CN1906268A

CN1906268A - New materials for injecting or transporting holes and organic electroluminescence devices using the same

Info

Publication number: CN1906268A
Application number: CNA2005800016672A
Authority: CN
Inventors: 金芝垠; 李载澈; 金公谦; 裴在顺; 张俊起; 全相映; 姜旼秀; 赵昱东; 全柄宣; 金渊焕
Original assignee: LG Chemical Co Ltd
Current assignee: LG Corp
Priority date: 2004-03-19
Filing date: 2005-03-18
Publication date: 2007-01-31
Also published as: TW200600565A; TWI294454B; KR20050118098A; JP2011068659A

Abstract

The present invention relates to a novel compound that can significantly improve the lifespan, efficiency and thermal stability of an organic light emitting device, and to an organic electroluminescence device or light emitting device comprising the compound in an organic compound layer is also disclosed.

Description

Be used to inject or the novel material of transporting holes and the organic electroluminescence device that uses this material

Technical field

The present invention relates to a kind of novel cpd that can significantly improve organic light-emitting device life-span, efficient and thermostability, and a kind of organic luminescent device that in organic compound layer, comprises this compound.

Background technology

In the epoch of 21 century advanced information technology, should be able to obtain bulk information rapidly easily, therefore increased the importance that is used for multimedia high-performance flat-panel monitor.Although up to the present liquid-crystal display (LCD) has been the major portion in the flat-panel monitor, carried out the effort that many exploitations have cost benefit, excellent properties and are different from the novel flat-plate indicating meter of liquid-crystal display in the whole world.Compare with liquid-crystal display, expection has the advantage at the visual angle of lower driving voltage, the higher speed of response, higher efficient and broad mainly as organic electroluminescent (EL) device of senior flat-panel monitor or organic luminescent device.In addition, owing to utilize the indicating meter of organic electroluminescent phenomenon to allow 2mm or littler module total thickness, and can be fabricated on the plastic base with 0.3mm or littler thickness, so can meet the thinner and littler development trend of indicating meter.In addition, display of organic electroluminescence has other advantage and is, compares the cost manufacturing that this display of organic electroluminescence can be lower with liquid-crystal display.

Organic luminescent device is based on following mechanism: electronics and the hole of injecting the organic membrane that is formed by organic compound by anode and negative electrode form exciton at its compound tense, launch the light with certain wavelength from this exciton then.In nineteen sixty-five, people such as Pope have found the electroluminescent character of anthracene single crystal body first.After this, in 1987, people such as the Tang of Kodak find, by organic materials form have separation function lamination (promptly laminated each other hole transmission layer and luminescent layer) even organic luminescent device under 10V or littler low voltage, also can provide 1000cd/m ²Or higher high brightness.After those were found, organic luminescent device had caused strong repercussion (Tang, C.W. in the display technology field; Vanslyke, S.A.Appl.Phys.Lett.1987,51,913).This organic luminescent device is divided into the device that uses fluorescence and the device that can provide up to 3 times to based on the high efficiency phosphorescence of fluorescence efficiency is provided.Perhaps, this organic luminescent device can be according to the molecular weight classification that forms the organic light-emitting device organic materials, promptly, by using the vacuum-sublimation method to form the device of the lower molecular weight method preparation of device, and by using the device that forms the high molecular method preparation of device such as the solution method of spin-coating method, ink jet printing method or rolling method.

As shown in Figure 1, conventional organic luminescent device comprise anode, accept to come from the anodic hole hole injection layer, transporting holes hole transmission layer, hole and electronics therein recombination luminescence luminescent layer, accept the electron transfer layer and the negative electrode that come from the electronics of negative electrode and transmit it to luminescent layer.Above-mentioned thin film layer forms by vacuum deposition method.Preparing the organic light-emitting device with multilayer film structure the reasons are as follows.Because the mobility in hole is significantly higher than the mobility of electronics in organic materials, so can be when using suitable hole transmission layer and electron transfer layer more effectively to luminescent layer transporting holes and electronics.In addition, when hole density in luminescent layer and electron density balance, can improve luminous efficiency.

Hereinafter, will describe with reference to the organic luminescent device of 1 pair of routine of figure.

Substrate 1 is the organic light-emitting device carrier, and can be formed by organosilicon wafer, quartz or sheet glass, metal sheet, plastic film or sheet etc.Preferred use sheet glass or by the transparent panel of making such as the synthetic resins of polyester, polymethacrylate or polysulfones.

First electrode (anode) 2 is placed on the substrate 1.Anode is used for to hole injection layer 3 injected holes, and can be by the metal as aluminium, gold and silver, nickel, palladium or platinum, as the metal oxide of tin indium oxide or indium zinc oxide, the halo metal, carbon black, or as gathering the conductive polymers formation of (3 methyl thiophene), polypyrrole or polyaniline.

Hole injection layer 3 is placed on the anode 2.The material that is used for hole injection layer must can provide from the high-level efficiency of anode injected hole, and must transmit injected holes efficiently.In this, this material should have low ionization potential, to the high-clarity of visible light and excellent hole stability.

The material that is used for hole injection layer comprise have excellent thermostability and can keep simultaneously and anode between the compound of stable interface.The representative example of this material comprises copper phthalocyanine (CuPc), its be Kodak at U.S. Patent number 4,356, the porphyrin copper complex compound that discloses in 429.Because CuPc is used for the most stable compound of hole injection layer, so it is widely used.Yet CuPc has absorption band at blue and red chromatic color area, and therefore has certain problem when making full color display device.Recently, known star aromatics arylamines compounds (starburst-like aromatic aryl amine compounds) does not have absorption band (U.S. Patent number 5 at blue chromatic color area, 256,945 and Japanese publication 1999-219788, and referring to following chemical formula 4～12).Specifically, do not have in the star amine of absorption band, use compound by chemical formula 8～12 expressions with 100 ℃ or higher second-order transition temperature and excellent stability at blue chromatic color area.

CuPc chemical formula 4

Chemical formula 5 chemical formulas 6

Chemical formula 7 chemical formulas 8

Chemical formula 9 Chemical formula 1s 0

Chemical formula 11 Chemical formula 12

Recently, many have higher second-order transition temperature and the bigger hole-injecting materials of thermostability improvement have been reported.Wherein great majority are that NPB by Kodak derives and the compound that comes, and by 3～17 expressions of following Chemical formula 1 (referring to, the flat 9-301934 of Japanese patent application publication No. and U.S. Patent number 6,334,283 and 6,541,129).

NPB Chemical formula 13

Chemical formula 14 Chemical formula 1s 5

Chemical formula 16 Chemical formula 1s 7

In addition, Japanese patent application publication No. 2003-238501 has disclosed aromatics oligomeric amine (aromatic oligoamine) derivative (Chemical formula 18 and 19) that has at least 5 nitrogen-atoms in a molecule.

Chemical formula 18

Chemical formula 19

In addition, recently, Japanese patent application publication No. 2003-317966 and U.S. Patent number 6,660,410 have all disclosed the material (Chemical formula 2 0) that a kind of carbazolyl-containing is rolled into a ball, it is specific to be used as the main body that forms luminescent layer in the organic luminescent device that uses phosphorescence, and compares with known CBP (phenylbenzene carbazole (carbazole biphenyl)) traditionally, and it is considered to improve the organic light-emitting device life-span.Other compound that is used for hole injection layer is by 1～27 expression of following Chemical formula 2.

Chemical formula 20 Chemical formula 21

Chemical formula 22 Chemical formula 2s 3

Chemical formula 24 Chemical formula 2s 5

Chemical formula 26 Chemical formula 2s 7

Hole transmission layer 4 is placed on the hole injection layer 3.Hole transmission layer is used for accepting the hole from hole injection layer, and with hole transport to organic luminous layer 5 placed on it.Hole transmission layer has higher cavity conveying ability and hole stability.It also is used as the blocking layer of block electrons.Except that above-mentioned basic requirement, for example, when it was used for Vehicular display device spare, the material that is preferred for hole transmission layer had thermotolerance and 80 ℃ or the higher second-order transition temperature of improvement.The material that satisfies such requirement comprises NPB, volution novel arylamine compound (spiro-arylamine compound), perylene-novel arylamine compound, nitrogen heterocyclic heptantriene compound (azacycloheptatriene compound), two (diphenylacetylene phenyl) anthracene, silicon germanium oxide compound, siliceous novel arylamine compound etc.

