# Patent

## Title
Aromatic amine derivative and organic electroluminescence device employing the same

## Abstract

A specified aromatic amine derivative having a chrysene structure. An organic electroluminescence device which comprises at least one organic thin film layer comprising a light emitting layer sandwiched between a pair of electrode consisting of an anode and a cathode, wherein at least one of the organic thin film layer comprises the aromatic amine derivative singly or as its mixture component. Organic electroluminescence devices having a long lifetime and a high efficiency of light emission, and aromatic amine derivatives capable of realizing such organic electroluminescence devices are provided.

## Background
TECHNICAL FIELD
The present invention relates to an aromatic amine derivative and an organic electroluminescence device using the derivative and, more particularly, to an organic electroluminescence device having long lifetime, an enhanced efficiency of light emission and emitting highly pure blue light; and to an aromatic amine derivative realizing the organic electroluminescence device.
BACKGROUND ART
Organic electroluminescence (“electroluminescence” will be occasionally referred to as “EL”, hereinafter) devices which utilize organic substances are expected to be useful for application as an inexpensive full color display device of the solid light emission type having a great size and various developments on the organic EL devices are being conducted. In general, an organic EL device has a construction comprising a light emitting layer and a pair of electrodes sandwiching the light emitting layer. The light emission of the organic EL device is a phenomenon in which, when an electric field is applied between the two electrodes, electrons are injected from the cathode side and holes are injected from the anode side, the electrons are recombined with the holes in the light emitting layer to form an excited state, and energy generated when the excited state returns to the ground state is emitted as light.
As compared with an inorganic light emitting diode, conventional organic EL devices requires high driving voltage and only exhibited low luminance or low efficiency of light emission. Moreover, characteristic degradation of the conventional organic EL devices was also extravagant and as a result, they were not practically used. Although recent organic EL devices are improved step by steps, it has been still demanded to develop organic EL devices with favorable efficiency of light emission and having long lifetime.
For example, there is disclosed such a technique using a single monoanthracene compound as an organic light-emitting material (refer to Patent Literature 1 below). However, in this technique, a luminance obtained by using the material is as low as 1650 cd/m2, for example, at a current density of 165 mA/cm2, and an efficiency of light emission thereof is very low, i.e., only 1 cd/A, which is practically unusable. Also, there is disclosed a technique using a single bisanthracene compound as an organic light emitting material (refer to Patent Literature 2 below). However, in this technique, an efficiency of light emission obtained by using the material is also as low as about 1 to 3 cd/A. Therefore, further improvement of the technique has bee demanded for rendering it practically usable. Further, there is disclosed a technique using a distyryl compound and adding styrylamine or so as organic light emitting material (refer to Patent Literature 3 below). However, the device described therein fails to show a sufficiently long lifetime and, therefore, further improvement has been demanded.
Furthermore, a technique of employing mono- or bis-anthracene compound and a distyryl compound as an organic light emitting medium layer is disclosed (refer to Patent Literature 4 below). However in these technologies, a conjugated structure of the styryl compound lengthened wave length of a light emission spectrum and deteriorated the purity of color.
Still further, Patent Literature 5 below discloses a blue luminescence device with the use of diaminochrysene derivatives. However, despite the superiority in light emission efficiency, because the device is not sufficient in its lifetime, further improvement was required.

    
    
        Patent Literature 1: Japanese Unexamined Patent Application Laid-Open No. Hei 11-3782A
        Patent Literature 2: Japanese Unexamined Patent Application Laid-Open No. Hei 8(1996)-012600
        Patent Literature 3: International Patent Application Published under PCT No. WO 00/06402
        Patent Literature 4: Japanese Unexamined Patent Application Laid-Open No. 2001-284050
        Patent Literature 5: International Application Published under PCT No. WO 04/04088
    
    


DISCLOSURE OF THE INVENTION
The present invention has been made to overcome the above problems. An object of the present invention is to provide organic EL devices having a long lifetime and a high efficiency of light emission, and aromatic amine derivatives capable of realizing such organic EL devices.
As a result of extensive researches for developing aromatic amine derivatives having the above suitable properties and organic EL devices using the aromatic amine derivatives, the inventors have found that the object of the present invention can be achieved by using aromatic amine derivatives represented by a following general formula (1) or (2) in which an amino group is bonded to a substituted chrysene structure. The present invention has been accomplished on the basis of the above finding.
Namely, the present invention provides an aromatic amine derivative represented by the following general formula (1) or general formula (2):




In the general formula (1), A1 to A4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 1 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 50 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 50 carbon atoms or a halogen atom;

    a, b, c and d each independently represents an integer of 0 to 5, when a, b, c or d each is 2 or greater, A1 to A4 may be the same with or different from each other, and may bond each other to form a saturated or unsaturated ring; and further, a couple of A1 and A2, and a couple of A3 and A4 may bond each other to form a saturated or unsaturated ring;
    R1 to R4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 20 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 ring carbon atoms or a substituted or unsubstituted silyl group having 3 to 50 carbon atoms; a couple of R1 and R2, and a couple of R3 and R4 may bond each other to form a saturated or unsaturated ring.


However, a case where all of R1 to R4 in the general formula (1) are hydrogen atoms is excluded.




In the general formula (2), A5 to A8 each independently represents a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 3 to 50 ring carbon atoms;

    R5 to R8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 20 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms or a substituted or unsubstituted heterocyclic group having 3 to 50 ring carbon atoms; and a couple of R5 and R6, and a couple of R7 and R8 may bond each other to form a saturated or unsaturated ring.


