CN102372693A - Carbazole compound and application thereof - Google Patents

Carbazole compound and application thereof Download PDF

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CN102372693A
CN102372693A CN201010258632XA CN201010258632A CN102372693A CN 102372693 A CN102372693 A CN 102372693A CN 201010258632X A CN201010258632X A CN 201010258632XA CN 201010258632 A CN201010258632 A CN 201010258632A CN 102372693 A CN102372693 A CN 102372693A
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CN102372693B (en
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邱勇
孙绪霞
李银奎
乔娟
段炼
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Abstract

The present invention provides a novel compound. The compound has characteristics of symmetric structure, simple preparation process, high stability and high carrier mobility, and can be used for an electronic transmission layer of an electroluminescent component. With the compound, the drive voltage of the device adopting the compound can be significantly reduced, and the current efficiency can be improved. The structural general formula of the compound is as follow, wherein the parent nucleus is selected from the 2,7 or 3,6-dipyridyl substituted N substituted carbazole, a terminal group Ar is selected from a phenyl group, a biphenyl group or a naphthyl group, R comprises a alkyl group with carbon atoms of 1-6 or a phenyl group.

Description

A kind of carbazole compound and application thereof
Technical field
The present invention relates to a kind of novel organic materials, and the application in the ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
The electron transport material that is used for organic electroluminescent research should possess following three specific; 1 has big electron affinity and high electronic mobility, thus the transmission that helps injecting electronics; 2 good stabilities can form unified fine and close film; 3 have high excited level, can avoid the ability transmission of excited state effectively, make exciton recombination zone form (electroluminescent organic material and device introduction, work such as Huang Chunhui, press of Fudan University 2005) in luminescent layer rather than in the electron transfer layer.
As a rule, electron transport material all has the plane aromatics of big conjugated structure, and they have the ability of accepting electronics preferably mostly, under certain forward bias, can effectively transmit electronics again simultaneously; Known well behaved electron transport material is also few at present, and one of them reason is to have electron capture, and the available electron transport material mainly contains oxine aluminium compounds at present; The furodiazole compound, quinoxaline compound, the polymkeric substance of nitrile group-containing; (Chem.Mater.2004,16,4556-4573 such as other nitrogen-containing heterocycle compound; J Mater.Chem.2005,15,94-106).
Summary of the invention
The objective of the invention is to propose a kind of novel cpd, this compounds can be used for the ORGANIC ELECTROLUMINESCENCE DISPLAYS field.
The rigid planar structure of carbazoles verivate can provide high electronics mobile, and from the cognation aspect of the structure and properties of material, the group of introducing electron deficiency usually can better improve the electron-transporting of material.The pyridyl group is typical drawing electron group, and it is linked to each other with nitrogen substituted carbazole base, has increased conjugated system on the one hand, has improved the charge mobility of compound, can improve the stability of this material so that electric charge more disperses on the other hand.Thereby the introducing of phenyl, xenyl and naphthyl both can increase the molecular weight (substituent variation also can change molecular weight on the nitrogen) of compound improve its second-order transition temperature; Can reduce the planarity of molecule again, the distortion that material molecule is formed to a certain degree on space multistory is more conducive to vacuum film formation.This material has stability preferably in air, can be used in the organic electroluminescence device.
The present invention develops a kind of novel organic materials, and preparation is simple and this material has good thermostability, and high electronic mobility can be used as electron transfer layer in organic electroluminescence device.
The present invention discloses one type of novel cpd, and its general structure is as follows:
Figure BSA00000237688200021
Wherein Ar is selected from phenyl group, xenyl group or naphthyl group.
Among the following formula I, the structural formula that is substituted of N substituted carbazole base is selected from Formula Il or III:
Figure BSA00000237688200022
Wherein R can be methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, n-pentyl, n-hexyl or phenyl.
The structural formula of Ar among the following formula I is selected from following formula I V, V, VI, VII or VIII:
Figure BSA00000237688200023
In order more to clearly demonstrate content of the present invention, the structure of the compound that following mask body narration the present invention relates to (R is an example with methyl or phenyl, and other mode of connection is together):
Figure BSA00000237688200024
Figure BSA00000237688200031
Figure BSA00000237688200041
Figure BSA00000237688200051
Figure BSA00000237688200061
Figure BSA00000237688200071
Figure BSA00000237688200081
Figure BSA00000237688200091
Figure BSA00000237688200101
Figure BSA00000237688200111
Figure BSA00000237688200121
Figure BSA00000237688200131
Figure BSA00000237688200141
Figure BSA00000237688200151
Organic materials of the present invention is used as electron transfer layer in organic electroluminescence device.