Simultaneously, as the important organic supramolecular that is used for hole transmission layer (organic singlemolecule), novel arylamine compound has higher hole mobility and excellent elctrical stability.In order to improve the thermostability of novel arylamine compound, reported naphthyl substituted base or volution base be introduced into hole mobile material (referring to, U.S. Patent number 5,554,459 and 5,840,217).Originally, often use N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-1,1 '-phenylbenzene-4,4 '-diamines (TPD) is as the organic hole transport material.Yet, because TPD is 60 ℃ or higher temperature instability, thus use at present have high glass transition based on N-naphthyl-N-phenyl-1,1 '-phenylbenzene-4,4 '-material of diamines (NPD) or with the amine compound of a large amount of aromatic groups replacements.Specifically, the organic supramolecular that is used for hole transmission layer should have higher hole transport rate.In addition, because hole transmission layer contacts with luminescent layer, and form the interface betwixt, should between the ionization potential value of the ionization potential value of hole injection layer and luminescent layer, have suitable ionization potential value so be used for organic single material (organic single materials) of hole transmission layer, thereby the interface of restraining between hole transmission layer and luminescent layer produces exciton.In addition, be used for organic single material require control of hole transmission layer from the luminescent layer electrons transmitted.

Organic luminous layer 5 is placed on the hole transmission layer 4.Organic luminous layer is formed by the material with higher quantum yield, and this organic luminous layer is used for by respectively by the recombination luminescence of anode and negative electrode injected holes and electronics.

Be used for therein being divided into material of main part and guest materials by function by the compound organic supramolecular of finishing luminous luminescent layer of hole and electronics.In general, when separately the main consuming body material or guest materials, can realize luminous.Yet, in order to solve the lower problem of efficient and brightness and except that the unique property of each molecule, to cause the problem from filling (self-packing) of the same molecular that the excite state molecular characterization occurs, with guest materials doped body material.

More particularly, as the green luminescence layer, oxine aluminium salt can be used alone, and material such as the quinacridone of the high-quantum efficiency that also can mix or C545t are to improve luminous efficiency.Compare with Alq3 as green light luminescent material, the organic materials that is used for blue light-emitting exist fusing point lower, at starting time (initial time) stability of photoluminescence low and relatively poor problem of life-span.In addition, send pale blue coloured light rather than ethereal blue coloured light owing to be used for the material of main part of blue light-emitting, so they are not suitable for the full color escope, and therefore mix perylene or distyryl base amine (distyryl amines) are (DSA) to improve luminous efficiency.As U.S. Patent number 5,516,577,5,366,811,5,840,217,5,150,006 and 5, disclosed in 645,948, the conventional organic materials that is used for blue light-emitting comprises aromatic hydrocarbon, volution type compound, aluminiferous organometallic compound, the heterogeneous ring compound with imidazolyl, condensed ring aromatic compound.Simultaneously, under the situation of red light luminescent layer, because the narrow band gap of characteristic of emitting red light has used a large amount of green light luminescent materials that are doped with a spot of red light-emitting material.Yet such material has the structural issue of the improvement that hinders the life-span.

Electron transfer layer 6 is placed on the organic luminous layer 5.In electron transfer layer 6, use from negative electrode 7 (second electrode) to have the material that higher injection electronic efficiency also can effectively transmit injected electrons.In order to be satisfied with this, this material should have higher electron affinity, electronic mobility and excellent electronic stability.The material that satisfies above-mentioned requirements comprises: as the aromatic substance (the clear 57-51781 of Japanese publication number) of tetraphenylbutadiene, metal complex as oxine aluminium (the clear 59-194393 of Japanese publication number), metal complex (the flat 6-322362 of Japanese patent application publication No.) as 10-hydrogen benzo [h] quinoline, cyclopentadiene derivant (the flat 2-289675 of Japanese patent application publication No.), bisstyryl benzene derivative (the flat 1-245087 peace of Japanese patent application publication No. 2-222484), perylene derivative (the flat 2-189890 peace of Japanese patent application publication No. 3-791), to penylene derivative (the flat 3-33183 peace of Japanese patent application publication No. 11-345686) ， oxazole derivative etc.

In addition, the organic supramolecular that preferably is used for electron transfer layer comprises the organometallic complex with higher relatively electronic stability and higher electronic mobility.Specifically, it is reported, because Alq3 has excellent stability and higher electron affinity, so it is a most preferred material.Except above-mentioned materials, known other electron transport material of those skilled in the art comprises Flavon or the silol series of buying from Chisso company.

Especially, not than the above-mentioned preferred candidate material of material that is used for electron transfer layer.In general, electron transport material uses with the form of the mixture that contains the metal that is useful on negative electrode.In addition, also can use inorganic materials as lithium fluoride (LiF).

Negative electrode 7 is used for injecting electronics to organic luminous layer 5.Can use the material of material used in the anode 2 as negative electrode.Yet, in order more effectively to inject electronics, the preferred metal that has than low work function that uses.The object lesson of described metal comprises lithium, caesium, sodium, tin, magnesium, indium, calcium, aluminium etc. and alloy thereof.

Yet, use the organic elctroluminescent device of the organic supramolecular of each layer be suitable for forming device to have the short life-span usually, and have storage weather resistance (shelf durability) and the relatively poor problem of reliability.This problem be considered to by the oxidation of the physics in the organic materials, chemistry, photochemistry and electrochemical change, negative electrode, middle layer separate and fusing, crystallization and the pyrolysis of organic compound produce.

Summary of the invention

As mentioned above, conventionally comprise that the hole-injecting material as the organometallic complex of the material of CuPc, novel arylamine compound and carbazolyl-containing has and be difficult to the problem that realizes full color and show bad stability.

The inventor is the organic compound of the carbazolyl-containing of being represented by Chemical formula 1 of synthesizing new.And when they have found that above-mentioned novel cpd is used as hole injection and transport material, efficient, life-span and the thermostability that can provide organic luminescent device significantly to improve.The present invention is based on this discovery.

As mentioned above, can in organic electroluminescence device, realize required color by the structure that changes suitable organic supramolecular.In this, various high efficiency organic electroluminescence devices are provided by the main consuming body-object system.Yet for practical application, such device shows the insufficient characteristics of luminescence, life-span and weather resistance.Therefore, the present invention considers the problems referred to above and makes.The purpose of this invention is to provide a kind of type material that is used for hole injection and hole transmission layer, it can improve luminous efficiency, stability and the life-span of organic electroluminescence device, and a kind of organic electroluminescence device that uses this material is provided.

Another object of the present invention provides a kind of material with the required distillation characteristic of high glass transition, excellent thermostability and vacuum evaporation sedimentation (vacuum vapor deposition processes).

According to an aspect of the present invention, provide a kind of organic compound and a kind of organic electroluminescence device of representing by following Chemical formula 1 that in organic compound layer, comprises this compound:

[Chemical formula 1]

Wherein A is

B is

C is

D be H,

In above-mentioned chemical formula, R1～R10 is identical or different, and preferably separately only once or repeat at least twice ground and comprise that at least one is selected from and comprise hydrogen atom, aliphatic hydrocarbon with 1～20 carbon atom, non-replacement or the aromatic hydrocarbon that replaces by nitro, nitrile, halogen, alkyl, alkoxyl group or amino, have the silica-based of aromatic substituent, non-replacement or the heterocyclic aromatic hydrocarbon that replaces by nitro, nitrile, halogen, alkyl, alkoxyl group or amino, group in the group of thienyl that replaces by the aromatic hydrocarbon of the hydrocarbon of C1～C20 or C6～C24 and the boryl that replaces by aromatic hydrocarbon; And

Ar is non-replacement or by nitro, nitrile, halogen, alkyl, alkoxyl group or the amino aromatic hydrocarbon that replaces.

In above-mentioned chemical formula, l, m and n respectively be 1 or bigger integer and o be 0 or bigger integer, preferred l, m and n represent simultaneously 1 and o be 0, condition is the compound that Chemical formula 1 is represented, wherein gets rid of R1, R2, R3, R4, R5 and R6 and represents that simultaneously hydrogen atom and D also are the situation of hydrogen atom.

Above-mentioned aromatic hydrocarbon comprises as the monocyclic aromatic ring of phenyl, phenylbenzene and triphenyl and as polycyclic aromatic ring of naphthyl, anthryl, phenanthrene, pyrenyl and perylene base etc.In addition, above-mentioned aromatic heterocycle hydrocarbon comprises thiophene, furans, pyrroles, imidazoles, thiazole, oxazole, oxadiazole, thiadiazole, triazole, pyridyl, pyridine amido (pyridazyl), pyrazine, quinoline, isoquinoline 99.9 etc.

