.42 (m,7H), 7.42-7.14 (m,20H), 7.14-7.05 (m,8H),7.02(ddd, 2H).
Example 6: preparation of Compound 59
Figure BDA0002059162880000192
Prepared according to the synthesis method of the compound 1, except that the intermediate D-6 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.28 percent, and the yield is 74.8 percent.
Elemental analysis Structure (molecular formula C)67H66N2O2): theoretical value: c, 88.52; h, 4.88; n, 3.08; o, 3.52; test values are: c, 88.53; h, 4.89; n, 3.09; and O, 3.49. ESI-MS (M/z) (M)+): theoretical value is 908.34, found 908.18. Nuclear magnetic hydrogen spectrum analysis: 7.99(ddd,2H),7.61-7.51(m,8H),7.51-7.31(m,10H),7.31-7.00(m, 24H).
Example 7: preparation of Compound 67
Figure BDA0002059162880000193
Prepared according to the synthesis method of the compound 1, except that the intermediate D-7 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.56 percent, and the yield is 65.2 percent.
Elemental analysis Structure (molecular formula C)73H46N2O3): theoretical value: c, 87.75; h, 4.64; n, 2.80; o, 4.80; test values are: c, 87.72; h, 4.65; n, 2.81; and O, 4.81. ESI-MS (M/z) (M)+): theoretical value is 998.35, found 998.21. Nuclear magnetic hydrogen spectrum analysis: 8.03-7.98(m,3H),7.85(d,2H),7.617.51(m,9H),7.51-7.43(m,5H),7.38(td,3H),7.32(s,1H),7.30-7.16(m,13H),7.14-6.99(m, 10H).
Example 8: preparation of Compound 77
Figure BDA0002059162880000201
Prepared according to the synthesis method of the compound 1, except that the intermediate D-8 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.19 percent, and the yield is 80.1 percent.
Elemental analysis Structure (molecular formula C)64H46N2O): theoretical value: c, 89.48; h, 5.40; n, 3.26; o, 1.86; test values are: c, 89.49; h, 5.41; n, 3.25; o, 1.85. ESI-MS (M/z) (M)+): theoretical value is 858.36, found 858.18. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H),7.72(dd,1H), 7.65-7.56 (m,3H),7.54(dq,3H),7.47(ddd,2H), 7.44-7.31 (m,7H), 7.30-7.21 (m,7H), 7.24-7.16 (m,6H), 7.15-7.04 (m,7H), 7.07-6.99 (m,2H),6.95(d,1H),1.58(s, 6H).
Example 9: preparation of Compound 83
Figure BDA0002059162880000202
Prepared according to the synthesis method of the compound 1, except that the intermediate D-9 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.83 percent, and the yield is 77.7 percent.
Elemental analysis Structure (molecular formula C)70H50N2O): theoretical value: c, 89.90; h, 5.39; n, 3.00; o, 1.71; test values are: c, 89.92; h, 5.37; n, 2.98; o, 1.73. ESI-MS (M/z) (M)+): theoretical value is 934.39, found 934.58. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H),7.72(d,1H), 7.61-7.50 (m,8H),7.48(td,1H), 7.44-7.31 (m,10H), 7.31-7.05 (m,21H), 7.05-6.99 (m,2H),1.59(s, 6H).
Example 10: preparation of Compound 85
Figure BDA0002059162880000203
Prepared according to the synthesis method of the compound 1, except that the intermediate D-10 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.91 percent, and the yield is 67.3 percent.
Elemental analysis Structure (molecular formula C)66H43N3O2): theoretical value: c, 87.10; h, 4.76; n, 4.62; o, 3.52; test values are: c, 87.11; h, 4.78; n, 4.61; and O, 3.50. ESI-MS (M/z) (M)+): theoretical value is 909.34, found 909.26. Nuclear magnetic hydrogen spectrum analysis: 8.66(d,1H),8.07(dd,1H), 8.05-7.98 (m,3H),7.68(d,1H), 7.61-7.54 (m,3H),7.54(dd,3H), 7.51-7.31(m,10H), 7.30-7.16(m, 11H), 7.15-7.06 (m,6H), 7.09-6.99 (m, 4H).
Example 11: preparation of Compound 97
Figure BDA0002059162880000211
Prepared according to the synthesis method of the compound 1, except that the intermediate D-11 is used for replacing the intermediate D-1, the raw material 4-3 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.52 percent, and the yield is 74.3 percent.
