CN105085374A - Aromatic amine compound and preparing method and application thereof - Google Patents

Aromatic amine compound and preparing method and application thereof Download PDF

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CN105085374A
CN105085374A CN201510492903.0A CN201510492903A CN105085374A CN 105085374 A CN105085374 A CN 105085374A CN 201510492903 A CN201510492903 A CN 201510492903A CN 105085374 A CN105085374 A CN 105085374A
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aryl
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heteroaryl
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高春吉
孙向南
陈明
崔明
崔敦洙
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention provides an aromatic amine compound provided with the structure of a formula (I). According to the light-emitting efficiency of the compound, under the circumstance that current density is 20 mA/cm<2>, current efficiency is up to 6.5 cd/A, and the service life is up to 6700 hours, and is far longer than that of an existing disclosed electroluminescent material.

Description

Aromatic amine compounds and its preparation method and application
Technical field
The present invention relates to field of organic electroluminescent materials, particularly relate to a kind of aromatic amine compounds and its preparation method and application.
Background technology
Since Tang in 1987 etc. are successfully prepared the small molecule light emitters part of low-voltage driving, organic light emission technology has achieved huge progress, and starts to enter industrialization process; Wherein, the performance of electroluminescent organic material to organic luminescent device plays very important effect.
According to the size of electroluminescent organic material molecular weight, small molecules electroluminescent organic material and polymer electroluminescent organic material can be divided into.At present in disclosed luminescent material, because the fluorescence quantum efficiency of small molecule electroluminescent material is high, easily purify, luminosity and purity of color are also better than macromolecular material, so, small molecule electroluminescent materials application in luminescent device to start to realize commercialization.
Aromatic amine compounds is the important small molecules electroluminescent organic material of a class, compound disclosed in TPD, α-NPD and publication number US20150014657,
But these aromatic amine compounds disclosed are all poor as thermostability during electroluminescent material, fast hole degree of excursion, twinkler efficiency and life-span at present.
Summary of the invention
In view of this, technical problem to be solved by this invention is a kind of aromatic amine compounds and its preparation method and application, and not only luminous efficiency is high for aromatic amine compounds provided by the invention, and long service life.
The invention provides a kind of aromatic amine compounds, there is formula (I) structure,
Wherein,
R 1for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 2for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 3for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 4for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1, Ar 2independently be selected from the arylidene of C6 ~ C50,
Or Ar 1, and Ar 1the nitrogen be directly connected and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the aryl of C6 ~ C50,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the aryl of C6 ~ C50.
Preferably, described alkyl be straight chained alkyl, the cycloalkyl that replaces of the branched-chain alkyl that replaces of branched-chain alkyl, cycloalkyl, at least 1 substituting group direct-connected alkyl, at least 1 substituting group that replace or at least 1 substituting group;
Described aryl is the aryl that unsubstituted aryl or at least 1 substituting group replace;
Described aralkyl is the aralkyl that unsubstituted aralkyl or at least 1 substituting group replace;
Described alkoxy aryl is the alkoxy aryl that unsubstituted alkoxy aryl or at least 1 substituting group replace;
Described aryl alkane sulfydryl is the aryl alkane sulfydryl that unsubstituted aryl alkane sulfydryl or at least 1 substituting group replace;
Described heteroaryl is the heteroaryl that unsubstituted heteroaryl or at least 1 substituting group replace,
Wherein, the heteroatoms in described heteroaryl is nitrogen, sulphur or oxygen;
Described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.
Preferably, described R 1, R 2, R 3, R 4independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C3 ~ C20, the aryl of C10 ~ C40, the aralkyl of C10 ~ C40, the alkoxy aryl of C10 ~ C40, the aryl alkane sulfydryl of C10 ~ C40 or C7 ~ C30.
Preferably, Ar 1, Ar 2independently be selected from the arylidene of C10 ~ C40,
Or Ar 1, and Ar 1the nitrogen be directly connected and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the arylidene of C10 ~ C40,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the arylidene of C10 ~ C40.
Preferably, described R 1, R 2, R 3, R 4independently be selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro-ethyl of 2-, 2-cyano-propyl, sec.-propyl, the tertiary butyl, pentyl, heptane base, dodecyl, formula (a-1) structure, formula (a-2) structure, formula (a-3) structure, formula (a-4) structure, formula (a-5) structure, formula (a-6) structure, formula (a-7) structure, formula (a-8) structure, formula (a-9) structure, formula (a-10) structure, formula (a-11) structure, formula (a-12) structure, formula (a-13) structure, formula (b-1) structure, formula (b-2) structure, formula (b-3) structure, formula (b-4) structure, formula (b-5) structure, formula (b-6) structure, formula (b-7) structure, formula (b-8) structure, formula (b-9) structure, formula (b-10) structure, formula (b-11) structure, formula (b-12) structure, formula (c-1) structure, formula (c-2) structure, formula (c-3) structure, formula (c-4) structure, formula (c-5) structure, formula (c-6) structure, formula (c-7) structure, formula (c-8) structure, formula (c-9) structure, formula (c-10) structure, formula (c-11) structure, formula (c-12) structure, formula (d-1) structure, formula (d-2) structure, formula (d-3) structure, formula (d-4) structure, formula (d-5) structure, formula (d-6) structure or formula (d-7) structure,
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.
Preferably, Ar 1, Ar 2independently be selected from formula (e-1) structure, formula (e-2) structure, formula (e-3) structure, formula (e-4) structure, formula (e-5) structure, formula (e-6) structure, formula (e-7) structure, formula (e-8) structure, formula (e-9) structure, formula (e-10) structure, formula (e-11) structure or formula (e-12) structure
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.