Preferably, the compound of being represented by above-mentioned Chemical formula 1 can be served as reasons and is selected from the compound of any one chemical formulation among following Chemical formula 2 a～2e:

[Chemical formula 2 a]

[Chemical formula 2 b]

[Chemical formula 2 c]

[Chemical formula 2 d]

[Chemical formula 2 e]

More preferably, the compound of being represented by above-mentioned Chemical formula 1 can be served as reasons and is selected from the compound of any one chemical formulation among following chemical formula 3a～3n:

[chemical formula 3a]

[chemical formula 3b]

[chemical formula 3c]

[chemical formula 3d]

[chemical formula 3e]

[chemical formula 3f]

[chemical formula 3g]

[chemical formula 3h]

[chemical formula 3i]

[chemical formula 3j]

[chemical formula 3k]

[chemical formula 3l]

[chemical formula 3m]

[chemical formula 3n]

In above-mentioned Chemical formula 2 a～2e and 3a～3n, R1～R8 each with Chemical formula 1 in define identical.

Hereinafter, will be described in more detail the present invention.

The organic compound of Chemical formula 1,2 or 3 expressions can be used as hole-injecting material and hole mobile material, therefore can be used for being selected from the one deck at least in organic light-emitting device hole injection layer, hole transmission layer and the luminescent layer.

Specifically, each compound comprises carbazyl and is convenient to accept also transporting holes., this function is considered to be produced by the existence of ring texture that exists in carbazyl and the aryl that is connected with carbazyl.Therefore, the organic material layer that comprises above-claimed cpd can be used as hole injection layer or hole transmission layer.In addition, this organic material layer can be used as the hole and electronics is compound therein to finish luminous luminescent layer.In other words, can finish at least a function that is selected from hole injection, hole transport and luminous group according to compound of the present invention.Similarly, comprising the layer of above-claimed cpd in organic luminescent device can be as the one deck at least that is selected from the group of hole injection layer, hole transmission layer and luminescent layer.In addition, the layer that comprises above-claimed cpd can be used as hole injection/hole transmission layer, hole injection/hole transport/luminescent layer etc.

More particularly, because aryl in the carbazyl or substituent aryl of conduct and the carbazyl itself that is connected with carbazyl, described compound is considered to can be stably and acceptance transporting holes also safely.In addition, the substituting group that is connected with carbazyl is derived by amido.This substituting group can be kept the motion in hole, and keeps compound according to the present invention and do not hinder flowing of hole in stable state.Therefore, the organic luminescent device that comprises described compound shows the excellent stability and the life-span of improvement.

In addition, as long as have the required function that can be implemented in the organic material layer in the organic luminescent device corresponding to the substituent compound of R1～R10, according to the substituting group of compound of the present invention, promptly R1～R10 can represent any other substituting group, but not group as defined above.For example, when R1～R10 represents substituting group that alkyl or alkyl replace, without limits to the length of each alkyl.Because the length that is included in the alkyl in the described compound does not influence the conjugate length of this compound, so the length of this alkyl is to the wavelength or the not directly influence of Devices Characteristics of this compound.Yet the effect length of alkyl is applied to the selection of organic light-emitting device method with this compound, for example, and vacuum deposition method or solution cladding process.Therefore, the length that can be included in the alkyl in the compound of above-mentioned chemical formulation has no particular limits.

About the R1～R10 in the above-mentioned chemical formula, the object lesson of aromatic substance comprises as the monocyclic aromatic ring of phenyl, phenylbenzene, triphenyl etc. with as the polycyclic aromatic ring of naphthyl, anthryl, pyrenyl, perylene base etc.The object lesson of heteroaromatic compound comprises thiophene, furans, pyrroles, imidazoles, thiazole, oxazole, oxadiazole, thiadiazole, triazole, pyridyl, pyridine amido, pyrazine, quinoline, isoquinoline 99.9 etc.

Aliphatic hydrocarbon with 1～20 carbon atom comprises straight chain aliphatic hydrocarbon and branched chain aliphatic hydrocarbons.The object lesson of this hydrocarbon comprises the alkyl as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl etc.; Alkenyl as styryl with two keys; And has a triple-linked alkynyl as acetylene.

Nonrestrictive example according to compound of the present invention comprises the compound of being represented by following Chemical formula 2 8～260.

