A heteroatom-containing condensed ring amine compound and its application

Abstract

The present invention provides a heteroatom-containing condensed ring amine compound with a structure of formula (I). The presence of the specific luminescent auxiliary material of the present invention enables holes transferred from the anode to move smoothly to the luminescent layer, reduces the potential barrier between the hole transport layer and the luminescent layer, and reduces the driving voltage of the device; the glass transition temperature is significantly improved; the utilization rate of holes is further increased, and the luminescent efficiency and life of the device are improved.

Description

Technical Field

[0001] The invention relates to the technical field of organic luminescent materials, in particular to a heteroatom-containing condensed ring amine compound and application thereof. Background Art

[0002] Organic electroluminescent (OLED) device technology can be used to manufacture new display products and new lighting products. It is expected to replace existing liquid crystal displays and fluorescent lighting, and has a wide range of applications. Organic electrical components that use organic light-emitting phenomena usually have an anode, a cathode, and an organic layer between them. In order to improve the efficiency and stability of organic electrical components, the organic layer is usually composed of a multilayer structure composed of various different substances.

[0003] OLED optoelectronic functional materials used in OLED devices can be divided into two categories based on their uses, namely charge injection transport materials and luminescent materials. Furthermore, charge injection transport materials can be divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and luminescent materials can be divided into main luminescent materials and doping materials.

[0004] The hole transport layer (HTL) is responsible for regulating the injection speed and injection amount of holes, and in the OLED, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc. are often used as compounds contained in the hole transport region. However, OLEDs using these materials have problems in deteriorating quantum efficiency and service life. This is because when the OLED is driven at a high current, thermal stress occurs between the anode and the hole injection layer, and the thermal stress significantly reduces the service life of the device. In addition, since the organic material used in the hole transport region has a very high hole mobility, the hole-electron charge balance may be destroyed and the quantum efficiency (cd / A) may be reduced.

[0005] Usually, a light-emitting auxiliary layer (multi-layer hole transport layer) is added between the hole transport layer and the light-emitting layer to improve the device life and efficiency. The light-emitting auxiliary layer can reduce the barrier between the hole transport layer and the light-emitting layer, reduce the driving voltage of the organic electroluminescent device, and further increase the utilization of holes, thereby improving the luminous efficiency and life of the device. It is particularly important to develop higher performance organic functional materials to meet the requirements of panel manufacturers. Summary of the invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a heteroatom-containing condensed ring amine compound. The organic electroluminescent device prepared from the compound provided by the present invention has higher luminous efficiency and longer life.

[0007] The present invention provides a heteroatom-containing fused ring amine compound of formula (I),

[0008]

[0009] Wherein, X is -O-, -S-, -C(R5)(R6)- or -N(R7)-; R5, R6 are independently selected from methyl, ethyl, phenyl, methylbenzene, biphenyl, naphthyl or cyclopentyl; R7 is selected from phenyl, methylbenzene, biphenyl, cyclopentyl, naphthyl or terphenyl;

[0010] X1 is C–R a or N; X2 is C–R b or N; X2 is C–R c or N; X3 is C–R d or N; X4 is C–R e or N; X5 is C–R f or N; X6 is C–R g or N; X7 is C–R h or N; X8 is C–R i or N; said R a , R b , R c , R d , R e , R f , R g , R h , R i is independently selected from hydrogen, deuterium, C1-C10 alkyl, structure A shown in formula II, substituted or unsubstituted C6-C24 arylene, and heteroarylene with 2-18 ring carbon atoms substituted or unsubstituted with one or more heteroatoms; the heteroatom is selected from O, N or S; or R a ~R i Any two adjacent groups in the group form a benzene ring with or without substituents with the C where they are located;

[0011] The position of N in the ring of X1-X8 described in the present invention is preferably X2, X3, X5 or X8; the number of N is 0-3; specifically, it can be 0, 1, 2 or 3.

[0012] R a ~R i At least one is a structure shown in general formula II; said R a ~R iThere are at most 3 structures represented by general formula II.