Preferably, the compound of described formula (I) structure is formula (I-1), formula (I-2) or formula (I-3),
Wherein,
R 1for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 2for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 3for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 4for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1, Ar 2independently be selected from the aryl of C6 ~ C50.
Preferably, the compound of described formula (I) structure is formula (I-1-1), formula (I-1-2), formula (I-1-3), formula (I-1-4), formula (I-1-5), formula (I-1-6), formula (I-1-7), formula (I-1-8), formula (I-1-9), formula (I-1-10), formula (I-1-11), formula (I-1-12), formula (I-1-13), formula (I-1-14), formula (I-2-1), formula (I-2-2), formula (I-2-3), formula (I-2-4), formula (I-2-5), formula (I-2-6), formula (I-2-7), formula (I-2-8), formula (I-2-9), formula (I-2-10), formula (I-2-11), formula (I-2-12), formula (I-2-13) or the compound shown in formula (I-3-1),
Present invention also offers the preparation method that one has formula (I) structure aromatic amine compounds, comprising:
The compound of the compound and formula (III) structure will with formula (II) structure reacts, and obtains the compound of formula (IV) structure,
R 1, R 3independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C1 ~ C30, the aryl of C6 ~ C50, the arylalkyl of C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1be selected from the arylidene of C6 ~ C50,
Or Ar 1, and Ar 1the nitrogen be directly connected and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the arylidene of C6 ~ C50;
The compound of the compound and formula (V) structure will with formula (IV) structure reacts, and obtains the compound of formula (I) structure.
R 2, R 4independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C1 ~ C30, the aryl of C6 ~ C50, the arylalkyl of C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 2be selected from the arylidene of C6 ~ C50,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the arylidene of C6 ~ C50.
The compound that present invention also offers a kind of formula of the present invention (I) structure is preparing the application in organic electroluminescence device.
Compared with prior art, the luminous efficiency of compound provided by the invention is 20mA/cm in current density 2when, current efficiency is up to 6.5cd/A, and work-ing life can up to 6700 hours, far above existing disclosed electroluminescent material.
Embodiment
The invention provides a kind of aromatic amine compounds, there is formula (I) structure,
Wherein,
R 1for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 2for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 3for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 4for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1, Ar 2independently be selected from the arylidene of C6 ~ C50,
Or Ar 1, and Ar 1the nitrogen be directly connected and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the arylidene of C6 ~ C50,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the arylidene of C6 ~ C50.
Wherein, described alkyl is preferably the cycloalkyl that straight chained alkyl, branched-chain alkyl, cycloalkyl, the direct-connected alkyl of at least 1 substituting group replacement, the branched-chain alkyl of at least 1 substituting group replacement or at least 1 substituting group replace; Wherein, described substituting group is independently selected from one or more in halogen, cyano group, hydroxyl and sulfydryl, and on described alkyl, substituent number is preferably 1 ~ 5, is more preferably 2,3 or 4.
Described aryl is preferably the aryl of unsubstituted aryl or at least 1 substituting group replacement; Wherein, described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; On described aryl, substituent number is preferably 1 ~ 5, is more preferably 2,3 or 4.
Described arylidene refers to, and aromatic nucleus has two to link key, and arylidene also can be the arylidene for unsubstituted arylidene or at least 1 substituting group replace; Wherein, described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; On described arylidene, substituent number is preferably 1 ~ 5, is more preferably 2,3 or 4.
Described arylalkyl is preferably the arylalkyl of unsubstituted arylalkyl or at least 1 substituting group replacement; Wherein, described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; On described arylalkyl, substituent number is preferably 1 ~ 5, is more preferably 2,3 or 4.
Described alkoxy aryl is preferably the alkoxy aryl of unsubstituted alkoxy aryl or at least 1 substituting group replacement; Wherein, described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; On described alkoxy aryl, substituent number is preferably 1 ~ 5, is more preferably 2,3 or 4.
Described aryl alkane sulfydryl is preferably the aryl alkane sulfydryl of unsubstituted aryl alkane sulfydryl or at least 1 substituting group replacement; Wherein, described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; On described aryl alkane sulfydryl, substituent number is preferably 1 ~ 5, is more preferably 2,3 or 4.
Described heteroaryl is preferably the heteroaryl of unsubstituted heteroaryl or at least 1 substituting group replacement; Wherein, the heteroatoms in heteroaryl is nitrogen, sulphur or oxygen; Described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; On described heteroaryl, substituent number is preferably 1 ~ 5, is more preferably 2,3 or 4.
And described in formula (I)-R1 and-R2 represents in the optional position of its place phenyl ring, is preferably the contraposition of position that nitrogen replaces on phenyl ring.
