CN104672126B - A kind of benzo naphtho- five-ring heterocycles derivative and its application - Google Patents

A kind of benzo naphtho- five-ring heterocycles derivative and its application Download PDF

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CN104672126B
CN104672126B CN201410856885.5A CN201410856885A CN104672126B CN 104672126 B CN104672126 B CN 104672126B CN 201410856885 A CN201410856885 A CN 201410856885A CN 104672126 B CN104672126 B CN 104672126B
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李银奎
李艳蕊
范洪涛
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Guan Eternal Material Technology Co Ltd
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Abstract

The present invention relates to a kind of new organic materials, more particularly to a kind of application for the compound and the compound of organic electroluminescence device in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.Benzo naphtho- five-ring heterocycles derivative of the present invention, with the structure shown in formula (P).Benzo naphtho- five-ring heterocycles derivant material of the present invention, organic electroluminescence device is prepared as hole injection layer material, hole transport layer material or light emitting host material, reduce device opens bright voltage, improve the luminous efficiency of device, the service life of device is added, is the selection of hole-injecting material of good performance, hole mobile material and light emitting host material.

Description

Benzonaphtho five-membered heterocyclic derivative and application thereof
Technical Field
The invention relates to a novel organic material, in particular to a compound for an organic electroluminescent device and application thereof in the technical field of organic electroluminescent display.
Background
The electroluminescence phenomenon was originally discovered in the thirties of the 20 th century, and the initial luminescent material was ZnS powder, so LED technology was developed and now widely applied to energy-saving light sources. The organic electroluminescence phenomenon is the earliest discovery of Pope et al in 1963, and the organic electroluminescence phenomenon shows that a single-layer crystal of anthracene can emit weak blue light under the driving of a voltage of more than 100V. Until 1987, Rooibos, Dengqing cloud, et al, from Kodak corporation, made organic fluorescent dyes into double-layer devices by vacuum evaporation, the external quantum efficiency reached 1% at a driving voltage less than 10V, so that organic electroluminescent materials and devices have the possibility of practicability, and the research on OLED materials and devices was greatly promoted.
Compared with inorganic luminescent materials, organic electroluminescent materials have the following advantages: 1. the organic material has good processing performance, and can form a film on any substrate by a method of evaporation or spin coating; 2. the diversity of the organic molecular structure can adjust the thermal stability, mechanical property, luminescence and conductivity of the organic material by the method of molecular structure design and modification, so that the material has great improvement space.
Organic electroluminescence is generated by recombination of carriers (electrons and holes) transported in an organic semiconductor material, which is known to have poor conductivity, unlike inorganic semiconductors, where there is no continuous energy band, and the transport of carriers is described by the hopping theory, i.e., electrons are excited or injected into the LUMO level of a molecule under the driving of an electric field, and reach the purpose of charge transport by hopping to the LUMO level of another molecule. In order to make organic electroluminescent devices breakthrough in application, the difficulties of poor charge injection and transport capabilities of organic materials must be overcome. Scientists have been able to adjust the device structure, such as increasing the number of organic material layers of the device, and making different organic layers play different roles, such as some functional materials assisting the injection of electrons from the cathode and holes from the anode, some materials assisting the transport of charges, some materials blocking the transport of electrons and holes, and certainly the most important luminescent materials of various colors in organic electroluminescence should also achieve the purpose of matching with the adjacent functional materials.
Common functionalized organic materials are: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like.
The Hole Injection Material (HIM) requires that its HOMO level is between the anode and the hole transport layer, which is beneficial for increasing hole injection between the interfaces. The Hole Transport Material (HTM) is required to have high thermal stability (high Tg), have a small barrier against an anode or a hole injection material, have high hole transport ability, and be capable of forming a pinhole-free thin film by vacuum evaporation. The host material (host) of the light-emitting layer needs to have the following characteristics: reversible electrochemical redox potential, HOMO and LUMO energy levels matched with adjacent hole and electron transport layers, good and matched hole and electron transport capacity, good high thermal stability and film forming properties, and appropriate singlet or triplet energy gaps for controlling excitons in the light emitting layer, as well as good energy transfer with corresponding fluorescent or phosphorescent dyes.
The hole injection and transport materials that have been used in organic electroluminescent devices are generally derivatives of the class of arylamines, which have the general structural feature that, as the injection material, at least one arylamine structural unit thereof is present in one molecule, and two of the N's are separated by a benzene ring (compound a); while the arylamine structural unit is generally two in one molecule and two N are separated by biphenyl as a transport material, a typical example of such a material is NPB (compound b).
In recent years, there have been new developments in the study of such materials, introducing one or more thienyl groups or one or more benzothienyl groups into the molecule (see compounds c, d), which consequently greatly increases the hole injection capability of the material; when one arylamine structural unit in the material is replaced by carbazole or dibenzofuran as the transmission material, the transmission capability of the material is greatly improved (see compounds e and f).
Disclosure of Invention
Therefore, the invention aims to provide a novel benzonaphtho five-membered heterocyclic derivative and further discloses a preparation method thereof.
The second technical problem solved by the present invention is to provide the application of the above derivatives in the field of organic electroluminescent display, specifically, the derivatives are used as hole injection materials or hole transport materials in organic electroluminescent displays, and can also be used as light emitting host materials or light emitting materials in fluorescent devices.