[0013] In formula (II):

[0014] L1, L2, L3, Ar1, Ar2 are independently selected from hydrogen, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C20 arylene, and one of substituted or unsubstituted heteroarylene with 2 to 18 ring carbon atoms containing one or more heteroatoms, wherein the heteroatom is selected from O, N or S.

[0015] More preferably, L1, L2, L3, Ar1, Ar2 are independently selected from hydrogen, cyclopentyl, cyclohexyl, aryloxy, phenyl, methylbenzene, biphenyl, naphthyl, terphenyl, fluorenyl, dimethylfluorene, diphenylfluorenyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl or carbazolyl;

[0016] L2, at least one of Ar1 is not hydrogen;

[0017] At least one of L3 and Ar3 is not hydrogen.

[0018] Particularly preferably, the R a ~R i are independently selected from hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, alkoxy, phenyl, methylbenzene, biphenyl, naphthyl, terphenyl, fluorine, cyano, butyl, pentyl, hexyl, dibenzofuranyl, dibenzothiophenyl, phenanthrenyl, carbazolyl or Formula II.

[0019] Most preferably, the structure shown in the general formula II of the present invention is selected from the following structures:

[0020]

[0021]

[0022] R a ~R i They are connected to any position on the ring through a single bond or by forming a benzo structure;

[0023] Ar1 and Ar2 can exist independently or bond to each other to form a ring.

[0024] The compound of formula (I) of the present invention is a compound of formula (I-1) to formula (I-14):

[0025]

[0026] in,

[0027] X is -O-, -S-, -C(R5)(R6)- or -N(R7)-; R5, R6 are independently selected from methyl, ethyl, phenyl, methylbenzene, biphenyl, naphthyl or cyclopentyl; R7 is selected from phenyl, methylbenzene, biphenyl, cyclopentyl, naphthyl or terphenyl;

[0028] R1, R2, R3, and R4 are independently selected from hydrogen, deuterium, C1-C10 alkyl, structure A shown in formula II, substituted or unsubstituted C6-C24 arylene, and heteroarylene with 2-18 ring carbon atoms and substituted or unsubstituted with one or more heteroatoms; the heteroatoms are selected from O, N, or S;

[0029] The preferred range of R1, R2, R3, R4 is a ~Ri are consistent, so I will not go into details here.

[0030] Furthermore, R1, R2, R3, and R4 in formula (1) to formula (5) contain at least one structure represented by formula II; the structure represented by formula II has been clearly described in the above invention and will not be repeated here.

[0031] In R1, R2, R3, and R4, R other than the structure shown in Formula II is preferably a substituent hydrogen, deuterium, methyl, phenyl, tert-butyl, methylphenyl, methoxyalkyl, biphenyl, or naphthyl;

[0032]

[0033] X, X1-X8, R1, R2, R3, R4 are the same as the above-mentioned selection ranges; they will not be repeated here.

[0034] Furthermore, in X1-X8, the number of heteroatoms is preferably 1-3, and the heteroatom is preferably N;

[0035] In each of formulae (6) to (10), R1, R2, R3, and R4 contain at least one structure represented by formula II. The structure represented by formula II has been clearly described in the above disclosure and will not be repeated here.

[0036] In R1, R2, R3, and R4, R other than the structure shown in Formula II is preferably a substituent hydrogen, deuterium, methyl, phenyl, tert-butyl, methylphenyl, methoxyalkyl, biphenyl, or naphthyl;

[0037]

[0038]

[0039] X, X5-X8, R1, R2, R3, R4 are the same as the above selection ranges; they will not be repeated here.

[0040] Further, in X5-X8, the number of heteroatoms is 1-3, and the heteroatom is preferably N;

[0041] R1, R2, R3, and R4 in formula (I-1) to formula (I-14) contain at least one structure represented by formula II; the structure represented by formula II has been clearly described in the above invention and will not be repeated here.

