阅读说明：本技术 螺环化合物及其应用 (Spiro compound and application thereof ) 是由 范洪涛 何为 于 2020-12-24 设计创作，主要内容包括：本发明公开了螺环化合物及其应用,属于有机电致发光技术领域。该化合物具有下式所示的通式结构：该结构含有两个处于不能充分共轭的苯环间位的N,N-取代基团,使其具有较浅的LUMO能级(＜2.2eV)和较高的三线态能级T1(2.4eV以上)；母体结构的螺环单元存在独特的螺共轭作用,玻璃化温度高,热稳定性和成膜性好,保持器件稳定性的同时提高分子间的载流子传输能力和空穴传输性,作为OLED屏体的通用空穴传输材料和红光有机电致发光器件的电子阻挡材料,可以满足商业化OLED屏体发光效率高、驱动电压低和使用寿命长的性能要求。(The invention discloses a spiro compound and application thereof, belonging to the technical field of organic electroluminescence. The compound has a general structure shown in the following formula: the structure contains two N, N-substituent groups which are positioned at the meta position of a benzene ring which cannot be fully conjugated, so that the structure has a shallow LUMO energy level (< 2.2eV) and a high triplet state energy level T1 (more than 2.4 eV); the spiro unit of the parent structure has unique spiro conjugation effect, high glass transition temperature, good thermal stability and film forming property, improves the carrier transmission capacity and hole transmission property among molecules while keeping the stability of the device, and can meet the performance requirements of high luminous efficiency, low driving voltage and long service life of the commercial OLED screen body as a general hole transmission material of the OLED screen body and an electronic barrier material of a red light organic electroluminescent device.)

1. A spiro compound having a general structure represented by [ chemical formula 1 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl, substituted or unsubstituted C9-C40 fused ring aryl, and substituted or unsubstituted C5-C40 fused ring heteroaryl.

2. The spiro compound according to claim 1, wherein in [ chemical formula 1], the substituted C6-C40 aryl group, the substituted C3-C40 heteroaryl group, the substituted C9-C40 fused ring aryl group, and the substituted C5-C40 fused ring heteroaryl group are substituted with a group independently selected from C1-C10 alkyl group, C1-C10 alkoxy group, or tri (organo) silyl group, respectively.

3. The spiro compound according to claim 2, wherein said C1-C10 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, or n-heptyl; the C1-C10 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy or n-heptoxy; the tri (organo) silyl group is selected from trimethylsilyl, triethylsilyl, tributylsilyl, or triphenylsilyl.

4. The spiro compound according to any one of claims 1 to 3, wherein said compound has a general structure represented by [ chemical formula 1-1 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 fused ring aryl, and substituted or unsubstituted C5-C30 fused ring heteroaryl.

5. The spiro compound according to claim 1, wherein the compound has a general structure represented by [ chemical formula 1-2 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from [ chemical formula 2]]Any of the structures shown:

a and B are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 fused ring aryl, substituted or unsubstituted C5-C30 fused ring heteroaryl;

x is selected from the group consisting of an O atom, an S atom, -NR-and-CR₂-。

6. The spiro compound according to claim 5, wherein in [ chemical formula 1-2], A and B are the same or different.

7. The spirocyclic compound of any one of claims 1 to 6, wherein Ar is Ar₁、Ar₂、Ar₃And Ar₄Each independently selected from any one of the following groups:

(a)Ar₁and Ar₂The same; (b) ar (Ar)₃And Ar₄The same; (c) ar (Ar)₁、Ar₂、Ar₃And Ar₄Are all the same; (d) ar (Ar)₁、Ar₂、Ar₃And Ar₄Are different from each other.

8. The spiro compound according to any one of claims 1 to 7, wherein said compound is selected from any one of the following structures:

9. use of a spiro compound according to any one of claims 1 to 8 in an organic electroluminescent device.

10. Use according to claim 9, wherein the spiro compound is used as a hole transport material for organic electroluminescent devices and/or as an electron blocking material for red-emitting organic electroluminescent devices.

11. A display panel is characterized by comprising an organic electroluminescent device, wherein the organic electroluminescent device comprises an anode and a cathode which are oppositely arranged, and a hole transport layer and a light-emitting layer which are positioned between the anode and the cathode; wherein the material of the hole transport layer comprises one or more of the spiro compounds according to any of claims 1 to 10.

12. The display panel of claim 11, further comprising an electron blocking layer between the anode and the cathode, the electron blocking layer comprising one or more of the spiro compounds of any of claims 1 to 10.

13. A display device comprising the display panel of claim 11 or 12.

Technical Field

The invention belongs to the field of organic electroluminescence, and particularly relates to a spiro compound and application thereof in an organic electroluminescent device.

Background

An Organic Light Emitting Diode (OLED) is a current-driven Light Emitting device using an Organic material as an active material, and particularly refers to a technology in which an Organic semiconductor material and an Organic Light Emitting material are driven by an electric field to emit Light through carrier injection and recombination. Different from inorganic materials, organic materials have the characteristics of low synthesis cost, adjustable functions, flexibility and good film forming property, devices based on the organic materials are generally simple in manufacturing process, easy to produce in a large area and environment-friendly, a thin film preparation method with low operation temperature can be adopted, the manufacturing cost is low, the market potential is large, and the organic materials cause wide attention and research of domestic and foreign scholars in the past 20 years.

