WO2019114769A1 - Compound containing pyridoindole and use thereof in organic electroluminescence device - Google Patents

Compound containing pyridoindole and use thereof in organic electroluminescence device Download PDF

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WO2019114769A1
WO2019114769A1 PCT/CN2018/120716 CN2018120716W WO2019114769A1 WO 2019114769 A1 WO2019114769 A1 WO 2019114769A1 CN 2018120716 W CN2018120716 W CN 2018120716W WO 2019114769 A1 WO2019114769 A1 WO 2019114769A1
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thickness
group
layer
compound
pyridoindole
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PCT/CN2018/120716
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French (fr)
Chinese (zh)
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王芳
李崇
张兆超
庞羽佳
蔡啸
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江苏三月光电科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

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  • the present invention relates to the field of semiconductor technology, and more particularly to a compound containing pyridoindole and its use in an organic electroluminescent device.
  • OLED Organic Light Emission Diodes
  • the OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device.
  • OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as televisions.
  • OLED devices have luminous efficiency and service life. Further improvement is needed.
  • Research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device.
  • OLED photoelectric functional materials applied to OLED devices can be divided into two categories, namely, charge injection transport materials and luminescent materials, and further, charge injection transport materials can be divided into electron injection transport materials, electron blocking materials, and holes. The transport material and the hole blocking material are injected, and the luminescent material can also be divided into a host luminescent material and a dopant material.
  • various organic functional materials are required to have good photoelectric characteristics. For example, as a charge transport material, it is required to have good carrier mobility, high glass transition temperature, etc., as a main body of the light-emitting layer. Materials require materials with good bipolarity, appropriate HOMO/LUMO energy levels, and the like.
  • the OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron.
  • a plurality of film layers such as a transport layer and an electron injection layer, that is, an optoelectronic functional material applied to an OLED device includes at least a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material, etc., and the material type and the collocation form are rich. Characteristics of sex and diversity.
  • the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in different structural devices may be completely different. Therefore, in view of the industrial application requirements of current OLED devices, and the different functional film layers of OLED devices, the photoelectric characteristics of the devices must be selected to be more suitable, and high-performance OLED functional materials or material combinations can achieve high efficiency and long device. Comprehensive characteristics of life and low voltage. As far as the actual demand of the current OLED display lighting industry is concerned, the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.
  • the present application provides a pyridinium-containing compound and its use in an organic electroluminescent device.
  • the compound of the invention has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, high hole mobility, and can be effectively used to improve the luminous efficiency of the device and the service life of the OLED device after being fabricated by the OLED device. .
  • A is represented by a single bond, an oxygen atom, a C 1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl substituted imido group or an aryl substituted imido group.
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 are each independently represented as CH or N atom, and the number of N atoms is 0, 1 or 2;
  • n, p, q are equal to 0 or 1; and m + n + p + q ⁇ 1;
  • E is a pyridoindole group optionally substituted with one or more R 1 ;
  • R 1 represents one of a substituted or unsubstituted C 6 to C 30 aryl group and a substituted or unsubstituted C 5 to C 30 heteroaryl group; the hetero atom is nitrogen, oxygen or sulfur.
  • the present invention can also make the following improvements.
  • a compound containing pyridoindole the E being represented by the formula (2);
  • Ar 1 is represented by one of a mono-, substituted or unsubstituted C 6 - 30 arylene, a substituted or unsubstituted C 5 - 30 heteroarylene; the hetero atom is nitrogen, oxygen or sulfur ;
  • Ar 2 is represented by one of a substituted or unsubstituted C 6 - 30 aryl group, a substituted or unsubstituted C 5 - 30 heteroaryl group; the hetero atom is nitrogen, oxygen or sulfur;
  • Z is represented by a C-H or N atom, and at least one Z represents an N atom.
  • a compound containing pyridoindole in the formula (1) Expressed as: Any of them.
  • a compound containing a pyridoindole the structure of the formula (2) can be expressed as: Any of them.
  • said Ar 1 represents a single bond, phenylene, naphthylene group, biphenylene group, anthracenyl group, a furyl group, a carbazolyl group, a naphthylene Of pyridine, quinolinol, thienylene, pyridylene, fluorenylene, 9,9-dimethylindenyl, phenanthrylene, dibenzofuranyl, dibenzothiophenyl One type;
  • the Ar 2 is represented by phenyl, naphthyl, biphenyl, anthracenyl, furyl, oxazolyl, naphthyridinyl, quinolyl, thienyl, pyridyl, fluorenyl, 9,9-dimethyl
  • a mercapto group a phenanthryl group, a dibenzofuranyl group, and a dibenzothiophene group.
  • a compound containing pyridoindole the specific structural formula of the compound is:
  • the invention also provides a preparation method of a compound containing pyridoindole, the preparation method relates to a reaction equation:
  • the raw material A and the intermediate M are dissolved in a mixed solution of toluene and ethanol, and after deoxidation, Pd(PPh 3 ) 4 and K 2 CO 3 are added , and the reaction is carried out at 95 to 110 ° C for 10 to 24 hours in an inert atmosphere until the raw materials are used. After the reaction is completed, the mixture is cooled and filtered, and the filtrate is evaporated to remove the solvent, and the crude product is passed through a silica gel column to obtain the target compound;
  • the amount of the toluene and the ethanol is 30 to 50 mL of toluene and 5 to 10 mL of ethanol per gram of the raw material A, and the molar ratio of the intermediate M to the raw material A is 1 to 3:1, Pd(PPh 3 ) 4 and the raw material.
  • the molar ratio of A is from 0.006 to 0.03:1, and the molar ratio of K 2 CO 3 to the raw material A is from 1.5 to 4.5:1.
  • the present invention also provides an organic electroluminescent device comprising at least one functional layer containing the pyridinium-containing compound.
  • an organic electroluminescent device comprises a hole transport layer/electron barrier layer, the hole transport layer/electron barrier layer containing the pyridinium-containing compound.
  • an organic electroluminescent device comprises a light-emitting layer containing the pyridinium-containing compound.
  • the invention also provides an illumination or display element comprising the organic electroluminescent device.
  • the compound of the present invention has asymmetry and avoids aggregation between molecules.
  • the compound of the present invention has strong rigidity, is incapable of crystallization, is difficult to aggregate, has good film forming property, and has high glass transition temperature and heat. Stability, therefore, when the compound of the present invention is applied to an OLED device, the film stability after film formation can be maintained, and the service life of the OLED device can be improved.
  • the structure of the compound of the invention makes the distribution of electrons and holes in the luminescent layer more balanced, and improves the hole injection/transport performance at the appropriate HOMO level; and at the appropriate LUMO level, it acts as an electron blocking. Enhancing the recombination efficiency of the excitons in the luminescent layer; when used as a luminescent functional layer material of the OLED illuminating device, the pyridine ruthenium combined with the branch within the scope of the invention can effectively improve the exciton utilization and the high fluorescence radiation efficiency, and the high Efficiency roll-off at current density reduces device voltage and increases current efficiency and lifetime of the device.
  • the compound of the invention has good application effects in OLED light-emitting devices and has good industrialization prospects.
  • FIG. 1 is a schematic structural view of a material exemplified in the present invention applied to an OLED device;
  • 1 is a transparent substrate layer
  • 2 is an ITO anode layer
  • 3 is a hole injection layer
  • 4 is a hole transport or electron blocking layer
  • 5 is a light emitting layer
  • 6 is an electron transport or hole blocking layer
  • 7 is an electron injection layer.
  • Layer, 8 is a cathode reflective electrode layer;
  • Figure 2 is a plot of current efficiency as a function of temperature.
  • the amount of the toluene and the ethanol is 30 to 50 mL of toluene and 5 to 10 mL of ethanol per gram of the raw material C
  • the molar ratio of the raw material B to the raw material C is (1 to 1.5): 1
  • Pd(PPh 3 ) 4 and The molar ratio of the raw material C was (0.006 to 0.02): 1
  • the molar ratio of K 2 CO 3 to the raw material C was (1.5 to 2): 1.
  • the molar ratio of the intermediate S to n-butyllithium is 1:1 to 1.5; and the molar ratio of the intermediate S to triisopropyl borate is 1:1 to 1.5.
  • the intermediate M was prepared by the synthesis method of the intermediate M-1, and the specific structure is shown in Table 1.
  • Compound 42 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-2 and the starting material B-1 was replaced with the intermediate M-2. Elemental analysis structure (Molecular formula C 52 H 34 N 2 ): Theory C, 90.93; H, 4.99; N, 4.08; ⁇ / RTI> C, 90.97; H, 5.05; N, 4.12. ESI-MS (m/z) (M + ): calc. 686.27.
  • Compound 64 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-4 and the starting material B-1 was replaced with the starting material B-4. Elemental analysis structure (Molecular formula C 42 H 28 N 2 ): calcd. C, 89.97; H, 5.03; N, 5.00; ⁇ / RTI> ⁇ /RTI> C, 90.03; H, 5.07; N, 5.02. ESI-MS (m/z) (M + ): 550.21.
  • Compound 70 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-4 and the starting material B-1 was replaced with the intermediate M-1. Elemental Analysis Structure (Molecular Formula C 48 H 32 N 2 ): Theory C, 90.54; H, 5.07; N, 4.40; Tests: C, 90.57; H, 5.11; N, 4.48. ESI-MS (m/z) (M + ): calc.
  • Compound 134 was prepared in the same manner as in Example 10 except that the starting material A-6 was replaced with the starting material A-5 and the intermediate material M-1 was used to replace the starting material B-1.
  • Elemental analysis structure (Molecular Formula C 48 H 30 N 2 ): Theory C, 90.82; H, 4.76; N, 4.41; Tests: C, 90.85; H, 4.79; N, 4.44.
  • Compound 140 was prepared in the same manner as in Example 10 except that the starting material B-1 was replaced with the intermediate M-3. Elemental Analysis Structure (Molecular Formula C 51 H 31 N 3 ): Theory C, 89.32; H, 4.56; N, 6.13; Tests: C, 89.34; H, 4.59; N, 6.17. ESI-MS (m/z) (M + ): calc. 685.