More specifically, described R 1be preferably hydrogen, halogen, cyano group, the alkyl of C3 ~ C20, the aryl of C10 ~ C40, the arylalkyl of C10 ~ C40, the alkoxy aryl of C10 ~ C40, the aryl alkane sulfydryl of C10 ~ C40 or the heteroaryl of C7 ~ C30, be more preferably hydrogen, halogen, cyano group, the alkyl of C5 ~ C15, the aryl of C15 ~ C30, the arylalkyl of C15 ~ C30, the alkoxy aryl of C15 ~ C30, the aryl alkane sulfydryl of C15 ~ C30 or the heteroaryl of C8 ~ C25, most preferably be hydrogen, halogen, cyano group, the alkyl of C5 ~ C10, the aryl of C12 ~ C25, the arylalkyl of C12 ~ C25, the alkoxy aryl of C12 ~ C25, the aryl alkane sulfydryl of C12 ~ C25 or the heteroaryl of C10 ~ C20, concrete, described R 1be selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro-ethyl of 2-, 2-cyano-propyl, sec.-propyl, the tertiary butyl, pentyl, heptane base, dodecyl, formula (a-1) structure, formula (a-2) structure, formula (a-3) structure, formula (a-4) structure, formula (a-5) structure, formula (a-6) structure, formula (a-7) structure, formula (a-8) structure, formula (a-9) structure, formula (a-10) structure, formula (a-11) structure, formula (a-12) structure, formula (a-13) structure, formula (b-1) structure, formula (b-2) structure, formula (b-3) structure, formula (b-4) structure, formula (b-5) structure, formula (b-6) structure, formula (b-7) structure, formula (b-8) structure, formula (b-9) structure, formula (b-10) structure, formula (b-11) structure, formula (b-12) structure, formula (c-1) structure, formula (c-2) structure, formula (c-3) structure, formula (c-4) structure, formula (c-5) structure, formula (c-6) structure, formula (c-7) structure, formula (c-8) structure, formula (c-9) structure, formula (c-10) structure, formula (c-11) structure, formula (c-12) structure, formula (d-1) structure, formula (d-2) structure, formula (d-3) structure, formula (d-4) structure, formula (d-5) structure, formula (d-6) structure or formula (d-7) structure,
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; And-Ra can in described substituent optional position, preferably in the contraposition of substituting group connecting key; And the number of Ra in substituting group is 0 ~ 5, is more preferably 1,2,3 or 4;
represent the connecting key of substituting group and compound.
Described R 2be preferably hydrogen, halogen, cyano group, the alkyl of C3 ~ C20, the aryl of C10 ~ C40, the arylalkyl of C10 ~ C40, the alkoxy aryl of C10 ~ C40, the aryl alkane sulfydryl of C10 ~ C40 or the heteroaryl of C7 ~ C30, be more preferably hydrogen, halogen, cyano group, the alkyl of C5 ~ C15, the aryl of C15 ~ C30, the arylalkyl of C15 ~ C30, the alkoxy aryl of C15 ~ C30, the aryl alkane sulfydryl of C15 ~ C30 or the heteroaryl of C8 ~ C25, most preferably be hydrogen, halogen, cyano group, the alkyl of C5 ~ C10, the aryl of C12 ~ C25, the arylalkyl of C12 ~ C25, the alkoxy aryl of C12 ~ C25, the aryl alkane sulfydryl of C12 ~ C25 or the heteroaryl of C10 ~ C20, concrete, described R 2be selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro-ethyl of 2-, 2-cyano-propyl, sec.-propyl, the tertiary butyl, pentyl, heptane base, dodecyl, formula (a-1) structure, formula (a-2) structure, formula (a-3) structure, formula (a-4) structure, formula (a-5) structure, formula (a-6) structure, formula (a-7) structure, formula (a-8) structure, formula (a-9) structure, formula (a-10) structure, formula (a-11) structure, formula (a-12) structure, formula (a-13) structure, formula (b-1) structure, formula (b-2) structure, formula (b-3) structure, formula (b-4) structure, formula (b-5) structure, formula (b-6) structure, formula (b-7) structure, formula (b-8) structure, formula (b-9) structure, formula (b-10) structure, formula (b-11) structure, formula (b-12) structure, formula (c-1) structure, formula (c-2) structure, formula (c-3) structure, formula (c-4) structure, formula (c-5) structure, formula (c-6) structure, formula (c-7) structure, formula (c-8) structure, formula (c-9) structure, formula (c-10) structure, formula (c-11) structure, formula (c-12) structure, formula (d-1) structure, formula (d-2) structure, formula (d-3) structure, formula (d-4) structure, formula (d-5) structure, formula (d-6) structure or formula (d-7) structure,
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; And Ra can in described substituent optional position, preferably in the contraposition of substituting group connecting key; And the number of Ra in substituting group is 0 ~ 5, is more preferably 1,2,3 or 4.
Described R 3be preferably hydrogen, halogen, cyano group, the alkyl of C3 ~ C20, the aryl of C10 ~ C40, the arylalkyl of C10 ~ C40, the alkoxy aryl of C10 ~ C40, the aryl alkane sulfydryl of C10 ~ C40 or the heteroaryl of C7 ~ C30, be more preferably hydrogen, halogen, cyano group, the alkyl of C5 ~ C15, the aryl of C15 ~ C30, the arylalkyl of C15 ~ C30, the alkoxy aryl of C15 ~ C30, the aryl alkane sulfydryl of C15 ~ C30 or the heteroaryl of C8 ~ C25, most preferably be hydrogen, halogen, cyano group, the alkyl of C5 ~ C10, the aryl of C12 ~ C25, the arylalkyl of C12 ~ C25, the alkoxy aryl of C12 ~ C25, the aryl alkane sulfydryl of C12 ~ C25 or the heteroaryl of C10 ~ C20, concrete, described R 3be selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro-ethyl of 2-, 2-cyano-propyl, sec.-propyl, the tertiary butyl, pentyl, heptane base, dodecyl, formula (a-1) structure, formula (a-2) structure, formula (a-3) structure, formula (a-4) structure, formula (a-5) structure, formula (a-6) structure, formula (a-7) structure, formula (a-8) structure, formula (a-9) structure, formula (a-10) structure, formula (a-11) structure, formula (a-12) structure, formula (a-13) structure, formula (b-1) structure, formula (b-2) structure, formula (b-3) structure, formula (b-4) structure, formula (b-5) structure, formula (b-6) structure, formula (b-7) structure, formula (b-8) structure, formula (b-9) structure, formula (b-10) structure, formula (b-11) structure, formula (b-12) structure, formula (c-1) structure, formula (c-2) structure, formula (c-3) structure, formula (c-4) structure, formula (c-5) structure, formula (c-6) structure, formula (c-7) structure, formula (c-8) structure, formula (c-9) structure, formula (c-10) structure, formula (c-11) structure, formula (c-12) structure, formula (d-1) structure, formula (d-2) structure, formula (d-3) structure, formula (d-4) structure, formula (d-5) structure, formula (d-6) structure or formula (d-7) structure,