In order to solve the technical problems, the benzo-naphtho five-membered heterocyclic derivative has a structure shown in a formula (P):
wherein: x is NAr, O or S;
Ar、Ar1、Ar2and Ar3Independently of one another from H, C6-C30Substituted or unsubstituted aromatic hydrocarbon radical of (2), C6-C30Substituted or unsubstituted fused ring aromatic hydrocarbon group of (A), C5-C30Substituted or unsubstituted fused heterocyclic group of (A), five-membered, six-membered or substituted heterocyclic ring, diarylamino group, triarylamino group, N, N-dialkylaminoaryl group, N-dialkyl-N-arylaminoaryl group, arylether group, aryloxy group, arylthio group, C1-C12Substituted or unsubstituted aliphatic alkyl groups of (a);
R1-R7independently of one another from H, C1-C12A substituted or unsubstituted aliphatic alkyl group of (2), C6-C20Substituted or unsubstituted aromatic hydrocarbon radical of (2), C6-C20Substituted or unsubstituted fused ring aromatic hydrocarbon group of (A), C5-C20The aromatic heterocyclic group can be substituted or unsubstituted fused heterocyclic group, five-membered heterocyclic ring, six-membered heterocyclic ring or substituted heterocyclic ring, diarylamino group, triarylamino group, aryl ether group, aryloxy group and arylthio group.
Further, Ar and Ar are1、Ar2And Ar3Independently of one another, are selected from the following groups:
wherein Ar is4Is H, or substituted or unsubstituted aryl, alkyl;
l is a substituted or unsubstituted single bond, arylene, or heterocyclylene.
Preferably, said R is1-R7Independently of one another, an alkane selected from H, C1-C7Phenyl, methylphenyl, ethylphenyl, methoxyphenyl, biphenyl or naphthyl.
Further preferably, R is1-R7All are H.
More preferably, when X is NAr, Ar is1Is not H, and said Ar2And Ar3Are all H; or,
when X is S or O, Ar1Is not H, and said Ar2And Ar3And only one is H.
Most preferably, the compound is selected from the following structural formulas:
the invention also discloses application of the benzo-naphtho five-membered heterocyclic derivative in preparing an organic electroluminescent device.
The benzo-naphtho five-membered heterocyclic derivative is used as a hole injection layer material, a hole transport layer material or a light-emitting host material.
The invention also discloses an organic electroluminescent device, which comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate;
the organic light-emitting functional layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer and an electron transport layer;
the hole injection layer and/or the hole transport layer comprise the benzo-naphtho five-membered heterocyclic derivative material.
The invention also discloses an organic electroluminescent device, which comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate;
the organic light-emitting functional layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer and an electron transport layer;
the host material of the organic light-emitting layer comprises the benzonaphtho five-membered heterocyclic derivative.
The benzo-naphtho five-membered heterocyclic derivative material is used as a hole injection layer material, a hole transport layer material or a luminescent main body material to prepare an organic electroluminescent device, reduces the turn-on voltage of the device, improves the luminescent efficiency of the device, prolongs the service life of the device, and is a choice of the hole injection material, the hole transport material and the luminescent main body material with good performance.
Particularly, when the parent structure of the benzonaphtho five-membered heterocyclic ring is only connected with condensed ring aromatic hydrocarbon, but not connected with triarylamine or condensed heterocyclic aromatic hydrocarbon, such as carbazole group, dibenzothiophene group, dibenzofuran group and the like, the material is suitable to be used as a luminescent main body material, so that the luminescent efficiency of a device is greatly improved, and the service life of the device is longer; and a triphenylaromatic amine or a fused heterocyclic aromatic hydrocarbon, such as a carbazole group, a dibenzothiophene group, a dibenzofuran group, etc., is bonded to the parent structure of the benzo-naphtho five-membered heterocyclic ring, and such a material is suitable as a hole transporting material.
Detailed Description
The basic raw materials used in the invention, such as 2-naphthylamine, 1-fluoro-4-bromo-2-nitrobenzene, 2-naphthol, 2-naphthylthiol, bromocarbazole derivatives, bromodibenzofuran, bromodibenzothiophene, bromophenanthrene, derivatives of bromoanthracene, bromopyrene and the like, can be purchased in various large chemical raw material markets in China. The various bromides can be prepared into corresponding boric acid compounds by a common method.
Preparation example 1 Synthesis of intermediate (A) 2-bromo-5H-benzo [ b ] carbazole
(1) Synthesis of secondary amines
A500 ml three-neck flask is stirred by magnetic force, 28.6g (molecular weight 143, 0.2mol) of 2-naphthylamine and 44g (molecular weight 219, 0.2mol) of 1-fluoro-4-bromo-2-nitrobenzene are added, 12g (molecular weight 94, 0.128mol) of potassium fluoride dihydrate are added, Ar gas is used for protection, stirring is carried out at 180 ℃ at 170 ℃ for 30hrs to obtain a brownish black solution, the solution is cooled to room temperature, CH2Cl2 is dissolved, the solution is separated by column chromatography, and the mixture is separated by 20:1 petroleum ether: leaching with ethyl acetate to obtain 46g of orange-red solid, wherein the molecular weight is 342, the purity is 99.2 percent, and the yield is 67.3 percent;
(2) reduction of
A 1000 ml three-neck flask is stirred by magnetic force, and 14.6g (with the molecular weight of 342, 0.0428mol) of the secondary amine compound containing the nitryl synthesized in the step (1) and SnCl are added22H2Using 55g of O (molecular weight 225, 0.24mol), 500ml of absolute ethanol, protecting with Ar gas, stirring under reflux, obtaining a colorless solution after 6hrs, distilling off most of ethanol, pouring into 600ml of water, neutralizing until the pH value is 9, extracting with CH2Cl2, distilling off CH2Cl2 and residual water to obtain a light brown solution, and cooling to obtain 13.4g of light yellow solid, wherein the molecular weight is 312, the purity is 100%, and the yield is 98.1%;