Further, the present invention provides an organic EL device which comprises at least one organic thin film layer comprising a light emitting layer sandwiched between a pair of electrode consisting of an anode and a cathode, wherein at least one of the organic thin film layers comprises the aromatic amine derivative singly or as its mixture component.
The organic EL device employing the aromatic amine derivative of the present invention reveals practically sufficient luminance even under low applied voltage, exhibits an enhanced efficiency of light emission, and is resistant to degrade even after a long time usage demonstrating a prolonged lifetime.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a chart showing a result of 1H-NMR measurement about Compound (4) obtained in Synthesis Example 1;
FIG. 2 is a chart showing a result of 1H-NMR measurement about Compound (9) obtained in Synthesis Example 2;
FIG. 3 is a chart showing a result of 1H-NMR measurement about Compound (20) obtained in Synthesis Example 3;
FIG. 4 is a chart showing a result of 1H-NMR measurement about Compound (23) obtained in Synthesis Example 4;
FIG. 5 is a chart showing a result of 1H-NMR measurement about Compound (25) obtained in Synthesis Example 5;
FIG. 6 is a chart showing a result of 1H-NMR measurement about Compound (39) obtained in Synthesis Example 6;
FIG. 7 is a chart showing a result of 1H-NMR measurement about Compound (57) obtained in Synthesis Example 7;
FIG. 8 is a chart showing a result of 1H-NMR measurement about Compound (95) obtained in Synthesis Example 8;
FIG. 9 is a chart showing a result of 1H-NMR measurement about Compound (D-973) obtained in Synthesis Example 9;
FIG. 10 is a chart showing a result of 1H-NMR measurement about Compound (D-974) obtained in Synthesis Example 10;
FIG. 11 is a chart showing a result of 1H-NMR measurement about Compound (D-998) obtained in Synthesis Example 11; and
FIG. 12 is a chart showing a result of 1H-NMR measurement about Compound (D-1000) obtained in Synthesis Example 12;



THE PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION
The present invention provides an aromatic amine derivative represented by a following general formula (1) or a general formula (2):




First, the aromatic amine derivative represented by the general formula (1) will be explained below.
In the general formula (1), A1 to A4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 (preferably 1 to 20) carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 (preferably 5 to 20) ring carbon atoms, a substituted or unsubstituted aralkyl group having 1 to 50 (preferably 6 to 20) ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 (preferably 5 to 12) ring carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 50 (preferably 1 to 6) carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 (preferably 5 to 18) ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 50 (preferably 5 to 18) ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 (preferably 1 to 6) carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 (preferably 3 to 20) ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 50 (preferably 3 to 20) carbon atoms or a halogen atom.
Examples of the substituted or unsubstituted alkyl group represented by A1 to A4 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, etc.
Examples of the substituted or unsubstituted aryl group represented by A1 to A4 include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, biphenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, 4-cyclohexylbiphenyl group, terphenyl group, 3,5-dichlorophenyl group, naphthyl group, 5-methylnaphthyl group, anthryl group, pyrenyl group, etc.
Examples of the substituted or unsubstituted aralkyl group represented by A1 to A4 include benzyl group, α,α-methylphenylbenzyl group, triphenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, -naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethy group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, α-phenoxybenzyl group, α-benzyloxy benzyl group, α,α-ditrifluoromethylbenzyl group, 1-pyrrolylmethyl group, 2-(1-pyrrolyl)ethyl, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group and 1-chloro-2-phenylisopropyl group, etc.
Examples of the cycloalkyl group represented by A1 to A4 include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.
Examples of the alkoxy group represented by A1 to A4 include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, various pentyloxy groups, various hexyloxy groups, etc.
Examples of the aryloxy group represented by A1 to A4 include phenoxy group, tolyloxy group, naphthyloxy group, etc.
Examples of the arylamino group represented by A1 to A4 include diphenylamino group, ditolylamino group, isopropyldiphenylamino group, t-butyldiphenylamino group, diisopropyldiphenylamino group, di-t-butyldiphenylamino group, dinaphthylamino group, naphthylphenylamino group, etc.
Examples of the alkylamino group represented by A1 to A4 include dimethylamino group, diethylamino group, dihexylamino group, etc.
Examples of the heterocyclic group represented by A1 to A4 include moieties of imidazole, benzimidazole, pyrrole, furan, thiophene, benzothiophene, oxadi azoline, indoline, carbazole, pyridine, quinoline, isoquinoline, benzoquinone, pyrazoline, imidazolidine, piperidine, etc.
Examples of the substituted or unsubstituted silyl group represented by A1 to A4 include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, methyldiphenylsilyl group, dimethylphenylsilyl group, triphenylsilyl group), etc.
Examples of the halogen atom represented by A1 to A4 include fluorine atom, chlorine atom, bromine atom, etc.
In the general formula (1), a, b, c and d each independently represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.
When a, b, c or d each is 2 or greater, A1 to A4 may be the same with or different from each other, and may bond each other to form a saturated or unsaturated ring; and further, a couple of A1 and A2, and a couple of A3 and A4 may bond each other to form a saturated or unsaturated ring;
Examples of the ring include cycloalkane having 4 to 12 carbon atoms such as cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, etc.; cycloalkene having 4 to 12 carbon atoms such as cyclobutene, cyclopentene, cyclohexene, cyclo heptene, cyclo octene, etc.; cycloalkadiene having 6 to 12 carbon atoms such as cyclohexa diene, cyclohepta diene, cyclo octadiene, etc.; aromatic ring having 6 to 50 carbon atoms such as benzene, naphthalene, phenanthrene, anthracene, pyrene, chrysene, acenaphthylene, etc.; and the like.
In the general formula (1), R1 to R4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a primary or a secondary alkyl group) having 1 to 50 (preferably 1 to 20) carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 (preferably 5 to 20) ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 (preferably 6 to 20) ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 (preferably 5 to 12) ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 20 (preferably 5 to 18) ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 (preferably 1 to 10) carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 (preferably 3 to 20) ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 50 (preferably 3 to 20) carbon atoms; a couple of R1 and R2, and a couple of R3 and R4 may bond each other to form a saturated or unsaturated ring.
Specific examples of the substituted or unsubstituted alkyl group, aryl group, aralkyl group, cycloalkyl group, arylamino group, alkylamino group, heterocyclic group, silyl group and the saturated or unsaturated ring represented by R1 to R4 are the same as those exemplified as A1 to A4 above.
It is particularly preferable that the alkyl group represented by R2 and R4 are primary or secondary.
Further, examples of the substituent for A1 to A4 and R1 to R4 include a substituted or unsubstituted aryl group having 5 to 50 (preferably 5 to 20) ring carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 (preferably 1 to 20) carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 (preferably 1 to 20) carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 (preferably 6 to 20) ring carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 (preferably 5 to 20) ring carbon atoms, a substituted or unsubstituted arylthio group having 5 to 50 (preferably 5 to 20) ring carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 (preferably 1 to 20) carbon atoms, amino group, halogen atom, cyano group, nitro group, hydroxyl group, carboxyl group, etc.
However, a case where all of R1 to R4 in the general formula (1) are hydrogen atoms is excluded.
Further in the general formula (1), it is preferable that R1 and/or R3 independently represents a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms. It is preferable that R1 and R3 each independently represents a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.
Still further in the general formula (1), it is preferable that R1 to R4 each independently represents a hydrogen atom, a substituted or unsubstituted arylamino group having 5 to 20 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring carbon atoms or a substituted or unsubstituted silyl group having 3 to 50 carbon atoms.
Further, it is preferable that R1 and/or R3 represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group or a cyclohexyl group.
Furthermore, it is preferable that R2 and/or R4 represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group or a cyclohexyl group.
Next, the aromatic amine derivative represented by the general formula (2) will be explained below.