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; And Ra can in described substituent optional position, preferably in the contraposition of substituting group connecting key; And the number of Ra in substituting group is 0 ~ 5, is more preferably 1,2,3 or 4;
Described R 4be preferably hydrogen, halogen, cyano group, the alkyl of C3 ~ C20, the aryl of C10 ~ C40, the arylalkyl of C10 ~ C40, the alkoxy aryl of C10 ~ C40, the aryl alkane sulfydryl of C10 ~ C40 or the heteroaryl of C7 ~ C30, be more preferably hydrogen, halogen, cyano group, the alkyl of C5 ~ C15, the aryl of C15 ~ C30, the arylalkyl of C15 ~ C30, the alkoxy aryl of C15 ~ C30, the aryl alkane sulfydryl of C15 ~ C30 or the heteroaryl of C8 ~ C25, most preferably be hydrogen, halogen, cyano group, the alkyl of C5 ~ C10, the aryl of C12 ~ C25, the arylalkyl of C12 ~ C25, the alkoxy aryl of C12 ~ C25, the aryl alkane sulfydryl of C12 ~ C25 or the heteroaryl of C10 ~ C20, concrete, described R 4be selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro-ethyl of 2-, 2-cyano-propyl, sec.-propyl, the tertiary butyl, pentyl, heptane base, dodecyl, formula (a-1) structure, formula (a-2) structure, formula (a-3) structure, formula (a-4) structure, formula (a-5) structure, formula (a-6) structure, formula (a-7) structure, formula (a-8) structure, formula (a-9) structure, formula (a-10) structure, formula (a-11) structure, formula (a-12) structure, formula (a-13) structure, formula (b-1) structure, formula (b-2) structure, formula (b-3) structure, formula (b-4) structure, formula (b-5) structure, formula (b-6) structure, formula (b-7) structure, formula (b-8) structure, formula (b-9) structure, formula (b-10) structure, formula (b-11) structure, formula (b-12) structure, formula (c-1) structure, formula (c-2) structure, formula (c-3) structure, formula (c-4) structure, formula (c-5) structure, formula (c-6) structure, formula (c-7) structure, formula (c-8) structure, formula (c-9) structure, formula (c-10) structure, formula (c-11) structure, formula (c-12) structure, formula (d-1) structure, formula (d-2) structure, formula (d-3) structure, formula (d-4) structure, formula (d-5) structure, formula (d-6) structure or formula (d-7) structure,
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; And-Ra can in described substituent optional position, preferably in the contraposition of substituting group connecting key; And the number of Ra in substituting group is 0 ~ 5, is more preferably 1,2,3 or 4.
Described Ar 1, Ar 2preferably independently select the arylidene of C10 ~ C40, be more preferably the arylidene of C15 ~ C30, most preferably be the arylidene of C20 ~ C25, concrete, described in
Ar 1, Ar 2independently be selected from formula (e-1) structure, formula (e-2) structure, formula (e-3) structure, formula (e-4) structure, formula (e-5) structure, formula (e-6) structure, formula (e-7) structure, formula (e-8) structure, formula (e-9) structure, formula (e-10) structure, formula (e-11) structure or formula (e-12) structure
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl; And Ra can in described substituent optional position, preferably in the contraposition of substituting group connecting key; And the number of Ra in substituting group is 0 ~ 5, is more preferably 1,2,3 or 4,
represent the connecting key of substituting group and compound, and one of them connecting key can at the arbitrary portion of aryl, preferably and the connecting key fixed or substituting group at least one, interval carbon.
More specifically, the compound of described formula (I) structure is preferably formula (I-1), formula (I-2) or the structure shown in formula (I-3),
Wherein, R 1, R 2, R 3, R 4, Ar 1, Ar 2selection as hereinbefore.
More specifically, the compound of described formula (I) structure is formula (I-1-1), formula (I-1-2), formula (I-1-3), formula (I-1-4), formula (I-1-5), formula (I-1-6), formula (I-1-7), formula (I-1-8), formula (I-1-9), formula (I-1-10), formula (I-1-11), formula (I-1-12), formula (I-1-13), formula (I-1-14), formula (I-2-1), formula (I-2-2), formula (I-2-3), formula (I-2-4), formula (I-2-5), formula (I-2-6), formula (I-2-7), formula (I-2-8), formula (I-2-9), formula (I-2-10), formula (I-2-11), formula (I-2-12), formula (I-2-13) or the compound shown in formula (I-3-1),
Present invention also offers the preparation method that one has formula (I) structure aromatic amine compounds, comprising:
The compound of the compound and formula (III) structure will with formula (II) structure reacts, and obtains the compound of formula (IV) structure,
R 1, R 3independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C1 ~ C30, the aryl of C6 ~ C50, the arylalkyl of C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1be selected from the arylidene of C6 ~ C50,
Or Ar 1, the nitrogen to be directly connected with Ar1 and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the arylidene of C6 ~ C50;
The compound of the compound and formula (V) structure will with formula (IV) structure reacts, and obtains the compound of formula (I) structure.
R 2, R 4independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C1 ~ C30, the aryl of C6 ~ C50, the arylalkyl of C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 2be selected from the aryl of C6 ~ C50,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the arylidene of C6 ~ C50.