(3) synthesis of intermediate (A) 2-bromo-5H benzo [ b ] carbazole
The intermediate (A), namely 2-bromo-5H-benzo [ b ] carbazole, is obtained by carrying out ring closing reaction treatment according to the method reported in the literature (Justus Liebigs Annalen der Chemie; vol.566; 1950; 162-179), and the specific synthetic route is as follows:
preparation example 2 Synthesis of intermediate (B) naphtho [2,3-B ] benzofuran dibromo
2-bromonaphtho [2,3-b ] benzofuran is obtained by using 2-naphthol and 1-fluoro-4-bromo-2-nitrobenzene as starting materials, synthesizing bromofuran derivatives according to the method described in the literature reports (J.org.chem.1995,60,4991-4994 and Organic Synthesis; Wiley: New York, 1943; Coll.Vol.II, p445), and separating the isomers by a column separation method; then brominating by a common method to obtain naphtho [2,3-B ] benzofuran dibromo compound, and separating two isomers (respectively marked as B1 and B2) by column chromatography. The specific synthetic route is as follows:
preparation example 3 Synthesis of intermediate (C) benzo [ b ] naphtho [2,3-d ] thiophene dibromo-Compound
Using 2-naphthothiophenol and 1-fluoro-4-bromo-2-nitrobenzene as starting materials, synthesizing bromothiophene derivatives according to the method described in the literature reports (J.org.chem.1995,60,4991-4994 and Organic Synthesis; Wiley: New York, 1943; Coll.Vol.II, p445), separating the isomers by column separation to obtain 2-bromobenzo [ b ] naphtho [2,3-d ] thiophene; then brominating by a common method to obtain benzo [ b ] naphtho [2,3-d ] thiophene dibromo compound, and separating two isomers (respectively marked as C1 and C2) by column chromatography; the synthetic route is as follows:
the compounds in the following examples were prepared based on the above intermediates (a), (B1), (B2), (C1), and (C2).
Example 1
This example prepares compound P1, and the specific synthetic route includes:
(1) a500 ml jar was taken and stirred magnetically, and then 10.33g (molecular weight 295, 0.035mol) of intermediate (A), 28g (molecular weight 399, 0.07mol) of p-iodophenyl-bis (4-tolyl) amine, 1.5g (molecular weight 190, 0.0079mol) of cuprous iodide, 13.8g (138, 0.1mol) of potassium carbonate and 250ml of DMPU solvent were added. The mixture was heated to 175 ℃ and stirred, and the progress of the reaction was monitored by a TCL plate and the reaction was completed for 13 hours. Cooling, pouring into water, filtering, drying, separating by column chromatography, eluting with a mixture of ethyl acetate and petroleum ether to obtain 13.63g of target molecule, with a molecular weight of 566 and a yield of 68.8%, wherein the specific synthetic route is as follows:
(2) taking a 1000 ml one-mouth bottle, stirring with magnetic force, adding 11.4g (molecular weight 566, 0.02mol) of the bromo intermediate of the reaction product in the previous step, adding 6.5g of 4- (di (4-tolyl) amino) phenylboronic acid (molecular weight 317, 0.025 mol), reacting for 1.5 hours, and supplementing 1.5g and Pd (PPh)3)4Amounts used were 1.16g (molecular weight 1154, 0.001mol), 150ml of sodium carbonate (2M), 150ml of toluene, 150ml of ethanol. Refluxing after argon replacement, monitoring the reaction by using TLC (thin layer chromatography), reacting completely after 3 hours, cooling, separating a base layer, evaporating to dryness, performing column separation by using 1/10 ethyl acetate/petroleum ether to obtain 10.8g of a product, detecting the molecular weight of the product to be 759, and obtaining the final product yield of 71.2%;
examining the product obtained above, and determining the MS (m/e): 759 elemental analysis (C)56H45N3): theoretical value C: 88.50%, H: 5.97%, N: 5.53 percent; found value C: 88.54%, H: 5.90%, N: 5.56 percent.
Example 2
This example prepared compound P2 with a two-step synthetic procedure:
the first reaction was carried out in the same manner as in the step (1) in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to p-iodophenyl- (1-naphthyl) aniline to obtain an intermediate monobromide;
the second reaction was carried out in the same manner as in the step (2) in example 1 except that one of the starting materials, 4- (di (4-tolyl) amino) phenylboronic acid, was changed to 4- (phenyl- (1-naphthyl) amino) phenylboronic acid, which was reacted with the monobromo compound synthesized in the step (1) in this example, to obtain compound P2.
Examining the product obtained above, and determining the MS (m/e): 803, elemental analysis (C)60H41N3): theoretical value C: 89.63%, H: 5.14%, N: 5.23 percent; found value C: 89.68%, H: 5.11%, N: 5.21 percent.
Example 3
This example prepared compound P3 with a two-step synthetic procedure:
the first reaction was carried out in the same manner as in the step (1) in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to p-iodophenyl- (2-naphthyl) aniline to obtain an intermediate monobromide;
the second reaction was identical to the reaction in step (2) of example 1, except that 4- (phenyl- (2-naphthyl) amino) phenylboronic acid was used as the starting material, and reacted with the monobromide compound synthesized in step (1) of this example, to give compound P3.
Examining the product obtained above, and determining the MS (m/e): 803, elemental analysis (C)60H41N3): theoretical value C: 89.63%, H: 5.14%, N: 5.23 percent; found value C: 89.60%, H: 5.12%, N: 5.28 percent.
Example 4
This example prepared compound P4 with a two-step synthetic procedure:
the first reaction was carried out in the same manner as in the step (1) in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to p-iodophenyl- (2-naphthyl) aniline to obtain an intermediate monobromo compound;
the second step is the same as the step (2) in example 1, except that (2-naphthyl) phenylamine is used as the raw material to react with the intermediate monobromide synthesized in the step (1) in this example, so as to obtain the compound P4.