  • Compound 182 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-8 and the starting material B-1 was replaced with the intermediate M-4. Elemental analysis structure (Molecular formula C 51 H 36 N 2 ): Theory C, 90.50; H, 5.36; N, 4.14; ⁇ / RTI> C, 90.54; H, 5.38; N, 4.17. ESI-MS (m/z) (M + ): s.
  • Compound 201 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-11. Elemental analysis structure (Molecular formula C 45 H 34 N 2 ): calcd. C, 89.67; H, 5.69; N, 4.65; ⁇ / RTI> ⁇ /RTI> C, 89.69; H, 5.71; N, 4.68. ESI-MS (m/z) (M + ): calc. 602.
  • Compound 215 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with starting material A-12. Elemental analysis structure (Molecular formula C 41 H 25 N 3 ): calcd. C, 87.99; H, 4.50; N, 7.51; ⁇ / RTI> ⁇ /RTI> C, 88.05; H, 4.53; N, 7.54. ESI-MS (m/z) (M + ): 553.
  • Compound 223 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-13 and the starting material B-1 was replaced with the intermediate M-2. Elemental analysis structure (Molecular formula C 51 H 31 N 3 ): Theory C, 89.32; H, 4.56; N, 6.13; Tests: C, 89.34; H, 4.62; N, 6.15. ESI-MS (m/z) (M + ): calc. 685.
  • the compound 243 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-14 and the starting material B-1 was replaced with the intermediate M-5. Elemental Analysis Structure (Molecular Formula C 52 H 32 N 4 ): Theory C, 87.62; H, 4.52; N, 7.86; Found: C, 87.65; H, 4.55; N, 7.89. ESI-MS (m/z) (M + ): s.
  • the organic compound is used in a light-emitting device, has a high Tg (glass transition temperature) temperature and a triplet level (T1), and a suitable HOMO, LUMO energy level can be used as a hole blocking/electron transport material, or as a The luminescent layer material is used.
  • Tg glass transition temperature
  • T1 triplet level
  • HOMO HOMO
  • LUMO energy level can be used as a hole blocking/electron transport material, or as a The luminescent layer material is used.
  • the thermal performance, T1 energy level and HOMO energy level test were carried out on the compound of the present invention and the existing materials, and the results are shown in Table 2.
  • the triplet energy level T1 is tested by Hitachi's F4600 fluorescence spectrometer.
  • the test conditions of the material are 2*10 -5 toluene solution;
  • the glass transition temperature Tg is by differential scanning calorimetry (DSC, Germany Benz DSC204F1 differential scanning) The calorimeter was measured at a heating rate of 10 ° C/min;
  • the thermogravimetric temperature Td was a temperature at which the weight loss was 1% in a nitrogen atmosphere, and was measured on a TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, and the flow rate of nitrogen was 20 mL/ Min;
  • the highest occupied molecular orbital HOMO level is tested by the ionization energy test system (IPS3) and tested as the atmospheric environment.
  • IPS3 ionization energy test system
  • the organic compound of the invention has high glass transition temperature, can improve the phase stability of the material film, further improve the service life of the device, and has a high triplet energy level, compared with the currently applied CBP and TPBi materials.
  • the energy loss of the luminescent layer can be blocked, thereby improving the luminous efficiency of the device.
  • the materials of the invention and the materials of application have similar HOMO levels. Therefore, the organic material containing pyridinium in the invention can effectively improve the luminous efficiency and the service life of the device after being applied to different functional layers of the OLED device.
  • the device examples 1 to 21 and the device comparative example 1 have the same fabrication process, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also maintained. Consistently, the difference between the device embodiments 2 and 13 is that the material of the light-emitting layer in the device is changed; the device embodiments 14 to 21 change the material of the hole blocking/electron transport layer of the device, and the devices obtained by the respective embodiments are The performance test results are shown in Table 3.
  • an electroluminescent device is prepared by: a) cleaning an ITO anode layer 2 on a transparent substrate layer 1 and ultrasonically cleaning each with deionized water, acetone, and ethanol for 15 minutes, respectively, and then plasma.
  • the body cleaner is treated for 2 minutes; b) on the ITO anode layer 2, the hole injection layer material HAT-CN is deposited by vacuum evaporation, the thickness is 10 nm, this layer serves as the hole injection layer 3; c) is empty On the hole injecting layer 3, a hole transporting material NPB is deposited by vacuum evaporation to a thickness of 80 nm, the layer is a hole transporting layer/electron blocking layer 4; d) is steamed on the hole transporting/electron blocking layer 4
  • the luminescent layer 5 is plated, the host material is the compound 2 and the compound GH of the invention, the doping material is Ir(ppy) 3 , and the compound 2, GH and Ir(ppy) 3 have a mass ratio of 50:50:10 and a thickness of 40 nm.
  • the electron transporting material TPBI is evaporated by vacuum evaporation to a thickness of 35 nm, and this organic material is used as the hole blocking/electron transporting layer 6; f) in hole blocking/electron transport Above the layer 6, vacuum-evaporating the electron-injecting layer LiF to a thickness of 1 nm, the layer is an electron injecting layer 7; g) in the electron injection On the layer 7, a cathode Al (100 nm) is vacuum-deposited, and the layer is a cathode reflective electrode layer 8; after the fabrication of the electroluminescent device is completed according to the above steps, the driving voltage and current efficiency of the device are measured, and the results are shown in Table 3. Show.
  • the molecular organization of the relevant material is as follows:
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 15, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 38, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / luminescent layer 5 (Thickness: 40 nm, material: Compound 42 and Ir(ppy) 3 are mixed by weight ratio of 90:10) / Hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / Electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 58, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 64, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 70 and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 98, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 102 and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 134, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 197, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 199, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / luminescent layer 5 (Thickness: 40 nm, material: compound 201, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 140) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 143) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 155) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 182) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 215) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 223) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 234) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / luminescent layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 243) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
  • ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
  • the detection data of the obtained electroluminescent device is shown in Table 3.
  • the OLED device prepared by the material of the invention is more stable when operating at a low temperature, and the device examples 2, 9, and 17 and the device comparative example 1 are tested in the range of -10 to 80 ° C, and the results are shown in Table 4 and Figure 2 shows.
  • device examples 2, 9, and 17 are device structures in which the materials of the present invention and known materials are matched, and compared with the device comparative example 1, not only the low temperature efficiency but also the temperature rise process. In the middle, efficiency has increased steadily.

Abstract

Disclosed are a compound containing pyridoindole and the use thereof in an organic electroluminescence device. The compound is composed of pyridoindole groups, and has a deep HOMO energy level and hole mobility and is suitable as a hole transport material or an electron blocking material; In addition, the group in the present compound has a strong strength, and has characteristics of not easy to crystallize and aggregate and of good film-forming property. As an organic electroluminescent functional layer material used in an OLED device, the current efficiency, power efficiency, and external quantum efficiency of the device are all greatly improved; at the same time, the improvement of the device lifetime is very significant.

Description

一种含有吡啶并吲哚的化合物及其在有机电致发光器件上的应用A compound containing pyridoindole and its application in organic electroluminescent devices 技术领域Technical field
本发明涉及半导体技术领域，尤其是涉及一种含有吡啶并吲哚的化合物及其在有机电致发光器件上的应用。The present invention relates to the field of semiconductor technology, and more particularly to a compound containing pyridoindole and its use in an organic electroluminescent device.
背景技术Background technique
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品，也可以用于制作新型照明产品，有望替代现有的液晶显示和荧光灯照明，应用前景十分广泛。OLED发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。作为电流器件，当对OLED发光器件的两端电极施加电压，并通过电场作用有机层功能材料膜层中的正负电荷，正负电荷进一步在发光层中复合，即产生OLED电致发光。Organic Light Emission Diodes (OLED) device technology can be used to manufacture new display products, as well as to create new lighting products. It is expected to replace existing liquid crystal displays and fluorescent lighting, and has a wide application prospect. The OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device. As a current device, when a voltage is applied to the electrodes of both ends of the OLED light-emitting device, and the positive and negative charges in the film layer of the organic layer functional material are applied by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, OLED electroluminescence is generated.
当前，OLED显示技术已经在智能手机，平板电脑等领域获得应用，进一步还将向电视等大尺寸应用领域扩展，但是，和实际的产品应用要求相比，OLED器件的发光效率，使用寿命等性能还需要进一步提升。对于OLED发光器件提高性能的研究包括：降低器件的驱动电压，提高器件的发光效率，提高器件的使用寿命等。为了实现OLED器件的性能的不断提升，不但需要从OLED器件结构和制作工艺的创新，更需要OLED光电功能材料不断研究和创新，创制出更高性能OLED的功能材料。应用于OLED器件的OLED光电功能材料从用途上可划分为两大类，即电荷注入传输材料和发光材料，进一步，还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料，还可以将发光材料分为主体发光材料和掺杂材料。为了制作高性能的OLED发光器件，要求各种有机功能材料具备良好的光电特性，譬如，作为电荷传输材料，要求具有良好的载流子迁移率，高玻璃化转化温度等，作为发光层的主体材料要求材料具有良好双极性，适当的HOMO/LUMO能阶等。At present, OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as televisions. However, compared with actual product application requirements, OLED devices have luminous efficiency and service life. Further improvement is needed. Research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device. In order to realize the continuous improvement of the performance of OLED devices, it is not only necessary to innovate from the structure and fabrication process of OLED devices, but also to continuously research and innovate OLED photoelectric functional materials, and to create functional materials with higher performance OLEDs. OLED photoelectric functional materials applied to OLED devices can be divided into two categories, namely, charge injection transport materials and luminescent materials, and further, charge injection transport materials can be divided into electron injection transport materials, electron blocking materials, and holes. The transport material and the hole blocking material are injected, and the luminescent material can also be divided into a host luminescent material and a dopant material. In order to produce high-performance OLED light-emitting devices, various organic functional materials are required to have good photoelectric characteristics. For example, as a charge transport material, it is required to have good carrier mobility, high glass transition temperature, etc., as a main body of the light-emitting layer. Materials require materials with good bipolarity, appropriate HOMO/LUMO energy levels, and the like.