The present invention also proposes a kind of organic electroluminescence device, comprises above-mentioned general formula compound in its organic function layer, and this compounds is as the electron transport material in the organic function layer.
Organic materials preparation technology of the present invention is simple, has advantages of higher stability and high electronic mobility, in display of organic electroluminescence, can be used as electron transfer layer.
Embodiment
Among the present invention used basic chemical industry raw materials such as haloperidid, phenylo boric acid, biphenyl boric acid, naphthalene boronic acids and dibrominated nitrogen substituted carbazole all at home Chemicals market bought, various aryl-pyridine boric acid all can adopt common organic method synthetic.
Embodiment
Compound process in the present invention mainly divided for three steps: (1) is normally through Suzuki linked reaction (Journal of Organometallic Chenistryl999; 576; 147-168) aryl boric acid and haloperidid are linked up; Generate single halogenated aryl-pyridine (2) with resulting halides in 1 become aryl-pyridine boric acid (Organic Syntheses2004, Vol.10, p.80; Vol.79, p.176 (2002) .); (3) boric acid of gained in 2 and the nitrogen substituting group carbazole coupling of two kinds of dibrominated are got up, get final product target molecule.Above-mentioned steps is concrete to be set forth as follows:
Embodiment 1 compound 1-1's is synthetic
(1) the first step
Figure BSA00000237688200161
23.5g 2,6-dibromo pyridine, 12.3g phenylo boric acid and 0.50g Pd (PPh 3) 4Be dissolved in the 300mL toluene, 22.0g salt of wormwood is dissolved in the 100mL water adds in the above reaction solution, add 200mL ethanol again, it is yellow that reaction solution is, and behind 50 ℃ of reaction 1.5h, adds the 3.0g phenylo boric acid, TLC monitoring reaction process.About 0.5h afterreaction finishes, with three anhydrous Na of organic layer washing 2SO 4Carry out column chromatography after the drying, eluent is a sherwood oil: dichloro=20: 1 (V 1/ V 2) must near-white solid 14.75g.MS (m/e): 234, productive rate 63.1%.
(2) second steps
Figure BSA00000237688200162
23.4g 2-bromo-6-phenyl-pyridine and 24.6 gram triisopropyl borate esters are dissolved in 200mL exsiccant THF, are cooled to-50 ℃ of Dropwise 5 0mL butyllithiums (2.5M), controlled temperature is between-40 ℃ to-50 ℃.Finish between-40 ℃ to-50 ℃ and be incubated 20 minutes, remove cryostat, be warming up to-20 ℃ naturally, slowly add the solution that 20 milliliters of concentrated hydrochloric acids and 80 ml waters are made into; Naturally rise to room temperature again, separatory, water layer transfers pH to neutral with 10% sodium carbonate solution, and it is saturated to add 40 gram sodium-chlor again; Extract with ETHYLE ACETATE 40mL * 3, merge organic layer, with dried over mgso 30 minutes, the elimination siccative; Be evaporated to driedly, obtain white solid 15.1 gram, MS (m/e): 199, productive rate 75.8%.
(3) the 3rd steps
Figure BSA00000237688200171
8.45g, 2,7-two bromo-N-methyl carbazole 12.0g 6-phenylpyridine-2 phenylo boric acids are dissolved in 400mL YLENE and the 300mL alcoholic acid mixing solutions, add 13.8g salt of wormwood and 0.5g Pd (PPh 3) 4, behind the backflow 2h, add 2.00g 6-phenylpyridine-2 boric acid.The TLC detection reaction finishes, and cooling has been left standstill a large amount of solids and separated out, with its washing three times.Boil twice with THF again.Get white powder 4.50g at last, be compound 1-1.MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.10%, H:5.12%, N:8.78%., productive rate 33.2%.
The preparation route in two steps is all with the preparation of compound 1-1 among the embodiment 1 behind all target molecules; Difference only is in the first step position of halogen in the aryl pyridyl; This can select different reaction substrates according to concrete target molecule; What participate in three-step reaction among the embodiment 2-30 is 3,6-dibrominated n-formyl sarcolysine base carbazole, and existing concrete the elaboration as follows:
Embodiment 2 compound 1-2's is synthetic
Selecting 2-chloro-4-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-2.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.05%, H:5.36%, N:8.59%.Overall yield is 31.6%.
Embodiment 3 compound 1-3's is synthetic
Select 3 for use, 5-dibromo pyridine and phenylo boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-3.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.36%, H:5.26%, N:8.38%.Overall yield is 37.5%.
Embodiment 4 compound 1-4's is synthetic
Selecting 2-iodo-4-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-4.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.17%, H:5.06%, N:8.77%.Overall yield is 38.3%.
Embodiment 5 compound 1-5's is synthetic
Select 2 for use, 6-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-5.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.38%, H:5.31%, N:6.31%.Overall yield 42.5%.