Elemental analysis Structure (molecular formula C)59H40N4O2): theoretical value: c, 84.67; h, 4.82; n, 6.69; o, 3.82; test values are: c, 84.65; h, 4.81; n, 6.71; and O, 3.84. ESI-MS (M/z) (M)+): theoretical value of 836.32, found 836.54. Nuclear magnetic hydrogen spectrum analysis: 8.84(d,2H),8.63(dd,2H),7.84(dt,2H), 7.64-7.58 (m,4H),7.36(t,2H), 7.31-7.16 (m,13H), 7.15-7.08 (m,4H), 7.12-7.03 (m,5H),7.02(td,2H), 6.96-6.88 (m,2H),6.73(s,1H),6.60(s, 1H).
Example 12: preparation of Compound 107
Figure BDA0002059162880000212
Prepared according to the synthetic method of the compound 1, except that the intermediate D-12 was used instead of the intermediate D-1, and the starting material 4-4 was used instead of the starting material 4-1, the purity of the obtained objective product was 99.69%, and the yield was 74.4%.
Elemental analysis Structure (molecular formula C)51H36N2OS): theoretical value: c, 84.50; h, 5.01; n, 3.86; o, 2.21; s, 4.42; test values are: c, 84.51; h, 5.02; n, 3.88; o, 2.20; s, 4.39. ESI-MS (M/z) (M)+): theoretical value is 724.25, found 724.01. Nuclear magnetic hydrogen spectrum analysis: 8.33(dd,1H),7.80(d,1H),7.74(s,1H),7.68(dd,1H), 7.56-7.50 (m,2H), 7.53-7.28 (m,14H),7.24(s,1H), 7.20-7.04 (m,8H),6.78(dd,1H),1.56(s, 6H).
Example 13: preparation of Compound 119
Figure BDA0002059162880000213
Prepared according to the synthesis method of the compound 1, except that the intermediate D-13 is used for replacing the intermediate D-1, the raw material 4-5 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.82 percent, and the yield is 66.9 percent.
Elemental analysis Structure (molecular formula C)60H40N2O2S): theoretical value: c, 84.48; h, 4.73; n, 3.28; o, 3.75; s, 3.76; test values are: c, 84.51; h, 4.71; n, 3.26; o, 3.74; and S, 3.78. ESI-MS (M/z) (M)+): theoretical value is 852.28, found 852.15. Nuclear magnetic hydrogen spectrum analysis: 7.63-7.56 (m,10H), 7.46-7.29(m,14H),7.21(td,4H),7.15(dd,1H),7.15–7.07(m,5H),7.07(td,1H),7.02(ddd,1H),6.93(d,2H),6.77(dd,1H),6.53(s,1H)。
Example 14: preparation of Compound 121
Figure BDA0002059162880000221
The compound is prepared according to the synthesis method of the compound 1, except that the intermediate D-8 is used for replacing the intermediate D-1, the raw material 4-6 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.87 percent, and the yield is 76.0 percent.
Elemental analysis Structure (molecular formula C)60H47N3O): theoretical value: c, 87.24; h, 5.74; n, 5.09; o, 1.94; test values are: c, 87.22; h, 5.72; n, 5.11; o, 1.96. ESI-MS (M/z) (M)+): theoretical value is 825.37, found 825.54. Nuclear magnetic hydrogen spectrum analysis: 7.72(dd,1H), 7.65-7.56 (m,3H), 7.56-7.51 (m,2H), 7.49-7.32 (m,8H), 7.32-7.25 (m,2H), 7.25-7.02 (m,15H), 6.97-6.93 (m,2H),6.77(d d,1H),6.66(s,1H),1.57(d, 12H).
Example 15: preparation of Compound 129
Figure BDA0002059162880000222
Prepared according to the synthetic method of the compound 1, except that the intermediate D-14 is used for replacing the intermediate D-1, the raw material 4-7 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.39 percent, and the yield is 72.4 percent.
Elemental analysis Structure (molecular formula C)64H41N3O2): theoretical value: c, 86.95; h, 4.67; n, 4.75; o, 3.62; test values are: c, 86.94; h, 4.66; n, 4.78; and O, 3.62. ESI-MS (M/z) (M)+): theoretical value is 883.32, found 883.61. Nuclear magnetic hydrogen spectrum analysis: 8.15(s,1H),8.00(ddd,2H), 7.91-7.84 (m,2H),7.70(dd,1H), 7.61-7.51(m,8H), 7.51-7.24 (m,13H), 7.24-7.14 (m,6H), 7.14-7.03 (m, 8H).