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构，则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层，也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料，空穴传输材料，发光材料，电子传输材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同 的材料在不同结构器件中的性能表现，也可能完全迥异。因此，针对当前OLED器件的产业应用要求，以及OLED器件的不同功能膜层，器件的光电特性需求，必须选择更适合，具有高性能的OLED功能材料或材料组合，才能实现器件的高效率、长寿命和低电压的综合特性。就当前OLED显示照明产业的实际需求而言，目前OLED材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能材料显得尤为重要。The OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron. a plurality of film layers such as a transport layer and an electron injection layer, that is, an optoelectronic functional material applied to an OLED device includes at least a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material, etc., and the material type and the collocation form are rich. Characteristics of sex and diversity. In addition, for OLED device combinations with different structures, the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in different structural devices may be completely different. Therefore, in view of the industrial application requirements of current OLED devices, and the different functional film layers of OLED devices, the photoelectric characteristics of the devices must be selected to be more suitable, and high-performance OLED functional materials or material combinations can achieve high efficiency and long device. Comprehensive characteristics of life and low voltage. As far as the actual demand of the current OLED display lighting industry is concerned, the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.
发明内容Summary of the invention
针对现有技术存在的上述问题，本申请提供一种含有吡啶并吲哚的化合物及其在有机电致发光器件上的应用。本发明的化合物具有较高的玻璃化温度和分子热稳定性，合适的HOMO和LUMO能级，高空穴迁移率，应用于OLED器件制作后，可有效提高器件的发光效率和OLED器件的使用寿命。In view of the above problems in the prior art, the present application provides a pyridinium-containing compound and its use in an organic electroluminescent device. The compound of the invention has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, high hole mobility, and can be effectively used to improve the luminous efficiency of the device and the service life of the OLED device after being fabricated by the OLED device. .
本发明的技术方案如下：一种含有吡啶并吲哚的化合物，该化合物的结构如通式(1)所示：The technical scheme of the present invention is as follows: a compound containing pyridoindole, the structure of which is as shown in the general formula (1):
Figure PCTCN2018120716-appb-000001
Figure PCTCN2018120716-appb-000001
其中，X表示为单键；i等于0或1；Wherein X is represented as a single bond; i is equal to 0 or 1;
A表示为单键、氧原子、C 1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基中的一种； A is represented by a single bond, an oxygen atom, a C 1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl substituted imido group or an aryl substituted imido group. a kind
X 1、X 2、X 3、X 4、X 5、X 6、X 7、X 8分别独立的表示为C-H或N原子，且N原子的数量为0、1或2； X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 are each independently represented as CH or N atom, and the number of N atoms is 0, 1 or 2;
m、n、p、q等于0或1；且m+n+p+q≥1；m, n, p, q are equal to 0 or 1; and m + n + p + q ≥ 1;
E是任选地被一个或多个R 1取代的吡啶并吲哚基团； E is a pyridoindole group optionally substituted with one or more R 1 ;
R 1表示为取代或未取代的C 6至C 30芳基和取代或未取代的C 5至C 30杂芳基中的一种；所述杂原子为氮、氧或硫。 R 1 represents one of a substituted or unsubstituted C 6 to C 30 aryl group and a substituted or unsubstituted C 5 to C 30 heteroaryl group; the hetero atom is nitrogen, oxygen or sulfur.
在上述方案的基础上，本发明还可以做以下改进。Based on the above scheme, the present invention can also make the following improvements.
优选的，一种含有吡啶并吲哚的化合物，所述E可用通式(2)表示；Preferably, a compound containing pyridoindole, the E being represented by the formula (2);
Figure PCTCN2018120716-appb-000002
Figure PCTCN2018120716-appb-000002
其中，Ar 1表示为单健、取代或未取代的C 6- 30亚芳基、取代或未取代的C 5- 30杂亚芳基中的一种；所述杂原子为氮、氧或硫； Wherein Ar 1 is represented by one of a mono-, substituted or unsubstituted C 6 - 30 arylene, a substituted or unsubstituted C 5 - 30 heteroarylene; the hetero atom is nitrogen, oxygen or sulfur ;
Ar 2表示为取代或未取代的C 6- 30芳基、取代或未取代的C 5- 30杂芳基中的一种；所述杂原子为氮、氧或硫； Ar 2 is represented by one of a substituted or unsubstituted C 6 - 30 aryl group, a substituted or unsubstituted C 5 - 30 heteroaryl group; the hetero atom is nitrogen, oxygen or sulfur;
Z表示为C-H或N原子，且至少有一个Z表示N原子。Z is represented by a C-H or N atom, and at least one Z represents an N atom.
优选的，一种含有吡啶并吲哚的化合物，所述通式(1)中
Figure PCTCN2018120716-appb-000003
表示为：
Figure PCTCN2018120716-appb-000004
Figure PCTCN2018120716-appb-000005
中的任一种。 Preferably, a compound containing pyridoindole, in the formula (1)
Figure PCTCN2018120716-appb-000003
Expressed as:
Figure PCTCN2018120716-appb-000004
Figure PCTCN2018120716-appb-000005
Any of them.
优选的，一种含有吡啶并吲哚的化合物，通式(2)的结构可表示为：
Figure PCTCN2018120716-appb-000006
Figure PCTCN2018120716-appb-000007
Figure PCTCN2018120716-appb-000008
中的任一种。 Preferably, a compound containing a pyridoindole, the structure of the formula (2) can be expressed as:
Figure PCTCN2018120716-appb-000006
Figure PCTCN2018120716-appb-000007
Figure PCTCN2018120716-appb-000008
Any of them.
优选的，一种含有吡啶并吲哚的化合物，所述Ar 1表示为单键、亚苯基、亚萘基、亚联苯基、亚蒽基、亚呋喃基、亚咔唑基、亚萘啶基、亚喹啉基、亚噻吩基、亚吡啶基、亚苝基、亚9,9-二甲基芴基、亚菲基、亚二苯并呋喃基、亚二苯并噻吩基中的一种； Preferred compounds, containing pyridine and indole, said Ar 1 represents a single bond, phenylene, naphthylene group, biphenylene group, anthracenyl group, a furyl group, a carbazolyl group, a naphthylene Of pyridine, quinolinol, thienylene, pyridylene, fluorenylene, 9,9-dimethylindenyl, phenanthrylene, dibenzofuranyl, dibenzothiophenyl One type;
所述Ar 2表示为苯基、萘基、联苯基、蒽基、呋喃基、咔唑基、萘啶基、喹啉基、噻吩基、吡啶基、苝基、9,9-二甲基芴基、菲基、二苯并呋喃基、二苯并噻吩基中的一种。 The Ar 2 is represented by phenyl, naphthyl, biphenyl, anthracenyl, furyl, oxazolyl, naphthyridinyl, quinolyl, thienyl, pyridyl, fluorenyl, 9,9-dimethyl One of a mercapto group, a phenanthryl group, a dibenzofuranyl group, and a dibenzothiophene group.
优选的，一种含有吡啶并吲哚的化合物，所述化合物的具体结构式为：Preferably, a compound containing pyridoindole, the specific structural formula of the compound is:
Figure PCTCN2018120716-appb-000009
Figure PCTCN2018120716-appb-000009
Figure PCTCN2018120716-appb-000010
Figure PCTCN2018120716-appb-000010
Figure PCTCN2018120716-appb-000011
Figure PCTCN2018120716-appb-000011
Figure PCTCN2018120716-appb-000012
Figure PCTCN2018120716-appb-000012
Figure PCTCN2018120716-appb-000013
Figure PCTCN2018120716-appb-000013
Figure PCTCN2018120716-appb-000014
Figure PCTCN2018120716-appb-000014
Figure PCTCN2018120716-appb-000015
Figure PCTCN2018120716-appb-000015
Figure PCTCN2018120716-appb-000016
Figure PCTCN2018120716-appb-000016
Figure PCTCN2018120716-appb-000017
Figure PCTCN2018120716-appb-000017
Figure PCTCN2018120716-appb-000018
中的任一种。
Figure PCTCN2018120716-appb-000018
Any of them.
本发明还提供一种含有吡啶并吲哚的化合物的制备方法，所述制备方法涉及的反应方程式为：The invention also provides a preparation method of a compound containing pyridoindole, the preparation method relates to a reaction equation:
Figure PCTCN2018120716-appb-000019
Figure PCTCN2018120716-appb-000019
具体反应过程为：The specific reaction process is:
将原料A和中间体M溶解于甲苯和乙醇的混合溶液中，除氧后加入Pd(PPh 3) 4和K 2CO 3，在惰性气氛下95～110℃反应10～24个小时，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物； The raw material A and the intermediate M are dissolved in a mixed solution of toluene and ethanol, and after deoxidation, Pd(PPh 3 ) 4 and K 2 CO 3 are added , and the reaction is carried out at 95 to 110 ° C for 10 to 24 hours in an inert atmosphere until the raw materials are used. After the reaction is completed, the mixture is cooled and filtered, and the filtrate is evaporated to remove the solvent, and the crude product is passed through a silica gel column to obtain the target compound;
其中，所述的甲苯和乙醇的用量为每克原料A使用30～50mL甲苯和5～10mL乙醇，中间体M与原料A的摩尔比为1～3:1，Pd(PPh 3) 4与原料A的摩尔比为0.006～0.03:1，K 2CO 3与原料A的摩尔比为1.5～4.5:1。 Wherein, the amount of the toluene and the ethanol is 30 to 50 mL of toluene and 5 to 10 mL of ethanol per gram of the raw material A, and the molar ratio of the intermediate M to the raw material A is 1 to 3:1, Pd(PPh 3 ) 4 and the raw material. The molar ratio of A is from 0.006 to 0.03:1, and the molar ratio of K 2 CO 3 to the raw material A is from 1.5 to 4.5:1.
本发明还提供一种有机电致发光器件，所述有机电致发光器件包括至少一层功能层含有所述的一种含有吡啶并吲哚的化合物。The present invention also provides an organic electroluminescent device comprising at least one functional layer containing the pyridinium-containing compound.