Examining the product obtained above, and determining the MS (m/e): 727 elemental analysis (C)54H37N3): theoretical value C: 89.10%, H: 5.12%, N: 5.77 percent; found value C: 89.15%, H: 5.14%, N: 5.71 percent.
Example 5
This example prepared compound P5 with a two-step synthetic procedure:
the first step was the same as in the step (1) in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to p-iodophenyl- (1-naphthyl) aniline to give an intermediate monobromide;
the second step is the same as the first step in example 1, except that (1-naphthyl) phenylamine is used as a raw material to react with the intermediate monobromide synthesized in the first step, so as to obtain a compound P5.
Examining the product obtained above, and determining the MS (m/e): 727 elemental analysis (C)54H37N3): theoretical value C: 89.10%, H: 5.12%, N: 5.77 percent; found value C: 89.12%, H: 5.15%, N: 5.73 percent.
Example 6
This example prepared compound P6 with a two-step synthetic procedure:
the first step is reacted with the first step in example 1 to obtain an intermediate monobromide;
the second reaction was identical to the first reaction in example 1 except that di (P-tolyl) amine was used as the starting material to react with the intermediate monobromide synthesized in the first reaction in this example, to obtain compound P6.
Detection product MS (m/e): 683 elemental analysis (C)50H41N3): theoretical value C: 87.81%, H: 6.04%, N: 6.14 percent; found value C: 87.85%, H: 6.03%, N: 6.12 percent.
Example 7
This example prepared compound P7 with a two-step synthetic procedure:
the first step was the same as the first step in example 1 except that one of the starting p-iodophenyl-di (4-tolyl) amine was changed to N-phenyl-3-iodocarbazole to give an intermediate monobromide;
the second reaction was carried out in the same manner as in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to N-phenylcarbazole-3-boronic acid, and the monobromide synthesized in the first reaction was reacted to obtain compound P7.
Detection ofProduct MS (m/e): 699 elemental analysis (C)52H33N3): theoretical value C: 89.24%, H: 4.75%, N: 6.00 percent; found value C: 89.21%, H: 4.73%, N: 6.06 percent.
Example 8
This example prepared compound P8 with a two-step synthetic procedure:
the first step was the same as the first step in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to N- (4-iodophenyl) carbazole to give an intermediate monobromide;
the second reaction was carried out in the same manner as in example 1 except that 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (9-carbazolyl) phenylboronic acid, which was the starting material, and reacted with the monobromide synthesized in the first reaction in this example to obtain compound P8.
Detection product MS (m/e): 699 elemental analysis (C)52H33N3): theoretical value C: 89.24%, H: 4.75%, N: 6.00 percent; found value C: 89.25%, H: 4.71%, N: 6.04 percent.
Example 9
This example prepared compound P9 with a two-step synthetic procedure:
the first step was the same as the first step in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to N- (4-iodophenyl) carbazole to give an intermediate monobromide;
the second step is the same as the first step in example 1, except that carbazole is used as a raw material to react with the intermediate monobromide synthesized in the first step of this example, so as to obtain compound P9.
Detection product MS (m/e): 623 elemental analysis (C)46H29N3): theoretical value C: 88.58%, H: 4.69%, N: 6.74 percent; found value C: 88.55%, H: 4.67%, N: 6.78 percent.
Example 10
This example prepared compound P10 with a two-step synthetic procedure:
the first reaction step was the same as the first reaction step in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to 2-iododibenzothiophene to give an intermediate monobromide;
the second reaction was carried out in the same manner as in example 1 except that 4- (di (4-tolyl) amino) phenylboronic acid as a starting material was changed to dibenzothiophene-2-boronic acid, which was reacted with the monobromide synthesized in the first reaction in this example to obtain compound P10.
Detection product MS (m/e): 581, elemental analysis (C)40H23NS2): theoretical value C: 82.58%, H: 3.98%, N: 2.41%, S: 11.02 percent; found value C: 82.55%, H: 3.97%, N: 2.43%, S: 11.05 percent.
Example 11
This example prepared compound P11 with a two-step synthetic procedure:
the first reaction step was the same as the first reaction step in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to 4-iododibenzothiophene to give an intermediate monobromide;
the second reaction was carried out in the same manner as in example 1 except that 4- (di (4-tolyl) amino) phenylboronic acid as a starting material was changed to dibenzothiophene-4-boronic acid, which was reacted with the monobromide synthesized in the first reaction in this example to obtain compound P11.
Detection product MS (m/e): 581, elemental analysis (C)40H23NS2): theoretical value C: 82.58%, H: 3.98%, N: 2.41%, S: 11.02 percent; found value C: 82.53%, H: 3.95%, N: 2.45%, S: 11.07 percent.
Example 12
This example prepared compound P12 with a two-step synthetic procedure:
the first reaction was performed in the same manner as in example 1 except that p-iodophenyl-di (4-tolyl) amine, one of the starting materials, was changed to 2-iododibenzofuran to give an intermediate monobromide;
the second reaction was carried out in the same manner as in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to dibenzofuran-2-boronic acid, which was reacted with the monobromide synthesized in the first reaction in example to obtain compound P12.
Detection product MS (m/e): 549 elemental analysis (C)40H23NO2): theoretical value C: 87.41%, H: 4.22%, N: 2.55%, O: 5.82 percent; found value C: 87.43%, H: 4.25%, N: 2.52%, O: 5.80 percent.
Example 13
This example prepared compound P13 with a two-step synthetic procedure:
the synthesis steps are divided into two steps, the first step is the same as the first step in example 1, except that one of the raw materials, p-iodophenyl-di (4-tolyl) amine, is changed into 4-iododibenzofuran to obtain an intermediate monobromide;
the second reaction was carried out in the same manner as in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to dibenzofuran-4-boronic acid, which was reacted with the monobromide synthesized in the first reaction in this example to obtain compound P13.