Chemical formula 28 Chemical formula 2s 9 chemical formulas 30

Chemical formula 31 chemical formulas 32 chemical formulas 33

Chemical formula 34 chemical formulas 35 chemical formulas 36

Chemical formula 37 chemical formulas 38 chemical formulas 39

Chemical formula 40 chemical formulas 41 chemical formulas 42

Chemical formula 43 chemical formulas 44 chemical formulas 45

Chemical formula 46 chemical formulas 47 chemical formulas 48

Chemical formula 49 chemical formulas 50

Chemical formula 51 chemical formulas 52

Chemical formula 53 chemical formulas 54

Chemical formula 55 chemical formulas 56

Chemical formula 57 chemical formulas 58

Chemical formula 59 chemical formulas 60

Chemical formula 61 chemical formulas 62

Chemical formula 63 chemical formulas 64

Chemical formula 65 chemical formulas 66

Chemical formula 67 chemical formulas 68

Chemical formula 69 chemical formulas 70

Chemical formula 71 chemical formulas 72

Chemical formula 73 chemical formulas 74

Chemical formula 75 chemical formulas 76

Chemical formula 77 chemical formulas 78

Chemical formula 79 chemical formulas 80

Chemical formula 81 chemical formulas 82

Chemical formula 83 chemical formulas 84

Chemical formula 85 chemical formulas 86

Chemical formula 87 chemical formulas 88

Chemical formula 89 chemical formulas 90

Chemical formula 91 chemical formulas 92

Chemical formula 93 chemical formulas 94

Chemical formula 95 chemical formulas 96

Chemical formula 97 chemical formulas 98

Chemical formula 99 Chemical formula 1s 00

Chemical formula 1 01 Chemical formula 1 02

Chemical formula 1 03 Chemical formula 1 04

Chemical formula 1 05 Chemical formula 1 06

Chemical formula 1 07 Chemical formula 1 08

Chemical formula 1 09 Chemical formula 1 10

Chemical formula 1 11 Chemical formula 1s 12

Chemical formula 1 13 Chemical formula 1s 14

Chemical formula 1 15 Chemical formula 1s 16

Chemical formula 1 17 Chemical formula 1s 18

Chemical formula 1 19 Chemical formula 1s 20

Chemical formula 1 21 Chemical formula 1s 22

Chemical formula 1 23 Chemical formula 1s 24

Chemical formula 1 25 Chemical formula 1s 26

Chemical formula 1 27 Chemical formula 1s 28

Chemical formula 1 29 Chemical formula 1s 30

Chemical formula 1 31 Chemical formula 1s 32

Chemical formula 1 33 Chemical formula 1s 34

Chemical formula 1 35 Chemical formula 1s 36

Chemical formula 1 37 Chemical formula 1s 38

Chemical formula 1 39 Chemical formula 1s 40

Chemical formula 1 41 Chemical formula 1s 42

Chemical formula 1 43 Chemical formula 1s 44

Chemical formula 1 45 Chemical formula 1s 46

Chemical formula 1 47 Chemical formula 1s 48

Chemical formula 1 49 Chemical formula 1s 50

Chemical formula 1 51 Chemical formula 1s 52

Chemical formula 1 53 Chemical formula 1s 54

Chemical formula 1 55 Chemical formula 1s 56

Chemical formula 1 57 Chemical formula 1s 58

Chemical formula 1 59 Chemical formula 1s 60

Chemical formula 1 61 Chemical formula 1s 62

Chemical formula 1 63 Chemical formula 1s 64

Chemical formula 1 65 Chemical formula 1s 66 Chemical formula 1s 67

Chemical formula 1 68 Chemical formula 1s 69

Chemical formula 1 70 Chemical formula 1s 71 Chemical formula 1s 72

Chemical formula 1 73 Chemical formula 1s 74

Chemical formula 1 75 Chemical formula 1s 76

Chemical formula 1 77 Chemical formula 1s 78

Chemical formula 1 79 Chemical formula 1s 80

Chemical formula 1 81 Chemical formula 1s 82

Chemical formula 1 83 Chemical formula 1s 84 Chemical formula 1s 85

Chemical formula 1 86 Chemical formula 1s 87 Chemical formula 1s 88

Chemical formula 1 89 Chemical formula 1s 90 Chemical formula 1s 91

Chemical formula 1 92 Chemical formula 1s 93 Chemical formula 1s 94

Chemical formula 1 95 Chemical formula 1s 96 Chemical formula 1s 97

Chemical formula 1 98 Chemical formula 1s 99 Chemical formula 2s 00

Chemical formula 2 01 Chemical formula 2 02 Chemical formula 2 03

Chemical formula 2 04 Chemical formula 2 05

Chemical formula 2 06 Chemical formula 2 07

Chemical formula 2 08 Chemical formula 2 09 Chemical formula 2 10

Chemical formula 2 11 Chemical formula 2s 12

Chemical formula 2 13 Chemical formula 2s 14

Chemical formula 2 15 Chemical formula 2s 16

Chemical formula 2 17 Chemical formula 2s 18 Chemical formula 2s 19

Chemical formula 2 20 Chemical formula 2s 21 Chemical formula 2s 22

Chemical formula 2 23 Chemical formula 2s 24 Chemical formula 2s 25

Chemical formula 2 26 Chemical formula 2s 27

Chemical formula 2 28 Chemical formula 2s 29

Chemical formula 2 30 Chemical formula 2s 31

Chemical formula 2 32 Chemical formula 2s 33

Chemical formula 2 34 Chemical formula 2s 35

Chemical formula 2 36 Chemical formula 2s 37

Chemical formula 2 38 Chemical formula 2s 39

Chemical formula 2 40 Chemical formula 2s 41

Chemical formula 2 42 Chemical formula 2s 43

Chemical formula 2 44 Chemical formula 2s 45

Chemical formula 2 46 Chemical formula 2s 47

Chemical formula 2 48 Chemical formula 2s 49

Chemical formula 2 50 Chemical formula 2s 51

Chemical formula 2 52 Chemical formula 2s 53

Chemical formula 2 54 Chemical formula 2s 55

Chemical formula 2 56 Chemical formula 2s 57

Chemical formula 2 58 Chemical formula 2s 59

Chemical formula 2 60

Organic compound by above-mentioned chemical formulation can be synthetic to eight step treatment steps by three steps by its starting material.In an embodiment of synthetic method, above-claimed cpd can be prepared from by carbazole.At first, handle carbazole, to form the starting material that replace by halogen or halogeno-benzene with halogen atom or halogeno-benzene.Then, the compound that corresponds respectively to A, B, C, D or R1～R10 in the above-mentioned Chemical formula 1 is added in the starting material replacing raw-material halogen atom, thereby form required compound.In this process, can use catalyzer.In the selection of halogen atom, have no particular limits.In general, can use bromine, chlorine etc.

Be understandable that those skilled in the art can design suitable synthetic method with reference to the structural formula according to compound of the present invention.

In the following embodiments, will the synthetic method of some compound be described.

Fig. 1 shows the preferred implementation of organic electroluminescence device.Organic compound according to the present invention can be used for placing at least one organic material layer between anode and the negative electrode, promptly is selected from the one deck at least that comprises in hole injection layer, hole transmission layer and the luminescent layer.More particularly, this compound can be used for hole injection layer, hole transmission layer, hole injection/hole transmission layer or hole injection/hole transport/luminescent layer.

Simultaneously, known material of main part with bigger bandwidth, CBP for example is doped with organic phosphorescent material as phenylpyridine iridium (phenylpyridine iridium) so that high efficiency device successfully to be provided.This expression can overcome the limited efficient that is caused by singlet state-singlet state transition by triplet state-triplet transition.Therefore, when novel hole-injecting material according to the present invention is used as based on the luminous material of main part of phosphorescence, can obtain to have the luminous efficiency of remarkable improvement and the organic electroluminescence device in life-span (C.Adachi, M.A.Baldo and S.R.Forrest, AppliedPhysics Letter, 77,904,2000., C.Adachi, M.A.Baldo, S.R.Forrest, S.Lamansky, M.E.Thompsom and R.C.Kwong, Applied Physics Letter, 78,1622,2001).

According to the present invention, comprising the organic electroluminescence device of compounds by above-mentioned Chemical formula 1～3 and 28～260 expressions in organic material layer can provide the efficient of remarkable improvement and life-span and show excellent stability.

Description of drawings

Fig. 1 is the sectional view that the structure of conventional organic electroluminescence device is shown.

The brief description of Reference numeral

1: substrate

2: anode

3: hole injection layer

4: hole transmission layer

5: organic luminous layer

6: electron transfer layer

7: negative electrode

Embodiment

Hereinafter, will be by embodiment and comparative example, to the synthetic method of the organic compound represented by above-mentioned Chemical formula 1 with use the preparation of the organic electroluminescence device of this compound to be described in more detail.Should be appreciated that the following examples only are illustrative, and the present invention is not limited.

In order to prepare the compound of being represented by above-mentioned Chemical formula 1, the compound of being represented by following chemical formula a～h can be used as starting material.

[chemical formula a] [chemical formula b]

[chemical formula c] [chemical formula d] [chemical formula e]

[chemical formula f] [chemical formula g]

[chemical formula h]

In above-mentioned chemical formula a～h, X represents halogen atom.In the selection of halogen atom, have no particular limits.In the following embodiments, selecting X wherein is that the compound represented of chemical formula a～h of Br is as starting material.According to following preparation example 1～8, the preparation starting material.

＜preparation example 1〉preparing raw material represented of chemical formula a

Make carbazole (5.00g, 29.9mmol), 1-bromo-4-phenyl-iodide (9.30g, 32.9mmol), K ₂CO ₃(16.5g, 120mmol), Cu (3.80g, 59.8mmol) and hexaoxacyclooctadecane-6-6 (0.40g 1.49mmol) refluxed in the orthodichlorobenzene of 50ml 15 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and filter out throw out.Wash this filtrate three times with water, use MgSO ₄Dry and under reduced pressure concentrated.By column chromatography this reaction mixture is purified, with the compound (5.85g, 61%) that obtains to represent as raw-material chemical formula a. ¹H?NMR(300MHz，CDCl ₃)8.13-8.11(d，2H)，7.71-7.69(d，2H)，7.44-7.21(m，8H)；MS[M+H]322。

＜preparation example 2〉preparing raw material represented of chemical formula b

Make carbazole (5.00g, 29.9mmol), 1-bromo-3-phenyl-iodide (9.30g, 32.9mmol), K ₂CO ₃(16.5g, 120mmol), Cu (3.80g, 59.8mmol) and hexaoxacyclooctadecane-6-6 (0.40g 1.49mmol) refluxed in the orthodichlorobenzene of 50ml 15 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and filter out throw out.Wash this filtrate three times with water, use MgSO ₄Dry and under reduced pressure concentrated.By column chromatography this reaction mixture is purified, with the compound (5.85g, 61%) that obtains to represent as raw-material chemical formula b.MS[M+H]322。

＜preparation example 3〉preparing raw material represented of chemical formula c

The starting material that chemical formula a is represented (1.50g, 4.66mmol) be dissolved in dimethyl formamide (DMF, 20ml) in, and to wherein add N-bromosuccinimide (NBS, 1.82g, 10.2mmol).This reaction mixture reacted 2 hours at 50～60 ℃, and to wherein adding entry (15ml).Filter out this reaction precipitation thing, wash with water, make its recrystallization in methylene dichloride/normal hexane then, thereby obtain the compound (1.93g, 86%) that chemical formula c represents. ¹H?NMR(300MHz，CDCl ₃)8.17(s，2H)，7.75-7.74(d，2H)，7.51-7.48(d，2H)，7.38-7.35(d，2H)，7.22-7.19(d，2H)；MS[M+H]478。

＜preparation example 4〉preparing raw material represented of chemical formula d

The starting material that chemical formula b is represented (1.50g, 4.66mmol) be dissolved in dimethyl formamide (DMF, 20ml) in, and to wherein add N-bromosuccinimide (NBS, 1.82g, 10.2mmol).This reaction mixture reacted 2 hours at 50～60 ℃, and to wherein adding entry (15ml).Filter out this reaction precipitation thing, wash with water, make its recrystallization in methylene dichloride/normal hexane then, thereby obtain the raw-material compound of conduct (1.93g, 86%) that chemical formula d represents.MS[M+H]478。

＜preparation example 5〉preparing raw material represented of chemical formula e

With 2,5-two bromo nitrobenzenes (12.0g, 42.7mmol) be dissolved in dimethyl formamide (DMF, 80ml) in, (6.0g, 93.94mmol), this reaction mixture reacted 3 hours at 120 ℃ then to wherein adding Cu.Cool off this reaction mixture to room temperature, filter out insoluble material, and concentrated filtrate.In ethanol, make resulting product recrystallization, thus obtain 4,4 '-two bromos-2,2 '-dinitrobenzene diphenyl (10.2g, 60%).MS[M+]354。

In HCl 30ml/EtOH 75ml, stir 4,4 '-two bromos-2,2 '-the dinitrobenzene diphenyl (6.1g, 15.17mmol), and to wherein adding the Sn powder (7.2g 60.68mmol), makes this reaction mixture refluxed 24 hours then.Then, cool off this reaction mixture,, make its recrystallization in ethanol then with the neutralization of 10% NaOH solution to room temperature, thus obtain 4,4 '-two bromos-2,2 '-diamino diphenyl (3.5g, 67%).MS[M+H]341。