优选的，一种有机电致发光器件，包括空穴传输层/电子阻挡层，所述空穴传输层/电子阻挡层含有所述的含有吡啶并吲哚的化合物。Preferably, an organic electroluminescent device comprises a hole transport layer/electron barrier layer, the hole transport layer/electron barrier layer containing the pyridinium-containing compound.
优选的，一种有机电致发光器件，包括发光层，所述发光层含有所述的含有吡啶并吲哚的化合物。Preferably, an organic electroluminescent device comprises a light-emitting layer containing the pyridinium-containing compound.
本发明还提供一种照明或显示元件，包含所述的有机电致发光器件。The invention also provides an illumination or display element comprising the organic electroluminescent device.
本发明有益的技术效果在于：The beneficial technical effects of the present invention are:
本发明化合物分子具有不对称性，避免分子间的聚集作用，本发明化合物基团刚性较强，具有分子间不易结晶、不易聚集、具有良好成膜性的特点，具有高的玻璃化温度及热稳定性，所以，本发明化合物应用于OLED器件时，可保持材料成膜后的膜层稳定性，提高OLED器件使用寿命。The compound of the present invention has asymmetry and avoids aggregation between molecules. The compound of the present invention has strong rigidity, is incapable of crystallization, is difficult to aggregate, has good film forming property, and has high glass transition temperature and heat. Stability, therefore, when the compound of the present invention is applied to an OLED device, the film stability after film formation can be maintained, and the service life of the OLED device can be improved.
本发明化合物结构使得电子和空穴在发光层的分布更加平衡，在恰当的HOMO能级下，提升了空穴注入/传输性能；在合适的LUMO能级下，又起到了电子阻挡的作用，提升激子在发光层中的复合效率；作为OLED发光器件的发光功能层材料使用时，吡啶并吲哚搭配本发明范围内的支链可有效提高激子利用率和高荧光辐射效率，降低高电流密度下的效率滚降，降低器件电压，提高器件的电流效率和寿命。The structure of the compound of the invention makes the distribution of electrons and holes in the luminescent layer more balanced, and improves the hole injection/transport performance at the appropriate HOMO level; and at the appropriate LUMO level, it acts as an electron blocking. Enhancing the recombination efficiency of the excitons in the luminescent layer; when used as a luminescent functional layer material of the OLED illuminating device, the pyridine ruthenium combined with the branch within the scope of the invention can effectively improve the exciton utilization and the high fluorescence radiation efficiency, and the high Efficiency roll-off at current density reduces device voltage and increases current efficiency and lifetime of the device.
本发明所述化合物在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。The compound of the invention has good application effects in OLED light-emitting devices and has good industrialization prospects.
附图说明DRAWINGS
图1为本发明所列举的材料应用于OLED器件的结构示意图；1 is a schematic structural view of a material exemplified in the present invention applied to an OLED device;
其中，1为透明基板层，2为ITO阳极层，3为空穴注入层，4为空穴传输或电子阻挡层，5为发光层，6为电子传输或空穴阻挡层，7为电子注入层，8为阴极反射电极层；Wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport or electron blocking layer, 5 is a light emitting layer, 6 is an electron transport or hole blocking layer, and 7 is an electron injection layer. Layer, 8 is a cathode reflective electrode layer;
图2为电流效率随温度变化的曲线。Figure 2 is a plot of current efficiency as a function of temperature.
具体实施方式Detailed ways
实施例1：中间体M的合成：Example 1: Synthesis of Intermediate M:
Figure PCTCN2018120716-appb-000020
Figure PCTCN2018120716-appb-000020
(1)将原料B和原料C溶解于甲苯和乙醇的混合溶液中，除氧后加入Pd(PPh 3) 4和K 2CO 3，在惰性气氛下95～110℃反应10～24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体S； (1) The raw material B and the raw material C are dissolved in a mixed solution of toluene and ethanol, and after deoxidation, Pd(PPh 3 ) 4 and K 2 CO 3 are added , and the reaction is carried out at 95 to 110 ° C for 10 to 24 hours in an inert atmosphere. During the reaction, the reaction process is continuously monitored by TLC. After the reaction of the raw materials is completed, the mixture is cooled and filtered, and the filtrate is evaporated to remove the solvent. The crude product is passed through a silica gel column to obtain an intermediate S;
其中，所述的甲苯和乙醇的用量为每克原料C使用30～50mL甲苯和5～10mL乙醇，原料B与原料C的摩尔比为(1～1.5):1，Pd(PPh 3) 4与原料C的摩尔比为(0.006～0.02):1，K 2CO 3与原料C的摩尔比为(1.5～2):1。 Wherein, the amount of the toluene and the ethanol is 30 to 50 mL of toluene and 5 to 10 mL of ethanol per gram of the raw material C, and the molar ratio of the raw material B to the raw material C is (1 to 1.5): 1, Pd(PPh 3 ) 4 and The molar ratio of the raw material C was (0.006 to 0.02): 1, and the molar ratio of K 2 CO 3 to the raw material C was (1.5 to 2): 1.
(2)在氮气保护下，称取中间体S 0.01mol溶于150mL四氢呋喃中，冷却至-78℃，然后向反应体系中加入1.6mol/L正丁基锂的四氢呋喃溶液，在-78℃下反应3h后加入硼酸三异丙酯，反应2h，然后将反应体系升至0℃，加入10ml 2mol/L盐酸溶液，搅拌3h，反应完全，加入乙醚萃取，萃取液加入无水硫酸镁干燥，旋蒸，用乙醇溶剂重结晶，得到中间体M；(2) Under the protection of nitrogen, 0.01 mol of the intermediate S was dissolved in 150 mL of tetrahydrofuran, cooled to -78 ° C, and then 1.6 mol / L of a solution of n-butyllithium in tetrahydrofuran was added to the reaction system at -78 ° C. After 3 h of reaction, triisopropyl borate was added and reacted for 2 h. Then the reaction system was raised to 0 ° C, 10 ml of 2 mol/L hydrochloric acid solution was added, and the mixture was stirred for 3 h. The reaction was completed, and the mixture was extracted with diethyl ether. Steaming, recrystallization from ethanol solvent to give intermediate M;
其中，所述中间体S与正丁基锂的摩尔比为1:1～1.5；所述中间体S与硼酸三异丙酯的摩尔比为1:1～1.5。Wherein, the molar ratio of the intermediate S to n-butyllithium is 1:1 to 1.5; and the molar ratio of the intermediate S to triisopropyl borate is 1:1 to 1.5.
以中间体M-1合成为例：Take the synthesis of intermediate M-1 as an example:
Figure PCTCN2018120716-appb-000021
Figure PCTCN2018120716-appb-000021
(1)将0.01mol原料C-1和0.012mol原料B-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到中间体S-1；元素分析结构(分子式C 23H 15BrN 2)：理论值C,69.19；H,3.79；Br,20.01；N,7.02；测试值：C,69.23；H,3.82；Br,20.06；N,7.04；ESI-MS(m/z)(M+)：理论值为398.04，实测值为398.15。 (1) Dissolving 0.01 mol of the raw material C-1 and 0.012 mol of the raw material B-1 in a mixed solution of 150 mL (V toluene : V ethanol = 5:1) of toluene and ethanol, and adding 0.0002 mol of Pd (PPh 3 ) after deoxidation. 4 and 0.02mol K 2 CO 3 , reacted in an inert atmosphere at 110 ° C for 24 hours, the reaction process was continuously monitored by TLC during the reaction. After the reaction of the raw materials was completed, it was cooled, filtered, and the filtrate was evaporated to remove the solvent. silica gel column to give intermediate S-1; the structure elemental analysis (molecular formula C 23 H 15 BrN 2): theory C, 69.19; H, 3.79; Br, 20.01; N, 7.02; test value: C, 69.23; H, 3.82; Br, 20.06; N, 7.04; ESI-MS (m/z) (M+): Theory: 398.04.
(2)在氮气保护下，称取中间体0.01mol S-1溶于150mL四氢呋喃中，冷却至-78℃，然后向反应体系中加入8ml 1.6mol/L正丁基锂的四氢呋喃溶液，在-78℃下反应3h后加入0.013mol硼酸三异丙酯，反应2h，然后将反应体系升至0℃，加入10ml 2mol/L盐酸溶液，搅拌3h，反应完全，加入乙醚萃取，萃取液加入无水硫酸镁干燥，旋蒸，用乙醇溶剂重结晶，得到中间体M-1；元素分析结构(分子式C 23H 17BN 2O 2)：理论值C,75.85；H,4.70；B,2.97；N,7.69；O,8.79；测试值：C,75.87；H,4.73；B,2.98；N,7.73；O,8.82。ESI-MS(m/z)(M +)：理论值为364.14，实测值为364.25。 (2) Under nitrogen protection, the intermediate 0.01 mol S-1 was weighed and dissolved in 150 mL of tetrahydrofuran, cooled to -78 ° C, and then 8 ml of a 1.6 mol/L solution of n-butyllithium in tetrahydrofuran was added to the reaction system. After reacting at 78 ° C for 3 h, add 0.013 mol of triisopropyl borate, react for 2 h, then raise the reaction system to 0 ° C, add 10 ml of 2 mol / L hydrochloric acid solution, stir for 3 h, complete the reaction, add ether to extract, add the extract to the water over magnesium sulfate, and rotary evaporated with a solvent and recrystallized from ethanol to give intermediate M-1; the structure elemental analysis (molecular formula C 23 H 17 BN 2 O 2 ): theory C, 75.85; H, 4.70; B, 2.97; N , 7.69; O, 8.79; Test value: C, 75.87; H, 4.73; B, 2.98; N, 7.73; O, 8.82. ESI-MS (m/z) (M + ): 355.
以中间体M-1的合成方法制备中间体M，具体结构如表1所示。The intermediate M was prepared by the synthesis method of the intermediate M-1, and the specific structure is shown in Table 1.