In the general formula (2), A5 to A8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 (preferably 1 to 20) carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 (preferably 5 to 20) ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 (preferably 5 to 12) ring carbon atoms or a substituted or unsubstituted heterocyclic group having 3 to 50 (preferably 3 to 20) ring carbon atoms;
In the general formula (2), R5 to R8 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 (preferably 1 to 20) carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 (preferably 5 to 20) ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 (preferably 6 to 20) ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 (preferably 5 to 12) ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 20 (preferably 5 to 12) ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 (preferably 1 to 10) carbon atoms or a substituted or unsubstituted heterocyclic group having 3 to 50 (preferably 3 to 20) ring carbon atoms; a couple of R5 and R6, and a couple of R7 and R8 may bond each other to form a saturated or unsaturated ring.
Specific examples of the groups represented by A5 to A8 and R5 to R8 in the general formula (2), specific examples of those substituent and specific examples of those saturated or unsaturated ring are the same as those exemplified as A1 to A4 and R1 to R4 in the foregoing general formula (1).
Specific examples of the aromatic amine derivatives represented by the general formula (1) or the general formula (2) will be illustrated below, though not particularly limited thereto. Meanwhile, in the following compounds, Me represents a methyl group.












































































































































TABLE 1







R1
R2
R3
R4








































D-1
Methyl
H
H
H


















 


D-2
Methyl
H
H
H


















 


D-3
Methyl
H
H
H


















 


D-4
Methyl
H
H
H


















 


D-5
Methyl
H
H
H


















 


D-6
Methyl
H
H
H


















 


D-7
Methyl
H
H
H


















 


D-8
Methyl
H
H
H


















 


D-9
Methyl
H
H
H


















 


D-10
Methyl
H
H
H


















 


D-11
Methyl
H
H
H


















 


D-12
Methyl
H
H
H








































TABLE 2






    R1
    R2
    R3
    R4























D-13
Methyl
H
H
H


















 


D-14
Methyl
H
H
H


















 


D-15
Methyl
H
H
H


















 


D-16
Methyl
H
H
H


















 


D-17
Methyl
H
H
H


















 


D-18
Methyl
H
H
H


















 


D-19
Methyl
H
H
H


















 


D-20
Methyl
H
H
H


















 


D-21
Methyl
H
H
H


















 


D-22
Methyl
H
H
H


















 


D-23
Methyl
H
H
H


















 


D-24
Methyl
H
H
H








































TABLE 3






    R1
    R2
    R3
    R4























D-25
Methyl
H
H
H


















D-26
Methyl
H
H
H


















D-27
Methyl
H
H
H


















D-28
Methyl
H
H
H


















D-29
Methyl
H
H
H


















D-30
Methyl
H
H
H


















D-31
Methyl
H
H
H


















D-32
Methyl
H
H
H


















D-33
Methyl
H
H
H


















D-34
Methyl
H
H
H


















D-35
Methyl
H
H
H


















D-36
Methyl
H
H
H








































TABLE 4






    R1
    R2
    R3
    R4























D-37
Methyl
H
H
H


















 


D-38
Methyl
H
H
H


















 


D-39
Methyl
H
H
H


















 


D-40
Methyl
H
H
H


















 


D-41
Methyl
H
H
H


















 


D-42
Methyl
H
H
H


















 


D-43
Methyl
H
H
H


















 


D-44
Methyl
H
H
H


















 


D-45
Methyl
H
H
H


















 


D-46
Methyl
H
H
H


















 


D-47
Methyl
H
H
H


















 


D-48
Methyl
H
H
H








































TABLE 5






    R1
    R2
    R3
    R4























D-49
Iso-pro-pyl
H
H
H


















 


D-50
Iso-pro-pyl
H
H
H


















 


D-51
Iso-pro-pyl
H
H
H


















 


D-52
Iso-pro-pyl
H
H
H


















 


D-53
Iso-pro-pyl
H
H
H


















 


D-54
Iso-pro-pyl
H
H
H


















 


D-55
Iso-pro-pyl
H
H
H


















 


D-56
Iso-pro-pyl
H
H
H


















 


D-57
Iso-pro-pyl
H
H
H


















 


D-58
Iso-pro-pyl
H
H
H


















 


D-59
Iso-pro-pyl
H
H
H


















 


D-60
Iso-pro-pyl
H
H
H








































TABLE 6






    R1
    R2
    R3
    R4























D-61
Isopropyl
H
H
H


















 


D-62
Isopropyl
H
H
H


















 


D-63
Isopropyl
H
H
H


















 


D-64
Isopropyl
H
H
H


















 


D-65
Isopropyl
H
H
H


















 


D-66
Isopropyl
H
H
H


















 


D-67
Isopropyl
H
H
H


















 


D-68
Isopropyl
H
H
H


















 


D-69
Isopropyl
H
H
H


















 


D-70
Isopropyl
H
H
H


















 


D-71
Isopropyl
H
H
H


















 


D-72
Isopropyl
H
H
H








































TABLE 7






    R1
    R2
    R3
    R4























D-73
Isopropyl
H
H
H


















 


D-74
Isopropyl
H
H
H


















 


D-75
Isopropyl
H
H
H


















 


D-76
Isopropyl
H
H
H


















 


D-77
Isopropyl
H
H
H


















 


D-78
Isopropyl
H
H
H


















 


D-79
Isopropyl
H
H
H


















 


D-80
Isopropyl
H
H
H


















 


D-81
Isopropyl
H
H
H


















 


D-82
Isopropyl
H
H
H


















 