Organic electroluminescence and related research was first traced back to 1963, where p.pope et al, new york university in the united states, observed luminescence when passing hundreds of volts through anthracene crystals, and therebyThe first literature on the electroluminescence of organic materials is published in the world, but this technology has not been regarded as important at that time because the driving voltage is too high and the luminous efficiency is too low. The hole transport layer was first introduced into an organic light emitting device by c.w.tang et al, kodak, usa in 1987, and a light emitting material tris (8-hydroxyquinoline) aluminum (Alq) having an electron transport property was applied by a vacuum evaporation technique₃) And N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD) with hole transport property to obtain an amorphous film type device (shown in the following formula) with a double-layer organic material structure, wherein the device has an external quantum efficiency of 1%, and has an operating voltage of less than 10V and an external quantum efficiency of more than 100cd/m²The efficiency of the OLED exceeds 1.5lm/W, so far, the OLED attracts the attention of the world (US 4356429). The device has the advantages of lightness, thinness, high brightness, wide visual angle, low driving voltage, rich colors, quick response, high contrast, low energy consumption, strong environmental adaptability, low cost and the like, can be widely used for plane light-emitting elements such as flat panel displays and surface light sources, research on the OLED is not limited to academic circles, and a plurality of international famous electronic companies and chemical companies invest in the field to promote commercialization of the OLED.

With the commercialization of OLED screens, the requirements for the photoelectric properties and the operating life of the OLED screens are higher and higher, and the device structure of the OLED undergoes a development process from a single-layer structure to a multi-layer structure, as shown in fig. 1. At present, in order to further improve the performance of OLED devices of various colors, exciton and carrier blocking layers are added on two sides of a light emitting layer in the device structure of various large panel manufacturers at home and abroad, excitons and carriers can be effectively limited in the light emitting layer, the light emitting efficiency is greatly improved, and meanwhile, the chromaticity adjustment and the service life of the device can be remarkably improved through the selection of materials of each layer of the OLED device.

Disclosure of Invention

The invention provides a spiro compound which is used as a universal Hole Transport Layer (HTL) of an OLED screen body and an Electron Blocking Layer (EBL) of a red light device, and meets the high requirements of a commercial OLED screen body on photoelectric performance indexes and the service life of the red light device. The spiro compound has a general structure represented by [ chemical formula 1 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl, substituted or unsubstituted C9-C40 fused ring aryl, and substituted or unsubstituted C5-C40 fused ring heteroaryl.

Further, in [ chemical formula 1], the substituted C6-C40 aryl group, the substituted C3-C40 heteroaryl group, the substituted C9-C40 fused ring aryl group and the substituted C5-C40 fused ring heteroaryl group are substituted with groups independently selected from C1-C10 alkyl group, C1-C10 alkoxy group or tri (organo) silyl group, respectively.

Still further, the C1-C10 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, or n-heptyl; the C1-C10 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy or n-heptoxy; the tri (organo) silyl group is selected from trimethylsilyl, triethylsilyl, tributylsilyl, or triphenylsilyl.

According to some embodiments of the spiro compound of the present invention, the compound has a general structure represented by [ chemical formula 1-1 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 fused ring arylUnsubstituted C5-C30 fused ring heteroaryl.

According to some embodiments of the spiro compound of the present invention, the compound has a general structure represented by [ chemical formula 1-2 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from [ chemical formula 2]]Any of the structures shown:

a and B are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 fused ring aryl, substituted or unsubstituted C5-C30 fused ring heteroaryl; x is selected from the group consisting of an O atom, an S atom, -NR-and-CR₂-。

Further, in [ chemical formula 1-2], A and B are each independently selected from a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 heteroaryl group, a substituted or unsubstituted C9-C20 fused ring aryl group, a substituted or unsubstituted C5-C20 fused ring heteroaryl group.

Further, in [ chemical formula 1-2], A and B are the same or different.

According to some embodiments of the spirocyclic compound of the present invention, Ar is any one of the spirocyclic compounds₁、 Ar₂、Ar₃And Ar₄Each independently selected from any one of the following groups: (a) ar (Ar)₁And Ar₂The same; (b) ar (Ar)₃And Ar₄The same; (c) ar (Ar)₁、Ar₂、Ar₃And Ar₄Are all the same; (d) ar (Ar)₁、Ar₂、Ar₃And Ar₄Are different from each other.

According to some embodiments of the spirocyclic compounds of the present invention, the compound is selected from any of the following structures:

the spiro compound has the following advantages as a general hole transport material of an OLED screen and an electron blocking material of a red light device:

(1) the material has a characteristic spiral ring structure, has strong molecular rigidity, high glass transition temperature (Tg), good thermal stability and film forming property, and can keep the stability of devices.

(2) The compound has two specific N, N-substituted positions and is positioned at a meta position of a benzene ring which cannot be fully conjugated, so that on one hand, the effect of lightening the HOMO energy level brought by two electron-donating groups is weakened, and on the other hand, the performance regulation selectivity of molecules is increased: the group at the position of large steric hindrance substitution can play a more role in adjusting the thermal stability of the material, and the group at the position of small steric hindrance substitution can effectively adjust and control the energy level and the carrier transport property of molecules.

(3) The spiro unit with a parent structure has a unique spiro conjugation effect (SpiroConjugation, appl. phys. lett.,2005,87,052103), can effectively improve the carrier transport capability among molecules, enables the molecules to have excellent hole transport property, and has a good effect of reducing the voltage of a device.

(4) Theoretical calculation and experimental tests on synthesized representative compounds show that the compounds have a shallow LUMO energy level (< 2.2eV) and a high triplet state energy level T1(2.4eV), and are used as electron blocking materials of red light devices to effectively improve the luminous efficiency of the devices in addition to high carrier mobility.