表1Table 1
Figure PCTCN2018120716-appb-000022
Figure PCTCN2018120716-appb-000022
Figure PCTCN2018120716-appb-000023
Figure PCTCN2018120716-appb-000023
实施例2：化合物2的合成：Example 2: Synthesis of Compound 2:
Figure PCTCN2018120716-appb-000024
Figure PCTCN2018120716-appb-000024
在250mL三口瓶中，将0.01mol原料A-1和0.012mol原料B-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标产物；元素分析结构(分子式C 42H 28N 2)：理论值C,89.97；H,5.03；N,5.00；测试值：C,89.98；H,5.07；N,5.01；ESI-MS(m/z)(M+)：理论值为560.23，实测值为560.27。 In a 250 mL three-necked flask, 0.01 mol of the raw material A-1 and 0.012 mol of the raw material B-1 were dissolved in a mixed solution of 150 mL (V toluene : V ethanol = 5:1) of toluene and ethanol, and 0.0002 mol of Pd was added after deoxidation ( PPh 3 ) 4 and 0.02 mol K 2 CO 3 , reacted at 110 ° C for 24 hours under an inert atmosphere, and the reaction progress was continuously monitored by TLC during the reaction. After the reaction of the raw materials was completed, the mixture was cooled, filtered, and the filtrate was evaporated to remove the solvent. The crude product over a silica gel column, to give the desired product; elemental analysis for structure (formula C 42 H 28 N 2): theory C, 89.97; H, 5.03; N, 5.00; test value: C, 89.98; H, 5.07 ; N, </ RTI> ESI-MS (m/z) (M+): calc.
实施例3：化合物15的合成：Example 3: Synthesis of Compound 15:
Figure PCTCN2018120716-appb-000025
Figure PCTCN2018120716-appb-000025
在250mL三口瓶中，将0.01mol原料A-2和0.012mol原料B-3溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰 性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标产物；元素分析结构(分子式C 42H 28N 2)：理论值C,89.97；H,5.03；N,5.00；测试值：C,89.98；H,5.08；N,5.07；ESI-MS(m/z)(M+)：理论值为560.23，实测值为560.28。 In a 250 mL three-necked flask, 0.01 mol of the raw material A-2 and 0.012 mol of the raw material B-3 were dissolved in a mixed solution of 150 mL (V toluene : V ethanol = 5:1) of toluene and ethanol, and 0.0002 mol of Pd was added after deoxidation ( PPh 3 ) 4 and 0.02 mol K 2 CO 3 , reacted at 110 ° C for 24 hours under an inert atmosphere, and the reaction progress was continuously monitored by TLC during the reaction. After the reaction of the raw materials was completed, the mixture was cooled, filtered, and the filtrate was evaporated to remove the solvent. The crude product over a silica gel column, to give the desired product; elemental analysis for structure (formula C 42 H 28 N 2): theory C, 89.97; H, 5.03; N, 5.00; test value: C, 89.98; H, 5.08 ; N, </ RTI> ESI-MS (m/z) (M+): calc.
实施例4：化合物38的合成：Example 4: Synthesis of Compound 38:
Figure PCTCN2018120716-appb-000026
Figure PCTCN2018120716-appb-000026
化合物38的制备方法同实施例2，不同之处在于用中间体M-1替换原料B-1。元素分析结构(分子式C 48H 32N 2)：理论值C,90.54；H,5.07；N,4.40；测试值：C,90.57；H,5.11；N,4.43。ESI-MS(m/z)(M +)：理论值为636.26，实测值为636.27。 Compound 38 was prepared in the same manner as in Example 2 except that the starting material B-1 was replaced with the intermediate M-1. Elemental analysis structure (Molecular formula C 48 H 32 N 2 ): Theory C, 90.54; H, 5.07; N, 4.40; </ RTI></RTI> C, 90.57; H, 5.11; N, 4.43. ESI-MS (m/z) (M + ): calc.
实施例5：化合物42的合成：Example 5: Synthesis of Compound 42:
Figure PCTCN2018120716-appb-000027
Figure PCTCN2018120716-appb-000027
化合物42的制备方法同实施例2，不同之处在于用原料A-2替换原料A-1，用中间体M-2替换原料B-1。元素分析结构(分子式C 52H 34N 2)：理论值C,90.93；H,4.99；N,4.08；测试值：C,90.97；H,5.05；N,4.12。ESI-MS(m/z)(M +)：理论值为686.27，实测值为686.31。 Compound 42 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-2 and the starting material B-1 was replaced with the intermediate M-2. Elemental analysis structure (Molecular formula C 52 H 34 N 2 ): Theory C, 90.93; H, 4.99; N, 4.08; </ RTI> C, 90.97; H, 5.05; N, 4.12. ESI-MS (m/z) (M + ): calc. 686.27.
实施例6：化合物58的合成：Example 6: Synthesis of Compound 58:
Figure PCTCN2018120716-appb-000028
Figure PCTCN2018120716-appb-000028
化合物58的制备方法同实施例2，不同之处在于用原料A-3替换原料A-1。元素分析结构(分子式C 42H 28N 2)：理论值C,89.97；H,5.03；N,5.00；测试值：C,90.01；H,5.06；N,5.03。 ESI-MS(m/z)(M +)：理论值为560.23，实测值为560.27。 Compound 58 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-3. Elemental analysis structure (Molecular formula C 42 H 28 N 2 ): calcd. C, 89.97; H, 5.03; N, 5.00; ESI-MS (m/z) (M + ): 550.21.
实施例7：化合物64的合成：Example 7: Synthesis of Compound 64:
Figure PCTCN2018120716-appb-000029
Figure PCTCN2018120716-appb-000029
化合物64的制备方法同实施例2，不同之处在于用原料A-4替换原料A-1，用原料B-4替换原料B-1。元素分析结构(分子式C 42H 28N 2)：理论值C,89.97；H,5.03；N,5.00；测试值：C,90.03；H,5.07；N,5.02。ESI-MS(m/z)(M +)：理论值为560.23，实测值为560.29。 Compound 64 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-4 and the starting material B-1 was replaced with the starting material B-4. Elemental analysis structure (Molecular formula C 42 H 28 N 2 ): calcd. C, 89.97; H, 5.03; N, 5.00; </ RTI></RTI> C, 90.03; H, 5.07; N, 5.02. ESI-MS (m/z) (M + ): 550.21.
实施例8：化合物70的合成：Example 8: Synthesis of Compound 70:
Figure PCTCN2018120716-appb-000030
Figure PCTCN2018120716-appb-000030
化合物70的制备方法同实施例2，不同之处在于用原料A-4替换原料A-1，用中间体M-1替换原料B-1。元素分析结构(分子式C 48H 32N 2)：理论值C,90.54；H,5.07；N,4.40；测试值：C,90.57；H,5.11；N,4.48。ESI-MS(m/z)(M +)：理论值为636.26，实测值为636.31。 Compound 70 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-4 and the starting material B-1 was replaced with the intermediate M-1. Elemental Analysis Structure (Molecular Formula C 48 H 32 N 2 ): Theory C, 90.54; H, 5.07; N, 4.40; Tests: C, 90.57; H, 5.11; N, 4.48. ESI-MS (m/z) (M + ): calc.
实施例9：化合物98的合成：Example 9: Synthesis of Compound 98:
Figure PCTCN2018120716-appb-000031
Figure PCTCN2018120716-appb-000031
化合物98的制备方法同实施例2，不同之处在于用原料A-4替换原料A-1，用中间体M-2替换原料B-1。元素分析结构(分子式C 54H 34N 2)：理论值C,90.93；H,4.99；N,4.08；测试值：C,90.97；H,5.03；N,4.13。ESI-MS(m/z)(M +)：理论值为686.27，实测值为686.31。 Compound 98 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-4 and the starting material B-1 was replaced with the intermediate M-2. Elemental Analysis Structure (Molecular Formula C 54 H 34 N 2 ): Theory C, 90.93; H, 4.99; N, 4.08; </ RTI></RTI> C, 90.97; H, 5.03; N, 4.13. ESI-MS (m/z) (M + ): calc. 686.27.
实施例10：化合物102的合成：Example 10: Synthesis of Compound 102:
Figure PCTCN2018120716-appb-000032
Figure PCTCN2018120716-appb-000032
在250mL三口瓶中，将0.01mol原料A-5和0.012mol原料B-1溶解于甲苯和乙醇的150mL(V 甲苯：V 乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh 3) 4和0.02mol K 2CO 3，在惰性气氛下110℃反应24个小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标产物；元素分析结构(分子式C 42H 26N 2)：理论值C,90.29；H,4.69；N,5.01；测试值：C,92.31；H,4.74；N,5.08。ESI-MS(m/z)(M +)：理论值为558.21，实测值为558.27。 In a 250 mL three-necked flask, 0.01 mol of the raw material A-5 and 0.012 mol of the raw material B-1 were dissolved in a mixed solution of 150 mL (V toluene : V ethanol = 5:1) of toluene and ethanol, and 0.0002 mol of Pd was added after deoxidation ( PPh 3 ) 4 and 0.02 mol K 2 CO 3 , reacted at 110 ° C for 24 hours under an inert atmosphere, and the reaction progress was continuously monitored by TLC during the reaction. After the reaction of the raw materials was completed, the mixture was cooled, filtered, and the filtrate was evaporated to remove the solvent. The crude product was passed through a silica gel column to give the titled product. The title compound (M. C 42 H 26 N 2 ): Theory C, 90.29; H, 4.69; N, 5.01; Test value: C, 92.31; H, 4.74; 5.08. ESI-MS (m/z) (M + ): 553.21.
实施例11：化合物134的合成：Example 11: Synthesis of Compound 134:
Figure PCTCN2018120716-appb-000033
Figure PCTCN2018120716-appb-000033
化合物134的制备方法同实施例10，不同之处在于用原料A-6换原料A-5，用中间体M-1替换原料B-1。元素分析结构(分子式C 48H 30N 2)：理论值C,90.82；H,4.76；N,4.41；测试值：C,90.85；H,4.79；N,4.44。ESI-MS(m/z)(M +)：理论值为634.24，实测值为634.27。 Compound 134 was prepared in the same manner as in Example 10 except that the starting material A-6 was replaced with the starting material A-5 and the intermediate material M-1 was used to replace the starting material B-1. Elemental analysis structure (Molecular Formula C 48 H 30 N 2 ): Theory C, 90.82; H, 4.76; N, 4.41; Tests: C, 90.85; H, 4.79; N, 4.44. ESI-MS (m/z) (M + ): calc.