[0042] At the same time, in formula (I-1) to formula (I-5), at least two of R1, R2, R3, and R4 are not hydrogen.

[0043] The term "substituted or unsubstituted" in the present application means substitution by at least one substituent selected from the following: deuterium, halogen group, nitrile group, hydroxyl group, carbonyl group, ester group, silyl group, boron group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylamino group, substituted or unsubstituted heterocyclylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclyl group, or substituted by two or more substituents connected to each other among the substituents shown above. The term "substituted or unsubstituted" means not having a substituent.

[0044] According to the present invention, the compound of formula (I) preferably has any of the following structures:

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052] The present invention does not limit the preparation method, and any method known to those skilled in the art for synthesizing the above-mentioned compound may be used.

[0053] The synthetic route of the present invention is preferably as follows:

[0054] 1. When X = -C(R5)(R6)-, the target compound is obtained by using the Grignard reaction, ring closing reaction, and Buchwald-Hartwig coupling reaction well known to those skilled in the art.

[0055] 2. When X=O, S, the target compound is obtained by using Suzuki reaction, ring closing reaction, or Buchwald–Hartwig coupling reaction which are well known to those skilled in the art.

[0056] 3. When X = -N(R7)-, the target compound is obtained by using the Buchwald-Hartwig coupling reaction well known to those skilled in the art.

[0057] The present invention provides a heteroatom-containing condensed ring amine compound and a preparation method thereof, and an organic electroluminescent device using the material as a light-emitting auxiliary layer or a hole transport material. The compound of the present invention contains a heteroatom condensed ring and an aromatic amine derivative as a core, has a high glass transition temperature, and can effectively improve the life and luminous efficiency of OLED devices through device structure optimization.

[0058] The present invention provides a luminescent auxiliary layer material, comprising a compound of the structure of formula (I) as described in any one of the above technical solutions.

[0059] The compound of the present invention is preferably used as a light-emitting auxiliary layer material.

[0060] The present invention provides an organic electroluminescent device, which comprises a first electrode, a second electrode and one or more organic compound layers disposed between the first electrode and the second electrode, wherein at least one organic compound layer comprises the compound described in any one of the above technical solutions.

[0061] The one or more organic compound layers of the present invention include at least one or more of a hole injection layer, a hole transport layer, a luminescence auxiliary layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transport layer and an electron injection layer.

[0062] In the present invention, the first electrode serves as an anode, and the anode preferably comprises a material having a high work function, such as indium tin oxide (ITO) or indium zinc oxide (IZO).

[0063] Since the lifetime of the device according to the invention is shortened in the presence of water and / or air, the device is appropriately (depending on the application) structured, provided with contacts and finally sealed.

[0064] The hole transport material is a material with high hole mobility, which can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer. Specific examples thereof include organic materials based on arylamine, conductive polymers, block copolymers having both conjugated and non-conjugated parts, and the like.

[0065] When the organic layer includes a light-emitting auxiliary layer, the light-emitting auxiliary layer may include a compound represented by Formula I.

[0066] The material of the light-emitting layer is a material that can emit visible light by receiving holes and electrons from the hole transport layer and the electron transport layer respectively and combining the received holes and electrons. In addition, the light-emitting layer may include a main material and a doping material; the mass ratio of the main material to the doping material is 90-99.5:0.5-10; the doping material may include fluorescent doping and phosphorescent doping.

[0067] The hole blocking layer material may be a compound with a hole blocking function known in the prior art, for example, phenanthroline derivatives such as bathocuproine (BCP), oxazole derivatives, triazole derivatives, triazine derivatives, etc., but is not limited thereto.

[0068] The electron transport layer can promote electron transport. Compounds with electron transport function known in the prior art can be used, for example, Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic free radical compounds; hydroxyflavone-metal complexes, etc.

[0069] The electron injection layer can promote electron injection. It has the ability to transport electrons and prevent the excitons generated in the light-emitting layer from migrating to the hole injection layer. The electron injection material used in the present invention includes fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, azole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenyl methane or anthrone, and derivatives thereof, metal complexes or nitrogen-containing five-membered ring derivatives, etc., but is not limited thereto.