D-83
Isopropyl
H
H
H


















 


D-84
Isopropyl
H
H
H








































TABLE 8






    R1
    R2
    R3
    R4























D-85
Isopropyl
H
H
H


















 


D-86
Isopropyl
H
H
H


















 


D-87
Isopropyl
H
H
H


















 


D-88
Isopropyl
H
H
H


















 


D-89
Isopropyl
H
H
H


















 


D-90
Isopropyl
H
H
H


















 


D-91
Isopropyl
H
H
H


















 


D-92
Isopropyl
H
H
H


















 


D-93
Isopropyl
H
H
H


















 


D-94
Isopropyl
H
H
H


















 


D-95
Isopropyl
H
H
H


















 


D-96
Isopropyl
H
H
H









































TABLE 9







  R1
  R2
  R3
  R4








































D-97
t-butyl
H
H
H


















 


D-98
t-butyl
H
H
H


















 


D-99
t-butyl
H
H
H


















 


D-100
t-butyl
H
H
H


















 


D-101
t-butyl
H
H
H


















 


D-102
t-butyl
H
H
H


















 


D-103
t-butyl
H
H
H


















 


D-104
t-butyl
H
H
H


















 


D-105
t-butyl
H
H
H


















 


D-106
t-butyl
H
H
H


















 


D-107
t-butyl
H
H
H


















 


D-108
t-butyl
H
H
H








































TABLE 10






    R1
    R2
    R3
    R4























D-109
t-butyl
H
H
H


















 


D-110
t-butyl
H
H
H


















 


D-111
t-butyl
H
H
H


















 


D-112
t-butyl
H
H
H


















 


D-113
t-butyl
H
H
H


















 


D-114
t-butyl
H
H
H


















 


D-115
t-butyl
H
H
H


















 


D-116
t-butyl
H
H
H


















 


D-117
t-butyl
H
H
H


















 


D-118
t-butyl
H
H
H


















 


D-119
t-butyl
H
H
H


















 


D-120
t-butyl
H
H
H








































TABLE 11






    R1
    R2
    R3
    R4























D-121
t-butyl
H
H
H


















D-122
t-butyl
H
H
H


















D-123
t-butyl
H
H
H


















D-124
t-butyl
H
H
H


















D-125
t-butyl
H
H
H


















D-126
t-butyl
H
H
H


















D-127
t-butyl
H
H
H


















D-128
t-butyl
H
H
H


















D-129
t-butyl
H
H
H


















D-130
t-butyl
H
H
H


















D-131
t-butyl
H
H
H


















D-132
t-butyl
H
H
H








































TABLE 12






    R1
    R2
    R3
    R4























D-133
t-butyl
H
H
H


















 


D-134
t-butyl
H
H
H


















 


D-135
t-butyl
H
H
H


















 


D-136
t-butyl
H
H
H


















 


D-137
t-butyl
H
H
H


















 


D-138
t-butyl
H
H
H


















 


D-139
t-butyl
H
H
H


















 


D-140
t-butyl
H
H
H


















 


D-141
t-butyl
H
H
H


















 


D-142
t-butyl
H
H
H


















 


D-143
t-butyl
H
H
H


















 


D-144
t-butyl
H
H
H








































TABLE 13 






    R1
    R2
    R3
    R4























D-145
Phenyl
H
H
H


















 


D-146
Phenyl
H
H
H


















 


D-147
Phenyl
H
H
H


















 


D-148
Phenyl
H
H
H


















 


D-149
Phenyl
H
H
H


















 


D-150
Phenyl
H
H
H


















 


D-151
Phenyl
H
H
H


















 


D-152
Phenyl
H
H
H


















 


D-153
Phenyl
H
H
H


















 


D-154
Phenyl
H
H
H


















 


D-155
Phenyl
H
H
H


















 


D-156
Phenyl
H
H
H








































TABLE 14 






    R1
    R2
    R3
    R4























D-157
1-naphtyl
H
H
H


















 


D-158
1-naphtyl
H
H
H


















 


D-159
1-naphtyl
H
H
H


















 


D-160
1-naphtyl
H
H
H


















 


D-161
1-naphtyl
H
H
H


















 


D-162
1-naphtyl
H
H
H


















 


D-163
1-naphtyl
H
H
H


















 


D-164
1-naphtyl
H
H
H


















 


D-165
1-naphtyl
H
H
H


















 


D-166
1-naphtyl
H
H
H


















 


D-167
1-naphtyl
H
H
H


















 


D-168
1-naphtyl
H
H
H








































TABLE 15






    R1
    R2
    R3
    R4























D-169
2-naphtyl
H
H
H


















 


D-170
2-naphtyl
H
H
H


















 


D-171
2-naphtyl
H
H
H


















 


D-172
2-naphtyl
H
H
H


















 


D-173
2-naphtyl
H
H
H


















 


D-174
2-naphtyl
H
H
H


















 


D-175
2-naphtyl
H
H
H


















 


D-176
2-naphtyl
H
H
H


















 


D-177
2-naphtyl
H
H
H


















 


D-178
2-naphtyl
H
H
H


















 


D-179
2-naphtyl
H
H
H


















 


D-180
2-naphtyl
H
H
H








































TABLE 16






    R1
    R2
    R3
    R4























D-181
Cyano
H
H
H


















 


D-182
Cyano
H
H
H


















 


D-183
Dimethylamino
H
H
H


















 


D-184
Dimethylamino
H
H
H


















 


D-185
Dimethylamino
H
H
H


















 


D-186
2-methylphenyl
H
H
H


















 


D-187
2-methylphenyl
H
H
H


















 


D-188
2-methylphenyl
H
H
H


















 


D-189
2-biphenyl
H
H
H


















 


D-190
2-biphenyl
H
H
H


















 


D-191
2-biphenyl
H
H
H


















 


D-192
2-biphenyl
H
H
H








































TABLE 17






    R1
    R2
    R3
    R4























D-193
Methyl
Methyl
H
H


















 


D-194
Methyl
Methyl
H
H


















 


D-195
Methyl
Methyl
H
H


















 


D-196
Methyl
Methyl
H
H


















 


D-197
Methyl
Methyl
H
H


















 


D-198
Methyl
Methyl
H
H


















 


D-199
Methyl
Methyl
H
H


















 