Detection product MS (m/e): 549 elemental analysis (C)40H23NO2): theoretical value C: 87.41%, H: 4.22%, N: 2.55%, O: 5.82 percent; found value C: 87.42%, H: 4.21%, N: 2.54%, O: 5.83 percent.
Example 14
The compound P14 prepared in this example was synthesized in the same manner as the second reaction in example 1 except that the intermediate (B1)2, 6-dibromonaphtho [2,3-B ] benzofuran in preparation example 2 was used as a starting material to obtain the compound P14.
Detection product MS (m/e): 760 elemental analysis (C)56H44N2O): theoretical value C: 88.39%, H: 5.83%, N: 3.68%, O: 2.10 percent; found value C: 88.35%, H: 5.86%, N: 3.65%, O: 2.14 percent.
Example 15
This example prepared compound P15 by following the same procedure as the second reaction in example 1 except that 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (N-phenyl-N- (1-naphthyl) amino) phenylboronic acid, which was reacted with intermediate (B1)2, 6-dibromonaphtho [2,3-B ] benzofuran in preparation example 2 to obtain compound P15.
Detection product MS (m/e): 804, elemental analysis (C)60H40N2O): theoretical value C: 89.52%, H: 5.01%, N: 3.48%, O: 1.99 percent; found value C: 89.56%, H: 5.03%, N: 3.44%, O: 1.97 percent.
Example 16
This example prepared compound P16 by following the same synthetic procedure as the second reaction of example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (N-phenyl-N- (2-naphthyl) amino) phenylboronic acid, which was reacted with the intermediate (B1)2, 6-dibromonaphtho [2,3-B ] benzofuran of preparation 2, to obtain compound P16.
Detection product MS (m/e): 804, elemental analysis (C)60H40N2O): theoretical value C: 89.52%, H: 5.01%, N: 3.48%, O: 1.99 percent; found value C: 89.54%, H: 5.04%, N: 3.46%, O: 1.96 percent.
Example 17
This example prepared compound P17 by following the same synthetic procedure as the second reaction in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (carbazol-9-yl) phenylboronic acid, which was reacted with the intermediate (B1)2, 6-dibromonaphtho [2,3-B ] benzofuran in preparation 2 to obtain compound P17.
Detection product MS (m/e): 700, elemental analysis (C)52H32N2O): theoretical value C: 89.12%, H: 4.60%, N: 4.00%, O: 2.28 percent; found value C: 89.10%, H: 4.64%, N: 4.02%, O: 2.24 percent.
Example 18
This example prepared compound P18, which was synthesized in the same manner as the second reaction in example 1, except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to 9-phenylcarbazole-3-boronic acid, which was reacted with intermediate (B1)2, 6-dibromonaphtho [2,3-B ] benzofuran in preparation example 2, to obtain compound P18.
Detection product MS (m/e): 700, elemental analysis (C)52H32N2O): theoretical value C: 89.12%, H: 4.60%, N: 4.00%, O: 2.28 percent; found value C: 89.11%, H: 4.61%, N: 4.03%, O: 2.25 percent.
Example 19
In this example, compound P19 was prepared by the same procedure as the first reaction in example 1, except that 1-naphthylphenylamine was used as the starting material to react with the intermediate (B2)2, 9-dibromonaphtho [2,3-B ] benzofuran of preparation 2, to give compound P19.
Detection product MS (m/e): 652 elemental analysis (C)48H32N2O): theoretical value C: 88.32%, H: 4.94%, N: 4.29%, O: 2.45 percent; found value C: 88.34%, H: 4.96%, N: 4.27%, O: 2.43 percent.
Example 20
In this example, compound P20 was prepared by the same procedure as the first reaction in example 1, except that 2-naphthylphenylamine was used as the starting material to react with the intermediate (B2)2, 9-dibromonaphtho [2,3-B ] benzofuran of preparation 2, to give compound P20.
Product MS (m/e): 652 elemental analysis (C)48H32N2O): theoretical value C: 88.32%, H: 4.94%, N: 4.29%, O: 2.45 percent; found value C: 88.31%, H: 4.98%, N: 4.26%, O: 2.45 percent.
Example 21
In this example, a compound P21 was prepared, and the synthesis procedure was the same as the second reaction in example 1, except that 4- (carbazol-9-yl) phenylboronic acid was used as a starting material to react with the intermediate (B2)2, 9-dibromonaphtho [2,3-B ] benzofuran prepared in preparation example 2, to obtain a compound P21.
Detection product MS (m/e): 700, elemental analysis (C)52H32N2O): theoretical value C: 89.12%, H: 4.60%, N: 4.00%, O: 2.28 percent; found value C: 89.14%, H: 4.63%, N: 4.02%, O: 2.21 percent.
Example 22
In this example, a compound P22 was prepared, and the synthesis procedure was the same as the second reaction in example 1, except that N-phenylcarbazole-3-boronic acid was used as a starting material to react with the intermediate (B2)2, 9-dibromonaphtho [2,3-B ] benzofuran prepared in preparation example 2, to obtain a compound P22.
Detection product MS (m/e): 700, elemental analysis (C)52H32N2O): theoretical value C: 89.12%, H: 4.60%, N: 4.00%, O: 2.28 percent; found value C: 89.11%, H: 4.62%, N: 4.04%, O: 2.23 percent.
Example 23
In this example, a compound P23 was prepared, and the synthesis procedure was the same as the first reaction in example 1, except that 3-benzenecarbazole was used as a starting material to react with the intermediate (B2)2, 9-dibromonaphtho [2,3-B ] benzofuran prepared in preparation example 2, thereby obtaining a compound P23.