Example 16: preparation of Compound 132
Figure BDA0002059162880000223
Prepared according to the synthetic method of the compound 1, except that the intermediate D-15 is used for replacing the intermediate D-1, the raw material 4-8 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.61 percent, and the yield is 79.3 percent.
Elemental analysis Structure (molecular formula C)62H42N4): theoretical value: c, 85.56; h, 4.63; n, 2.22; o, 7.60; test value C, 85.58; h, 4.65; n, 2.20; and O, 7.57. ESI-MS (M/z) (M)+): theoretical value is 842.34, found 842.05. Nuclear magnetic hydrogen spectrum analysis: 8.05-7.98 (m,1H),7.86(dd,1H), 7.83-7.75 (m,2H),7.71(ddd,2H), 7.64-7.57 (m,1H), 7.60-7.54 (m,2H), 7.54-7.04 (m, 33H).
Example 17: preparation of Compound 149
Figure BDA0002059162880000231
Prepared according to the synthetic method of the compound 1, except that the intermediate D-16 is used for replacing the intermediate D-1, the raw material 4-9 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.79 percent, and the yield is 75.6 percent.
Elemental analysis Structure (molecular formula C)49H36N2): theoretical value: c, 90.15; h, 5.56; n, 4.29; test values are: c, 90.12; h, 5.57; and N, 4.31. ESI-MS (M/z) (M)+): theoretical value is 652.29, found 652.21. Nuclear magnetic hydrogen spectrum analysis: 7.86-7.77 (m,4H), 7.77-7.72 (m,2H), 7.56-7.06 (m,23H),7.04(s,1H),1.56(s, 6H).
Example 18: preparation of Compound 160
Figure BDA0002059162880000232
Prepared according to the synthesis method of the compound 1, except that the raw material 4-10 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.81 percent, and the yield is 75.2 percent.
Elemental analysis Structure (molecular formula C)62H44N4): theoretical value: c, 88.12; h, 5.25; n, 6.63; test values are: c, 88.13; h, 5.23; and N, 6.64. ESI-MS (M/z) (M)+): theoretical value is 844.36, found 844.69. Nuclear magnetic hydrogen spectrum analysis: 7.61-7.51(m,8H), 7.42-7.31 (m,7H), 7.31-7.00(m, 29H).
Example 19: preparation of Compound 177
Figure BDA0002059162880000233
Prepared according to the synthesis method of the compound 1, except that the raw material 4-11 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.95 percent, and the yield is 76.8 percent.
Elemental analysis Structure (molecular formula C)64H48N2): theoretical value: c, 90.96; h, 5.73; n, 3.31; test values are: c, 90.99; h, 5.71; and N, 3.30. ESI-MS (M/z) (M)+): theoretical value is 844.38, found 844.51. Nuclear magnetic hydrogen spectrum analysis: 7.62-7.56 (m,5H), 7.56-7.51 (m,4H), 7.45-7.09 (m,30H), 7.09-7.04 (m,2H),7.01(ddd,2H),1.61(s, 5H).
Example 20: preparation of Compound 194
Figure BDA0002059162880000234
Prepared according to the synthesis method of the compound 1, except that the intermediate D-17 is used for replacing the intermediate D-1, the raw material 4-12 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.49 percent, and the yield is 64.3 percent.
Elemental analysis Structure (molecular formula C)70H50N2S): theoretical value: c, 88.39; h, 5.30; n, 2.94; s, 3.37; test value：C,88.38；H,5.33；N,2.93；S,3.36。ESI-MS(m/z)(M+): theoretical value is 950.37, found 950.11. Nuclear magnetic hydrogen spectrum analysis: 8.34(dd,1H),7.82(dd,1H),7.76(dd,1H), 7.62-7.56 (m,3H), 7.55-7.49 (m,2H), 7.51-7.30 (m,14H), 7.30-7.18 (m,9H), 7.17-7.09 (m,9H), 7.09-7.04 (m,2H),7.04(s,1H),7.01(ddd,2H),1.56(s, 6H).
Example 21: preparation of Compound 204
Figure BDA0002059162880000241
Prepared according to the synthetic method of the compound 1, except that the intermediate D-18 is used for replacing the intermediate D-1, the raw material 4-13 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.53 percent, and the yield is 83.1 percent.