Embodiment 6 compound 1-6's is synthetic
Selecting 2-chloro-4-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-6.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.18%, H:5.34%, N:6.48%.Overall yield 41.8%.
Embodiment 7 compound 1-7's is synthetic
Select 3 for use, 5-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-7.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.32%, H:5.12%, N:6.56%.Overall yield 35.3%.
Embodiment 8 compound 1-8's is synthetic
Selecting 2-iodo-4-bromopyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-8.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.37%, H:5.02%, N:6.61%.Overall yield 42.6%.
Embodiment 9 compound 1-9's is synthetic
Select 2 for use, 6-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-9.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.36%, H:5.32%, N:6.41%.Overall yield 32.4%.
Embodiment 10 compound 1-10's is synthetic
Selecting 2-chloro-4-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-10.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.28%, H:5.04%, N:6.68%.Overall yield 41.3%.
Embodiment 11 compound 1-11's is synthetic
Select 3 for use, 5-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-11.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.32%, H:5.12%, N:6.56%.Overall yield 35.3%.
Embodiment 12 compound 1-12's is synthetic
Selecting 2-iodo-4-bromopyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-12.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.39%, H:5.12%, N:6.49%.Overall yield 42.7%.
Embodiment 13 compound 1-13's is synthetic
Select 2 for use, 6-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-13.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.65%, H:5.02%, N:7.33%.Overall yield 34.5%.
Embodiment 14 compound 1-14's is synthetic
Selecting 2-chloro-4-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-14.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.65%, H:5.02%, N:7.33%.Overall yield 43.8%.
Embodiment 15 compound 1-15's is synthetic
Select 3 for use, 5-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-15.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.69%, H:5.01%, N:7.30%.Overall yield 34.8%.Embodiment 16 compound 1-16's is synthetic
Selecting 2-iodo-4-bromopyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-16.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.96%, H:4.73%, N:7.31%.Overall yield 41.2%.
Embodiment 17 compound 1-17's is synthetic
Select 2 for use, 6-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-17.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.81%, H:5.03%, N:7.16%.Overall yield 36.7%.
Embodiment 18 compound 1-18's is synthetic
Selecting 2-chloro-4-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-18.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.62%, H:5.04%, N:7.34%.Overall yield 34.5%.44.6％。
Embodiment 19 compound 1-19's is synthetic
Select 3 for use, 5-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-19.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.99%, H:4.82%, N:7.19%.Overall yield 33.7%.
Embodiment 20 compound 1-20's is synthetic
Selecting 2-iodo-4-bromopyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-20.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.74%, H:4.83%, N:7.43%.Overall yield 42.5%.
Embodiment 21 compound 1-21's is synthetic
Selecting 2-bromo-5-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-21.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.16%, H:5.38%, N:8.46%.Overall yield is 36.3%.
Embodiment 22 compound 1-22's is synthetic
Selecting 2-iodo-5-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-22.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.32%, H:5.31%, N:8.37%.Overall yield is 43.5%.
Embodiment 23 compound 1-23's is synthetic
Selecting 2-chloro-5-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-23.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.36%, H:5.32%, N:6.32%.Overall yield 40.6%.
Embodiment 24 compound 1-24's is synthetic
To select 2-iodo-5-bromopyridine and 3-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-24.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.19%, H:5.32%, N:6.49%.Overall yield 42.1%.
Embodiment 25 compound 1-25's is synthetic
Selecting 2-chloro-5-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-25.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.31%, H:5.38%, N:6.31%.Overall yield 40.8%.
Embodiment 26 compound 1-26's is synthetic
To select 2-iodo-5-bromopyridine and 4-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-26.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.08%, H:5.37%, N:6.55%.Overall yield 42.6%.
Embodiment 27 compound 1-27's is synthetic
Selecting 2-chloro-5-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-27.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.94%, H:4.81%, N:7.25%.Overall yield 41.2%.
Embodiment 28 compound 1-28's is synthetic
To select 2-iodo-5-bromopyridine and 1-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-28.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.71%, H:4.93%, N:7.36%.Overall yield 41.8%.
Embodiment 29 compound 1-29's is synthetic
Selecting 2-chloro-5-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-29.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.98%, H:4.90%, N:7.12%.Overall yield 40.9%.
Embodiment 30 compound 1-30's is synthetic
To select 2-iodo-5-bromopyridine and 2-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-30.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.76%, H:4.85%, N:7.39%.Overall yield 41.3%.Embodiment 31-60, reaction substrate was 2 during reaction went on foot with embodiment 1, the three, 7-dibrominated n-formyl sarcolysine base carbazole, existing concrete the elaboration as follows:
Embodiment 31 compound 1-31's is synthetic
Select 2 for use, 6-dibromo pyridine and phenylo boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-31.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.35%, H:5.16%, N:8.49%.Overall yield is 33.6%.