The invention also provides application of any spiro compound in an organic electroluminescent device. The spiro compound can be used as a hole transport material of an organic electroluminescent device, particularly a blue, green and red organic electroluminescent device, and can also be used as an electron blocking material of the red organic electroluminescent device.

The invention also provides a display panel, which comprises an organic electroluminescent device, wherein the organic electroluminescent device comprises an anode, a cathode, a hole transport layer and a light-emitting layer, wherein the anode and the cathode are oppositely arranged, and the hole transport layer and the light-emitting layer are positioned between the anode and the cathode; wherein the material of the hole transport layer comprises one or more of the spiro compounds. According to some embodiments of the present invention, the organic electroluminescent device further includes a substrate, and an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode layer sequentially formed on the substrate.

According to some embodiments of the invention, the organic electroluminescent device further comprises an electron blocking layer between the anode and the cathode, the electron blocking layer comprising one or more of any of the spiro compounds described above. Preferably, the organic electroluminescent device further comprises a substrate, and an anode layer, a hole transport layer, an electron blocking layer, an organic light emitting layer, an electron transport layer and a cathode layer which are sequentially formed on the substrate.

The invention also provides a display device comprising any one of the display panels.

The display panel or the display device comprising the organic electroluminescent device has the following advantages: high luminous efficiency, low driving voltage and long service life.

Drawings

Fig. 1 is a schematic structural diagram of an OLED device.

Detailed Description

The present invention is further illustrated by the following examples and comparative examples, which are intended to be illustrative only and are not to be construed as limiting the invention. The technical scheme of the invention is to be modified or replaced equivalently without departing from the scope of the technical scheme of the invention, and the technical scheme of the invention is covered by the protection scope of the invention.

The present invention provides a spiro compound having a general structure represented by [ chemical formula 1 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl, substituted or unsubstituted C9-C40 fused ring aryl, and substituted or unsubstituted C5-C40 fused ring heteroaryl.

Some embodiments of the present invention, in [ chemical formula 1], the substituted C6-C40 aryl group, the substituted C3-C40 heteroaryl group, the substituted C9-C40 fused ring aryl group, and the substituted C5-C40 fused ring heteroaryl group are substituted with a group independently selected from C1-C10 alkyl group, C1-C10 alkoxy group, or tri (organo) silyl group, respectively.

In some embodiments of the invention, the C1-C10 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, or n-heptyl; C1-C10 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy or n-heptoxy; the tri (organo) silyl group is selected from trimethylsilyl, triethylsilyl, tributylsilyl or triphenylsilyl.

In some embodiments of the present invention, the mule ring compound has a general structure represented by [ chemical formula 1-1 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 fused ring aryl, and substituted or unsubstituted C5-C30 fused ring heteroaryl.

In some embodiments of the present invention, the mule ring compound has a general structure represented by [ chemical formula 1-2 ]:

wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from [ chemical formula 2]]Any of the structures shown:

a and B are respectively and independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C9-C30 fused ring aryl, substituted or unsubstituted C5-C30 fused ring heteroaryl, and X is selected from O atom, S atom, -NR-or-CR₂-。

Some embodiments of the present invention, in [ chemical formula 1-2], A and B are each independently selected from a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 heteroaryl group, a substituted or unsubstituted C9-C20 fused ring aryl group, and a substituted or unsubstituted C5-C20 fused ring heteroaryl group.

In some embodiments of the present invention, in [ chemical formulas 1 to 2], A and B are the same or different.

In some embodiments of the present invention, in the above spiro compound, Ar₁、Ar₂、Ar₃And Ar₄Each independently selected from any one of the following groups: (a) ar (Ar)₁And Ar₂The same; (b) ar (Ar)₃And Ar₄The same; (c) ar (Ar)₁、Ar₂、Ar₃And Ar₄Are all the same; (d) ar (Ar)₁、Ar₂、Ar₃And Ar₄Are different from each other.

The synthesis of mule ring compounds P1, P19, P34, P40, P41, P44, P47, P48, P52, P54, P56, P58, P62, P65, P80, P86, P89, P96 and P106 is exemplarily described in the following synthetic examples 1 to 22, in which diarylamines, carbazoles and other starting materials, which are not indicated for the preparation method, are commercially available.

Synthesis example 1

Intermediate M1, the structural formula and synthetic route of which is shown below, was prepared as required in this example:

the preparation method comprises the following specific steps:

(1) preparation of M1-1: 26.2g of methyl o-iodobenzoate (0.1mol) is dissolved in 200mL of 1, 4-dioxane solvent, the mixture is stirred under nitrogen, 28g of 2, 4-dibromophenylboronic acid (0.1mol), 20.8g (0.25mol) of potassium carbonate and 1.15g (1mmol) of tetrakis (triphenylphosphine) palladium are sequentially added, the temperature is raised to reflux reaction, after 5h, HPLC (high performance liquid chromatography) detects that the raw materials basically react, the reaction liquid is decompressed and dried, and the residue is subjected to column chromatography to obtain 31.8g of light yellow intermediate M1-1 with the yield of 86%.

(2) Preparation of M1-2: 31.8g of the solid was dissolved in 150mL of hf, 100mL of an aqueous solution of 7.5g of lioh was added, the reaction was stirred at room temperature for 5 hours to complete the reaction, the reaction system was adjusted to pH 1 with 6M hydrochloric acid, and extracted with 2 × 250mL of dichloromethane, and the obtained organic phases were combined, dried over anhydrous magnesium sulfate, and the organic solvent was dried by spin-drying to obtain an off-white solid M1-2 in an amount of 27g by weight, with a yield of 88%.