Detection product MS (m/e): 700, elemental analysis (C)52H32N2O): theoretical value C: 89.12%, H: 4.60%, N: 4.00%, O: 2.28 percent; found value C: 89.14%, H: 4.63%, N: 4.02%, O: 2.21 percent.
Example 24
This example prepared compound P24, which was synthesized in the same manner as the second reaction in example 1, except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to dibenzothiophene-2-boronic acid, which was reacted with intermediate (B1)2, 6-dibromonaphtho [2,3-B ] benzofuran prepared in preparation 2 to obtain compound P24.
Product MS (m/e): 582, elemental analysis (C)40H22OS2): theoretical value C: 82.44%, H: 3.81%, O: 2.75%, S: 11.01 percent; found value C: 82.45%, H: 3.83%, O: 2.70%, S：11.02％。
Example 25
This example prepared compound P25, which was synthesized in the same manner as the second reaction in example 1, except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to dibenzothiophene-2-boronic acid, which was reacted with intermediate (B2)2, 9-dibromonaphtho [2,3-B ] benzofuran prepared in preparation 2 to obtain compound P25.
Detection product MS (m/e): 582, elemental analysis (C)40H22OS2): theoretical value C: 82.44%, H: 3.81%, O: 2.75%, S: 11.01 percent; found value C: 82.41%, H: 3.84%, O: 2.72%, S: 11.03 percent.
Example 26
This example prepared compound P26, the synthetic procedure being the same as the second reaction in example 1 except that the reactants of the first reaction in example 1 were changed to the intermediate (C1)2, 6-dibromobenzo [ b ] naphtho [2,3-d ] thiophene prepared in preparation 3 to give compound P26.
Product MS (m/e): 776 elemental analysis (C)56H44N2S): theoretical value C: 86.56%, H: 5.71%, O: 3.61%, S: 4.13 percent; found value C: 86.52%, H: 5.73%, O: 3.64%, S: 4.11 percent.
Example 27
This example prepared compound P27 by following the same synthetic procedure as the second reaction in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (N-phenyl-N- (1-naphthyl)) phenylboronic acid, and the intermediate (C1)2, 6-dibromobenzo [ b ] naphtho [2,3-d ] thiophene prepared in preparation 3 gave compound P27.
Product MS (m/e): 820, elemental analysis (C)60H40N2S): theoretical value C: 87.77%, H: 4.91%, N: 3.41%, S: 3.91 percent; found value C: 87.72%, H: 4.93%, N: 3.42%, S: 3.93 percent.
Example 28
This example prepared compound P28, which was synthesized in the same manner as the second reaction in example 1, except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to N-phenylcarbazole-3-boronic acid, and reacted with the intermediate (C1)2, 6-dibromobenzo [ b ] naphtho [2,3-d ] thiophene prepared in preparation 3, to obtain compound P28.
Product MS (m/e): 716 elemental analysis (C)52H32N2S): theoretical value C: 87.12%, H: 4.50%, N: 3.91%, S: 4.47%; found value C: 87.11%, H: 4.52%, N: 3.94%, S: 4.43 percent.
Example 29
This example prepared compound P29 and the synthetic procedure was the same as the second reaction in example 1 except that 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (carbazol-9-yl) phenylboronic acid, which was reacted with (C1)2, 6-dibromobenzo [ b ] naphtho [2,3-d ] thiophene, which was the intermediate prepared in preparation 3, to obtain compound P29.
Product MS (m/e): 716 elemental analysis (C)52H32N2S): theoretical value C: 87.12%, H: 4.50%, N: 3.91%, S: 4.47%; found value C: 87.14%, H: 4.53%, N: 3.91%, S: 4.42 percent.
Example 30
This example prepared compound P30 and the synthetic procedure was the same as the second reaction in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (carbazol-9-yl) phenylboronic acid, and the intermediate (C2)2, 9-dibromobenzo [ b ] naphtho [2,3-d ] thiophene prepared in preparation 3 gave compound P30.
Product MS (m/e): 716 elemental analysis (C)52H32N2S): theoretical value C: 87.12%, H: 4.50%, N: 3.91%, S: 4.47%; found value C: 87.14%, H: 4.53%, N: 3.91%, S: 4.42 percent.
Example 31
This example prepared compound P31, which was synthesized in the same manner as the second reaction in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to N-phenylcarbazole-3-boronic acid, and reacted with the intermediate (C2)2, 9-dibromobenzo [ b ] naphtho [2,3-d ] thiophene prepared in preparation example 3 to obtain compound P31.
Detection product MS (m/e): 716 elemental analysis (C)52H32N2S): theoretical value C: 87.12%, H: 4.50%, N: 3.91%, S: 4.47%; found value C: 87.13%, H: 4.52%, N: 3.92%, S: 4.43 percent.
Example 32
This example prepared compound P32, which was synthesized in the same manner as the first reaction step in example 1 except that P-iodophenyl-di (4-tolyl) amine was changed to 1-naphthylphenylamine, and reacted with (C2)2, 9-dibromobenzo [ b ] naphtho [2,3-d ] thiophene, which was an intermediate prepared in preparation example 3, to obtain compound P32.
Detection product MS (m/e): 668 elemental analysis (C)48H32N2S): theoretical value C: 86.20%, H: 4.82%, N: 4.19%, S: 4.79 percent; found value C: 86.23%, H: 4.84%, N: 4.16%, S: 4.77 percent.
Example 33
This example prepared compound P33, which was synthesized by the same procedure as the first reaction in example 1, except that P-iodophenyl-di (4-tolyl) amine was changed to 2-naphthylphenylamine, and reacted with (C2)2, 9-dibromobenzo [ b ] naphtho [2,3-d ] thiophene, which was an intermediate prepared in preparation example 3, to obtain compound P33.