D-200
Methyl
Methyl
H
H


















 


D-200
Methyl
Methyl
H
H


















 


D-201
Methyl
Methyl
H
H


















 


D-202
Methyl
Methyl
H
H


















 


D-203
Methyl
Methyl
H
H


















 


D-204
Methyl
Methyl
H
H








































TABLE 18






    R1
    R2
    R3
    R4























D-205
Methyl
Methyl
H
H


















 


D-206
Methyl
Methyl
H
H


















 


D-207
Methyl
Methyl
H
H


















 


D-208
Methyl
Methyl
H
H


















 


D-209
Methyl
Methyl
H
H


















 


D-210
Methyl
Methyl
H
H


















 


D-211
Methyl
Methyl
H
H


















 


D-212
Methyl
Methyl
H
H


















 


D-213
Methyl
Methyl
H
H


















 


D-214
Methyl
Methyl
H
H


















 


D-215
Methyl
Methyl
H
H


















 


D-216
Methyl
Methyl
H
H








































TABLE 19






    R1
    R2
    R3
    R4























D-217
Methyl
Methyl
H
H


















D-218
Methyl
Methyl
H
H


















D-219
Methyl
Methyl
H
H


















D-220
Methyl
Methyl
H
H


















D-221
Methyl
Methyl
H
H


















D-222
Methyl
Methyl
H
H


















D-223
Methyl
Methyl
H
H


















D-224
Methyl
Methyl
H
H


















D-225
Methyl
Methyl
H
H


















D-226
Methyl
Methyl
H
H


















D-227
Methyl
Methyl
H
H


















D-228
Methyl
Methyl
H
H








































TABLE 20






    R1
    R2
    R3
    R4























D-229
Methyl
Methyl
H
H


















 


D-230
Methyl
Methyl
H
H


















 


D-231
Methyl
Methyl
H
H


















 


D-232
Methyl
Methyl
H
H


















 


D-233
Methyl
Methyl
H
H


















 


D-234
Methyl
Methyl
H
H


















 


D-235
Methyl
Methyl
H
H


















 


D-236
Methyl
Methyl
H
H


















 


D-237
Methyl
Methyl
H
H


















 


D-238
Methyl
Methyl
H
H


















 


D-239
Methyl
Methyl
H
H


















 


D-240
Methyl
Methyl
H
H








































TABLE 21






    R1
    R2
    R3
    R4























D-241
Methyl
Methyl
Methyl
Methyl


















 


D-242
Methyl
Methyl
Methyl
Methyl


















 


D-243
Methyl
Methyl
Methyl
Methyl


















 


D-244
Methyl
Methyl
Methyl
Methyl


















 


D-245
Methyl
Methyl
Methyl
Methyl


















 


D-246
Methyl
Methyl
Methyl
Methyl


















 


D-247
Methyl
Methyl
Methyl
Methyl


















 


D-248
Methyl
Methyl
Methyl
Methyl


















 


D-249
Methyl
Methyl
Methyl
Methyl


















 


D-250
Methyl
Methyl
Methyl
Methyl


















 


D-251
Methyl
Methyl
Methyl
Methyl


















 


D-252
Methyl
Methyl
Methyl
Methyl








































TABLE 22






    R1
    R2
    R3
    R4























D-253
Methyl
Methyl
Methyl
Methyl


















 


D-254
Methyl
Methyl
Methyl
Methyl


















 


D-255
Methyl
Methyl
Methyl
Methyl


















 


D-256
Methyl
Methyl
Methyl
Methyl


















 


D-257
Methyl
Methyl
Methyl
Methyl


















 


D-258
Methyl
Methyl
Methyl
Methyl


















 


D-259
Methyl
Methyl
Methyl
Methyl


















 


D-260
Methyl
Methyl
Methyl
Methyl


















 


D-261
Methyl
Methyl
Methyl
Methyl


















 


D-262
Methyl
Methyl
Methyl
Methyl


















 


D-263
Methyl
Methyl
Methyl
Methyl


















 


D-264
Methyl
Methyl
Methyl
Methyl








































TABLE 23






    R1
    R2
    R3
    R4























D-253
Methyl
Methyl
Methyl
Methyl


















 


D-254
Methyl
Methyl
Methyl
Methyl


















 


D-255
Methyl
Methyl
Methyl
Methyl


















 


D-256
Methyl
Methyl
Methyl
Methyl


















 


D-257
Methyl
Methyl
Methyl
Methyl


















 


D-258
Methyl
Methyl
Methyl
Methyl


















 


D-259
Methyl
Methyl
Methyl
Methyl


















 


D-260
Methyl
Methyl
Methyl
Methyl


















 


D-261
Methyl
Methyl
Methyl
Methyl


















 


D-262
Methyl
Methyl
Methyl
Methyl


















 


D-263
Methyl
Methyl
Methyl
Methyl


















 


D-264
Methyl
Methyl
Methyl
Methyl








































TABLE 24






R1
R2
R3
R4























D-277
Di-phenylAmino
H
H
H


















 


D-278
Di-phenylAmino
H
H
H


















 


D-279
Di-phenylAmino
H
H
H


















 


D-280
Di-phenylAmino
H
H
H


















 


D-281
Di-phenylAmino
H
H
H


















 


D-282
Di-phenylAmino
H
H
H


















 


D-283
Di-phenylAmino
H
H
H


















 


D-284
Di-phenylAmino
H
H
H


















 


D-285
Di-phenylAmino
H
H
H


















 


D-286
Di-phenylAmino
H
H
H


















 


D-287
Di-phenylAmino
H
H
H


















 


D-288
Di-phenylAmino
H
H
H








































TABLE 25






R1
R2
R3
R4























D-289
Methyl
H
Methyl
H


















 


D-290
Methyl
H
Methyl
H


















 


D-291
Methyl
H
Methyl
H


















 


D-292
Methyl
H
Methyl
H


















 


D-293
Methyl
H
Methyl
H


















 


D-294
Methyl
H
Methyl
H


















 


D-295
Methyl
H
Methyl
H


















 


D-296
Methyl
H
Methyl
H


















 


D-297
Methyl
H
Methyl
H


















 


D-298
Methyl
H
Methyl
H


















 


D-299
Methyl
H
Methyl
H


















 