实施例12：化合物140的合成：Example 12: Synthesis of Compound 140:
Figure PCTCN2018120716-appb-000034
Figure PCTCN2018120716-appb-000034
化合物140的制备方法同实施例10，不同之处在于用中间体M-3替换原料B-1。元素分析结构(分子式C 51H 31N 3)：理论值C,89.32；H,4.56；N,6.13；测试值：C,89.34；H,4.59；N,6.17。ESI-MS(m/z)(M +)：理论值为685.25，实测值为685.31。 Compound 140 was prepared in the same manner as in Example 10 except that the starting material B-1 was replaced with the intermediate M-3. Elemental Analysis Structure (Molecular Formula C 51 H 31 N 3 ): Theory C, 89.32; H, 4.56; N, 6.13; Tests: C, 89.34; H, 4.59; N, 6.17. ESI-MS (m/z) (M + ): calc. 685.
实施例13：化合物143的合成：Example 13: Synthesis of Compound 143:
Figure PCTCN2018120716-appb-000035
Figure PCTCN2018120716-appb-000035
化合物143的制备方法同实施例10，不同之处在于用原料A-7替换原料A-5。元素分析结构(分子式C 45H 32N 2)：理论值C,89.97；H,5.37；N,4.66；测试值：C,90.02；H,5.41；N,4.69。ESI-MS(m/z)(M +)：理论值为600.26，实测值为600.32。 Compound 143 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-7. Elemental Analysis Structure (Molecular Formula C 45 H 32 N 2 ): Theory C, 89.97; H, 5.37; N, 4.66; Tests: C, 90.02; H, 5.41; N, 4.69. ESI-MS (m/z) (M + ): calcd.
实施例14：化合物155的合成：Example 14: Synthesis of Compound 155:
Figure PCTCN2018120716-appb-000036
Figure PCTCN2018120716-appb-000036
化合物155的制备方法同实施例10，不同之处在于用原料A-8替换原料A-5。元素分析结构(分子式C 45H 32N 2)：理论值C,89.97；H,5.37；N,4.66；测试值：C,90.01；H,5.43；N,4.69。ESI-MS(m/z)(M +)：理论值为600.26，实测值为600.33。 Compound 155 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-8. Elemental Analysis Structure (Molecular Formula C 45 H 32 N 2 ): Theory C, 89.97; H, 5.37; N, 4.66; Tests: C, 90.01; H, 5.43; N, 4.69. ESI-MS (m/z) (M + ): calcd.
实施例15：化合物182的合成：Example 15: Synthesis of Compound 182:
Figure PCTCN2018120716-appb-000037
Figure PCTCN2018120716-appb-000037
化合物182的制备方法同实施例10，不同之处在于用原料A-8替换原料A-5，用中间体M-4替换原料B-1。元素分析结构(分子式C 51H 36N 2)：理论值C,90.50；H,5.36；N,4.14；测试值：C,90.54；H,5.38；N,4.17。ESI-MS(m/z)(M +)：理论值为676.29，实测值为676.32。 Compound 182 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-8 and the starting material B-1 was replaced with the intermediate M-4. Elemental analysis structure (Molecular formula C 51 H 36 N 2 ): Theory C, 90.50; H, 5.36; N, 4.14; </ RTI> C, 90.54; H, 5.38; N, 4.17. ESI-MS (m/z) (M + ): s.
实施例16：化合物197的合成：Example 16: Synthesis of Compound 197:
Figure PCTCN2018120716-appb-000038
Figure PCTCN2018120716-appb-000038
化合物197的制备方法同实施例2，不同之处在于用原料A-9替换原料A-1。元素分析结构(分子式C 42H 28N 2O)：理论值C,87.47；H,4.89；N,4.86；O,2.77；测试值：C,87.55；H,4.93；N,4.88； O,2.81。ESI-MS(m/z)(M +)：理论值为576.22，实测值为576.31。 Compound 197 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-9. Elemental analysis structure (Molecular formula C 42 H 28 N 2 O): Theory C, 87.47; H, 4.89; N, 4.86; O, 2.77; Test: C, 87.55; H, 4.93; N, 4.88; O, 2.81 . ESI-MS (m/z) (M + ): calc.
实施例17：化合物199的合成：Example 17: Synthesis of Compound 199:
Figure PCTCN2018120716-appb-000039
Figure PCTCN2018120716-appb-000039
化合物199的制备方法同实施例2，不同之处在于用原料A-10替换原料A-1。元素分析结构(分子式C 42H 28N 2O)：理论值C,87.47；H,4.89；N,4.86；O,2.77；测试值：C,87.54；H,4.93；N,4.88；O,2.79。ESI-MS(m/z)(M +)：理论值为576.22，实测值为576.28。 Compound 199 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-10. Elemental analysis structure (Molecular formula C 42 H 28 N 2 O): Theory C, 87.47; H, 4.89; N, 4.86; O, 2.77; Tests: C, 87.54; H, 4.93; N, 4.88; O, 2.79 . ESI-MS (m/z) (M + ): calc.
实施例18：化合物201的合成：Example 18: Synthesis of Compound 201:
Figure PCTCN2018120716-appb-000040
Figure PCTCN2018120716-appb-000040
化合物201制备方法同实施例2，不同之处在于用原料A-11替换原料A-1。元素分析结构(分子式C 45H 34N 2)：理论值C,89.67；H,5.69；N,4.65；测试值：C,89.69；H,5.71；N,4.68。ESI-MS(m/z)(M +)：理论值为602.27，实测值为602.29。 Compound 201 was prepared in the same manner as in Example 2 except that the starting material A-1 was replaced with the starting material A-11. Elemental analysis structure (Molecular formula C 45 H 34 N 2 ): calcd. C, 89.67; H, 5.69; N, 4.65; </ RTI></RTI> C, 89.69; H, 5.71; N, 4.68. ESI-MS (m/z) (M + ): calc. 602.
实施例19：化合物215的合成：Example 19: Synthesis of Compound 215:
Figure PCTCN2018120716-appb-000041
Figure PCTCN2018120716-appb-000041
化合物215制备方法同实施例10，不同之处在于用原料A-12替换原料A-5。元素分析结构(分子式C 41H 25N 3)：理论值C,87.99；H,4.50；N,7.51；测试值：C,88.05；H,4.53；N,7.54。ESI-MS(m/z)(M +)：理论值为559.20，实测值为559.26。 Compound 215 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with starting material A-12. Elemental analysis structure (Molecular formula C 41 H 25 N 3 ): calcd. C, 87.99; H, 4.50; N, 7.51; </ RTI></RTI> C, 88.05; H, 4.53; N, 7.54. ESI-MS (m/z) (M + ): 553.
实施例20：化合物223的合成：Example 20: Synthesis of Compound 223:
Figure PCTCN2018120716-appb-000042
Figure PCTCN2018120716-appb-000042
化合物223的制备方法同实施例10，不同之处在于用原料A-13替换原料A-5，用中间体M-2替换原料B-1。元素分析结构(分子式C 51H 31N 3)：理论值C,89.32；H,4.56；N,6.13；测试值：C,89.34；H,4.62；N,6.15。ESI-MS(m/z)(M +)：理论值为685.25，实测值为685.31。 Compound 223 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-13 and the starting material B-1 was replaced with the intermediate M-2. Elemental analysis structure (Molecular formula C 51 H 31 N 3 ): Theory C, 89.32; H, 4.56; N, 6.13; Tests: C, 89.34; H, 4.62; N, 6.15. ESI-MS (m/z) (M + ): calc. 685.
实施例21：化合物234的合成：Example 21: Synthesis of Compound 234:
Figure PCTCN2018120716-appb-000043
Figure PCTCN2018120716-appb-000043
化合物234的制备方法同实施例10，不同之处在于用原料A-14替换原料A-5。元素分析结构(分子式C 40H 24N 4)：理论值C,85.69；H,4.31；N,9.99；测试值：C,85.73；H,4.33；N,10.03。ESI-MS(m/z)(M +)：理论值为560.20，实测值为560.04。 Compound 234 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-14. Elemental Analysis Structure (Molecular Formula C 40 H 24 N 4 ): Theory C, 85.69; H, 4.31; N, 9.99; </ RTI> C, 85.73; H, 4.33; N, 10.03. ESI-MS (m/z) (M + ): 520.20.
实施例22：化合物243的合成：Example 22: Synthesis of Compound 243:
Figure PCTCN2018120716-appb-000044
Figure PCTCN2018120716-appb-000044
化合物243的制备方法同实施例10，不同之处在于用原料A-14替换原料A-5，用中间体M-5替换原料B-1。元素分析结构(分子式C 52H 32N 4)：理论值C,87.62；H,4.52；N,7.86；测试值：C,87.65；H,4.55；N,7.89。ESI-MS(m/z)(M +)：理论值为712.26，实测值为712.31。 The compound 243 was prepared in the same manner as in Example 10 except that the starting material A-5 was replaced with the starting material A-14 and the starting material B-1 was replaced with the intermediate M-5. Elemental Analysis Structure (Molecular Formula C 52 H 32 N 4 ): Theory C, 87.62; H, 4.52; N, 7.86; Found: C, 87.65; H, 4.55; N, 7.89. ESI-MS (m/z) (M + ): s.
本有机化合物在发光器件中使用，具有高的Tg(玻璃转化温度)温度和三线态能级(T1)，合适的HOMO、LUMO能级，可作为空穴阻挡/电子传输材料使用，也可作为发光层材料使用。对本发明化合物及现有材料分别进行热性能、T1能级以及HOMO能级测试，结果如表2所示。The organic compound is used in a light-emitting device, has a high Tg (glass transition temperature) temperature and a triplet level (T1), and a suitable HOMO, LUMO energy level can be used as a hole blocking/electron transport material, or as a The luminescent layer material is used. The thermal performance, T1 energy level and HOMO energy level test were carried out on the compound of the present invention and the existing materials, and the results are shown in Table 2.