With 4,4 '-two bromos-2,2 '-the diamino diphenyl (3.5g 10.23mmol) is dissolved in the phosphoric acid, and 190 ℃ the heating 24 hours.Cool off this reaction mixture to room temperature, then to wherein adding NaHCO gradually ₃Thereby the aqueous solution produces solid.Then, filter out this solid, thereby obtain the compound 2 that chemical formula e represents, 7-bromo carbazole (2.2g, 66%).MS[M+]323。

＜preparation example 6〉preparing raw material represented of chemical formula f

With 3,6-dibromo carbazole (1.63g, 5.00mmol), 4-bromophenyl boric acid (2.95g, 15.0mmol), (29.0mg 0.25mmol) adds among the THF of 100ml for the solution of potassium carbonate (10ml) of 2M and tetrakis triphenylphosphine palladium.Under refluxing, stir this reaction mixture 24 hours, then it is cooled to room temperature.Then, this reaction mixture is added in toluene and the salt solution, and separate this toluene layer.Use MgSO ₄Dry this isolating layer filters and concentrates.Then, this reaction mixture is purified by column chromatography, thus the compound (1.15g, 48%) that acquisition is represented as raw-material chemical formula f. ¹H?NMR(300MHz，CDCl ₃)10.1(s，1H)，7.77(s，2H)，7.49-7.46(m，6H)，7.37(d，4H)，7.30(d，2H)；MS[M+H]476。

＜preparation example 7〉preparing raw material represented of chemical formula g

Make the compound that chemical formula f represents (1.43g, 3.00mmol), 1-bromo-4-phenyl-iodide (1.87g, 6.60mmol), K ₂CO ₃(3.32g, 24mmol), Cu (0.76g, 12.0mmol) and hexaoxacyclooctadecane-6-6 (0.08g 0.30mmol) refluxed in the orthodichlorobenzene of 10ml 15 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and filter out throw out.Wash this filtrate three times with water, use MgSO ₄Dry and under reduced pressure concentrated.By column chromatography this reaction mixture is purified, with the compound (1.02g, 54%) that obtains to represent as raw-material chemical formula g. ¹H?NMR(300MHz，CDCl ₃)7.77(s，2H)，7.49-7.40(m，8H)，7.37(d，4H)，7.30(d，2H)，7.20(d，2H)；MS[M+H]630。

＜preparation example 8〉preparing raw material represented of chemical formula h

The compound that chemical formula c is represented (2.40g, 5.00mmol), 4-bromophenyl boric acid (3.94g, 20.0mmol), (58.0mg 0.50mmol) adds among the THF of 100ml for the solution of potassium carbonate (20ml) of 2M and tetrakis triphenylphosphine palladium.Under refluxing, stir this reaction mixture 24 hours, then it is cooled to room temperature.Then, this reaction mixture is added in toluene and the salt solution, and separate this toluene layer.Use MgSO ₄Dry this isolating layer filters and concentrates.Then, this reaction mixture is purified by column chromatography, thus the compound (2.09g, 59%) that acquisition is represented as raw-material chemical formula h. ¹H?NMR(300MHz，CDCl ₃)7.77(s，2H)，7.50-7.46(m，10H)，7.37(m，6H)，7.30(m，4H)；MS[M+H]706。

＜embodiment 1〉preparation of the compound of chemical formula 61 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), pentanoic (1.16g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.16g, 75%) of chemical formula 61 expressions. ¹H?NMR(300MHz，CDCl ₃)6.78(d，2H)，6.96(m，14H)，7.12(m，6H)，7.25(s，2H)，7.5-7.51(m，14H)，7.65(d，2H)；MS[M+H]745。

＜embodiment 2〉preparation of the compound of chemical formula 62 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), the N-phenyl-1-naphthylamine (1.50g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.46g, 79%) of chemical formula 62 expressions. ¹H?NMR(300MHz，CDCl ₃)6.78(d，2H)，6.96-7.12(m，14H)，7.25(s，2H)，7.5-7.51(m，8H)，7.65-7.66(m，8H)，7.80-7.81(m，6H)，8.11-8.12(m，6H)；MS[M+H]895。

＜embodiment 3〉preparation of the compound of chemical formula 63 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), N-phenyl-2-naphthylamines (1.50g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.21g, 65%) of chemical formula 63 expressions. ¹H?NMR(300MHz，CDCl ₃)6.78(d，2H)，6.96-7.0(m，8H)，7.12(m，3H)，7.25-7.29(m，8H)，7.51-7.73(m，16H)，7.94-8.05(m，9H)；MS[M+H]895。

＜embodiment 4〉preparation of the compound of chemical formula 64 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), N-phenyl-(9-phenanthryl) amine (1.85g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (0.93g, 43%) of chemical formula 64 expressions. ¹H?NMR(300MHz，CDCl ₃)6.78(d，2H)，6.96-6.97(m，8H)，7.12(t，3H)，7.25(s，2H)，7.41(m，3H)，7.5-7.51(m，8H)，7.65(d，2H)，8.32-8.38(m，12H)，8.62(d，6H)，9.43(m，6H)；MS[M+H]1045。

＜embodiment 5〉preparation of the compound of chemical formula 65 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), N-phenyl-(9-anthrene base) amine (1.85g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.24g, 57%) of chemical formula 65 expressions. ¹H?NMR(300MHz，CDCl ₃)6.78(d，2H)，6.96-6.6.98(m，8H)，7.12(t，3H)，7.23(s，2H)，7.5-7.51(m，8H)，7.65-7.66(m，7H)，7.81-7.84(m，10H)，8.14-8.15(m，12H)；MS[M+H]1045。

＜embodiment 6〉preparation of the compound of chemical formula 68 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), two-(1-naphthyl) amine (1.85g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.04g, 48%) of chemical formula 68 expressions. ¹H?NMR(300MHz，CDCl ₃)6.78(d，2H)，7.0-7.05(m，8H)，7.25(s，2H)，7.50-7.66(m，16H)，7.80-7.81(m，12H)，8.11-8.16(m，12H)；MS[M+H]1045。

＜embodiment 7〉preparation of the compound of chemical formula 69 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), two-(1-naphthyl) amine (1.85g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (0.89g, 41%) of chemical formula 69 expressions. ¹H?NMR(300MHz，CDCl ₃)6.78(d，2H)，7.0(d，2H)，7.26-7.29(m，14H)，7.5-7.53(m，16H)，7.94-8.05(m，18H)；MS[M+H]1045。

＜embodiment 8〉preparation of the compound of chemical formula 71 expression

The compound that chemical formula c is represented (1.50g, 3.13mmol), p, p '-xylidene(s) (2.03g, l0.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.31g, 50%) of chemical formula 71 expressions. ¹H?NMR(300MHz，CDCl ₃)2.55(s，18H)，6.48-6.70(m，16H)，6.95-7.01(m，14H)，7.2-7.35(m，4H)；MS[M+H]829。

＜embodiment 9〉preparation of the compound of chemical formula 72 expression

The compound that chemical formula c is represented (1.50g, 3.13mmol), m, m '-xylidene(s) (1.96ml, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.55g, 60%) of chemical formula 72 expressions. ¹H?NMR(300MHz，CDCl ₃)2.55(s，18H)，6.48-6.70(m，16H)，6.95-7.01(m，14H)，7.2-7.35(m，4H)；MS[M+H]829。

＜embodiment 10〉preparation of the compound of chemical formula 89 expression

The compound that chemical formula c is represented (1.50g, 3.13mmol), 3 methyl diphenylamine (1.88g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.62g, 66%) of chemical formula 89 expressions.MS[M+H]787。

＜embodiment 11〉preparation of the compound of chemical formula 95 expression

The compound that chemical formula c is represented (1.50g, 3.13mmol), N-(3-tolyl)-naphthalidine (2.40g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.92g, 65%) of chemical formula 95 expressions.MS[M+H]937。

＜embodiment 12〉preparation of the compound of chemical formula 96 expression

The compound that chemical formula c is represented (1.50g, 3.13mmol), N-(4-tolyl)-naphthalidine (2.40g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.92g, 65%) of chemical formula 96 expressions.MS[M+H]937。

＜embodiment 13〉preparation of the compound of Chemical formula 1 01 expression

The compound that chemical formula c is represented (1.50g, 3.13mmol), N-(3-tolyl)-2-naphthylamines (2.40g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.92g, 65%) of Chemical formula 1 01 expression.MS[M+H]937。

＜embodiment 14〉preparation of the compound of Chemical formula 1 02 expression

The compound that chemical formula c is represented (1.50g, 3.13mmol), N-(4-tolyl)-2-naphthylamines (2.40g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.92g, 65%) of Chemical formula 1 02 expression.MS[M+H]937。