(3) Preparation of M1-3: 18g of M1-2(50mmol) was dissolved in 150mL of dichloromethane, the reaction was cooled to 0 ℃ and 50g of polyphosphoric acid (PPA) was added with vigorous stirring, then the reaction was slowly warmed to room temperature and vigorously stirred at room temperature for 10h, the reaction was checked by TLC for completion, the organic phase was separated, washed twice with 100mL of dichloromethane, the organic phases were combined, washed twice with 1M NaOH solution, dried over anhydrous magnesium sulfate, the solvent was dried by spinning off, and purified by column chromatography to give about 15g of intermediate M1-3 in 88% yield.

(4) Synthesis of intermediate M1: 16.4g of 2, 2' -dibromophenyl ether (50mmol) are dissolved in 150mL of anhydrous THF, the reaction is cooled to-78 ℃ with a dry ice-acetone bath, 70mL of n-butyllithium (1.6M, 0.115mol) are slowly added, after complete addition, the temperature is maintained for 1h, and then 6.7g of sublimed AlCl are initially added₃Then stirring for 30min, adding 17g of M1-3(50mmol) of 100mL of anhydrous THF solution, keeping at-78 ℃ for 30min after the addition is finished, slowly raising the temperature to room temperature, stirring for 10h at room temperature, adding 1M of dilute hydrochloric acid to quench the reaction, extracting the organic phase with ethyl acetate for 3 times, combining the organic phases, drying with anhydrous magnesium sulfate, spin-drying the solvent, and then carrying out column chromatography separation to obtain 19.1g of intermediate M1 which is white solid in total and has the yield of 78%.

Synthesis example 2

Intermediate M2, the structural formula and synthetic route of which is shown below, was prepared as required in this example:

the preparation method comprises the following specific steps: intermediate M2 was obtained in full accordance with Synthesis example 1, except that 2-bromo-4-chlorobenzeneboronic acid was used in place of 2, 4-dibromophenylboronic acid.

Synthesis example 3

Intermediate M3, the structural formula and synthetic route of which is shown below, was prepared as required in this example:

the preparation method comprises the following specific steps: intermediate M3 was obtained in full accordance with Synthesis example 1, except that 2-chloro-4-bromobenzeneboronic acid was used in place of 2, 4-dibromophenylboronic acid.

Synthesis example 4

The compound P1, which was prepared as required in this example, has the following structural formula and synthetic route:

the preparation method comprises the following specific steps:

in N₂To a 250mL three-necked flask equipped with magnetic stirring, 100mL of toluene, 9.8g M1 (20mmol), and 7.4g of diphenylamine (44mmol) were added, followed by 2.9g of sodium tert-butoxide (30mmol) with stirring, and 90mg of Pd (dba) were added₂(palladium bis (dibenzylidene acetone) (0.15 mmol)) and the color becomes dark, then 0.6g of 10 percent tri-tert-butylphosphine n-hexane solution (0.3mmol) is added, the heating reflux is carried out, the reaction solution becomes green, the mixture is dripped after the reflux is carried out for 8 hours, basically no raw material is left, when the temperature is reduced to below 45 ℃, the mixed solution of 5mL of concentrated hydrochloric acid and 100mL of water is added, the liquid is separated, the water phase is extracted by 100mL of toluene, the crude product is obtained by merging and spin-drying, and the crude product is a crude productRecrystallization from a dichloromethane/ethanol (volume ratio 1: 1) system gave 11.5g of a white solid, yield: 86 percent. MS (m/z): 666.2, elemental analysis: ForC₄₉H₃₄N₂O, theoretical value: c: 88.26 percent; h: 5.14 percent; n: 4.20 percent; experimental determination C: 88.38 percent; h: 5.22 percent; n: 3.99 percent.

Synthesis example 5

The compound P19, which was prepared as required in this example, has the following structural formula and synthetic route:

the diphenylamine in synthesis example 4 was replaced with an equivalent of phenyl-4-biphenylamine, and the other raw materials and steps were the same as those described above to obtain 14.7g of a white solid, yield: 90 percent. MS (m/z): 818.3, elemental analysis: for C₆₁H₄₂N₂O, theoretical value: c: 89.46 percent; h: 5.17 percent; n: 3.42 percent; experimental determination C: 89.21%, H: 5.25 percent; n: 3.42 percent.

Synthesis example 6

The compound P34, prepared as required in this example, has the following structural formula:

the diphenylamine in synthesis example 4 was replaced with an equivalent of phenyl-4-dibenzofuran amine, and the other raw materials and steps were the same as those described above to obtain 13.7g of a white solid, yield: 81 percent. MS (m/z): 846.3, elemental analysis: for C₆₁H₃₈N₂O₃The theoretical value is as follows: c: 86.50 percent; h: 4.52 percent; n: 3.31 percent; experimental determination C: 86.19%, H: 4.47%; n: 3.49 percent.

Synthesis example 7

The structural formula and the synthetic route of compound P40, which is prepared in this example, are shown below:

the specific implementation steps are as follows:

(1) preparation of intermediate P40-1: n is a radical of₂Under protection, adding intermediate M2(8.86g, 20mmol), diphenylamine 3.75g (22mmol), cuprous chloride 0.6g (6mmol, 30%), hydrated 1, 10-phenanthroline 0.88g (4.4mol, 20%), potassium hydroxide 3.4g (60mmol, 3eq) and xylene 250mL into a 500mL three-necked bottle. Starting stirring, heating to about 80 ℃ to change the system from black to khaki, heating to 130 ℃ to change the system from khaki to tan, keeping reflux reaction for 16h, cooling the reaction solution to 60 ℃, dropwise adding 10mL of concentrated hydrochloric acid, and stirring for 1h after dropwise adding. Filtering, leaching a filter cake by 200mL of dimethylbenzene, and standing for liquid separation. The organic phase was washed 2 times with water, dried over anhydrous magnesium sulfate, the organic solvent was removed under reduced pressure, and the residue was subjected to column chromatography to give intermediate P40-1 as a white solid (8.3 g, yield 75%).