[0070] In the present invention, the second electrode is used as a cathode, and is preferably a material with a small work function so that electrons can be smoothly injected into the organic material layer. For example, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof. The layer thickness of this layer is preferably between 0.5 and 2 nm.

[0071] The present invention also provides an organic electroluminescent device, comprising the above organic luminescent compound or the organic luminescent compound prepared by the above preparation method; the organic electroluminescent device can be an organic electroluminescent device well known to those skilled in the art.

[0072] Compared with the prior art, the present invention provides a heteroatom-containing condensed ring amine compound with a structure of formula (I). The presence of the specific luminescent auxiliary material of the present invention enables the holes transferred from the anode to move smoothly to the luminescent layer, reduces the potential barrier between the hole transport layer and the luminescent layer, and reduces the driving voltage of the device; the glass transition temperature is significantly improved; the utilization rate of holes is further increased, and the luminescent efficiency and life of the device are improved. DETAILED DESCRIPTION

[0073] The present invention provides a heteroatom-containing fused ring amine compound and application. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve it. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they all fall within the scope of protection of the present invention. The method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0074] In order to further illustrate the present invention, a heteroatom-containing fused ring amine compound and application provided by the present invention are described in detail below in conjunction with examples.

[0075] Example 1: Synthesis of Chemical Formula 1

[0076]

[0077] Step 1: Compound A-1 (50 mmol) was mixed with THF (500 mL), and Me-Mg-Br (55 mmol) was added. After stirring at 60°C for 12 hours, the reaction solution was slowly added into distilled water at room temperature. It was extracted with ethyl acrylate and dried over magnesium sulfate. Column separation gave reactant B-1 (16.2 g, Ms: 391.31, yield: 83%);

[0078] Step 2: Add intermediate B-1 (40 mmol) into a three-necked flask, add glacial acetic acid, heat to 120°C, add concentrated sulfuric acid dropwise, and stir for 5 min; cool to room temperature, add sodium bicarbonate solution to terminate the reaction, separate the liquids, extract the aqueous phase with dichloromethane three times, collect the organic phase, add anhydrous magnesium sulfate to dry, and remove the solvent by rotary evaporator to obtain intermediate C-1 (12.8 g, Ms: 372.05, yield: 86%);

[0079] Step 3: After adding intermediate C-1 (30mmol) and reactant D-1 (36mmol) to the reaction vessel and dissolving in 500ml toluene, Pd2(dba)3 (0.3mmol), P(t-Bu)3 (1.8mmol), and t-BuONa (72mmol) were added under a nitrogen atmosphere. After addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 10h. Celite was used for hot filtration to remove salts and catalysts. After the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a dichloromethane: petroleum ether volume ratio of 1: (1-9) as the eluent to obtain compound 1 (15.9g, yield 81%).

[0080] Mass spectrometry test: theoretical value is 653.87; tested value is 653.46.

[0081] Elemental Analysis:

[0082] Theoretical value: C, 91.85; H, 6.01; N, 2.14

[0083] Test value: C, 91.86; H, 6.00; N, 2.15

[0084] Example 2: Synthesis of Chemical Formula 58

[0085]

[0086] Step 1: Under N2 protection, reactant A-58 (50mmol), reactant B-58 (55mmol), tetrakis(triphenylphosphine)palladium (0.5mmol) and potassium carbonate (110mmol) were added to a mixed solvent of 400mL toluene, 150mL ethanol and 150mL water, respectively, and the temperature was raised to 100°C for reflux reaction for 8h. After the reaction was completed, it was cooled to room temperature. After the solid was precipitated, it was filtered and washed with water to remove the salt, and then rinsed with a small amount of ethanol, and the filter cake was dried. It was placed in 1,4-dioxane for recrystallization to obtain intermediate C-58 (13.7g, Ms: 333.09, 82%);