＜embodiment 15〉preparation of the compound of Chemical formula 1 13 expression

The compound that chemical formula d is represented (1.00g, 2.08mmol), pentanoic (1.16g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.16g, 75%) of Chemical formula 1 13 expressions.MS[M+H]745。

＜embodiment 16〉preparation of the compound of Chemical formula 1 14 expression

The compound that chemical formula d is represented (1.00g, 2.08mmol), the N-phenyl-1-naphthylamine (1.50g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.46g, 79%) of Chemical formula 1 14 expressions.MS[M+H]895。

＜embodiment 17〉preparation of the compound of Chemical formula 1 15 expression

The compound that chemical formula d is represented (1.00g, 2.08mmol), N-phenyl-2-naphthylamines (1.50g, 6.86mmol), Pd ₂(dba) ₃(0.125g, 0.13mmol), P (t-Bu) ₃(0.04g, 0.2mmol) and sodium tert-butoxide (1.80g 18.7mmol) adds in the dimethylbenzene (40ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.21g, 65%) of Chemical formula 1 15 expressions.MS[M+H]895。

＜embodiment 18〉preparation of the compound of Chemical formula 1 16 expression

The compound that chemical formula d is represented (1.50g, 3.13mmol), 3 methyl diphenylamine (1.88g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.62g, 66%) of Chemical formula 1 16 expressions.MS[M+H]787。

＜embodiment 19〉preparation of the compound of Chemical formula 1 20 expression

The compound that chemical formula d is represented (1.50g, 3.13mmol), N-(3-tolyl)-naphthalidine (2.40g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.92g, 65%) of Chemical formula 1 20 expressions.MS[M+H]937。

＜embodiment 20〉preparation of the compound of Chemical formula 1 21 expression

The compound that chemical formula d is represented (1.50g, 3.13mmol), N-(3-tolyl)-2-naphthylamines (2.40g, 10.3mmol), Pd ₂(dba) ₃(0.19g, 0.21mmol), P (t-Bu) ₃(0.06g, 0.31mmol) and sodium tert-butoxide (1.05g 10.96mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.92g, 65%) of Chemical formula 1 21 expressions.MS[M+H]937。

＜embodiment 21〉preparation of the compound of Chemical formula 1 92 expression

1) compound (5.0g that chemical formula e is represented, 15.38mmol) and di-tert-butyl dicarbonic acid ester (di-tert-butyl-dicarbonate) (5.04g, 23.08mmol) be dissolved among the THF of 50ml, and to wherein add 4-(dimethylamino) pyridine (0.19g, 1.54mmol).Then, this reaction mixture reacted 24 hours in room temperature.After this reaction finishes, concentrate this reaction mixture and make its recrystallization in ethanol, thereby obtain product (6.16g, 94%).

2) product that will obtain by step 1) (6.16g, 14.49mmol), pentanoic (5.89g, 34.78mmol), sodium tert-butoxide (4.18g, 43.47mmol), Pd ₂(dba) ₃(0.17g, 0.29mmol) and P (t-Bu) ₃(0.06g 0.29mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain compound (5.88g, 67%).

3) will be by step 2) (5.88g 9.77mmol) is dissolved in trifluoroacetic acid/trichloromethane of 50ml/50ml, and this solution was refluxed 3 hours for the compound that obtains.Cool off this reaction mixture to room temperature, carry out quenching with the NaOH aqueous solution, (MC) extracts with methylene dichloride, washes with water repeatedly then.With the resulting product of dried over mgso and make its evaporation.By column chromatography (ethyl acetate/hexane=1/9) this crude product is purified, thereby obtain compound (2.9g, 59%).

4) product that will obtain by step 3) (2.9g, 5.78mmol), 4-bromophenyl-pentanoic (1.36g, 4.21mmol), Pd ₂(dba) ₃(0.05g, 0.084mmol), P (t-Bu) ₃(0.017g, 0.084mmol) and sodium tert-butoxide (1.21g 12.63mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.5g, 49%) of Chemical formula 1 92 expressions.MS[M+H]745。

＜embodiment 22〉preparation of the compound of Chemical formula 1 93 expression

1) compound that chemical formula e is represented (5.0g, 15.38mmol) and di-tert-butyl dicarbonic acid ester (5.04g 23.08mmol) is dissolved among the THF of 50ml, and to wherein add 4-(dimethylamino) pyridine (0.19g, 1.54mmol).Then, this reaction mixture reacted 24 hours in room temperature.After this reaction finishes, concentrate this reaction mixture and make its recrystallization in ethanol, thereby obtain product (6.16g, 94%).

2) product that will obtain by step 1) (6.16g, 14.49mmol), the N-phenyl-1-naphthylamine (7.63g, 34.78mmol), sodium tert-butoxide (4.18g, 43.47mmol), Pd ₂(dba) ₃(0.17g, 0.29mmol) and P (t-Bu) ₃(0.06g 0.29mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain compound (6.0g, 59%).

3) will be by step 2) (6.0g 8.54mmol) is dissolved in trifluoroacetic acid/trichloromethane of 50ml/50ml, and this solution was refluxed 3 hours for the compound that obtains.Cool off this reaction mixture to room temperature, carry out quenching, extract, wash with water repeatedly then with methylene dichloride with the NaOH aqueous solution.With the resulting product of dried over mgso and make its evaporation.By column chromatography (ethyl acetate/hexane=1/9) this crude product is purified, thereby obtain compound (3.8g, 74%).

4) product that will obtain by step 3) (3.8g, 6.31mmol), 4-bromophenyl-N-phenyl-1-naphthylamine (1.57g, 4.21mmol), Pd ₂(dba) ₃(0.05g, 0.084mmol), P (t-Bu) ₃(0.017g, 0.084mmol) and sodium tert-butoxide (1.21g 12.63mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.2g, 32%) of Chemical formula 1 93 expressions.MS[M+H]895。

＜embodiment 23〉preparation of the compound of Chemical formula 1 94 expression

2) product that will obtain by step 1) (6.16g, 14.49mmol), N-phenyl-2-naphthylamines (7.63g, 34.78mmol), sodium tert-butoxide (4.18g, 43.4mmol), Pd ₂(dba) ₃(0.17g, 0.29mmol) and P (t-Bu) ₃(0.06g 0.29mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain compound (6.0g, 59%).

4) product that will obtain by step 3) (3.8g, 6.31mmol), 4-bromophenyl-N-phenyl-2-naphthylamines (1.57g, 4.21mmol), Pd ₂(dba) ₃(0.05g, 0.084mmol), P (t-Bu) ₃(0.017g, 0.084mmol) and sodium tert-butoxide (1.21g 12.63mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.2g, 32%) of Chemical formula 1 94 expressions.MS[M+H]895。

＜embodiment 24〉preparation of the compound of Chemical formula 1 97 expression

2) product that will obtain by step 1) (6.16g, 14.49mmol), 3-methyl-pentanoic (6.37g, 34.78mmol), sodium tert-butoxide (4.18g, 43.47mmol), Pd ₂(dba) ₃(0.17g, 0.29mmol) and P (t-Bu) ₃(0.06g 0.29mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain compound (6.3g, 69%).

3) will be by step 2) (6.3g 10.0mmol) is dissolved in trifluoroacetic acid/trichloromethane of 50ml/50ml, and this solution was refluxed 3 hours for the compound that obtains.Cool off this reaction mixture to room temperature, carry out quenching, extract, wash with water repeatedly then with methylene dichloride with the NaOH aqueous solution.With the resulting product of dried over mgso and make its evaporation.By column chromatography (ethyl acetate/hexane=1/9) this crude product is purified, thereby obtain compound (3.8g, 71%).

4) product that will obtain by step 3) (3.8g, 7.17mmol), 4-bromophenyl-(3-methyl)-pentanoic (1.42g, 4.21mmol), Pd ₂(dba) ₃(0.05g, 0.084mmol), P (t-Bu) ₃(0.017g, 0.084mmol) and sodium tert-butoxide (1.21g 12.63mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.2g, 36%) of Chemical formula 1 97 expressions.MS[M+H]787。

＜embodiment 25〉preparation of the compound of Chemical formula 2 18 expression

3) will be by step 2) (5.88g 9.77mmol) is dissolved in trifluoroacetic acid/trichloromethane of 50ml/50ml, and this solution was refluxed 3 hours for the compound that obtains.Cool off this reaction mixture to room temperature, carry out quenching, extract, wash with water repeatedly then with methylene dichloride with the NaOH aqueous solution.With the resulting product of dried over mgso and make its evaporation.By column chromatography (ethyl acetate/hexane=1/9) this crude product is purified, thereby obtain compound (2.9g, 59%).