Detection product MS (m/e): 668 elemental analysis (C)48H32N2S): theoretical value C: 86.20%, H: 4.82%, N: 4.19%, S: 4.79 percent; found value C: 86.22%, H: 4.85%, N: 4.18%, S: 4.75 percent.
Example 34
This example prepared compound P34, which was synthesized in the same manner as the second reaction in example 1, except that the reactants in example 1 were changed to intermediate (C2)2, 9-dibromobenzo [ b ] naphtho [2,3-d ] thiophene, which was prepared in preparation 3, to obtain compound P34.
Product MS (m/e): 776 elemental analysis (C)56H44N2S): theoretical value C: 86.56%, H: 5.71%, N: 3.61%, S: 4.13 percent; found value C: 86.53%, H: 5.74%, N: 3.62%, S: 4.11.
example 35
This example prepared compound P35, which was synthesized in the same manner as the first reaction step in example 1 except that P-iodophenyl-di (4-tolyl) amine was changed to 3-phenylcarbazole, and reacted with (C2)2, 9-dibromobenzo [ b ] naphtho [2,3-d ] thiophene, which was an intermediate prepared in preparation example 3, to obtain compound P35.
Detection product MS (m/e): 716 elemental analysis (C)52H32N2S): theoretical value C: 87.12%, H: 4.50%, N: 3.91%, S: 4.47%; found value C: 87.15%, H: 4.52%, N: 3.90%, S: 4.43 percent.
Example 36
This example was prepared as compound P36 by the same synthetic procedure as the first reaction step in example 1 except that P-iodophenyl-di (4-tolyl) amine was changed to 4- (1-naphthyl) iodobenzene to give compound P36.
Product MS (m/e): 621 elemental analysis (C)48H31N): theoretical value C: 92.72%, H: 5.03%, N: 2.25 percent; found value C: 92.70%, H: 5.04%, N: 2.26 percent.
Example 37
This example prepared compound P37 by the same synthetic procedure as the first reaction step in example 1 except that P-iodophenyl-di (4-tolyl) amine was changed to 9-iodophenanthrene to give compound P37.
Product MS (m/e): 569 elemental analysis (C)44H27N): theoretical value C: 92.76%, H: 4.78%, N: 2.46 percent; found value C: 92.78%, H: 4.74%, N: 2.48 percent.
Example 38
This example prepared compound P38, which was synthesized in the same manner as the second reaction in example 1, except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to pyrene-1-boronic acid, which was reacted with intermediate (C1)2, 6-dibromobenzo [ b ] naphtho [2,3-d ] thiophene prepared in preparation example 3, to obtain compound P38.
Product MS (m/e): 634, elemental analysis (C)48H26S): theoretical value C: 90.82%, H: 4.13%, S: 5.05 percent; found value C: 90.84%, H: 4.10%, S: 5.06 percent.
Example 39
This example prepared compound P39 by following the same synthetic procedure as the second reaction in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to 4- (9-phenylanthracen-10-yl) phenylboronic acid, which was reacted with the intermediate (B2)2, 9-dibromonaphtho [2,3-, B ] benzofuran prepared in preparation 2 to obtain compound P39.
Product MS (m/e): 874 elemental analysis (C)68H42O): theoretical value C: 93.33%, H: 4.84%, O: 1.83 percent; found value C: 93.35%, H: 4.81%, O: 1.84 percent.
Example 40
This example prepared compound P40 by following the same synthetic procedure as the second reaction in example 1 except that the starting 4- (di (4-tolyl) amino) phenylboronic acid was changed to 9-phenylanthracene-10-boronic acid, and the intermediate (C2)2, 9-dibromobenzo [ b ] naphtho [2,3-d ] thiophene prepared in preparation 3 gave compound P40.
Product MS (m/e): 738 elemental analysis (C)56H34S): theoretical value C: 91.02%, H: 4.64%, S: 4.34 percent; found value C: 91.05%, H: 4.62%, S: 4.33 percent.
The following are examples of the use of the compounds of the present invention, and several materials used in the present invention have the following specific structures:
EXAMPLE 41
This example illustrates the compound of the present invention as an example of a hole injection layer.
The structure of the organic electroluminescent device used in this embodiment is: substrate/anode/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/cathode.
The substrate may be a glass substrate, plastic or stainless steel, and in this embodiment, a glass substrate is used.
The anode layer may be a metal, alloy, conductive oxide or mixture thereof having a large work function (greater than 4.0eV), such as ITO (indium tin oxide), IZO (indium zinc oxide) or ZnO. In this example, ITO was used in a thickness of 180 nm.
The hole-injecting layer, the hole-injecting material used in this example, was a compound of the present invention (specific compounds are shown in the following table). For better device performance, these materials may also be doped with some oxidizing agents to provide hole injection, such as F4-TCNQ, at a weight ratio of 100:4, and a total thickness of 150 nm.
The hole transport layer may be an aromatic amine chemical such as N, N '-di- (1-naphthyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine (NPB). NPB was used in this example with a thickness of 20 nm.
The light-emitting layer can be formed by host doping with a luminescent dye, the luminescent dye can be a dye emitting any color of red, green, blue, yellow, orange, white, or the like, AND in this embodiment, DSA-ph (AND doping DSA-ph) is used, ADN (9, 10-di (2-naphthyl) anthracene) is used as a host material, DSA-ph (4-di- (4-N, N-diphenyl) amino-styrylbenzene) is used as a sky blue luminescent dye, the doping ratio is 5% (weight ratio), that is, the ratio of ADN to DSA-ph is 100:5, AND the thickness of the light-emitting layer is 30 nm.