D-300
Methyl
H
Methyl
H








































TABLE 26






R1
R2
R3
R4























D-301
Methyl
H
Methyl
H


















 


D-302
Methyl
H
Methyl
H


















 


D-303
Methyl
H
Methyl
H


















 


D-304
Methyl
H
Methyl
H


















 


D-305
Methyl
H
Methyl
H


















 


D-306
Methyl
H
Methyl
H


















 


D-307
Methyl
H
Methyl
H


















 


D-308
Methyl
H
Methyl
H


















 


D-309
Methyl
H
Methyl
H


















 


D-310
Methyl
H
Methyl
H


















 


D-311
Methyl
H
Methyl
H


















 


D-312
Methyl
H
Methyl
H








































TABLE 27






    R1
    R2
    R3
    R4























D-313
Methyl
H
Methyl
H


















 


D-314
Methyl
H
Methyl
H


















 


D-315
Methyl
H
Methyl
H


















 


D-316
Methyl
H
Methyl
H


















 


D-317
Methyl
H
Methyl
H


















 


D-318
Methyl
H
Methyl
H


















 


D-319
Methyl
H
Methyl
H


















 


D-320
Methyl
H
Methyl
H


















 


D-321
Methyl
H
Methyl
H


















 


D-322
Methyl
H
Methyl
H


















 


D-323
Methyl
H
Methyl
H


















 


D-324
Methyl
H
Methyl
H








































TABLE 28






    R1
    R2
    R3
    R4























D-325
Methyl
H
Methyl
H


















 


D-326
Methyl
H
Methyl
H


















 


D-327
Methyl
H
Methyl
H


















 


D-328
Methyl
H
Methyl
H


















 


D-329
Methyl
H
Methyl
H


















 


D-330
Methyl
H
Methyl
H


















 


D-331
Methyl
H
Methyl
H


















 


D-332
Methyl
H
Methyl
H


















 


D-333
Methyl
H
Methyl
H


















 


D-334
Methyl
H
Methyl
H


















 


D-335
Methyl
H
Methyl
H


















 


D-336
Methyl
H
Methyl
H








































TABLE 29






R1
R2
R3
R4























D-337
Iso-propyl
H
Iso-propyl
H


















 


D-338
Iso-propyl
H
Iso-propyl
H


















 


D-339
Iso-propyl
H
Iso-propyl
H


















 


D-340
Iso-propyl
H
Iso-propyl
H


















 


D-341
Iso-propyl
H
Iso-propyl
H


















 


D-342
Iso-propyl
H
Iso-propyl
H


















 


D-343
Iso-propyl
H
Iso-propyl
H


















 


D-344
Iso-propyl
H
Iso-propyl
H


















 


D-345
Iso-propyl
H
Iso-propyl
H


















 


D-346
Iso-propyl
H
Iso-propyl
H


















 


D-347
Iso-propyl
H
Iso-propyl
H


















 


D-348
Iso-propyl
H
Iso-propyl
H








































TABLE 30






    R1
    R2
    R3
    R4























D-349
Isopropyl
H
Isopropyl
H


















 


D-350
Isopropyl
H
Isopropyl
H


















 


D-351
Isopropyl
H
Isopropyl
H


















 


D-352
Isopropyl
H
Isopropyl
H


















 


D-353
Isopropyl
H
Isopropyl
H


















 


D-354
Isopropyl
H
Isopropyl
H


















 


D-355
Isopropyl
H
Isopropyl
H


















 


D-356
Isopropyl
H
Isopropyl
H


















 


D-357
Isopropyl
H
Isopropyl
H


















 


D-358
Isopropyl
H
Isopropyl
H


















 


D-359
Isopropyl
H
Isopropyl
H


















 


D-360
Isopropyl
H
Isopropyl
H








































TABLE 31






    R1
    R2
    R3
    R4























D-361
Isopropyl
H
Isopropyl
H


















 


D-362
Isopropyl
H
Isopropyl
H


















 


D-363
Isopropyl
H
Isopropyl
H


















 


D-364
Isopropyl
H
Isopropyl
H


















 


D-365
Isopropyl
H
Isopropyl
H


















 


D-366
Isopropyl
H
Isopropyl
H


















 


D-367
Isopropyl
H
Isopropyl
H


















 


D-368
Isopropyl
H
Isopropyl
H


















 


D-369
Isopropyl
H
Isopropyl
H


















 


D-370
Isopropyl
H
Isopropyl
H


















 


D-371
Isopropyl
H
Isopropyl
H


















 


D-372
Isopropyl
H
Isopropyl
H








































TABLE 32






    R1
    R2
    R3
    R4























D-373
Isopropyl
H
Isopropyl
H


















 


D-374
Isopropyl
H
Isopropyl
H


















 


D-375
Isopropyl
H
Isopropyl
H


















 


D-376
Isopropyl
H
Isopropyl
H


















 


D-377
Isopropyl
H
Isopropyl
H


















 


D-378
Isopropyl
H
Isopropyl
H


















 


D-379
Isopropyl
H
Isopropyl
H


















 


D-380
Isopropyl
H
Isopropyl
H


















 


D-381
Isopropyl
H
Isopropyl
H


















 


D-382
Isopropyl
H
Isopropyl
H


















 


D-383
Isopropyl
H
Isopropyl
H


















 


D-384
Isopropyl
H
Isopropyl
H








































TABLE 33






R1
R2
R3
R4























D-385
t-bu-tyl
H
t-bu-tyl
H


















 


D-386
t-bu-tyl
H
t-bu-tyl
H


















 


D-387
t-bu-tyl
H
t-bu-tyl
H


















 


D-388
t-bu-tyl
H
t-bu-tyl
H


















 


D-389
t-bu-tyl
H
t-bu-tyl
H


















 


D-390
t-bu-tyl
H
t-bu-tyl
H


















 


D-391
t-bu-tyl
H
t-bu-tyl
H


















 


D-392
t-bu-tyl
H
t-bu-tyl
H


















 


D-393
t-bu-tyl
H
t-bu-tyl
H


















 


D-394
t-bu-tyl
H
t-bu-tyl
H


















 


D-395
t-bu-tyl
H
t-bu-tyl
H


















 


D-396
t-bu-tyl
H
t-bu-tyl
H








































TABLE 34






    R1
    R2
    R3
    R4















D-397
t-butyl
H
t-butyl
H


















 