4) product that will obtain by step 3) (2.9g, 57.8mmol), 4-bromophenyl-N-phenyl-1-naphthylamine (1.57g, 4.21mmol), Pd ₂(dba) ₃(0.05g, 0.084mmol), P (t-Bu) ₃(0.017g, 0.084mmol) and sodium tert-butoxide (1.21g 12.63mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.5g, 49%) of Chemical formula 2 18 expressions.MS[M+H]795。

＜embodiment 26〉preparation of the compound of Chemical formula 2 19 expression

2) product that will obtain by step 1) (6.16g, 14.49mmol), N-phenyl-2-naphthylamines (7.63g, 34.78mmol), sodium tert-butoxide (4.18g, 43.47mmol), Pd ₂(dba) ₃(0.17g, 0.29mmol) and P (t-Bu) ₃(0.06g 0.29mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain compound (6.0g, 59%).

4) product that will obtain by step 3) (3.8g, 6.31mmol), 4-bromophenyl-N-phenyl-1-naphthylamine (1.57g, 4.21mmol), Pd ₂(dba) ₃(0.05g, 0.084mmol), P (t-Bu) ₃(0.017g, 0.084mmol) and sodium tert-butoxide (1.21g 12.63mmol) adds in the dimethylbenzene (30ml), and this mixture was refluxed about 3 hours.After this reaction finishes, cool off this reaction mixture to room temperature, and it is added THF and H ₂In the mixing solutions of O.Separate this organic layer, use MgSO ₄Drying concentrates then.By column chromatography resulting product is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.2g, 32%) of Chemical formula 2 19 expressions.MS[M+H]895。

＜embodiment 27〉preparation of the compound of Chemical formula 2 52 expression

The compound that chemical formula c is represented (1.00g, 2.08mmol), triphenylamine-4-boric acid (1.99g, 6.87mmol), (0.07g 0.06mmol) adds among the THF of 40ml for the solution of potassium carbonate (10ml) of 2M and tetrakis triphenylphosphine palladium.Under refluxing, stir this reaction mixture 24 hours, then it is cooled to room temperature.Then, this reaction mixture is added in toluene/salt solution, and separate this toluene layer, use MgSO ₄Dry this isolating layer filters and concentrates.Then, this reaction mixture is purified, and make its recrystallization in ethyl acetate/normal hexane, thereby obtain the compound (1.15g, 55%) of Chemical formula 2 52 expressions by column chromatography. ¹H?NMR(300MHz，CDCl ₃)6.76-6.82(m，18H)，6.92-6.95(m，6H)，7.31-7.35(m，12H)，7.53-7.60(m，10H)，7.76-8.07(m，6H)；MS[M+H]973。

＜embodiment 28〉the organic light-emitting device manufacturing

The glass substrate that is coated with ITO (tin indium oxide) film of 1000  thickness on it immersed comprise in the distilled water of washing composition, thereby with this substrate of ultrasonic washing.Described washing composition is the commercially available prod of Fisher company.Described distilled water is by using the commercially available strainer of Millipore company to filter twice.ITO is after 30 minutes in washing, repeats twice of ultrasonic washing with 10 minutes times use distilled water.After the distilled water wash end, use Virahol, acetone and methyl alcohol to carry out ultrasonic washing successively.Dry resulting substrate, and be sent to the plasma body washing machine.Then, use oxygen plasma to wash this substrate 5 minutes, and be sent to vacuum deposition apparatus.

On the ito transparent electrode (first electrode) of preparation as mentioned above, apply the thickness of compound to 600  of above-mentioned chemical formula 61 expressions by the thermovacuum sedimentation, thereby form hole injection layer.Then, thereon by the thickness of vacuum deposition method coating as NPB to 400  of hole mobile material.In addition, apply the thickness of Alq3 to 500  that is used as luminous/electronics injection/electron transport material thereon by vacuum deposition method, thereby finish the formation of organic material film.On the Alq3 layer, depositing fluorinated lithium of vacuum (LiF) and aluminium is respectively to 15  and 2500  in succession, thereby forms negative electrode (second electrode).In said process, the sedimentation rate of each organic materials remains on 0.5-1.0 /sec, and the sedimentation rate of lithium fluoride and aluminium remains on 0.2 /sec and 2～3 /sec respectively.

Applying under the positive field with 7.17V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.87cd/A brightness.

＜embodiment 29〉the organic light-emitting device manufacturing

On the ito transparent electrode of preparation as described in embodiment 28, apply the thickness of compound to 800  of above-mentioned chemical formula 62 expressions by the thermovacuum sedimentation, thereby form hole injection layer.Then, thereon by the thickness of vacuum deposition method coating as NPB to 400  of hole mobile material.In addition, apply the thickness of Alq3 to 300  that is used as luminous/electronics injection/electron transport material thereon by vacuum deposition method, thereby finish the formation of organic material film.Remaining step is identical with embodiment 28.

Applying under the positive field with 7.8V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.86cd/A brightness.

＜embodiment 30〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 63 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.8V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.8cd/A brightness.

＜embodiment 31〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 64 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 8.1V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.61cd/A brightness.

＜embodiment 32〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 69 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 8.0V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.82cd/A brightness.

＜embodiment 33〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 71 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.6V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 4.4cd/A brightness.

＜embodiment 34〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 72 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.8V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 4.15cd/A brightness.

＜embodiment 35〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 89 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.5V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 4.3cd/A brightness.

＜embodiment 36〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 95 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.3V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 4.5cd/A brightness.

＜embodiment 37〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned chemical formula 96 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.2V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 4.4cd/A brightness.

＜embodiment 38〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 1 13 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.7V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 4.2cd/A brightness.

＜embodiment 39〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 1 14 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.6V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 4.1cd/A brightness.

＜embodiment 40〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 1 20 expressions replaces the compound of above-mentioned chemical formula 61 expressions, repeat embodiment 28 to make organic electroluminescence device.

Applying under the positive field with 7.8V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.98cd/A brightness.

＜embodiment 41〉the organic light-emitting device manufacturing

On the ito transparent electrode of preparation as described in embodiment 28, apply the thickness of compound to 800  of above-mentioned Chemical formula 1 92 expressions by the thermovacuum sedimentation, thereby form hole injection layer.Then, thereon by the thickness of vacuum deposition method coating as NPB to 300  of hole mobile material.In addition, apply the thickness of Alq3 to 300  that is used as luminous/electronics injection/electron transport material thereon by vacuum deposition method, thereby finish the formation of organic material film.Remaining step is identical with embodiment 28.

Applying under the positive field with 6.7V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.7cd/A brightness.

＜embodiment 42〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 1 93 expressions replaces the compound of above-mentioned Chemical formula 1 92 expressions, repeat embodiment 41 to make organic electroluminescence device.

Applying under the positive field with 6.9V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.6cd/A brightness.

＜embodiment 43〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 1 94 expressions replaces the compound of above-mentioned Chemical formula 1 92 expressions, repeat embodiment 41 to make organic electroluminescence device.

Applying under the positive field with 6.8V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.5cd/A brightness.

＜embodiment 44〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 1 97 expressions replaces the compound of above-mentioned Chemical formula 1 92 expressions, repeat embodiment 41 to make organic electroluminescence device.

Applying under the positive field with 6.9V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.9cd/A brightness.

＜embodiment 45〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 2 18 expressions replaces the compound of above-mentioned Chemical formula 1 92 expressions, repeat embodiment 41 to make organic electroluminescence device.

Applying under the positive field with 6.8V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.8cd/A brightness.

＜embodiment 46〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 2 19 expressions replaces the compound of above-mentioned Chemical formula 1 92 expressions, repeat embodiment 41 to make organic electroluminescence device.

Applying under the positive field with 6.8V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.6cd/A brightness.

＜embodiment 47〉the organic light-emitting device manufacturing

Except the compound that uses above-mentioned Chemical formula 2 52 expressions replaces the compound of above-mentioned Chemical formula 1 92 expressions, repeat embodiment 41 to make organic electroluminescence device.

Applying under the positive field with 6.88V driving voltage, resulting organic electroluminescence device is at 100mA/cm ²Current density under show spectrum with 3.2cd/A brightness.

From the foregoing description as seen, as under the positive field of about 6.88V, at 100mA/cm ²Current density under 3.2～4.5cd/A brightness proved, use compound according to the present invention can provide excellent electroluminescent effect as the organic electroluminescence device of hole-injecting material.In other words, compare with the device of routine, when compound according to the present invention comprising when being used as hole-injecting material as the NPB of hole mobile material with as the organic electroluminescence device of the Alq3 of luminous/electronics injection/electron transport material, can significantly improve the electroluminescent effect.