According to the present invention, the compound of compound and formula (III) structure that the present invention will have formula (II) structure reacts, and obtains the compound of formula (IV) structure, wherein, and R 1, Ar 1and R 3r in the selection of group and aforesaid compound 1, Ar 1and R 3identical; The mol ratio of the compound of described formula (II) structure and the compound of formula (III) structure is 1:(0.9 ~ 1.2); The catalyzer of described reaction is preferably three (dibenzalacetone) two palladium and triphenyl phosphorus; The alkali of described reaction is sodium tert-butoxide; The temperature of described reaction is preferably 90 ~ 150 DEG C, is preferably 110 ~ 130 DEG C; The time of described reaction is preferably 10 ~ 40 hours, is more preferably 20 ~ 35 hours.
The source of the present invention to the compound of the compound of formula (II) structure and formula (III) structure is not particularly limited, and is obtained by preparation method well known in the art.
According to the present invention, the compound of compound and formula (V) structure that the present invention will have formula (IV) structure reacts, and obtains the compound of formula (I) structure; Wherein, R 2, Ar 2and R 4r in the selection of group and aforesaid compound 2, Ar 2and R 4identical; The mol ratio of the compound of described formula (IV) structure and the compound of formula (V) structure is 1:(0.9 ~ 1.2); In described reaction, alkali used is sodium tert-butoxide, and the catalyzer of described reaction is three (dibenzalacetone) two palladium and triphenyl phosphorus; The temperature of described reaction is preferably 60 ~ 100 DEG C, is preferably 70 ~ 80 DEG C; The time of described reaction is preferably 20 ~ 40 hours, is more preferably 30 ~ 35 hours.
The compound that present invention also offers a kind of formula of the present invention (I) structure is preparing the application in organic electroluminescence device;
Concrete, described organic electroluminescence device is preferably, and comprising:
First electrode, the second electrode and the organic matter layer be placed between described two electrodes, wherein, include the compound of structure shown in formula (I) in described organic matter layer; The compound of structure shown in formula (I) can be that single form or mix with other material is present in organic matter layer.
Wherein, described organic matter layer at least comprises hole injection layer, hole transmission layer, not only possess hole injects but also possesses hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and not only possess electric transmission but also possess one or more in electron injection technical ability layer.
Described hole injection layer, described hole transmission layer, described not only possessed hole inject but also possess that hole transport technical ability layer has at least one to be conventional hole injecting material, hole transporting material or not only possessed hole and inject but also possess hole transport technical ability material, be also likely the material that electron-transporting material generates.
In this patent, " organic matter layer " refers to the term of whole layers that dispose between organic electronic devices first electrode and the second electrode.
Concrete, when the compound of formula (I) structure is present in the luminescent layer in described organic layer, the compound of described formula (I) structure or can be entrained in other fluorescent host as light emitting host; Such as: luminescent layer can be red, yellow or cyan luminescent layer.And compound doped in cyan main body by formula (I) structure, the efficiency of the luminescent device obtained, brightness, resolving power and long lifetime can be provided.
When the compound of formula (I) structure is present in electron transfer layer, described electron transfer layer also comprises the compound containing metal.
When described organic layer comprises luminescent layer and electron transfer layer, the compound of described formula (I) structure may reside in wherein one deck or two-layer.
Device prepared by the compound including formula (I) structure of the present invention may be used for organic luminescent device (OLED), organic photovoltaic cell (OSC), Electronic Paper (e-Paper), Organophotoreceptor (OPC) or OTFT (OTFT).
Device of the present invention can by the methods such as film vapor deposition, electron beam evaporation, physical vapor deposition evaporation metal and have the oxide compound of electroconductibility and their alloy forms anode on substrate, and spin-coating (spin-coating) or strip also can be adopted to take the lead evaporation; The method reduction layer numeral systems such as shaping (tape-casting), scraping blade method (doctor-blading), silk screen printing (Screen-Printing), ink jet printing or thermal imaging (Thermal-Imaging) can also be adopted to make.
Compared with prior art, aromatic amine compounds provided by the invention has formula (I) structure, by nitrogenous aromatic group being in respectively 4 and 3 of biphenyl, make the compound prepared for electroluminescent material, its current efficiency and work-ing life are all higher than existing aromatic amine compounds.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, and obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1 ~ 21
1) preparation of formula (II-1) structural compounds
P-Bromofluorobenzene (40mmol; 7g), 4-fluoroaniline (44mmol; 4.9g) add 250mL there-necked flask, under nitrogen, add three (dibenzalacetone) two palladium (2mmol, 1.2g); tertiary butyl sodium alkoxide (120mmol; 11.5g), toluene 100mL, after stirring at normal temperature 30min; add tri-butyl phosphine (8mmol, 1.6g) under nitrogen protection and be warming up to 80 DEG C of reaction 20h.Be extracted with ethyl acetate, sherwood oil recrystallization is used after merging organic phase evaporate to dryness, thick product is crossed column chromatography, eluent sherwood oil/methylene dichloride=5:1 will obtain two (4-fluorophenyl) amine shown in formula (II-1) after organic phase evaporate to dryness, output is 5.74g, and yield is 70%.
The synthetic method of formula (II-2) ~ formula (II-16) and the synthetic method of formula (II-1) similar, the raw material of its synthesis and product and yield are in table 1, and table 1 is the product shown in formula (II-2) ~ formula (II-15) and raw material thereof and productive rate;
Table 1 is the product shown in formula (II-2) ~ formula (II-15) and raw material thereof and productive rate
2) preparation of structural compounds shown in formula (IV)
Two (4-fluorophenyl) amine (20mmol, 4.1g), 3,4 '-'-dibromobiphenyl (22mmol, 6.86g) adds in 100mL there-necked flask, be dissolved in toluene 30mL, add two palladium (1mmol, 0.58g) under a nitrogen, sodium tert-butoxide (60mmol, 5.76g), tri-butyl phosphine (4mmol, 0.8g), 110 DEG C of reaction 24h.Be extracted with ethyl acetate, ethyl alcohol recrystallization is used after merging organic phase evaporate to dryness, ethyl acetate/petroleum ether=1/10 is used to be eluent afterwards, cross column chromatography post, the bromo-N of 3-shown in formula (IV-1) is obtained obtaining after revolving steaming, N-bis-(4-fluorophenyl)-4-phenylaniline, output is 5.23g, and yield is 60%.