The electron injection layer and the cathode can be a metal, alloy, conductive oxide or mixture thereof with a low work function (less than 4eV), such as Mg and Ag doped as the cathode layer, or LiF/Al, or Li2O/Al, or LiQ/Al. The electron injection layer and the cathode layer in this example were LiF and Al with thicknesses of 0.5nm and 150nm, respectively, and the Al layer was platedCovering the LiF layer.
The method for producing the organic electroluminescent device in this example was as follows:
firstly, cleaning a glass substrate by using a boiling detergent ultrasonic and deionized water ultrasonic method, and drying the glass substrate under an infrared lamp;
secondly, sputtering a layer of ITO on the glass as an anode, wherein the thickness of the film is 180 nm;
③ placing the glass substrate with anode ITO in a vacuum chamber, and vacuumizing to 1 × 10-5Pa, evaporating 1-TNATA and F4-TCNQ doped layers on the anode layer film as a hole injection layer at a speed of 0.1nm/s and a thickness of 150nm as a comparative example; F4-TCNQ is respectively doped into the compounds 1, 4, 6, 8, 10, 16, 26 and 33 in the invention by evaporation to be used as hole injection layers in the embodiment;
fourthly, continuously evaporating an NPB film as a hole transport layer at the speed of 0.1nm/s and the thickness of the evaporated film is 20 nm;
carrying out evaporation doping on the luminescent layer by adopting a double-source co-evaporation method, wherein the main material of the luminescent layer is ADN, the luminescent dye is DSA-ph, the doping concentration is 5 wt%, and the thickness of the evaporation film is 30 nm;
⑥ depositing an electron transport layer Alq on the light-emitting layer3The evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 20 nm;
and finally, sequentially evaporating a LiF layer and an Al layer on the luminous layer to serve as an electron injection layer and a cathode layer of the device, wherein the evaporation rate of the LiF layer is 0.01-0.02 nm/s, the thickness of the LiF layer is 0.5nm, the evaporation rate of the Al layer is 1nm/s, and the thickness of the Al layer is 150 nm.
The device structure of the comparative example is the same as that of the present example, differing only in the material used for the hole injection layer, and the hole injection layer 3 in the comparative example may be star-shaped polyamine, polyaniline, or the like, such as m-MTDATA,2-TNATA, 1-TNATA. Device comparative example 1 used 1-TNATA, while device comparative example 2 used 1-TNATA doped 2,3,5, 6-tetrafluorotetracyanoquinodimethane (F4-TCNQ) in a weight ratio of 100:4 and a total thickness of 150 nm.
The results of the performance tests on the devices prepared in this example and comparative examples 1 and 2 of the devices are shown in table 1 below.
Table 1 organic electroluminescent device properties in example 41
From the above examples, it can be seen that the use of the compounds 1, 4, 6, 8, 10, 16, 26, and 33 of the present invention as the hole injection layer of the device can achieve higher efficiency and lower voltage than the hole injection layer materials commonly used in the industry (1-TNATA or 1-TNATA doped with 2,3,5, 6-tetrafluorotetracyanoquinodimethane). When the compound of the present invention is used as a hole injection layer, F4-TCNQ may be undoped, but F4-TCNQ may be doped to achieve a better effect. Example 42
This example illustrates the compound of the present invention as an example of a hole transport layer. The device structure of the embodiment is as follows: ITO/1-TNATA: F4-TCNQ (150nm,4 wt%)/Compound of the present invention (20 nm)/AND: DSA-ph (30nm, 5 wt%)/Alq 3(20nm)/LiF (0.5nm)/Al (150 nm). The preparation method is as in example 41, except that the hole injection layer in the device structure is doped with F4-TCNQ by 1-TNATA, and the hole transport layer is doped with the compounds 2,3, 15, 19, 24, 27 and 34 of the present invention, and the rest are the same.
The results of the performance tests on the devices prepared in this example and the comparative examples of the devices are shown in table 2 below.
Table 2 organic electroluminescent device properties in example 42
As can be seen from the above examples, the organic electroluminescent device using the compound 2,3, 15, 19, 24, 27, 34 of the present invention for the hole transport layer achieves higher efficiency and lower voltage compared to the device prepared using NPB, which is commonly used in the art.
Example 43
In this example, the compound of the present invention is exemplified as a host material. The device structure and fabrication method of this example are different from those of example 42 in that NPB is used for the hole transport layer in the device structure, and the host materials of the light-emitting layer are the same as those of compounds 36, 38 and 40 in the present invention.
The results of the performance tests on the devices prepared in this example and the comparative examples of the devices are shown in Table 3 below.
Table 3 organic electroluminescent device properties in example 43
As can be seen from the above examples, using the compounds 36, 38, 40 of the present invention as host materials for the devices, higher efficiencies and lower voltages can be achieved than for the comparative examples.
The results show that the novel organic material is used for the organic electroluminescent device, can effectively reduce the take-off and landing voltage and improve the current efficiency, and is a hole injection material and a luminescent main body material with good performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (5)

1. A benzonaphtho five-membered heterocycle derivative, wherein said compound is selected from the following formulae:
2. use of a benzonaphtho five-membered heterocycle derivative according to claim 1 for the preparation of an organic electroluminescent device.
3. Use according to claim 2, wherein the benzonaphtho five-membered heterocycle derivative is used as a hole injection layer material, a hole transport layer material or a light emitting host material.
4. An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate;
the organic light-emitting functional layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer and an electron transport layer;
the method is characterized in that:
the hole injection layer and/or the hole transport layer comprise the benzonaphtho five-membered heterocyclic derivative material of claim 1.
5. An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate;
the organic light-emitting functional layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer and an electron transport layer;
the method is characterized in that:
the host material of the organic light emitting layer includes the benzonaphtho five-membered heterocyclic derivative according to claim 1.
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