[0087] Step 2: Stir a mixture of intermediate C-58 (40 mmol), tetrahydrofuran (120 mL, THF), and 160 mL of glacial acetic acid (HOAc) at -10 ° C, and add (CH3)3CONO (tert-butyl nitrite) (120 mmol) dropwise within 10 min. The reaction mixture was stirred at -10 ° C for 2 hours, then slowly warmed to room temperature and reacted for 5 hours. After the reaction was completed, 700 mL of water was added for dilution. The crude precipitate was purified by column chromatography on silica gel to obtain intermediate D-58 (8.5 g, Ms: 302.76, yield: 70%);

[0088] Step 3: After adding intermediate D-58 (25mmol) and reactant E-58 (27.5mmol) to a reaction vessel and dissolving in 100ml toluene, Pd2(dba)3 (0.25mmol), P(t-Bu)3 (13.8mmol), and t-BuONa (55mmol) were added under a nitrogen atmosphere. After addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 10h. Celite was used for hot filtration to remove salts and catalysts. After the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layer was then dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a dichloromethane: petroleum ether volume ratio of 1: (1-9) as the eluent to obtain compound 58 (18.6g, 80% yield).

[0089] Mass spectrometry test: theoretical value is 663.26; tested value is 663.51.

[0090] Elemental Analysis:

[0091] Theoretical values: C, 90.47; H, 5.01; N, 2.11; O, 2.41

[0092] Test values: C, 90.45; H, 5.01; N, 2.12; O, 2.42

[0093] Example 3: Synthesis of Chemical Formula 67

[0094]

[0095] Step 1: After adding intermediate C-67 (50mmol) and reactant D-67 (60mmol) to a reaction vessel and dissolving in 500ml toluene, Pd2(dba)3 (0.5mmol), P(t-Bu)3 (3mmol), and t-BuONa (100mmol) were added under a nitrogen atmosphere. After addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 10h. Celite was used for hot filtration to remove salts and catalysts. After the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a dichloromethane: petroleum ether volume ratio of 1: (1-9) as the eluent to obtain compound 67 (28.7g, 80% yield).

[0096] Mass spectrometry test: theoretical value is 716.28; tested value is 716.35.

[0097] Elemental Analysis:

[0098] Theoretical values: C, 88.80; H, 5.06; N, 3.91; O, 2.23

[0099] Test values: C, 88.80; H, 5.08; N, 3.90; O, 2.21

[0100] Example 4: Synthesis of Chemical Formula 84

[0101]

[0102] Step 1: Under N2 protection, reactant A-84 (50mmol), reactant B-84 (55mmol), tetrakis(triphenylphosphine)palladium (0.5mmol) and potassium carbonate (110mmol) were added to a mixed solvent of 400mL toluene, 150mL ethanol and 150mL water, respectively, and the temperature was raised to 100℃ for reflux reaction for 8h. After the reaction was completed, it was cooled to room temperature. After the solid was precipitated, it was filtered and washed with water to remove the salt, and then rinsed with a small amount of ethanol, and the filter cake was dried. It was placed in 1,4-dioxane for recrystallization to obtain intermediate C-84 (16.6g, Ms: 410.90, 81%);

[0103] Step 2: Stir a mixture of intermediate C-84 (40 mmol), tetrahydrofuran (120 mL, THF), and 160 mL of glacial acetic acid (HOAc) at -10 ° C, and add (CH3)3CONO (tert-butyl nitrite) (120 mmol) dropwise within 10 min. The reaction mixture was stirred at -10 ° C for 2 hours, then slowly warmed to room temperature and reacted for 5 hours. After the reaction was completed, 700 mL of water was added for dilution. The crude precipitate was purified by column chromatography on silica gel to obtain intermediate D-84 (10.6 g, Ms: 379.08, yield: 75%);

[0104] Step 3: After adding intermediate D-84 (25mmol) and reactant E-84 (27.5mmol) to a reaction vessel and dissolving in 100ml toluene, Pd2(dba)3 (0.25mmol), P(t-Bu)3 (13.8mmol), and t-BuONa (55mmol) were added under a nitrogen atmosphere. After addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 10h. Celite was used for hot filtration to remove salts and catalysts. After the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography using a dichloromethane: petroleum ether volume ratio of 1: (1-9) as an eluent to obtain compound 84 (14.5g, 84% yield).