(2) Preparation of compound P40: in N₂To a 250mL three-necked flask equipped with magnetic stirring, 100mL of toluene, 10.6g P40-1(20mmol) and 6.7g of 4- (4-dibenzofuranyl) phenyl-N-phenylamine (22mmol) were added in this order under stirring, 2.9g of sodium tert-butoxide (30mmol) and 90mg of Pd (dba) were added₂(palladium bis (dibenzylidene acetone) (0.15 mmol)) and the color is darkened, then 0.6g of 10% tri-tert-butylphosphine n-hexane solution (0.3mmol) is added, heating reflux is carried out, the reaction solution is turned into green, after refluxing for 8h, the plate is placed, basically no raw material is generated, when the temperature is reduced to below 45 ℃, a mixed solution of 5mL of concentrated hydrochloric acid and 100mL of water is added, liquid separation is carried out, the water phase is extracted by 100mL of toluene, crude products are obtained by combination and spin drying, the crude products are separated by column chromatography, and light yellow solid 14.5g is obtained, and the yield is: 87 percent. MS (m/z): 832.3, elemental analysis: ForC₆₁H₄₀N₂O₂The theoretical value is as follows: c: 87.96 percent; h: 4.84 percent; n: 3.36 percent; experimental determination C: 88.21%, H: 5.02 percent; n: 3.45 percent.

Synthesis example 8

The compound P41, prepared as required in this example, has the following structural formula:

synthesis example 7 was repeated except for changing 4- (4-dibenzofuranyl) phenyl-N-phenylamine to 4- (2-dibenzothiophenyl) phenyl-N-phenylamine in an equivalent amount in the second reaction step of Synthesis example 7, and the other starting materials and procedures were the same as those in Synthesis example 7 to give 14.7g of a white solid in yield: 87 percent. MS (m/z): 848.3, elemental analysis: for C₆₁H₄₀N₂OS, theoretical value: c: 86.29 percent; h: 4.75 percent; n: 3.30 percent; experimental determination C: 86.23%, H: 4.57 percent; n: 3.38 percent.

Synthesis example 9

The compound P44, prepared as required in this example, has the following structural formula:

synthesis example 7 was repeated except for changing 4- (4-dibenzofuranyl) phenyl-N-phenylamine to equivalent of phenyl-9-phenanthrylamine in the second reaction, and the other raw materials and procedures were the same as those in Synthesis example 7 to give 12.7g of a white solid in yield: 83 percent. MS (m/z): 766.3, elemental analysis: for C₅₇H₃₈N₂O, theoretical value: c: 89.27 percent; h: 4.99 percent; n: 3.65 percent; experimental determination C: 89.23%, H: 4.87 percent; n: 3.498 percent.

Synthesis example 10

The structural formula and the synthetic route of compound P47, which is prepared in this example, are shown below:

the specific implementation steps are as follows:

(1) preparation of intermediate P47-1: n is a radical of₂Under protection, adding intermediate M3(8.86g, 20mmol), diphenylamine 3.75g (22mmol), cuprous chloride 0.6g (6mmol, 30%), hydrated 1, 10-phenanthroline 0.88g (4.4M) into a 500mL three-necked bottleol, 20%), potassium hydroxide 3.4g (60mmol, 3eq), xylene 250 mL. Starting stirring, heating to about 80 ℃ to change the system from black to khaki, heating to 130 ℃ to change the system from khaki to tan, keeping reflux reaction for 16h, cooling the reaction solution to 60 ℃, dropwise adding 10mL of concentrated hydrochloric acid, and stirring for 1h after dropwise adding. Filtering, leaching a filter cake by 200mL of dimethylbenzene, and standing for liquid separation. The organic phase was washed 2 times with water, dried over anhydrous magnesium sulfate, the organic solvent was removed under reduced pressure, and the residue was subjected to column chromatography to give intermediate P47-1 as a white solid (8.7 g, yield 78%).

(2) Preparation of compound P47: in N₂To a 250mL three-necked flask equipped with magnetic stirring, 100mL of toluene, 10.6g P47-1(20mmol) and 5.4g of 3-biphenyl-phenylamine (22mmol) were added in this order under stirring, 2.9g of sodium tert-butoxide (30mmol) and 90mg of Pd (dba) were added₂(palladium bis (dibenzylidene acetone) (0.15 mmol)) and the color becomes dark, then 0.6g of 10% tri-tert-butylphosphine n-hexane solution (0.3mmol) is added, heating reflux is carried out, the reaction solution becomes green, after refluxing for 8h, the plate is placed, basically no raw material is generated, when the temperature is reduced to below 45 ℃, a mixed solution of 5mL of concentrated hydrochloric acid and 100mL of water is added, liquid separation is carried out, the water phase is extracted by 100mL of toluene, crude products are obtained by combining and spin-drying, the crude products are separated by column chromatography, and the off-white solid 13.2g is obtained, and the yield is: 89 percent. MS (m/z): 742.3, elemental analysis: ForC₅₅H₃₈N₂O, theoretical value: c: 88.92 percent; h: 5.16 percent; n: 3.77 percent; experimental determination C: 88.71%, H: 5.22 percent; n: 3.58 percent.