表2Table 2
Figure PCTCN2018120716-appb-000045
Figure PCTCN2018120716-appb-000045
注：三线态能级T1是由日立的F4600荧光光谱仪测试，材料的测试条件为2*10 -5的甲苯溶液；玻璃化温度Tg由示差扫描量热法(DSC，德国耐驰公司DSC204F1示差扫描量热仪)测定，升温速率10℃/min；热失重温度Td是在氮气气氛中失重1％的温度，在日本岛津公司的TGA-50H热重分析仪上进行测定，氮 气流量为20mL/min；最高占据分子轨道HOMO能级是由电离能量测试系统(IPS3)测试，测试为大气环境。 Note: The triplet energy level T1 is tested by Hitachi's F4600 fluorescence spectrometer. The test conditions of the material are 2*10 -5 toluene solution; the glass transition temperature Tg is by differential scanning calorimetry (DSC, Germany Benz DSC204F1 differential scanning) The calorimeter was measured at a heating rate of 10 ° C/min; the thermogravimetric temperature Td was a temperature at which the weight loss was 1% in a nitrogen atmosphere, and was measured on a TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, and the flow rate of nitrogen was 20 mL/ Min; the highest occupied molecular orbital HOMO level is tested by the ionization energy test system (IPS3) and tested as the atmospheric environment.
由上表数据可知，对比目前应用的CBP和TPBi材料，本发明的有机化合物具有高的玻璃转化温度，可提高材料膜相态稳定性，进一步提高器件使用寿命；具有高的三线态能级，可以阻挡发光层能量损失，从而提升器件发光效率。同时本发明材料和应用材料具有相似的HOMO能级。因此，本发明含有吡啶并吲哚的有机材料在应用于OLED器件的不同功能层后，可有效提高器件的发光效率及使用寿命。It can be seen from the above table data that the organic compound of the invention has high glass transition temperature, can improve the phase stability of the material film, further improve the service life of the device, and has a high triplet energy level, compared with the currently applied CBP and TPBi materials. The energy loss of the luminescent layer can be blocked, thereby improving the luminous efficiency of the device. At the same time, the materials of the invention and the materials of application have similar HOMO levels. Therefore, the organic material containing pyridinium in the invention can effectively improve the luminous efficiency and the service life of the device after being applied to different functional layers of the OLED device.
以下通过器件实施例1～21和器件比较例1详细说明本发明合成的OLED材料在器件中的应用效果。本发明所述器件实施例2～21、器件比较例1与器件实施例1相比所述器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是器件实施例2～13对器件中的发光层材料做了变换；器件实施例14～21对器件的空穴阻挡/电子传输层材料做了变换，各实施例所得器件的性能测试结果如表3所示。The application effects of the OLED material synthesized by the present invention in the device will be described in detail below by the device examples 1 to 21 and the device comparative example 1. The device embodiments 2-21 of the present invention, the device comparative example 1 and the device embodiment 1 have the same fabrication process, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also maintained. Consistently, the difference between the device embodiments 2 and 13 is that the material of the light-emitting layer in the device is changed; the device embodiments 14 to 21 change the material of the hole blocking/electron transport layer of the device, and the devices obtained by the respective embodiments are The performance test results are shown in Table 3.
器件实施例1：Device Example 1:
如图1所示，一种电致发光器件，其制备步骤包括：a)清洗透明基板层1上的ITO阳极层2，分别用去离子水、丙酮、乙醇超声清洗各15分钟，然后在等离子体清洗器中处理2分钟；b)在ITO阳极层2上，通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN，厚度为10nm，这层作为空穴注入层3；c)在空穴注入层3上，通过真空蒸镀方式蒸镀空穴传输材料NPB，厚度为80nm，该层为空穴传输层/电子阻挡层4；d)在空穴传输/电子阻挡层4之上蒸镀发光层5，主体材料为本发明化合物2和化合物GH，掺杂材料为Ir(ppy) 3，化合物2、GH和Ir(ppy) 3三者质量比为50:50:10，厚度为40nm；e)在发光层5之上，通过真空蒸镀方式蒸镀电子传输材料TPBI，厚度为35nm，这层有机材料作为空穴阻挡/电子传输层6使用；f)在空穴阻挡/电子传输层6之上，真空蒸镀电子注入层LiF，厚度为1nm，该层为电子注入层7；g)在电子注入层7之上，真空蒸镀阴极Al(100nm)，该层为阴极反射电极层8；按照上述步骤完成电致发光器件的制作后，测量器件的驱动电压，电流效率，其结果见表3所示。相关材料的分子机构式如下所示： As shown in FIG. 1, an electroluminescent device is prepared by: a) cleaning an ITO anode layer 2 on a transparent substrate layer 1 and ultrasonically cleaning each with deionized water, acetone, and ethanol for 15 minutes, respectively, and then plasma. The body cleaner is treated for 2 minutes; b) on the ITO anode layer 2, the hole injection layer material HAT-CN is deposited by vacuum evaporation, the thickness is 10 nm, this layer serves as the hole injection layer 3; c) is empty On the hole injecting layer 3, a hole transporting material NPB is deposited by vacuum evaporation to a thickness of 80 nm, the layer is a hole transporting layer/electron blocking layer 4; d) is steamed on the hole transporting/electron blocking layer 4 The luminescent layer 5 is plated, the host material is the compound 2 and the compound GH of the invention, the doping material is Ir(ppy) 3 , and the compound 2, GH and Ir(ppy) 3 have a mass ratio of 50:50:10 and a thickness of 40 nm. e) On the luminescent layer 5, the electron transporting material TPBI is evaporated by vacuum evaporation to a thickness of 35 nm, and this organic material is used as the hole blocking/electron transporting layer 6; f) in hole blocking/electron transport Above the layer 6, vacuum-evaporating the electron-injecting layer LiF to a thickness of 1 nm, the layer is an electron injecting layer 7; g) in the electron injection On the layer 7, a cathode Al (100 nm) is vacuum-deposited, and the layer is a cathode reflective electrode layer 8; after the fabrication of the electroluminescent device is completed according to the above steps, the driving voltage and current efficiency of the device are measured, and the results are shown in Table 3. Show. The molecular organization of the relevant material is as follows:
Figure PCTCN2018120716-appb-000046
Figure PCTCN2018120716-appb-000046
Figure PCTCN2018120716-appb-000047
Figure PCTCN2018120716-appb-000047
器件实施例2：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物15、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 2: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 15, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例3：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物38、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 3: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 38, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例4：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物42和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 4: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / luminescent layer 5 (Thickness: 40 nm, material: Compound 42 and Ir(ppy) 3 are mixed by weight ratio of 90:10) / Hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / Electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例5：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物58、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 5: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 58, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例6：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物64、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 6: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 64, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例7：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物70和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 7: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 70 and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例8：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN) /空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物98、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 8: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 98, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例9：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物102和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 9: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 102 and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例10：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物134、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 10: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: compound 134, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例11：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物197、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 11: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 197, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例12：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物199、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 12: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (Thickness: 40 nm, material: compound 199, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例13：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：化合物201、GH和Ir(ppy) 3按重量比50:50:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 13: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / luminescent layer 5 (Thickness: 40 nm, material: compound 201, GH, and Ir(ppy) 3 are mixed by weight ratio of 50:50:10)/hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection Layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例14：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物140)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 14: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 140) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例15：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物143)/电子注入 层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 15: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 143) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例16：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物155)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 16: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 155) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例17：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物182)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 17: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 182) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例18：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物215)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 18: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 215) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例19：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物223)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 19: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 223) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例20：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物234)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 20: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 234) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件实施例21：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：化合物243)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。 Device Example 21: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / luminescent layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: compound 243) / electron injection layer 7 (thickness) : 1 nm, material: LiF) / Al (thickness: 100 nm).
器件比较例1：ITO阳极层2(厚度：150nm)/空穴注入层3(厚度：10nm，材料：HAT-CN)/空穴传输层4(厚度：80nm，材料：NPB)/发光层5(厚度：40nm，材料：CBP和Ir(ppy) 3按重量比90:10混掺构成)/空穴阻挡/电子传输层6(厚度：35nm，材料：TPBI)/电子注入层7(厚度：1nm，材料：LiF)/Al(厚度：100nm)。所得电致发光器件的检测数据见表3所示。 Device Comparative Example 1: ITO anode layer 2 (thickness: 150 nm) / hole injection layer 3 (thickness: 10 nm, material: HAT-CN) / hole transport layer 4 (thickness: 80 nm, material: NPB) / light-emitting layer 5 (thickness: 40 nm, material: CBP and Ir(ppy) 3 are mixed by weight ratio of 90:10) / hole blocking/electron transport layer 6 (thickness: 35 nm, material: TPBI) / electron injection layer 7 (thickness: 1 nm, material: LiF) / Al (thickness: 100 nm). The detection data of the obtained electroluminescent device is shown in Table 3.
表3table 3
Figure PCTCN2018120716-appb-000048
Figure PCTCN2018120716-appb-000048
由表3的结果可以看出本发明有机化合物可应用于OLED发光器件制作，并且与比较例相比，无论是效率还是寿命均比已知OLED材料获得较大改观，特别是器件的使用寿命获得较大的提升。It can be seen from the results of Table 3 that the organic compound of the present invention can be applied to the fabrication of an OLED light-emitting device, and compared with the comparative example, both the efficiency and the lifetime are greatly improved than the known OLED materials, in particular, the service life of the device is obtained. A big boost.
进一步的本发明材料制备的OLED器件在低温下工作时效率也比较稳定，将器件实施例2、9、17和器件比较例1在-10～80℃区间进行效率测试，所得结果如表4和图2所示。Further, the OLED device prepared by the material of the invention is more stable when operating at a low temperature, and the device examples 2, 9, and 17 and the device comparative example 1 are tested in the range of -10 to 80 ° C, and the results are shown in Table 4 and Figure 2 shows.
表4Table 4
Figure PCTCN2018120716-appb-000049
Figure PCTCN2018120716-appb-000049
从表4和图2的数据可知，器件实施例2、9、17为本发明材料和已知材料搭配的器件结构， 和器件比较例1相比，不仅低温效率高，而且在温度升高过程中，效率平稳升高。As can be seen from the data in Table 4 and FIG. 2, device examples 2, 9, and 17 are device structures in which the materials of the present invention and known materials are matched, and compared with the device comparative example 1, not only the low temperature efficiency but also the temperature rise process. In the middle, efficiency has increased steadily.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection of the present invention. Within the scope.