[0105] Mass spectrometry test: theoretical value is 688.25; tested value is 688.72.

[0106] Elemental Analysis:

[0107] Theoretical value: C, 88.93; H, 4.68; N, 4.07; O, 2.32

[0108] Test values: C, 88.94; H, 4.69; N, 4.07; O, 2.30

[0109] Example 5: Synthesis of Chemical Formula 124

[0110]

[0111] Step 1: Compound A-124 (50 mmol) was mixed with THF (500 mL), and Me-Mg-Br (55 mmol) (144.26 mmol, 3.0 M in ether) was added. After stirring at 60 °C for 12 hours, the reaction solution was slowly added into distilled water at room temperature. It was extracted with ethyl acrylate and dried over magnesium sulfate. Column separation gave reactant B-124 (18.0 g, Ms: 440.08, yield: 82%);

[0112] Step 2: Add intermediate B-124 (40 mmol) into a three-necked flask, add glacial acetic acid, heat to 120°C, add concentrated sulfuric acid dropwise, and stir for 5 min; cool to room temperature, add sodium bicarbonate solution to terminate the reaction, separate the liquids, extract the aqueous phase with dichloromethane three times, collect the organic phase, add anhydrous magnesium sulfate to dry, and remove the solvent by rotary evaporator to obtain intermediate C-124 (14.0 g, Ms: 422.07, yield: 83%);

[0113] Step 3: After adding intermediate C-124 (30 mmol) and reactant D-124 (36 mmol) to a reaction vessel and dissolving in 500 ml of toluene, Pd2(dba)3 (0.3 mmol), P(t-Bu)3 (1.8 mmol), and t-BuONa (72 mmol) were added under a nitrogen atmosphere. After addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 10 hours. Celite was used for hot filtration to remove salts and catalysts. After the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layer was then dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography using a dichloromethane: petroleum ether volume ratio of 1: (1-9) as the eluent to obtain compound 124 (16.5 g, 73% yield).

[0114] Mass spectrometry test: theoretical value is 753.34; tested value is 753.58.

[0115] Elemental Analysis:

[0116] Theoretical values: C, 92.39; H, 5.75; N, 1.86

[0117] Test values: C, 92.37; H, 5.76; N, 1.87

[0118] Example 6 to Example 18

[0119] The synthesis of compounds 18, 23, 36, 48, 60, 70, 78, 90, 95, 100, 105, 120 and 128 was completed by referring to the synthesis methods of Examples 1 to 5. The mass spectra, molecular formulas and yields are shown in Table 1.

[0120] Table 1:

[0121]

[0122]

[0123] [Device Application Example 1] Organic electroluminescent device prepared as a luminescent auxiliary material:

[0124] The ITO glass substrate with a coating thickness of 150nm produced by Fisher was washed twice in distilled water, ultrasonically washed for 30 minutes, and repeatedly washed twice with distilled water, ultrasonically washed for 10 minutes. After the distilled water washing, isopropanol, acetone, methanol and other solvents were ultrasonically washed in sequence and then dried, transferred to a plasma cleaning machine, and the above substrate was washed for 5 minutes and sent to a vapor deposition machine. Compound HT and P-dopant (3%) were introduced into the chamber of a vacuum vapor deposition device, and the pressure in the chamber of the device was controlled to 10-6 Torr. Thereafter, an electric current was applied to the chamber to evaporate the above introduced materials, thereby forming a hole injection layer with a thickness of 10nm on the ITO substrate. HT with a thickness of 35 nm is vacuum-deposited on the formed hole injection layer to form a hole transport layer. Compound 1 of the present invention is vacuum-deposited with a thickness of 20 nm on the above hole transport layer to form a light-emitting auxiliary layer to prepare the light-emitting layer of the OLED light-emitting device. Its structure includes Host as the main material used in the OLED light-emitting layer, Dopant as the doping material, the doping ratio of the doping material is 3% by weight, and the light-emitting layer has a film thickness of 40 nm.