The synthetic method of formula (IV-2) ~ formula (IV-16) and the synthetic method of formula (IV-1) similar, the raw material of its synthesis and product and yield are in table 2, and table 2 is the product shown in formula (IV-2) ~ formula (IV-16) and raw material thereof and productive rate;
Table 2 is the product shown in formula (IV-2) ~ formula (IV-16) and raw material thereof and productive rate
3) preparation of formula (I) structural compounds
The bromo-N of 3-, N-bis-(4-fluorophenyl)-4-phenylaniline (22.9mmol, 10g), carbazole (11mmol, 1.84g) add in 100mL there-necked flask, be dissolved in toluene 50mL, add two palladium (0.5mmol, 0.28g) under a nitrogen, sodium tert-butoxide (30mmol, 2.88g), tri-butyl phosphine (2mmol, 0.4g), 110 DEG C of reaction 20h.Be extracted with ethyl acetate, merge organic phase, use sherwood oil recrystallization by after organic phase evaporate to dryness, thick product is crossed column chromatography, eluent sherwood oil/methylene dichloride=8:1, obtains the product shown in formula (I), is designated as the product that embodiment 1 obtains.Output is 3.13g, and yield is 60%.
Proton nmr spectra is adopted to detect the product that embodiment 1 prepares, result is as follows: 1HNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.20 (d, J=10.0Hz, 2H), 7.71 – 7.32 (m, 9H), 7.26 – 6.99 (m, 12H).Visible, the present invention has prepared the compound described in embodiment 1.
The synthetic method of the synthetic method of the product described in embodiment 2 ~ 21 and the product described in embodiment 1 is similar, the raw material of its synthesis and product and yield in table 3, table 3 be embodiment 2 ~ 28 preparation product, prepare the yield productive rate of product desired raw material and product thereof.
Product prepared by table 3 embodiment 2 ~ 28, the yield productive rate preparing product desired raw material and product thereof
Adopt the compound structure of proton nmr spectra to the embodiment 2 of preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.20 (d, J=10.0Hz, 2H), 7.70 – 7.44 (m, 10H), 7.43 – 7.31 (m, 7H), 7.16 (dd, J=27.5,17.5Hz, 4H).Visible, the present invention has prepared the product described in embodiment 2.
Adopt embodiment 3 compound structure of proton nmr spectra to preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.20 (d, J=10.0Hz, 2H), 7.75 (s, 2H), 7.70 – 7.33 (m, 16H), 7.29 – 6.95 (m, 9H).Visible, the present invention has prepared the product described in embodiment 3.
Adopt the compound structure of proton nmr spectra to the embodiment 18 of preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.98 (s, 1H), 8.84 (s, 1H), 8.55 (s, 1H), 8.15 (d, J=40.0Hz, 2H), 7.97 – 7.86 (m, 6H), 7.73 – 7.49 (m, 6H), 7.40 (s, 1H), 7.29 – 6.95 (m, 12H), visible, the present invention has prepared the product described in embodiment 18.
Adopt the compound structure of proton nmr spectra to preparation embodiment 22 to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.32 (s, 1H), 8.26 – 8.05 (m, 4H), 7.69 – 7.28 (m, 19H), 7.16 (dd, J=27.5,17.5Hz, 4H).Visible, the present invention has prepared the product described in embodiment 22.
Adopt the compound structure of proton nmr spectra to the embodiment 23 of preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.20 (d, J=10.0Hz, 2H), 7.70 – 7.32 (m, 13H), 7.25 – 6.98 (m, 8H), 2.52 (s, 2H), 1.63 (s, 2H), 1.26 (s, 9H), 0.89 (s, 3H), visible, the present invention has prepared the product described in embodiment 23.
Adopt the compound structure of proton nmr spectra to the embodiment 24 of preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 9.24 (s, 1H), 8.70 (s, 1H), 8.55 (s, 1H), 8.33 (s, 1H), 8.20 (d, J=10.0Hz, 2H), 7.70 – 7.32 (m, 18H), 7.16 (dd, J=27.5,17.5Hz, 4H).Visible, the present invention prepares the product of knowing clearly described in embodiment 24.
Adopt the compound structure of proton nmr spectra to the embodiment 25 of preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.20 (d, J=10.0Hz, 2H), 7.93 (s, 2H), 7.70 – 7.34 (m, 9H), 7.29 – 6.94 (m, 11H), 6.76 (s, 2H), 6.37 (s, 2H), 5.87 (d, J=37.3Hz, 4H), 5.38 (s, 2H).Visible, the present invention has prepared the product described in embodiment 25.
Adopt the compound structure of proton nmr spectra to the embodiment 26 of preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.19 (s, 1H), 7.91 (d, J=5.0Hz, 4H), 7.75 (s, 2H), 7.46 (dt, J=20.0,15.0Hz, 15H), 7.32 – 7.04 (m, 12H), 4.33 (s, 2H).Visible, the present invention has prepared the product described in embodiment 26.
Adopt the compound structure of proton nmr spectra to the embodiment 27 of preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.19 (s, 1H), 8.04 (d, J=10.0Hz, 2H), 7.91 (d, J=5.0Hz, 4H), 7.75 (s, 3H), 7.54 (dd, J=40.0,25.0Hz, 6H), 7.48 – 7.25 (m, 8H), 7.24 – 7.03 (m, 9H), 6.79 (s, 2H), 5.60 (s, 2H).Visible, the present invention has prepared the product described in embodiment 27.