Claims (11)

  1. 一种含有吡啶并吲哚的化合物，其特征在于，该化合物的结构如通式(1)所示：A compound containing pyridoindole, characterized in that the structure of the compound is as shown in the formula (1):
    Figure PCTCN2018120716-appb-100001
    Figure PCTCN2018120716-appb-100001
    其中，X表示为单键；i等于0或1；Wherein X is represented as a single bond; i is equal to 0 or 1;
    A表示为单键、氧原子、C 1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基中的一种； A is represented by a single bond, an oxygen atom, a C 1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl substituted imido group or an aryl substituted imido group. a kind
    X 1、X 2、X 3、X 4、X 5、X 6、X 7、X 8分别独立的表示为C-H或N原子，且N原子的数量为0、1或2； X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 are each independently represented as CH or N atom, and the number of N atoms is 0, 1 or 2;
    m、n、p、q等于0或1；且m+n+p+q≥1；m, n, p, q are equal to 0 or 1; and m + n + p + q ≥ 1;
    E是任选地被一个或多个R 1取代的吡啶并吲哚基团； E is a pyridoindole group optionally substituted with one or more R 1 ;
    R 1表示为取代或未取代的C 6至C 30芳基和取代或未取代的C 5至C 30杂芳基中的一种；所述杂原子为氮、氧或硫。 R 1 represents one of a substituted or unsubstituted C 6 to C 30 aryl group and a substituted or unsubstituted C 5 to C 30 heteroaryl group; the hetero atom is nitrogen, oxygen or sulfur.
  2. 根据权利要求1所述的一种含有吡啶并吲哚的化合物，其特征在于，所述E可用通式(2)表示；The pyridoindole-containing compound according to claim 1, wherein the E is represented by the formula (2);
    Figure PCTCN2018120716-appb-100002
    Figure PCTCN2018120716-appb-100002
    其中，Ar 1表示为单健、取代或未取代的C 6-30亚芳基、取代或未取代的C 5-30杂亚芳基中的一种；所述杂原子为氮、氧或硫； Wherein Ar 1 is represented by one of a mono-, substituted or unsubstituted C 6-30 arylene, a substituted or unsubstituted C 5-30 heteroarylene; the hetero atom is nitrogen, oxygen or sulfur ;
    Ar 2表示为取代或未取代的C 6-30芳基、取代或未取代的C 5-30杂芳基中的一种；所述杂原子为氮、氧或硫； Ar 2 is represented by one of a substituted or unsubstituted C 6-30 aryl group, a substituted or unsubstituted C 5-30 heteroaryl group; the hetero atom is nitrogen, oxygen or sulfur;
    Z表示为C-H或N原子，且至少有一个Z表示N原子。Z is represented by a C-H or N atom, and at least one Z represents an N atom.
  3. 根据权利要求1所述的一种含有吡啶并吲哚的化合物，其特征在于，所述通式(1)中
    Figure PCTCN2018120716-appb-100003
    表示为：     A pyridoindole-containing compound according to claim 1, wherein said compound (1)
    Figure PCTCN2018120716-appb-100003
    Expressed as:
    Figure PCTCN2018120716-appb-100004
    Figure PCTCN2018120716-appb-100005
    中的任一种。
    Figure PCTCN2018120716-appb-100004
    Figure PCTCN2018120716-appb-100005
    Any of them.
  4. 根据权利要求2所述的一种含有吡啶并吲哚的化合物，其特征在于，通式(2)的结构可表示为：
    Figure PCTCN2018120716-appb-100006
    Figure PCTCN2018120716-appb-100007
    中的任一种。     A pyridoindole-containing compound according to claim 2, wherein the structure of the formula (2) can be expressed as:
    Figure PCTCN2018120716-appb-100006
    Figure PCTCN2018120716-appb-100007
    Any of them.
  5. 根据权利要求2所述的一种含有吡啶并吲哚的化合物，其特征在于，所述Ar 1表示为单键、亚苯基、亚萘基、亚联苯基、亚蒽基、亚呋喃基、亚咔唑基、亚萘啶基、亚喹啉基、亚噻吩基、亚吡啶基、亚苝基、亚9,9-二甲基芴基、亚菲基、亚二苯并呋喃基、亚二苯并噻吩基中的一种； The pyridoindole-containing compound according to claim 2, wherein the Ar 1 is represented by a single bond, a phenylene group, a naphthylene group, a biphenylylene group, an anthranylene group, and a furylene group. , oxazolyl, naphthyridinyl, quinolinyl, thienylene, pyridylene, fluorenylene, 9,9-dimethylindenyl, phenanthrylene, dibenzofuranyl, One of the subdibenzothiophenes;
    所述Ar 2表示为苯基、萘基、联苯基、蒽基、呋喃基、咔唑基、萘啶基、喹啉基、噻吩基、吡啶基、苝基、9,9-二甲基芴基、菲基、二苯并呋喃基、二苯并噻吩基中的一种。 The Ar 2 is represented by phenyl, naphthyl, biphenyl, anthracenyl, furyl, oxazolyl, naphthyridinyl, quinolyl, thienyl, pyridyl, fluorenyl, 9,9-dimethyl One of a mercapto group, a phenanthryl group, a dibenzofuranyl group, and a dibenzothiophene group.
  6. 根据权利要求1所述的一种含有吡啶并吲哚的化合物，其特征在于，所述化合物的具体结构式为：A pyridoindole-containing compound according to claim 1, wherein the specific structural formula of the compound is:
    Figure PCTCN2018120716-appb-100008
    Figure PCTCN2018120716-appb-100008
    Figure PCTCN2018120716-appb-100009
    Figure PCTCN2018120716-appb-100009
    Figure PCTCN2018120716-appb-100010
    Figure PCTCN2018120716-appb-100010
    Figure PCTCN2018120716-appb-100011
    Figure PCTCN2018120716-appb-100011
    Figure PCTCN2018120716-appb-100012
    Figure PCTCN2018120716-appb-100012
    Figure PCTCN2018120716-appb-100013
    Figure PCTCN2018120716-appb-100013
    Figure PCTCN2018120716-appb-100014
    Figure PCTCN2018120716-appb-100014
    Figure PCTCN2018120716-appb-100015
    Figure PCTCN2018120716-appb-100015
    Figure PCTCN2018120716-appb-100016
    Figure PCTCN2018120716-appb-100016
    Figure PCTCN2018120716-appb-100017
    Figure PCTCN2018120716-appb-100018
    中的任一种。
    Figure PCTCN2018120716-appb-100017
    Figure PCTCN2018120716-appb-100018
    Any of them.
  7. 一种如权利要求1～6任一项所述的一种含有吡啶并吲哚的化合物的制备方法，其特征在于，所述制备方法涉及的反应方程式为：A method for preparing a pyridinium-containing compound according to any one of claims 1 to 6, wherein the preparation method involves a reaction equation of:
    Figure PCTCN2018120716-appb-100019
    Figure PCTCN2018120716-appb-100019
    具体反应过程为：The specific reaction process is:
    将原料A和中间体M溶解于甲苯和乙醇的混合溶液中，除氧后加入Pd(PPh 3) 4和K 2CO 3，在惰性气氛下95～110℃反应10～24个小时，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物； The raw material A and the intermediate M are dissolved in a mixed solution of toluene and ethanol, and after deoxidation, Pd(PPh 3 ) 4 and K 2 CO 3 are added , and the reaction is carried out at 95 to 110 ° C for 10 to 24 hours in an inert atmosphere until the raw materials are used. After the reaction is completed, the mixture is cooled and filtered, and the filtrate is evaporated to remove the solvent, and the crude product is passed through a silica gel column to obtain the target compound;
    其中，所述的甲苯和乙醇的用量为每克原料A使用30～50mL甲苯和5～10mL乙醇，中间体M与原料A的摩尔比为1～3:1，Pd(PPh 3) 4与原料A的摩尔比为0.006～0.03:1，K 2CO 3与原料A的摩尔比为1.5～4.5:1。 Wherein, the amount of the toluene and the ethanol is 30 to 50 mL of toluene and 5 to 10 mL of ethanol per gram of the raw material A, and the molar ratio of the intermediate M to the raw material A is 1 to 3:1, Pd(PPh 3 ) 4 and the raw material. The molar ratio of A is from 0.006 to 0.03:1, and the molar ratio of K 2 CO 3 to the raw material A is from 1.5 to 4.5:1.
  8. 一种有机电致发光器件，其特征在于，所述有机电致发光器件包括至少一层功能层含有权利要求1-6任一项所述的含有吡啶并吲哚的化合物。An organic electroluminescent device characterized in that the organic electroluminescent device comprises at least one functional layer comprising the pyridinium-containing compound according to any one of claims 1 to 6.
  9. 根据权利要求8所述的有机电致发光器件，包括空穴传输层/电子阻挡层，其特征在于，所述空穴传输层/电子阻挡层含有权利要求1-6任一项所述的含有吡啶并吲哚的化合物。The organic electroluminescent device according to claim 8, comprising a hole transport layer/electron barrier layer, wherein the hole transport layer/electron barrier layer contains the content according to any one of claims 1 to 6. A compound of pyridoindole.
  10. 根据权利要求8所述的有机电致发光器件，包括发光层，其特征在于，所述发光层含有权利要求1-6任一项所述的含有吡啶并吲哚的化合物。The organic electroluminescent device according to claim 8, comprising a light-emitting layer, wherein the light-emitting layer contains the pyridinium-containing compound according to any one of claims 1 to 6.
  11. 一种照明或显示元件，其特征在于，包含权利要求8-10任一所述的有机电致发光器件。An illumination or display element comprising the organic electroluminescent device of any of claims 8-10.
PCT/CN2018/120716 2017-12-13 2018-12-12 Compound containing pyridoindole and use thereof in organic electroluminescence device WO2019114769A1 (en)

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