[0125] On the light-emitting layer, TPBi was vacuum-deposited with a thickness of 12 nm as a hole blocking layer, and on the hole blocking layer, ET was vacuum-deposited with a thickness of 40 nm as an electron transport layer; on the electron transport layer, lithium hydroxyquinoline (Liq) was vacuum-deposited with a thickness of 1.0 nm as an electron injection layer. On the electron injection layer, an Al electrode layer with a film thickness of 150 nm was made, which was used as a cathode layer.

[0126] Device structure:

[0127] ITO / HT:p-dopant / HT / Compound 1 / Host:Dopant / TPBi / ET / Liq / Al.

[0128] After the OLED light emitting device is completed as described above, the anode and cathode are connected with a known driving circuit, and the current efficiency and life of the device are measured. After the electroluminescent device is completed according to the above steps, the driving voltage, luminous efficiency and life of the device are measured.

[0129] The molecular structure formula of the relevant materials is shown below:

[0130]

[0131] [Device Application Example 2]-[Device Application Example 136]

[0132] Referring to the above method, the compound 1 used in the device application example 1 is replaced by the compound 2-136 in formula I as the light-emitting auxiliary layer to prepare the corresponding organic electroluminescent device.

[0133] [Device Comparison Example 1]-[Device Comparison Example 4]

[0134] Referring to the above method, the compound 1 used in the device application example 1 was replaced by the comparative compound 1, comparative compound 2, comparative compound 3, and comparative compound 4 as the light-emitting auxiliary layer to prepare the corresponding organic electroluminescent device.

[0135]

[0136] The organic electroluminescent device prepared above was subjected to a forward DC bias voltage, and the organic electroluminescent characteristics were measured using a PR-650 photometric measuring device from Photo Research Company. The brightness was 6000 cd / m 2 The life span of T95 was measured using a life span measuring device from McScience. The results are shown in Table 2.

[0137] Table 2 Luminescence characteristics test results of organic electroluminescent devices prepared in device application examples 1 to 136 and device comparison examples 1 to 4 (brightness value is 6000 cd / m2 )

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144] From Table 2, we can see that

[0145] The device performance shows that device examples 1 to 136 have significant improvements in lifespan, luminous efficiency, and glass device performance compared to comparative examples 1 to 4.

[0146] The driving voltage is mainly affected by the main body. When the main body is consistent, the driving voltage is slightly reduced to 0.1-0.3V.

[0147] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A compound having a structure represented by formula (I-1): in, X is -O-, -S-, -C(R5)(R6)- or -N(R7)-; R5, R6 are independently selected from methyl, ethyl, phenyl, methylbenzene, biphenyl, naphthyl or cyclopentyl; R7 is selected from phenyl, methylbenzene, biphenyl, cyclopentyl, naphthyl or terphenyl; R1, R2, and R3 are independently selected from hydrogen, deuterium, C1-C10 alkyl, the structure shown in Formula II, unsubstituted C6-C24 aryl, and unsubstituted heteroaryl with 2-18 ring carbon atoms containing one or more heteroatoms; the heteroatoms are selected from O, N or S; at least one of R1, R2, and R3 is the structure shown in Formula II; The structure shown in general formula II is selected from the following structures:

2. A compound, characterized in that The compound has any of the following structures:

3. A light-emitting auxiliary layer material, characterized in that: The invention comprises the compound according to any one of claims 1 to 2.

4. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic compound layers disposed between the first electrode and the second electrode, wherein at least one organic compound layer comprises the compound according to any one of claims 1 to 2.

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