D-398
t-butyl
H
t-butyl
H


















 


D-399
t-butyl
H
t-butyl
H


















 


D-400
t-butyl
H
t-butyl
H


















 


D-401
t-butyl
H
t-butyl
H


















 


D-402
t-butyl
H
t-butyl
H


















 


D-403
t-butyl
H
t-butyl
H


















 


D-404
t-butyl
H
t-butyl
H


















 


D-404
t-butyl
H
t-butyl
H


















 


D-405
t-butyl
H
t-butyl
H


















 


D-406
t-butyl
H
t-butyl
H


















 


D-407
t-butyl
H
t-butyl
H


















 


D-408
t-butyl
H
t-butyl
H








































TABLE 35






    R1
    R2
    R3
    R4























D-409
t-butyl
H
t-butyl
H


















 


D-410
t-butyl
H
t-butyl
H


















 


D-411
t-butyl
H
t-butyl
H


















 


D-412
t-butyl
H
t-butyl
H


















 


D-413
t-butyl
H
t-butyl
H


















 


D-414
t-butyl
H
t-butyl
H


















 


D-415
t-butyl
H
t-butyl
H


















 


D-416
t-butyl
H
t-butyl
H


















 


D-417
t-butyl
H
t-butyl
H


















 


D-418
t-butyl
H
t-butyl
H


















 


D-419
t-butyl
H
t-butyl
H


















 


D-420
t-butyl
H
t-butyl
H








































TABLE 36






    R1
    R2
    R3
    R4























D-421
t-butyl
H
t-butyl
H


















 


D-422
t-butyl
H
t-butyl
H


















 


D-423
t-butyl
H
t-butyl
H


















 


D-424
t-butyl
H
t-butyl
H


















 


D-425
t-butyl
H
t-butyl
H


















 


D-426
t-butyl
H
t-butyl
H


















 


D-427
t-butyl
H
t-butyl
H


















 


D-428
t-butyl
H
t-butyl
H


















 


D-429
t-butyl
H
t-butyl
H


















 


D-430
t-butyl
H
t-butyl
H


















 


D-431
t-butyl
H
t-butyl
H


















 


D-432
t-butyl
H
t-butyl
H








































TABLE 37






R1
R2
R3
R4























D-433
Phe-nyl
H
Phe-nyl
H


















 


D-434
Phe-nyl
H
Phe-nyl
H


















 


D-435
Phe-nyl
H
Phe-nyl
H


















 


D-436
Phe-nyl
H
Phe-nyl
H


















 


D-437
Phe-nyl
H
Phe-nyl
H


















 


D-438
Phe-nyl
H
Phe-nyl
H


















 


D-439
Phe-nyl
H
Phe-nyl
H


















 


D-440
Phe-nyl
H
Phe-nyl
H


















 


D-441
Phe-nyl
H
Phe-nyl
H


















 


D-442
Phe-nyl
H
Phe-nyl
H


















 


D-443
Phe-nyl
H
Phe-nyl
H


















 


D-444
Phe-nyl
H
Phe-nyl
H








































TABLE 38






    R1
    R2
    R3
    R4























D-445
Phenyl
H
Phenyl
H


















 


D-446
Phenyl
H
Phenyl
H


















 


D-447
Phenyl
H
Phenyl
H


















 


D-448
Phenyl
H
Phenyl
H


















 


D-449
Phenyl
H
Phenyl
H


















 


D-450
Phenyl
H
Phenyl
H


















 


D-451
Phenyl
H
Phenyl
H


















 


D-452
Phenyl
H
Phenyl
H


















 


D-453
Phenyl
H
Phenyl
H


















 


D-454
Phenyl
H
Phenyl
H


















 


D-455
Phenyl
H
Phenyl
H


















 


D-456
Phenyl
H
Phenyl
H








































TABLE 39






    R1
    R2
    R3
    R4























D-457
Phenyl
H
Phenyl
H


















D-458
Phenyl
H
Phenyl
H


















D-459
Phenyl
H
Phenyl
H


















D-460
Phenyl
H
Phenyl
H


















D-461
Phenyl
H
Phenyl
H


















D-462
Phenyl
H
Phenyl
H


















D-463
Phenyl
H
Phenyl
H


















D-464
Phenyl
H
Phenyl
H


















D-465
Phenyl
H
Phenyl
H


















D-466
Phenyl
H
Phenyl
H


















D-467
Phenyl
H
Phenyl
H


















D-468
Phenyl
H
Phenyl
H








































TABLE 40








    R1
    R2
    R3
    R4





















D-469
Phenyl
H
Phenyl
H


















 


D-470
Phenyl
H
Phenyl
H


















 


D-471
Phenyl
H
Phenyl
H


















 


D-472
Phenyl
H
Phenyl
H


















 


D-473
Phenyl
H
Phenyl
H


















 


D-474
Phenyl
H
Phenyl
H


















 


D-476
Phenyl
H
Phenyl
H


















 


D-477
Phenyl
H
Phenyl
H


















 


D-478
Phenyl
H
Phenyl
H


















 


D-479
Phenyl
H
Phenyl
H


















 


D-480
Phenyl
H
Phenyl
H








































TABLE 41






R1
R2
R3
R4























D-481
H
Methyl
H
H


















 


D-482
H
Methyl
H
H


















 


D-483
H
Methyl
H
H


















 


D-484
H
Methyl
H
H


















 


D-485
H
Methyl
H
H


















 


D-486
H
Methyl
H
H


















 


D-487
H
Methyl
H
H


















 


D-488
H
Methyl
H
H


















 


D-489
H
Methyl
H
H


















 


D-490
H
Methyl
H
H


















 


D-491
H
Methyl
H
H


















 


D-492
H
Methyl
H
H









































TABLE 42







R1
R2
R3
R4








































D-493
H
Methyl
H
H


















 


D-494
H
Methyl
H
H


















 


D-495
H
Methyl
H
H


















 


D-496
H
Methyl
H
H


















 


D-497
H
Methyl
H
H


















 


D-498
H
Methyl
H
H


















 


D-499
H
Methyl
H
H


















 


D-500
H
Methyl
H
H


















 


D-501
H
Methyl
H
H


















 


D-502
H
Methyl
H
H


















 


D-503
H
Methyl
H
H


















 