Adopt Compound C-28 structure of proton nmr spectra to preparation to characterize, result is as follows: 1hNMR (500MHz, Chloroform) δ 8.55 (s, 1H), 8.19 (s, 1H), 7.91 (d, J=5.0Hz, 4H), 7.54 (d, J=15.0Hz, 2H), 7.40 (s, 1H), 7.29 – 6.95 (m, 26H).Visible, the present invention has prepared the product described in embodiment 28.
4) carrying out performance test to the compound formula obtained (I) Suo Shi by Fisher Co., Ltd's coat-thickness is ito glass substrate be placed in distilled water clean 2 times, ultrasonic washing 30 minutes, 30 minutes are washed in order by Virahol, acetone, methyl alcohol, 2 times are repeatedly cleaned with distilled water, ultrasonic washing 10 minutes, dry, transfer in plasma washing machine, aforesaid substrate is washed 5 minutes, deliver in evaporator.Evaporation hole injection layer 2-TNATA evaporation successively on ready ito transparent electrode the embodiment material recorded in hole transmission layer a-NPD or table 4 the cyan main body A DN (9,10-Di (2-naphthyl) anthracene) of doping 5wt%TPPDA hole blocking layer and electron transfer layer negative electrode in above-mentioned evaporate process, organic matter vaporization plating speed keeps 1 / sec, LiF are / sec, Al are / sec.Evaporation is complete obtains luminescent device, tests the performance characteristics of luminescence of the device obtained, and measures and adopts KEITHLEY Keithley 2400 type source measuring unit, CS-2000 spectroradio luminance meter, to evaluate driving voltage, and luminosity, luminous efficiency, glow color.The results are shown in Table 4, the characteristics of luminescence test result of the compound that table 4 is prepared for the embodiment of the present invention and luminescent device prepared by a-NPD.
The characteristics of luminescence test result of compound prepared by table 4 embodiment of the present invention and luminescent device prepared by a-NPD
The luminous efficiency of compound provided by the invention is tied and the life-span increases significantly relative to a-NPD from table 4.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.

Claims (10)

1. an aromatic amine compounds, has formula (I) structure,
Wherein,
R 1for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 2for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 3for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 4for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1, Ar 2independently be selected from the arylidene of C6 ~ C50,
Or Ar 1, and Ar 1the nitrogen be directly connected and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the aryl of C6 ~ C50,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the aryl of C6 ~ C50.
2. compound according to claim 1, it is characterized in that, described alkyl is straight chained alkyl, branched-chain alkyl that direct-connected alkyl that branched-chain alkyl, cycloalkyl, at least 1 substituting group replace, at least 1 substituting group replace or the cycloalkyl that at least 1 substituting group replaces;
Described aryl is the aryl that unsubstituted aryl or at least 1 substituting group replace;
Described aralkyl is the aralkyl that unsubstituted aralkyl or at least 1 substituting group replace;
Described alkoxy aryl is the alkoxy aryl that unsubstituted alkoxy aryl or at least 1 substituting group replace;
Described aryl alkane sulfydryl is the aryl alkane sulfydryl that unsubstituted aryl alkane sulfydryl or at least 1 substituting group replace;
Described heteroaryl is the heteroaryl that unsubstituted heteroaryl or at least 1 substituting group replace,
Wherein, the heteroatoms in described heteroaryl is nitrogen, sulphur or oxygen;
Described substituting group independently selects halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.
3. compound according to claim 1, is characterized in that, described R 1, R 2, R 3, R 4independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C3 ~ C20, the aryl of C10 ~ C40, the aralkyl of C10 ~ C40, the alkoxy aryl of C10 ~ C40, the aryl alkane sulfydryl of C10 ~ C40 or C7 ~ C30.
4. compound according to claim 1, is characterized in that, Ar 1, Ar 2independently be selected from the arylidene of C10 ~ C40,
Or Ar 1, and Ar 1the nitrogen be directly connected and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the arylidene of C10 ~ C40,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the arylidene of C10 ~ C40.
5. compound according to claim 1, is characterized in that, described R 1, R 2, R 3, R 4independently be selected from H, F, Cl, Br, I, methyl, ethyl, the fluoro-ethyl of 2-, 2-cyano-propyl, sec.-propyl, the tertiary butyl, pentyl, heptane base, dodecyl, formula (a-1) structure, formula (a-2) structure, formula (a-3) structure, formula (a-4) structure, formula (a-5) structure, formula (a-6) structure, formula (a-7) structure, formula (a-8) structure, formula (a-9) structure, formula (a-10) structure, formula (a-11) structure, formula (a-12) structure, formula (a-13) structure, formula (b-1) structure, formula (b-2) structure, formula (b-3) structure, formula (b-4) structure, formula (b-5) structure, formula (b-6) structure, formula (b-7) structure, formula (b-8) structure, formula (b-9) structure, formula (b-10) structure, formula (b-11) structure, formula (b-12) structure, formula (c-1) structure, formula (c-2) structure, formula (c-3) structure, formula (c-4) structure, formula (c-5) structure, formula (c-6) structure, formula (c-7) structure, formula (c-8) structure, formula (c-9) structure, formula (c-10) structure, formula (c-11) structure, formula (c-12) structure, formula (d-1) structure, formula (d-2) structure, formula (d-3) structure, formula (d-4) structure, formula (d-5) structure, formula (d-6) structure or formula (d-7) structure,
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.
6. compound according to claim 1, is characterized in that, Ar 1, Ar 2independently be selected from formula (e-1) structure, formula (e-2) structure, formula (e-3) structure, formula (e-4) structure, formula (e-5) structure, formula (e-6) structure, formula (e-7) structure, formula (e-8) structure, formula (e-9) structure, formula (e-10) structure, formula (e-11) structure or formula (e-12) structure
Wherein, Ra is halogen, amino, cyano group, nitro, hydroxyl or sulfydryl.