Elemental analysis Structure (molecular formula C)66H53N3): theoretical value: c, 89.25; h, 6.02; n, 4.73; test values are: c, 89.22; h, 6.04; n, 4.74. ESI-MS (M/z) (M)+): theoretical value is 887.42, found 887.28. Nuclear magnetic hydrogen spectrum analysis: 8.08(dd,1H), 7.80-7.76 (m,1H), 7.63-7.55 (m,3H), 7.57-7.48 (m,8H), 7.51-7.42 (m,2H), 7.42-7.33 (m,2H), 7.36-7.30 (m,1H), 7.33-7.22 (m,2H), 7.25-7.17 (m,6H),7.18(s,2H),7.17(s,1H),7.13(dd,1H), 7.11-7.02 (m,4H),7.00(d,1H), 6.42-6.35 (m,1H), 6.27-6.17 (m,2H), 5.91-5.84 (m,1H),3.72(dd, 1H),2.72(dd, 1H), 1.72 (ddp,1H), 1H, 62(s, 6H).
Example 22: preparation of Compound 212
Figure BDA0002059162880000242
Prepared according to the synthesis method of the compound 1, except that the intermediate D-19 is used for replacing the intermediate D-1, the raw material 4-14 is used for replacing the raw material 4-1, the purity of the obtained target product is 99.78 percent, and the yield is 71.9 percent.
Elemental analysis Structure (molecular formula C)64H43F3N2O): theoretical value: c, 84.19; h, 4.75; f, 6.24; n, 3.07; o, 1.75; test values are: c, 84.17; h, 4.76; f, 6.26; n, 3.05; o, 1.76. ESI-MS (M/z) (M)+): theoretical value is 912.33, found 912.21. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H),7.76(d,1H), 7.58-7.50 (m,4H),7.47(td,1H), 7.43-7.31 (m,6H), 7.31-7.01 (m,20H),7.01(ddd,2H), 6.65-6.58 (m,2H),1.56(s, 6H).
Example 23: preparation of Compound 225
Figure BDA0002059162880000251
Prepared according to the synthesis method of the compound 1, except that the intermediate D-20 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.49 percent, and the yield is 78.5 percent.
Elemental analysis Structure (molecular formula C)73H48N2O2): theoretical value: c, 89.00; h, 4.91; n, 2.84; o, 3.25; test values are: c, 89.02; h, 4.93; n, 2.82; and O, 3.23. ESI-MS (M/z) (M)+): theoretical value is 984.37, found 984.25. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H), 7.82-7.77 (m,2H), 7.61-7.06 (m,41H),7.03(dd,2H),6.99(dd,1H),6.87(dd, 1H).
Example 24: preparation of Compound 230
Figure BDA0002059162880000252
Prepared according to the synthetic method of the compound 1, except that the intermediate D-21 is used instead of the intermediate D-1, the purity of the obtained target product is 99.46%, and the yield is 80.5%.
Elemental analysis Structure (molecular formula C)64H46N2O): theoretical value: c, 89.48; h, 5.40; n, 3.26; o, 1.86; test values are: c, 89.49; h, 5.39; n, 3.25; o, 1.87. ESI-MS (M/z) (M)+): theoretical value is 858.36, found 858.52. Nuclear magnetic hydrogen spectrum analysis: 8.01(dd,1H),7.60(d,1H), 7.57-7.49 (m,3H),7.51–7.44(m,3H),7.44–7.31(m,8H),7.31–7.06(m,21H),7.02(ddd,2H),6.94(d,1H),1.59(s,6H)。
Example 25: preparation of Compound 237
Figure BDA0002059162880000253
Prepared according to the synthesis method of the compound 1, except that the intermediate D-22 is used for replacing the intermediate D-1, the purity of the obtained target product is 99.47 percent, and the yield is 71.6 percent.
Elemental analysis Structure (molecular formula C)63H39N5O): theoretical value: c, 85.79; h, 4.46; n, 7.94; o, 1.81; test values are: c, 85.82; h, 4.45; n, 7.93; o, 1.80. ESI-MS (M/z) (M)+): theoretical value is 881.32, found 881.48. Nuclear magnetic hydrogen spectrum analysis: 8.06-7.98 (m,2H),7.68(d,1H), 7.66-7.60 (m,4H), 7.60-7.56 (m,1H),7.54(dd,1H), 7.53-7.42 (m,5H),7.38(td,1H), 7.34-7.06 (m,22H),7.02(ddd, 2H).