Synthesis example 11

The compound P48, prepared as required in this example, has the following structural formula:

synthesis example 10 was repeated except for replacing (3-biphenyl) phenylamine by equivalent of 3- (9-phenanthryl) phenyl-N-phenylamine in the second reaction step of Synthesis example 10, and the other starting materials and procedures were the same as those of Synthesis example 10 to give 13.7g of a white solid in yield: 81 percent. MS (m/z): 842.3, elemental analysis: for C₆₃H₄₂N₂O, theoretical value: c: 89.76 percent; h: 5.02 percent; n: 3.32 percent; experimental determination C: 89.89%, H: 4.97 percent; n: 3.45 percent.

Synthesis example 12

The compound P52, prepared as required in this example, has the following structural formula:

synthesis example 10 was repeated except that diphenylamine in the first reaction step was changed to equivalent of (4-biphenyl) -phenylamine and (3-biphenyl) phenylamine in the second reaction step was changed to equivalent of phenothiazine, and the other raw materials and steps were identical to those of Synthesis example 10, to give 11.7g of a white solid in yield: 75 percent. MS (m/z): 772.3, elemental analysis: for C₅₅H₃₆N₂OS, theoretical value: c: 85.46 percent; h: 4.69 percent; n: 3.62 percent; experimental determination C: 85.72%, H: 4.81 percent; n: 3.54 percent.

Synthesis example 13

The structural formula and the synthetic route of compound P54, which is prepared in this example, are shown below:

the specific implementation steps are as follows:

in N₂To a 250mL three-necked flask equipped with magnetic stirring, 100mL of toluene, 9.8g M1 (20mmol) and 8.1g of phenoxazine (44mmol) were added sequentially with stirring, 2.9g of sodium tert-butoxide (30mmol) and then 90mg of Pd (dba)₂(palladium bis (dibenzylidene acetone) (0.15 mmol) and darkening in color, then adding 0.6g of 10% tri-tert-butylphosphine n-hexane solution (0.3mmol), heating and refluxing, enabling the reaction solution to turn green, adding a spot plate after refluxing for 6h, cooling to room temperature, adding a mixed solution of 5mL of concentrated hydrochloric acid and 100mL of water, separating, extracting the water phase with 100mL of toluene, combining, and spin-drying to obtain a crude product, and recrystallizing the crude product with a dichloromethane/ethanol (volume ratio 1: 1) system to obtain the productWhite solid 10.3g, yield: 74 percent. MS (m/z): 694.2, elemental analysis: ForC₄₉H₃₀N₂O₃The theoretical value is as follows: c: 84.71 percent; h: 4.35 percent; n: 4.03 percent; experimental determination C: 84.67%, H: 4.22 percent; n: 3.99 percent.

Synthesis example 14

The compound P56, prepared as required in this example, has the following structural formula:

phenoxazine in synthesis example 13 was changed to equivalent 9, 9-dimethyl-9, 10-dihydroacridine, and other raw materials and procedures were the same as in synthesis example 13 to obtain off-white solid 10.2g, yield: and 69 percent. MS (m/z): 746.3, elemental analysis: for C₅₅H₄₂N₂O, theoretical value: c: 88.44 percent; h: 5.67 percent; n: 3.75 percent; experimental determination C: 88.57%, H: 5.81 percent; n: 3.68 percent.

Synthesis example 15

The structural formula and the synthetic route of compound P58, which is prepared in this example, are shown below:

the specific implementation steps are as follows:

a500 mL three-necked flask was stirred by magnetic force, and then added with intermediate M19.8g (20mmol), carbazole 8.1g (50mmol), cuprous iodide 1.9g (10mmol), potassium carbonate 13.8g (0.1mol), and DMPU solvent 250 mL. The mixture was heated to 175 ℃ with vigorous stirring and the reaction was monitored by a TCL plate for 14h to completion. Cooling, pouring into water, filtering off, drying, separation by column chromatography, rinsing with a mixture of ethyl acetate and petroleum ether gave 8.8g of a white solid in 67% yield. MS (m/e): 662.2 elemental analysis (C)₄₉H₃₀N₂O): theoretical value C: 88.80%, H: 4.56%, N: 4.23 percent; found value C: 88.74%, H: 4.51%, N: 4.45 percent.

Synthesis example 16

The compound P62, prepared as required in this example, has the following structural formula:

the carbazole in the synthesis example 15 was changed to 3-phenylcarbazole in equivalent amount, and the other raw materials and steps were the same as in the synthesis example 15, to obtain 11.4g of a white solid, with a yield: 70 percent. MS (m/z): 814.3, elemental analysis: for C₆₁H₃₈N₂O, theoretical value: c: 89.90 percent; h: 4.70 percent; n: 3.44 percent; experimental determination C: 89.78%, H: 4.85 percent; n: 3.39 percent.

Synthesis example 17

The structural formula and the synthetic route of compound P65, which is prepared in this example, are shown below:

the specific implementation steps are as follows:

(1) synthesis of intermediate P65-1: a500 mL three-necked flask was stirred magnetically, and then added with intermediate M38.9g (20mmol), carbazole 4.1g (25mmol), cuprous iodide 1g (5mmol), potassium carbonate 6.9g (50mmol) and DMPU solvent 250 mL. The mixture was heated to 175 ℃ with vigorous stirring and the reaction was monitored with a TCL plate and allowed to complete for 12 h. Cooling, pouring into water, filtering off, drying, separation by column chromatography, rinsing with a mixture of ethyl acetate and petroleum ether gave 7.5g of a white solid with a yield of 71%.