7. compound according to claim 1, is characterized in that, the compound of described formula (I) structure is formula (I-1), formula (I-2) or formula (I-3),
Wherein,
R 1for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 2for the heteroaryl of the arylalkyl of the aryl of the alkyl of hydrogen, halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 3for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
R 4for the heteroaryl of the arylalkyl of the aryl of the alkyl of halogen, cyano group, C1 ~ C30, C6 ~ C50, C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1, Ar 2independently be selected from the aryl of C6 ~ C50.
8. compound according to claim 1, it is characterized in that, the compound of described formula (I) structure is formula (I-1-1), formula (I-1-2), formula (I-1-3), formula (I-1-4), formula (I-1-5), formula (I-1-6), formula (I-1-7), formula (I-1-8), formula (I-1-9), formula (I-1-10), formula (I-1-11), formula (I-1-12), formula (I-1-13), formula (I-1-14), formula (I-2-1), formula (I-2-2), formula (I-2-3), formula (I-2-4), formula (I-2-5), formula (I-2-6), formula (I-2-7), formula (I-2-8), formula (I-2-9), formula (I-2-10), formula (I-2-11), formula (I-2-12), formula (I-2-13) or the compound shown in formula (I-3-1),
9. there is a preparation method for formula (I) structure aromatic amine compounds, comprising:
The compound of the compound and formula (III) structure will with formula (II) structure reacts, and obtains the compound of formula (IV) structure,
R 1, R 3independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C1 ~ C30, the aryl of C6 ~ C50, the arylalkyl of C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 1be selected from the arylidene of C6 ~ C50,
Or Ar 1, and Ar 1the nitrogen be directly connected and substituent R 1the phenyl ring at place forms carbazoles structure, wherein, and Ar 1independently be selected from the arylidene of C6 ~ C50;
The compound of the compound and formula (V) structure will with formula (IV) structure reacts, and obtains the compound of formula (I) structure,
R 2, R 4independently be selected from the heteroaryl of hydrogen, halogen, cyano group, the alkyl of C1 ~ C30, the aryl of C6 ~ C50, the arylalkyl of C7 ~ C50, the alkoxy aryl of C7 ~ C50, the aryl alkane sulfydryl of C7 ~ C50 or C5 ~ C50;
Ar 2be selected from the arylidene of C6 ~ C50,
Or Ar 2, and Ar 2the nitrogen be directly connected and substituent R 2the phenyl ring at place forms carbazoles structure, wherein, and Ar 2independently be selected from the arylidene of C6 ~ C50.
10. compound prepared by formula (I) compound shown in claim 1 ~ 8 any one and preparation method according to claim 9 is preparing the application in organic electroluminescence device.
CN201510492903.0A 2015-08-12 2015-08-12 Aromatic amine compound and preparing method and application thereof Pending CN105085374A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019196351A (en) * 2018-05-08 2019-11-14 ピョクサン ペイント アンド コーティングス カンパニー，リミテッド Hole transport compound and organic light emitting element comprising thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006156635A (en) * 2004-11-29 2006-06-15 Konica Minolta Holdings Inc Organic electroluminescent element and indicating device
JP2009021335A (en) * 2007-07-11 2009-01-29 Konica Minolta Holdings Inc Organic electroluminescent element, display device, and lighting device
CN101473464A (en) * 2006-06-22 2009-07-01 出光兴产株式会社 Organic electroluminescent element using heterocyclic aromatic amine derivative
CN101587308A (en) * 2008-05-20 2009-11-25 夏普株式会社 Multiple layer electronic photographic photoreceptor and the image forming apparatus that it is installed
JP4770033B2 (en) * 2001-02-13 2011-09-07 コニカミノルタホールディングス株式会社 Organic electroluminescence device
CN103204798A (en) * 2012-11-12 2013-07-17 吉林奥来德光电材料股份有限公司 Aromatic amine derivative, its preparation method and organic electroluminescent device made through using it
KR20130106255A (en) * 2012-03-19 2013-09-27 덕산하이메탈(주) Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4770033B2 (en) * 2001-02-13 2011-09-07 コニカミノルタホールディングス株式会社 Organic electroluminescence device
JP2006156635A (en) * 2004-11-29 2006-06-15 Konica Minolta Holdings Inc Organic electroluminescent element and indicating device
CN101473464A (en) * 2006-06-22 2009-07-01 出光兴产株式会社 Organic electroluminescent element using heterocyclic aromatic amine derivative
JP2009021335A (en) * 2007-07-11 2009-01-29 Konica Minolta Holdings Inc Organic electroluminescent element, display device, and lighting device
CN101587308A (en) * 2008-05-20 2009-11-25 夏普株式会社 Multiple layer electronic photographic photoreceptor and the image forming apparatus that it is installed
KR20130106255A (en) * 2012-03-19 2013-09-27 덕산하이메탈(주) Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof
CN103204798A (en) * 2012-11-12 2013-07-17 吉林奥来德光电材料股份有限公司 Aromatic amine derivative, its preparation method and organic electroluminescent device made through using it

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019196351A (en) * 2018-05-08 2019-11-14 ピョクサン ペイント アンド コーティングス カンパニー，リミテッド Hole transport compound and organic light emitting element comprising thereof
CN110452154A (en) * 2018-05-08 2019-11-15 碧山油漆股份公司 Hole transport compound and organic illuminating element comprising the compound
CN110452154B (en) * 2018-05-08 2023-03-31 贝匹科有限公司 Hole transport compound and organic light emitting device including the same

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