Embodiment 32 compound 1-32's is synthetic
Selecting 2-chloro-4-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-32.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.07%, H:5.38%, N:8.55%.Overall yield is 39.4%.
Embodiment 33 compound 1-33's is synthetic
Select 3 for use, 5-dibromo pyridine and phenylo boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-33.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.32%, H:5.27%, N:841%.Overall yield is 32.8%.
Embodiment 34 compound 1-34's is synthetic
Selecting 2-iodo-4-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-34.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.14%, H:5.26%, N:8.60%.Overall yield is 38.7%.
Embodiment 35 compound 1-35's is synthetic
Select 2 for use, 6-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-35.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.36%, H:5.31%, N:6.33%.Overall yield 32.7%.
Embodiment 36 compound 1-36's is synthetic
Selecting 2-chloro-4-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-36.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.12%, H:5.24%, N:6.64%.Overall yield 41.5%.
Embodiment 37 compound 1-37's is synthetic
Select 3 for use, 5-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-37.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.38%, H:5.11%, N:6.51%.Overall yield 35.3%.
Embodiment 38 compound 1-38's is synthetic
Selecting 2-iodo-4-bromopyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-38.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.35%, H:5.22%, N:6.43%.Overall yield 41.7%.
Embodiment 39 compound 1-39's is synthetic
Select 2 for use, 6-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-39.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.36%, H:5.12%, N:6.52%.Overall yield 32.6%.
Embodiment 40 compound 1-40's is synthetic
Selecting 2-chloro-4-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-40.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.38%, H:5.04%, N:6.58%.Overall yield 41.6%.
Embodiment 41 compound 1-41's is synthetic
Select 3 for use, 5-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-41.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.32%, H:5.12%, N:6.56%.Overall yield 35.3%.
Embodiment 42 compound 1-42's is synthetic
Selecting 2-iodo-4-bromopyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-42.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.39%, H:5.21%, N:6.40%.Overall yield 42.7%.
Embodiment 43 compound 1-43's is synthetic
Select 2 for use, 6-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-43.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.67%, H:5.02%, N:7.31%.Overall yield 33.5%.
Embodiment 44 compound 1-44's is synthetic
Selecting 2-chloro-4-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-44.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.85%, H:5.02%, N:7.13%.Overall yield 34.5%.43.7％。
Embodiment 45 compound 1-45's is synthetic
Select 3 for use, 5-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-45.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.69%, H:5.12%, N:7.19%.Overall yield 34.3%.
Embodiment 46 compound 1-46's is synthetic
Selecting 2-iodo-4-bromopyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-46.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.95%, H:5.13%, N:6.92%.Overall yield 43.2%.
Embodiment 47 compound 1-47's is synthetic
Select 2 for use, 6-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-47.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.74%, H:5.08%, N:7.18%.Overall yield 34.8%.
Embodiment 48 compound 1-48's is synthetic
Selecting 2-chloro-4-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-48.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.66%, H:5.07%, N:7.27%.Overall yield 45.6%.
Embodiment 49 compound 1-49's is synthetic
Select 3 for use, 5-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-49.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:88.19%, H:4.82%, N:6.99%.Overall yield 34.3%.
Embodiment 50 compound 1-50's is synthetic
Selecting 2-iodo-4-bromopyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-50.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.81%, H:4.86%, N:7.33%.Overall yield 43.6%.
Embodiment 51 compound 1-51's is synthetic
Selecting 2-bromo-5-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-51.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.12%, H:5.32%, N:8.56%.Overall yield is 36.7%.
Embodiment 52 compound 1-52's is synthetic
Selecting 2-iodo-5-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-52.Product MS (m/e): 487, ultimate analysis (C 35H 25N 3): theoretical value C:86.21%, H:5.17%, N:8.62%; Measured value C:86.37%, H:5.21%, N:8.42%.Overall yield is 43.8%.
Embodiment 53 compound 1-53's is synthetic
Selecting 2-chloro-5-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-53.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.47%, H:5.22%, N:6.31%.Overall yield 41.6%.
Embodiment 54 compound 1-54's is synthetic
To select 2-iodo-5-bromopyridine and 3-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-54.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.16%, H:5.32%, N:6.52%.Overall yield 42.8%.
Embodiment 55 compound 1-55's is synthetic
Selecting 2-chloro-5-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-55.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.34%, H:5.31%, N:6.35%.Overall yield 40.6%.