(2) Preparation of compound P65: in N₂To a 250mL three-necked flask equipped with magnetic stirring, 100mL of toluene, 10.6g P65-1(20mmol) and 7.1g of bis (4-biphenylyl) amine (22mmol) were added in this order under stirring, 2.9g of sodium tert-butoxide (30mmol) and 90mg of Pd (dba) were added₂(palladium bis (dibenzylideneacetone, 0.15 mmol)) and the color became dark, 0.6g of a 10% n-hexane solution of tri-tert-butylphosphine (0.3mmol) was added thereto, and the mixture was refluxed with heating to turn the reaction solution into greenAnd (3) carrying out color separation, adding a plate after refluxing for 6 hours, basically removing raw materials, cooling to room temperature, adding a mixed solution of 5mL of concentrated hydrochloric acid and 100mL of water, separating liquid, extracting a water phase by using 100mL of toluene, combining, carrying out spin drying to obtain a crude product, and separating the crude product by using column chromatography to obtain 14.7g of off-white solid, wherein the yield is as follows: 90 percent. MS (m/z): 816.3, elemental analysis: ForC₆₁H₄₀N₂O, theoretical value: c: 89.68 percent; h: 4.94 percent; n: 3.43 percent; experimental determination C: 89.76%, H: 5.10 percent; n: 3.39 percent.

Synthesis example 18

The compound P80, prepared as required in this example, has the following structural formula:

synthesis example 17 was repeated except for replacing di (4-biphenylyl) amine with an equivalent amount of phenyl-2-dibenzothiophenylamine and carrying out the same procedures as in Synthesis example 17 to give 12.9g of a white solid in a yield: 84 percent. MS (m/z): 770.2, elemental analysis: for C₅₅H₃₄N₂OS, theoretical value: c: 85.69 percent; h: 4.45 percent; n: 3.63 percent; experimental determination C: 85.67%, H: 4.52 percent; n: 3.75 percent.

Synthetic example 19

The compound P86, prepared as required in this example, has the following structural formula:

the bis (4-biphenylyl) amine in synthesis example 17 was replaced with an equivalent amount of phenyl-4- (N-phenyl-carbazolyl) amine, and the other raw materials and steps were the same as in synthesis example 17 to obtain 13.8g of a white solid, yield: 83 percent. MS (m/z): 829.3, elemental analysis: for C₆₁H₃₉N₃O, theoretical value: c: 88.27 percent; h: 4.74 percent; n: 5.06 percent; experimental determination C: 88.42%, H: 4.69 percent; n: 5.28 percent.

Synthesis example 20

The compound P89, prepared as required in this example, has the following structural formula:

intermediate M3 in the first reaction step of Synthesis example 17 was replaced with equivalent M2, and the other starting materials and procedures were the same as those of Synthesis example 17 to give 7.71g of a white solid in yield: 88 percent. MS (m/z): 816.3, elemental analysis: for C₆₁H₄₀N₂O, theoretical value: c: 89.68 percent; h: 4.94 percent; n: 3.43 percent; experimental determination C: 89.38%, H: 5.09%; n: 3.25 percent.

Synthesis example 21

The compound P96, prepared as required in this example, has the following structural formula:

synthesis example 17 was repeated except that intermediate M3 in the first reaction of Synthesis example 17 was changed to equivalent M2 and bis (4-biphenylyl) amine in the second reaction was changed to equivalent phenyl- (4- (4-dibenzofuranyl) phenyl) amine, and the other starting materials and procedures were the same as those of Synthesis example 17 to give 12.9g of a white solid in yield: 79 percent. MS (m/z): 830.3, elemental analysis: for C₆₁H₃₈N₂O₂The theoretical value is as follows: c: 88.17 percent; h: 4.61 percent; n: 3.37 percent; experimental determination C: 88.38%, H: 4.49 percent; n: 3.25 percent.

Synthesis example 22

The compound P106 desired to be prepared in this example has the following structural formula:

the intermediate M3 in the first reaction step of Synthesis example 17 was replaced with an equivalent of M2, and the di (4-biphenylyl) amine in the second reaction step was replaced with an equivalent of phenoxazineOxazine, other starting materials and procedures were the same as in Synthesis example 17, giving 11.1g of a white solid in yield: 82 percent. MS (m/z): 678.2, elemental analysis: for C₄₉H₃₀N₂O₂The theoretical value is as follows: c: 86.70 percent; h: 4.45 percent; n: 4.13 percent; experimental determination C: 86.58%, H: 4.31 percent; n: 4.29 percent.

The invention also provides an organic electroluminescent device, and the spiro compound is used as a hole transport material of the organic electroluminescent device, particularly a blue, green and red organic electroluminescent device, or an electron blocking material of the red organic electroluminescent device.

In some embodiments of the present invention, a general organic electroluminescent device includes a substrate, and an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode layer sequentially formed on the substrate; the red light organic electroluminescent device comprises a substrate, and an anode layer, a hole transport layer, an electron blocking layer, an organic light emitting layer, an electron transport layer and a cathode layer which are sequentially formed on the substrate.

The manufacturing process of the organic electroluminescent device comprises the following steps: an anode is formed on a transparent or opaque smooth substrate, an organic thin film layer is formed on the anode, and a cathode is formed on the organic thin film layer. The organic thin film layer can be formed by a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or the like. The organic thin film layer at least comprises a hole transport layer and a light emitting layer, and can also comprise an electron blocking layer. Wherein:

the anode material may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof, and may also be selected from metal oxides such as indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), etc.; the anode material may also be selected from conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), and the like. In addition, the anode material may also be selected from materials that facilitate hole injection in addition to the anode materials listed above, and combinations thereof, including known materials suitable for use as anodes.