Example 26: preparation of Compound 254
Figure BDA0002059162880000261
Prepared according to the synthesis method of the compound 1, except that the raw material F-1 is replaced by 4-15, the purity of the obtained target product is 99.41 percent, and the yield is 65.5 percent.
Elemental analysis Structure (molecular formula C)69H50N4): theoretical value: c, 88.62; h, 5.39; n, 5.99; test values are: c, 88.61; h, 5.38; and N, 6.01. ESI-MS (M/z) (M)+): theoretical value is 934.40, found 934.65. Nuclear magnetic hydrogen spectrum analysis: 8.10(dd,1H),8.01(d,1H), 7.62-7.47 (m,13H),7.44(dq,2H), 7.42-7.07 (m,28H),7.05(dd,1H),1.58(s, 6H).
The organic 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, can be used as a hole transport/electron blocking material, and can also be used as a light-emitting layer material. The compound prepared in the example of the present invention and the existing material were respectively tested for thermal performance, T1 energy level and HOMO energy level, and the results are shown in table 2.
TABLE 2
Figure BDA0002059162880000262
Figure BDA0002059162880000271
The data in the table show that the organic compound prepared by the invention has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the material disclosed by the invention is suitable for the HOMO energy level, and also has a high triplet state energy level (T1), so that the energy loss of a light-emitting layer can be blocked, and the light-emitting efficiency of a device is improved. Therefore, after the organic material containing the dibenzo six-membered ring 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.
Preparation of the organic electroluminescent device of the present invention
The application effect of the synthesized OLED material of the present invention in the device is detailed by device examples 1-26 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 26 and the device comparative example 1 of the present invention have the same device manufacturing process, and adopt the same substrate material and electrode material, and the film thickness of the electrode material is also kept consistent, except that the hole transport layer material or the electron blocking layer material in the device is replaced. The compositions of the layers of the devices obtained in the examples are shown in table 3.
Device example 1
As shown in fig. 1, the transparent substrate layer 1 is a transparent PI film, and the ITO/Ag anode layer 2 (film thickness 100/10nm) is washed, i.e., washed with alkali, washed with pure water, dried, and then washed with ultraviolet rays and ozone to remove organic residues on the surface of the anode layer. HT-1 and P-1 having a film thickness of 10nm were deposited on the anode layer 2 after the above washing as the hole injection layer 3 by a vacuum deposition apparatus, and the mass ratio of HT-1 to P-1 was 97: 3. Next, HT-1 was evaporated to a thickness of 130nm as a hole transport layer 4. EB-1 was then evaporated to a thickness of 40nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, a light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the OLED light emitting device comprises that GH-1 and GH-2 used by the OLED light emitting layer 6 are used as main body materials, GD-1 is used as a doping material, the doping proportion of the doping material is 6% by weight, and the thickness of the light emitting layer is 40 nm. After the light-emitting layer 6, ET-1 and Liq are continuously evaporated, wherein the mass ratio of ET-1 to Liq is 1: 1. The vacuum-deposited film thickness of this material was 35nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a Yb layer having a film thickness of 1nm, which is an electron-injecting layer 8, was formed by a vacuum evaporation apparatus. On the electron injection layer 8, a vacuum deposition apparatus was used to produce a 15 nm-thick Mg: the Ag electrode layer is used as a cathode layer 9, and the mass ratio of Mg to Ag is 1: 9. On the cathode layer 9, 70nm of CP-1 was vacuum-deposited as a CPL layer 10.
Figure BDA0002059162880000272
Figure BDA0002059162880000281
TABLE 3
Figure BDA0002059162880000282
Figure BDA0002059162880000291
TABLE 4
Figure BDA0002059162880000292
Figure BDA0002059162880000301
From the results in table 4, it can be seen that the organic compound of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative examples, the efficiency and lifetime of the organic compound are greatly improved compared with those of the known OLED materials, especially the lifetime of the organic compound is greatly prolonged.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 5, 13 and 24 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in Table 5.