Embodiment 56 compound 1-56's is synthetic
To select 2-iodo-5-bromopyridine and 4-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-56.Product MS (m/e): 639, ultimate analysis (C 47H 33N 3): theoretical value C:88.23%, H:5.20%, N:6.57%; Measured value C:88.08%, H:5.37%, N:6.55%.Overall yield 42.6%.
Embodiment 57 compound 1-57's is synthetic
Selecting 2-chloro-5-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-57.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.91%, H:4.81%, N:7.28%.Overall yield 44.2%.
Embodiment 58 compound 1-58's is synthetic
To select 2-iodo-5-bromopyridine and 1-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-58.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.73%, H:4.87%, N:7.40%.Overall yield 41.3%.
Embodiment 59 compound 1-59's is synthetic
Selecting 2-chloro-5-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-59.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.96%, H:4.91%, N:7.13%.Overall yield 40.9%.
Embodiment 60 compound 1-60's is synthetic
To select 2-iodo-5-bromopyridine and 2-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 1-60.Product MS (m/e): 587, ultimate analysis (C 43H 29N 3): theoretical value C:87.88%, H:4.97%, N:7.15%; Measured value C:87.81%, H:4.85%, N:7.34%.Overall yield 41.8%.
Embodiment 61-90, the substrate of three-step reaction is 3,6-dibrominated pyridyl carbazole.The concrete elaboration as follows:
Embodiment 61 compound 2-1's is synthetic
Select 2 for use, 6-dibromo pyridine and phenylo boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-1.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.32%, H:4.91%, N:7.77%.Overall yield is 34.2%.。
Embodiment 62 compound 2-2's is synthetic
Selecting 2-chloro-4-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-2.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.27%, H:5.04%, N:7.69%.Overall yield is 38.6%.
Embodiment 63 compound 2-3's is synthetic
Select 3 for use, 5-dibromo pyridine and phenylo boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-3.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.31%, H:5.08%, N:7.61%.Overall yield is 33.5%.
Embodiment 64 compound 2-4's is synthetic
Selecting 2-iodo-4-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-4.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.52%, H:5.02%, N:7.46%.Overall yield is 42.3%.
Embodiment 65 compound 2-5's is synthetic
Select 2 for use, 6-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-5.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.86%, H:5.11%, N:6.03%.Overall yield 42.8%.
Embodiment 66 compound 2-6's is synthetic
Selecting 2-chloro-4-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-6.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.92%, H:5.12%, N:5.96%.Overall yield 41.8%.
Embodiment 67 compound 2-7's is synthetic
Select 3 for use, 5-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-7.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.87%, H:5.10%, N:6.03%.Overall yield 34.3%.
Embodiment 68 compound 2-8's is synthetic
Selecting 2-iodo-4-bromopyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-8.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:89.07%, H:5.02%, N:5.91%.Overall yield 42.6%.
Embodiment 69 compound 2-9's is synthetic
Select 2 for use, 6-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-9.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.95%, H:5.13%, N:5.92%.Overall yield 32.6%.
Embodiment 70 compound 2-10's is synthetic
Selecting 2-chloro-4-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-10.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.86%, H:5.14%, N:6.00%.Overall yield 44.3%.
Embodiment 71 compound 2-11's is synthetic
Select 3 for use, 5-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-11.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:89.02%, H:5.11%, N:5.87%.Overall yield 35.7%.
Embodiment 72 compound 2-12's is synthetic
Selecting 2-iodo-4-bromopyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-12.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:89.09%, H:5.12%, N:5.79%.Overall yield 42.7%.
Embodiment 73 compound 2-13's is synthetic
Select 2 for use, 6-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-13.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.69%, H:4.87%, N:6.44%.Overall yield 34.1%.
Embodiment 74 compound 2-14's is synthetic
Selecting 2-chloro-4-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-14.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.73%, H:4.92%, N:6.35%.Overall yield 42.5%.
Embodiment 75 compound 2-15's is synthetic
Select 3 for use, 5-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-15.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.79%, H:4.91%, N:6.30%.Overall yield 33.8%.
Embodiment 76 compound 2-16's is synthetic
Selecting 2-iodo-4-bromopyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-16.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.65%, H:4.90%, N:6.45%.Overall yield 41.2%.
Embodiment 77 compound 2-17's is synthetic
Select 2 for use, 6-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-17.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.84%, H:4.71%, N:6.45%.Overall yield 34.2%.
Embodiment 78 compound 2-18's is synthetic
Selecting 2-chloro-4-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-18.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.68%, H:4.84%, N:6.48%.Overall yield 44.6%.
Embodiment 79 compound 2-19's is synthetic
Select 3 for use, 5-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-19.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.66%, H:4.92%, N:6.42%.Overall yield 33.6%.
Embodiment 80 compound 2-20's is synthetic
Selecting 2-iodo-4-bromopyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-20.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.76%, H:4.85%, N:6.39%.Overall yield 42.5%.