Industrial applicibility

From foregoing as seen, be used for one of luminescent device when novel compound according to the present invention The organic compound layer of organic electroluminescent (EL) device the time, this compound can be realized sending out The raising in optical efficiency and life-span. Therefore, can be advantageously used in according to compound of the present invention and comprise The electrical part field of organic luminescent device.

Claims

1, a kind of compound of representing by following Chemical formula 1:

[Chemical formula 1]

Wherein A is

Or

B is

Or

C is Or

D be H, Or

R1～R10 is identical or different, and separately only once or repeat at least twice ground and comprise that at least one is selected from and comprise hydrogen atom, aliphatic hydrocarbon with 1～20 carbon atom, non-replacement or the aromatic hydrocarbon that replaces by nitro, nitrile, halogen, alkyl, alkoxyl group or amino, have the silica-based of aromatic substituent, non-replacement or the heterocyclic aromatic hydrocarbon that replaces by nitro, nitrile, halogen, alkyl, alkoxyl group or amino, group in the group of thienyl that replaces by the aromatic hydrocarbon of the hydrocarbon of C1～C20 or C6～C24 and the boryl that replaces by aromatic hydrocarbon;

Ar is non-replacement or by nitro, nitrile, halogen, alkyl, alkoxyl group or the amino aromatic hydrocarbon that replaces; And

1, m and n respectively be 1 or bigger integer and o be 0 or bigger integer;

Condition is the compound that Chemical formula 1 is represented, wherein gets rid of R1, R2, R3, R4, R5 and R6 and represents that simultaneously hydrogen atom and D also are the situation of hydrogen atom.

2, compound according to claim 1, wherein, described aromatic hydrocarbon comprises phenyl, phenylbenzene, triphenyl, naphthyl, anthryl, phenanthrene, pyrenyl and perylene base.

3, compound according to claim 1, wherein, described heterocyclic aromatic hydrocarbon comprises thiophene, furans, pyrroles, imidazoles, thiazole, oxazole, oxadiazole, thiadiazole, triazole, pyridyl, pyridine amido, pyrazine, quinoline and isoquinoline 99.9.

4, compound according to claim 1, wherein, described compound is represented by any one chemical formula that is selected from the group that comprises following Chemical formula 2 a～2e:

[Chemical formula 2 a]

[Chemical formula 2 b]

[Chemical formula 2 c]

[Chemical formula 2 d]

[Chemical formula 2 e]

Wherein, l, m, n, o and R1～R8 each with claim 1 in the definition identical.

5, compound according to claim 1, wherein, described compound is represented by any one chemical formula that is selected among following chemical formula 3a～3n:

[chemical formula 3a]

[chemical formula 3b]

[chemical formula 3c]

[chemical formula 3d]

[chemical formula 3e]

[chemical formula 3f]

[chemical formula 3g]

[chemical formula 3h]

[chemical formula 3i]

[chemical formula 3j]

[chemical formula 3k]

[chemical formula 3l]

[chemical formula 3m]

[chemical formula 3n]

Wherein, R1～R8 each with claim 1 in the definition identical.

6, compound according to claim 1, wherein, the compound that described Chemical formula 1 is represented is any compound by chemical formula 61～227 expressions:

Chemical formula 61 chemical formulas 62

Chemical formula 63 chemical formulas 64

Chemical formula 65 chemical formulas 66

Chemical formula 67 chemical formulas 68

Chemical formula 69 chemical formulas 70

Chemical formula 71 chemical formulas 72

Chemical formula 73 chemical formulas 74

Chemical formula 75 chemical formulas 76

Chemical formula 77 chemical formulas 78

Chemical formula 79 chemical formulas 80

Chemical formula 81 chemical formulas 82

Chemical formula 83 chemical formulas 84

Chemical formula 85 chemical formulas 86

Chemical formula 87 chemical formulas 88

Chemical formula 89 chemical formulas 90

Chemical formula 91 chemical formulas 92

Chemical formula 93 chemical formulas 94

Chemical formula 95 chemical formulas 96

Chemical formula 97 chemical formulas 98

Chemical formula 99 Chemical formula 1s 00

Chemical formula 1 01 Chemical formula 1 02

Chemical formula 1 03 Chemical formula 1 04

Chemical formula 1 05 Chemical formula 1 06

Chemical formula 1 07 Chemical formula 1 08

Chemical formula 1 09 Chemical formula 1 10

Chemical formula 1 11 Chemical formula 1s 12

Chemical formula 1 13 Chemical formula 1s 14

Chemical formula 1 15 Chemical formula 1s 16

Chemical formula 1 17 Chemical formula 1s 18

Chemical formula 1 19 Chemical formula 1s 20

Chemical formula 1 21 Chemical formula 1s 22

Chemical formula 1 23 Chemical formula 1s 24

Chemical formula 1 25 Chemical formula 1s 26

Chemical formula 1 27 Chemical formula 1s 28

Chemical formula 1 29 Chemical formula 1s 30

Chemical formula 1 31 Chemical formula 1s 32

Chemical formula 1 33 Chemical formula 1s 34

Chemical formula 1 35 Chemical formula 1s 36

Chemical formula 1 37 Chemical formula 1s 38

Chemical formula 1 39 Chemical formula 1s 40

Chemical formula 1 41 Chemical formula 1s 42

Chemical formula 1 43 Chemical formula 1s 44

Chemical formula 1 45 Chemical formula 1s 46

Chemical formula 1 47 Chemical formula 1s 48

Chemical formula 1 49 Chemical formula 1s 50

Chemical formula 1 51 Chemical formula 1s 52

Chemical formula 1 53 Chemical formula 1s 54

Chemical formula 1 55 Chemical formula 1s 56

Chemical formula 1 57 Chemical formula 1s 58

Chemical formula 1 59 Chemical formula 1s 60

Chemical formula 1 61 Chemical formula 1s 62

Chemical formula 1 63 Chemical formula 1s 64

Chemical formula 1 65 Chemical formula 1s 66 Chemical formula 1s 67

Chemical formula 1 68 Chemical formula 1s 69

Chemical formula 1 70 Chemical formula 1s 71 Chemical formula 1s 72

Chemical formula 1 73 Chemical formula 1s 74

Chemical formula 1 75 Chemical formula 1s 76

Chemical formula 1 77 Chemical formula 1s 78

Chemical formula 1 79 Chemical formula 1s 80

Chemical formula 1 81 Chemical formula 1s 82

Chemical formula 1 83 Chemical formula 1s 84 Chemical formula 1s 85

Chemical formula 1 86 Chemical formula 1s 87 Chemical formula 1s 88

Chemical formula 1 89 Chemical formula 1s 90 Chemical formula 1s 91

Chemical formula 1 92 Chemical formula 1s 93 Chemical formula 1s 94

Chemical formula 1 95 Chemical formula 1s 96 Chemical formula 1s 97

Chemical formula 1 98 Chemical formula 1s 99 Chemical formula 2s 00

Chemical formula 2 01 Chemical formula 2 02 Chemical formula 2 03

Chemical formula 2 04 Chemical formula 2 05

Chemical formula 2 06 Chemical formula 2 07

Chemical formula 2 08 Chemical formula 2 09 Chemical formula 2 10

Chemical formula 2 11 Chemical formula 2s 12

Chemical formula 2 13 Chemical formula 2s 14

Chemical formula 2 15 Chemical formula 2s 16

Chemical formula 2 17 Chemical formula 2s 18 Chemical formula 2s 19

Chemical formula 2 20 Chemical formula 2s 21 Chemical formula 2s 22

Chemical formula 2 23 Chemical formula 2s 24 Chemical formula 2s 25

Chemical formula 2 26 Chemical formula 2s 27.

7, a kind of organic luminescent device comprises first electrode, second electrode and places one or more organic compound layers between described two electrodes that wherein at least one organic compound layer comprises at least a as each defined compound of claim 1～6.

8, organic luminescent device according to claim 7, wherein, described to comprise at least a organic compound layer as each defined compound of claim 1～6 be to have that the hole is injected and the hole injection/hole transmission layer of hole transport function.

9, organic luminescent device according to claim 7, it is wherein, described that to comprise at least a organic compound layer as each defined compound of claim 1～6 be the hole injection/hole transport/luminescent layer with hole injection, hole transport and lighting function.

10, organic luminescent device according to claim 7, wherein, described to comprise at least a organic compound layer as each defined compound of claim 1～6 be the hole injection layer with hole function of injecting.

11, organic luminescent device according to claim 7, this device comprises substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and negative electrode from the bottom, wherein said to comprise at least a organic compound layer as each defined compound of claim 1～6 be the one deck at least that is selected from the group that comprises hole injection layer, hole transmission layer and luminescent layer.