TABLE 5
Figure BDA0002059162880000302
As can be seen from the data in table 5, device examples 5, 13, and 24 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is steadily 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 (8)

1. A compound having a dibenzo six-membered ring as a core, which has a structure represented by the general formula (1):
Figure FDA0002059162870000011
in the general formula (1), L represents substituted or unsubstituted C6-C30Arylene radical, containingOne of a 5-to 30-membered heteroarylene group substituted or unsubstituted with one or more heteroatoms;
L1、L2each independently represents a single bond, substituted or unsubstituted C6-C30One of arylene, 5 to 30 membered heteroarylene substituted or unsubstituted with one or more heteroatoms;
x represents an oxygen atom, a sulfur atom, -CR4＝CR5-、-C(R6)(R7)-、-Si(R8)(R9) -or-N (R)10) -one of the above;
R4to R10Each independently is represented by C1-C20Straight or branched alkyl, substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r6And R7、R8And R9May be bonded to each other to form a 5-to 30-membered aliphatic, aromatic or heteroaromatic ring; r4、R5May also be represented as a hydrogen atom;
R1、R2each independently represents substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms;
in the general formula (1), R3Represented by the structure represented by the general formula (2):
Figure FDA0002059162870000012
in the general formula (2), X1、X2Each independently represents a single bond, an oxygen atom, a sulfur atom, -CR11＝CR12-、-C(R13)(R14)-、-Si(R15)(R16) -or-N (R)17) -one of (A) and X1、X2Not simultaneously represent a single bond;
R11to R17Each independently is represented by C1-C20Straight or branched alkyl, substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r11And R12、R13And R14、R15And R16May be bonded to each other to form a 5-to 30-membered aliphatic, aromatic or heteroaromatic ring;
formula (2) is connected by fusing two adjacent positions of the label with two adjacent positions of the label in formula (1);
the substituent for substituting the above-mentioned substitutable group is selected from the group consisting of halogen, cyano, C1-C20Alkyl radical, C6-C30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is selected from one or more of oxygen atom, sulfur atom or nitrogen atom.
2. The compound of claim 1, wherein in the general formula (1), L represents one of a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted benzofuranyl group, and a substituted or unsubstituted benzothiophene group;
said L1、L2Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted benzofuranylene group and a substituted or unsubstituted benzothiophenylene group;
the R is1、R2Each independently represents one of phenyl, naphthyl, biphenyl, pyridyl, furyl and fluorenyl;
the R is4To R17Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl,One of biphenyl, pyridyl, furyl and fluorenyl; r4、R5May also be represented as a hydrogen atom;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, amyl group, phenyl group, naphthyl group, biphenyl group, fluorenyl group, pyridyl group or furyl group.
3. The dibenzo six-membered ring-centered compound according to claim 1, wherein the structure of the compound is represented by any one of general formula (3) to general formula (5):
Figure FDA0002059162870000021
4. a dibenzo six-membered ring-centered compound according to any one of claims 1 to 3, wherein the specific structure of the compound of formula (1) is any one of the following structures:
Figure FDA0002059162870000022
Figure FDA0002059162870000031
Figure FDA0002059162870000041
Figure FDA0002059162870000051
Figure FDA0002059162870000061
Figure FDA0002059162870000071
Figure FDA0002059162870000081
Figure FDA0002059162870000091
Figure FDA0002059162870000101
Figure FDA0002059162870000111
Figure FDA0002059162870000121
5. a process for the preparation of a dibenzo-six membered ring centered compound according to any one of claims 1 to 4, wherein said process involves the reaction equation:
Figure FDA0002059162870000122
the preparation method comprises the following steps:
under the protection of nitrogen, sequentially weighing the intermediate D, the raw material F, sodium tert-butoxide and Pd2(dba)3Adding toluene into the tri-tert-butylphosphine, stirring and mixing, heating to 100-120 ℃, carrying out reflux reaction for 12-24 hours,sampling a spot plate, wherein no intermediate D remains and the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain a target product; the molar ratio of the intermediate D to the raw material F is 1 (1-2); the Pd2(dba)3The molar ratio of the tri-tert-butylphosphine to the intermediate D is (0.006-0.02):1, and the molar ratio of the tri-tert-butylphosphine to the intermediate D is (0.006-0.02): 1; the molar ratio of the sodium tert-butoxide to the intermediate D is (2.0-3.0): 1; the amount of toluene used was 0.01mol of intermediate D to 150ml of toluene.
6. An organic electroluminescent element, characterized in that at least one functional layer contains a dibenzo-six-membered ring-centered compound according to any one of claims 1 to 4.
7. The organic electroluminescent device according to claim 6, wherein the functional layer is a hole transport layer and/or an electron blocking layer, and the material of the hole transport layer or the electron blocking layer is a compound with the dibenzo six-membered ring as a core.
8. A lighting or display element comprising an organic electroluminescent device as claimed in any one of claims 6 to 7.
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