Embodiment 81 compound 2-21's is synthetic
Selecting 2-bromo-5-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-21.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.36%, H:5.08%, N:7.56%.Overall yield is 44.3%.
Embodiment 82 compound 2-22's is synthetic
Selecting 2-iodo-5-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-22.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.30%, H:5.02%, N:7.68%.Overall yield is 43.5%.
Embodiment 83 compound 2-23's is synthetic
Selecting 2-chloro-5-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-23.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.84%, H:5.20%, N:5.96%.Overall yield 41.6%.
Embodiment 84 compound 2-24's is synthetic
To select 2-iodo-5-bromopyridine and 3-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-24.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.97%, H:5.12%, N:5.93%.Overall yield 42.1%.
Embodiment 85 compound 2-25's is synthetic
Selecting 2-chloro-5-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-25.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.81%, H:5.38%, N:5.81%.Overall yield 40.3%.
Embodiment 86 compound 2-26's is synthetic
To select 2-iodo-5-bromopyridine and 4-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-26.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.86%, H:5.36%, N:5.78%.Overall yield 42.6%.
Embodiment 87 compound 2-27's is synthetic
Selecting 2-chloro-5-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-27.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.84%, H:4.83%, N:6.33%.Overall yield 41.2%.
Embodiment 88 compound 2-28's is synthetic
To select 2-iodo-5-bromopyridine and 1-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-28.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.73%, H:4.93%, N:6.34%.Overall yield 41.8%.
Embodiment 89 compound 2-29's is synthetic
Selecting 2-chloro-5-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-29.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.78%, H:4.86%, N:6.36%.Overall yield 40.9%.
Embodiment 90 compound 2-30's is synthetic
To select 2-iodo-5-bromopyridine and 2-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-30.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.76%, H:4.85%, N:6.39%.Overall yield 41.3%.
Embodiment 91-120, reaction substrate was 2 during reaction went on foot with embodiment 1, the three, 7-dibrominated pyridyl carbazole, existing concrete the elaboration as follows:
Embodiment 91 compound 2-31's is synthetic
Select 2 for use, 6-dibromo pyridine and phenylo boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-31.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.35%, H:5.06%, N:7.59%.Overall yield is 33.6%.
Embodiment 92 compound 2-32's is synthetic
Selecting 2-chloro-4-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-32.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.27%, H:4.98%, N:7.75%.Overall yield is 39.4%.
Embodiment 93 compound 2-33's is synthetic
Select 3 for use, 5-dibromo pyridine and phenylo boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-33.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.32%, H:5.02%, N:7.66%.Overall yield is 32.8%.
Embodiment 94 compound 2-34's is synthetic
Selecting 2-iodo-4-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-34.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.24%, H:5.08%, N:7.68%.Overall yield is 38.7%.
Embodiment 95 compound 2-35's is synthetic
Select 2 for use, 6-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-35.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.84%, H:5.11%, N:6.05%.Overall yield 32.9%.
Embodiment 96 compound 2-36's is synthetic
Selecting 2-chloro-4-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-36.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.95%, H:5.02%, N:6.03%.Overall yield 41.3%.
Embodiment 97 compound 2-37's is synthetic
Select 3 for use, 5-dibromo pyridine and 3-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-37.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.86%, H:5.10%, N:6.04%.Overall yield 33.3%.
Embodiment 98 compound 2-38's is synthetic
Selecting 2-iodo-4-bromopyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-38.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.95%, H:5.12%, N:5.93%.Overall yield 41.7%.
Embodiment 99 compound 2-39's is synthetic
Select 2 for use, 6-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-39.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.92%, H:5.11%, N:5.87%.Overall yield 33.6%.
Embodiment 100 compound 2-40's is synthetic
Selecting 2-chloro-4-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-40.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.82%, H:5.04%, N:6.14%.Overall yield 41.6%.
Embodiment 101 compound 2-41's is synthetic
Select 3 for use, 5-dibromo pyridine and 4-biphenyl boric acid are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-41.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.88%, H:5.10%, N:6.02%.Overall yield 35.3%.
Embodiment 102 compound 2-42's is synthetic
Selecting 2-iodo-4-bromopyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-42.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.99%, H:5.01%, N:6.00%.Overall yield 42.7%.
Embodiment 103 compound 2-43's is synthetic
Select 2 for use, 6-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-43.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.81%, H:4.93%, N:6.26%.Overall yield 33.8%.
Embodiment 104 compound 2-44's is synthetic
Selecting 2-chloro-4-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-44.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.65%, H:5.01%, N:6.34%.Overall yield 34.5%.