The cathode material may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, and the like, and othersAlloys thereof. The cathode material may also be selected from multi-layered metallic materials such as LiF/Al, LiO₂/Al、BaF₂Al, etc. In addition to the cathode materials listed above, the cathode materials can also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as cathodes.

The technical effects of the compounds of the invention are explained in detail below by means of device examples.

Example 23

The compound of the invention is used as a hole transport layer material in a phosphorescent OLED device, and in addition, HTM1 is selected as a comparison material of the invention, and the structure of the general device is as follows:

ITO/HIL1(1nm)/HTL1(60nm)/Host1：Ir(ppy)₃[10％](30nm)/ETL1:ETL2[100％] (30nm)/LiF(0.5nm)/Al(150nm)。

the structural formula of the used material is as follows:

device example 1

The compound P1 is used for preparing an organic electroluminescent device, and the specific steps are as follows:

(1) the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonic degreasing in ethanol mixed solvent, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding the surface with low-energy cation beam.

(2) Placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^－5～9×10^－3Pa, performing vacuum evaporation on the anode layer film to form HIL1 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a hole transport layer HTM1 at a rate of 0.1nm/s and a thickness of60nm。

(3) And (3) performing vacuum evaporation on the hole transport layer to obtain a light-emitting main body material Host 1: ir (ppy)₃[10％]As a light emitting layer of the device, the deposition rate was 0.1nm/s, and the total deposition thickness was 30nm (Ir (ppy)₃[10％]: namely Host1 and Ir (ppy)₃In a weight ratio of 10: 1).

(4) The electron transport layer material of the device is evaporated on the luminescent layer in vacuum, the evaporation rate of ETL-1 and ETL-2 is adjusted to be 0.1nm/s by using a double-source co-evaporation method, and the total film thickness of evaporation is 30 nm;

(5) LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.

Device examples 2 to 12

Organic electroluminescent devices of device examples 2 to 12 were produced in a similar manner to device example 1 except that the compound P1 in device example 1 was replaced with the compound P14, the compound P15, the compound P19, the compound 32, the compound 34, the compound 42, the compound 54, the compound P89, the compound P94, the compound P101, and the compound P106, respectively, in this order.

Comparative device example 1

An organic electroluminescent device of comparative example 1 was prepared in a similar manner to device example 1, except that compound P1 in device example 1 was replaced with a compound such as HTM1 shown.

Table 1: photoelectric property of device

As can be seen from Table 1, the device using the compound of the present invention as a hole transporting material was in the range of 10000cd/cm, as compared with the device using HTM1, which is currently commercialized, as a hole transporting material²A lower operating voltage and a higher current efficiency are obtained at the luminance of (a).

The compound of the invention is used as an electron (exciton) blocking material EBL in a red phosphorescent OLED device, and an EBL material is not adopted as a comparison material, so that the structure of the implemented universal device is as follows:

red phosphorescent device structure:

ITO/HIL1(1nm)/HTM1((70-x)nm)/EBL(xnm)/Host2：Ir(piq)₂(acac) (5 wt%) (30nm)/ETL1 ETL2 (100%) (30nm)/LiF (0.5nm)/Al (150nm), where x is 20nm, the structural formula of the material used is as follows:

device example 13

The compound P60 is used for preparing an organic electroluminescent device, and the specific steps are as follows:

(1) the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonic degreasing in ethanol mixed solvent, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding the surface with low-energy cation beam.

(2) The glass substrate with the anode is placed in a vacuum chamber and is vacuumized to 1 x 10^－5～9×10^－3Pa, performing vacuum evaporation on the anode layer film to form HIL1 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a hole transport layer HTM1 at the evaporation rate of 0.1nm/s and the thickness of 50 nm; compound P60 was vapor-deposited on the hole injection layer as an electron (exciton) blocking layer at a rate of 0.1nm/s and a thickness of 20 nm.

(3) And (3) performing vacuum evaporation on the hole transport layer to obtain a light-emitting main body material Host 2: ir (pig)₂(acac)[5％]As a light emitting layer of the device, the deposition rate was 0.1nm/s, and the total deposition thickness was 30nm (Ir (piq))₂(acac) [5％]: namely Host1 and Ir (piq)₂The weight ratio of (acac) is 100: 5).

(4) The electron transport layer material of the device is evaporated on the luminescent layer in vacuum, the evaporation rate of ETL-1 and ETL-2 is adjusted to be 0.1nm/s by using a double-source co-evaporation method, and the total film thickness of evaporation is 30 nm.

(5) And (3) evaporating LiF with the thickness of 0.5nm and Al with the thickness of 150nm on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.

Device examples 14 to 19

Organic electroluminescent devices of device examples 14 to 19 were produced in a similar manner to device example 13 except that the compound P60 in device example 13 was replaced with the compound P62, the compound P64, the compound P68, the compound 73, the compound 85, and the compound 88, respectively, in this order.

Comparative device example 2

An organic electroluminescent device of comparative device example 2 was prepared in a similar manner to device example 13, except that the 20nm EBL material compound P60 in device example 13 was removed and replaced with the compound HTM1 with an increase in thickness of 70 nm.

Table 2: photoelectric property of device

As can be seen from table 2, due to the higher triplet level and hole mobility and the HOMO level matching property with the red host, when the partial compound of the present invention is used as an EBL layer material of a red phosphorescent device, the working voltage of the device can be effectively reduced and the efficiency of the device can be significantly improved.