Embodiment 105 compound 2-45's is synthetic
Select 3 for use, 5-dibromo pyridine and 1-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-45.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.62%, H:4.90%, N:6.48%.Overall yield 34.0%.
Embodiment 106 compound 2-46's is synthetic
Selecting 2-iodo-4-bromopyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-46.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.85%, H:4.77%, N:6.38%.Overall yield 43.1%.
Embodiment 107 compound 2-47's is synthetic
Select 2 for use, 6-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-47.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.71%, H:4.98%, N:6.31%.Overall yield 33.4%.
Embodiment 108 compound 2-48's is synthetic
Selecting 2-chloro-4-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-48.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.59%, H:5.05%, N:6.36%.Overall yield 44.6%.
Embodiment 109 compound 2-49's is synthetic
Select 3 for use, 5-dibromo pyridine and 2-naphthalene boronic acids are raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-49.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.69%, H:4.82%, N:6.49%.Overall yield 34.3%.
Embodiment 110 compound 2-50's is synthetic
Selecting 2-iodo-4-bromopyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-50.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.81%, H:4.83%, N:6.36%.Overall yield 43.6%.
Embodiment 111 compound 2-51's is synthetic
Selecting 2-bromo-5-iodine pyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-51.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.32%, H:5.02%, N:7.66%.Overall yield is 43.7%.
Embodiment 112 compound 2-52's is synthetic
Selecting 2-iodo-5-bromopyridine and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-52.Product MS (m/e): 549, ultimate analysis (C 40H 27N 3): theoretical value C:87.40%, H:4.95%, N:7.64%; Measured value C:87.38%, H:5.01%, N:7.61%.Overall yield is 42.8%.
Embodiment 113 compound 2-53's is synthetic
Selecting 2-chloro-5-iodine pyridine and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-53.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.86%, H:5.11%, N:6.03%.Overall yield 41.6%.
Embodiment 114 compound 2-54's is synthetic
To select 2-iodo-5-bromopyridine and 3-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-54.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.92%, H:5.17%, N:5.91%.Overall yield 42.3%.
Embodiment 115 compound 2-55's is synthetic
Selecting 2-chloro-5-iodine pyridine and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-55.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.88%, H:5.11%, N:6.01%.Overall yield 42.6%.
Embodiment 116 compound 2-56's is synthetic
To select 2-iodo-5-bromopyridine and 4-biphenyl boric acid for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-56.Product MS (m/e): 701, ultimate analysis (C 52H 35N 3): theoretical value C:88.99%, H:5.03%, N:5.99%; Measured value C:88.87%, H:5.08%, N:6.05%.Overall yield 42.6%.
Embodiment 117 compound 2-57's is synthetic
Selecting 2-chloro-5-iodine pyridine and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-57.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.85%, H:4.83%, N:6.32%.Overall yield 44.1%.
Embodiment 118 compound 2-58's is synthetic
To select 2-iodo-5-bromopyridine and 1-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-58.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.77%, H:4.87%, N:6.36%.Overall yield 41.3%.
Embodiment 119 compound 2-59's is synthetic
Selecting 2-chloro-5-iodine pyridine and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-59.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.68%, H:4.98%, N:6.34%.Overall yield 41.9%.
Embodiment 120 compound 2-60's is synthetic
To select 2-iodo-5-bromopyridine and 2-naphthalene boronic acids for use be the raw material warp with embodiment 1 identical three-step reaction obtains compound 2-60.Product MS (m/e): 649, ultimate analysis (C 48H 31N 3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.64%, H:4.95%, N:6.41%.Overall yield 42.7%.Be the application implementation example of The compounds of this invention below:
Embodiment 121: the preparation of electroluminescence device and result
The preferred implementation of fabricate devices:
(1) designs
The transmission performance that compares these electron transport materials for ease; The present invention has designed a simple electroluminescence device (substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode); Only use compound 1-1,1-3,1-7,1-11,1-19 and 2-1 as the electron transport material illustration, efficent electronic transport material Alq 3As comparative material, EM1 is as luminescent material illustration (EM1 is a material of main part, is not luminescent material, and purpose is not to pursue high-level efficiency, but verifies the possibility that these materials are practical).Alq 3With the structure of EM1 be:
Figure BSA00000237688200341
Substrate can use the substrate in traditional organic luminescent device, for example: glass or plastics.In element manufacturing of the present invention, select glass substrate for use, ITO makes anode material.
Hole transmission layer can adopt various tri-arylamine group materials.The hole mobile material of in element manufacturing of the present invention, being selected for use is NPB.
Negative electrode can adopt metal and composition thereof structure, like Mg:Ag, Ca:Ag etc., also can be electron injecting layer/metal-layer structure, like LiF/Al, Li 2Common cathode construction such as O.The electronics injecting material of in element manufacturing of the present invention, being selected for use is LiF, and cathode material is Al.
Element manufacturing
With the sheet glass that has been coated with ITO transparency conducting layer supersound process in commercial clean-out system; In deionized water, wash, at acetone: ultrasonic oil removing in the alcohol mixed solvent is baked under clean environment and removes moisture content fully; With UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
Place the above-mentioned anodic glass substrate that has in the vacuum chamber, be evacuated to 1 * 10 -5～9 * 10 -3Pa, vacuum evaporation NPB is as hole transmission layer on above-mentioned anode tunic, and vapor deposition speed is 0.1nm/s, and the vapor deposition thickness is 50nm;
Vacuum evaporation EM1 is as the luminescent layer of device on hole transmission layer, and vapor deposition speed is 0.1nm/s, and the vapor deposition total film thickness is 30nm;
Vacuum evaporation one deck compound 1-1,1-3,1-7,1-11,1-19,2-1 or Alq on luminescent layer 3As the electron transfer layer of device, its vapor deposition speed is 0.1nm/s, and the vapor deposition total film thickness is 50nm;
Go up the negative electrode of vacuum evaporation Al layer as device at electron transfer layer (ETL), thickness is 150nm.
Device performance see the following form (device architecture: ITO/NPB (40nm)/EM1 (30nm)/ETL material (20nm)/LiF (0.5nm)/Al (150nm))
Figure BSA00000237688200351
Above result shows that novel organic materials of the present invention can be preferably used as electron transfer layer in organic electroluminescence device.
Although describe the present invention in conjunction with embodiment, the present invention is not limited to the foregoing description, should be appreciated that those skilled in the art can carry out various modifications and improvement under the guiding of the present invention's design, and accompanying claims has been summarized scope of the present invention.

Claims (7)

1. organic cpds, its general structure is as shown in the formula shown in the I:
Figure FSA00000237688100011
Wherein Ar is selected from phenyl group, xenyl group or naphthyl group.R is alkyl or the phenyl of carbon atom number from 1-6.
2. according to the organic materials of claim 1, it is characterized in that the pyridine group the position of substitution on N substituted carbazole base among the formula I is selected from 3,6 two replacements or 2,7 two replacements, the structural formula that is substituted of N substituted carbazole group is selected from Formula Il or III:
Figure FSA00000237688100012
3. compound according to claim 1 is characterized in that the substituent R among formula I, II or the III is selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, n-pentyl, n-hexyl or phenyl.
4. compound according to claim 1 is characterized in that, the structural formula of Ar is selected from following formula I V, V, VI, VII or VIII among the formula I:
5. according to claim 1, one of 2 or 3 described compounds, structural formula is selected from following formula:
Figure FSA00000237688100014
Figure FSA00000237688100021
Figure FSA00000237688100031
Figure FSA00000237688100041
Figure FSA00000237688100051
Figure FSA00000237688100061
Figure FSA00000237688100071
Figure FSA00000237688100081
Figure FSA00000237688100091
Figure FSA00000237688100111
Figure FSA00000237688100131
Figure FSA00000237688100141
Figure FSA00000237688100151
6. the described compound of claim 1 is used as the electric transmission layer material in organic electroluminescence device.
7. an organic electroluminescence device wherein comprises pair of electrodes and is arranged on the organic light emitting medium between this counter electrode, comprises a kind of described compound of claim 1 that is selected from this organic light emitting medium at least.
CN201010258632.XA 2010-08-20 2010-08-20 Carbazole compound and application thereof Expired - Fee Related CN102372693B (en)

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Publication number Priority date Publication date Assignee Title
KR101791122B1 (en) 2009-12-03 2017-10-27 제이엔씨 주식회사 Benzo[c]carbazole compound that has substituent bearing pyridine ring, and organic electroluminescent element
JP2014022079A (en) * 2012-07-12 2014-02-03 Hiroshima Univ DONOR-π-ACCEPTOR TYPE COMPOUND AND DYE FOR DYE-SENSITIZED SOLAR CELL
CN104004507A (en) * 2013-02-21 2014-08-27 海洋王照明科技股份有限公司 Organic electroluminescence phosphorescence host material, preparation method thereof and organic electroluminescence device
WO2019128112A1 (en) * 2017-12-29 2019-07-04 昆山国显光电有限公司 Electron transport layer, organic electroluminescent device, and display
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CN112701238A (en) * 2021-01-06 2021-04-23 长春海谱润斯科技股份有限公司 Organic light-emitting device comprising covering layer and sealing layer
CN112701238B (en) * 2021-01-06 2022-11-11 长春海谱润斯科技股份有限公司 Organic light-emitting device comprising covering layer and sealing layer

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