D-504
H
Methyl
H
H









































TABLE 43







R1
R2
R3
R4








































D-505
H
Methyl
H
H


















 


D-506
H
Methyl
H
H


















 


D-507
H
Methyl
H
H


















 


D-508
H
Methyl
H
H


















 


D-509
H
Methyl
H
H


















 


D-510
H
Methyl
H
H


















 


D-511
H
Methyl
H
H


















 


D-512
H
Methyl
H
H


















 


D-513
H
Methyl
H
H


















 


D-514
H
Methyl
H
H


















 


D-515
H
Methyl
H
H


















 


D-516
H
Methyl
H
H









































TABLE 44







R1
R2
R3
R4








































D-517
H
Methyl
H
H


















 


D-518
H
Methyl
H
H


















 


D-519
H
Methyl
H
H


















 


D-520
H
Methyl
H
H


















 


D-521
H
Methyl
H
H


















 


D-522
H
Methyl
H
H


















 


D-523
H
Methyl
H
H


















 


D-524
H
Methyl
H
H


















 


D-525
H
Methyl
H
H


















 


D-526
H
Methyl
H
H


















 


D-527
H
Methyl
H
H


















 


D-528
H
Methyl
H
H









































TABLE 45







R1
R2
R3
R4








































D-529
H
Isopropyl
H
H


















 


D-530
H
Isopropyl
H
H


















 


D-531
H
Isopropyl
H
H


















 


D-532
H
Isopropyl
H
H


















 


D-533
H
Isopropyl
H
H


















 


D-534
H
Isopropyl
H
H


















 


D-535
H
Isopropyl
H
H


















 


D-536
H
Isopropyl
H
H


















 


D-537
H
Isopropyl
H
H


















 


D-538
H
Isopropyl
H
H


















 


D-539
H
Isopropyl
H
H


















 


D-540
H
Isopropyl
H
H









































TABLE 46







R1
R2
R3
R4








































D-541
H
Isopropyl
H
H


















 


D-542
H
Isopropyl
H
H


















 


D-543
H
Isopropyl
H
H


















 


D-544
H
Isopropyl
H
H


















 


D-545
H
Isopropyl
H
H


















 


D-546
H
Isopropyl
H
H


















 


D-547
H
Isopropyl
H
H


















 


D-548
H
Isopropyl
H
H


















 


D-549
H
Isopropyl
H
H


















 


D-550
H
Isopropyl
H
H


















 


D-551
H
Isopropyl
H
H


















 


D-552
H
Isopropyl
H
H









































TABLE 47







R1
R2
R3
R4








































D-553
H
Isopropyl
H
H


















 


D-554
H
Isopropyl
H
H


















 


D-555
H
Isopropyl
H
H


















 


D-556
H
Isopropyl
H
H


















 


D-557
H
Isopropyl
H
H


















 


D-558
H
Isopropyl
H
H


















 


D-559
H
Isopropyl
H
H


















 


D-560
H
Isopropyl
H
H


















 


D-561
H
Isopropyl
H
H


















 


D-562
H
Isopropyl
H
H


















 


D-563
H
Isopropyl
H
H


















 


D-564
H
Isopropyl
H
H









































TABLE 48







R1
R2
R3
R4








































D-565
H
Isopropyl
H
H


















 


D-566
H
Isopropyl
H
H


















 


D-567
H
Isopropyl
H
H


















 


D-568
H
Isopropyl
H
H


















 


D-569
H
Isopropyl
H
H


















 


D-570
H
Isopropyl
H
H


















 


D-571
H
Isopropyl
H
H


















 


D-572
H
Isopropyl
H
H


















 


D-573
H
Isopropyl
H
H


















 


D-574
H
Isopropyl
H
H


















 


D-575
H
Isopropyl
H
H


















 


D-576
H
Isopropyl
H
H









































TABLE 49







R1
R2
R3
R4








































D-577
H
t-butyl
H
H


















 


D-578
H
t-butyl
H
H


















 


D-579
H
t-butyl
H
H


















 


D-580
H
t-butyl
H
H


















 


D-581
H
t-butyl
H
H


















 


D-582
H
t-butyl
H
H


















 


D-583
H
t-butyl
H
H


















 


D-584
H
t-butyl
H
H


















 


D-585
H
t-butyl
H
H


















 


D-586
H
t-butyl
H
H


















 


D-587
H
t-butyl
H
H


















 


D-588
H
t-butyl
H
H









































TABLE 50







R1
R2
R3
R4








































D-589
H
t-butyl
H
H


















 


D-590
H
t-butyl
H
H


















 


D-591
H
t-butyl
H
H


















 


D-592
H
t-butyl
H
H


















 


D-593
H
t-butyl
H
H


















 


D-594
H
t-butyl
H
H


















 


D-595
H
t-butyl
H
H


















 


D-596
H
t-butyl
H
H


















 


D-597
H
t-butyl
H
H


















 


D-598
H
t-butyl
H
H


















 


D-599
H
t-butyl
H
H


















 


D-600
H
t-butyl
H
H









































TABLE 51







R1
R2
R3
R4








































D-601
H
t-butyl
H
H


















 


D-602
H
t-butyl
H
H


















 


D-603
H
t-butyl
H
H


















 


D-604
H
t-butyl
H
H


















 


D-605
H
t-butyl
H
H


















 


D-606
H
t-butyl
H
H


















 


D-607
H
t-butyl
H
H


















 


D-608
H
t-butyl
H
H


















 


D-609
H
t-butyl
H
H


















 


D-610
H
t-butyl
H
H


















 


D-611
H
t-butyl
H
H


















 


D-612
H
t-butyl
H
H









































TABLE 52







R1
R2
R3
R4








































D-613
H
t-butyl
H
H


















 


D-614
H
t-butyl
H
H


















 


D-615
H
t-butyl
H
H


















 


D-616
H
t-butyl
H
H


















 


D-617
H
t-butyl
H
H


















 


D-618
H
t-butyl
H
H


















 


D-619
H
t-butyl
H
H


















 


D-620
H
t-butyl
H
H


















 


D-621
H
t-butyl
H
H


















 


D-622
H
t-butyl
H
H


















 


D-623
H
t-butyl
H
H


















 


D-624
H
t-butyl
H
H









































TABLE 53







R1
R2
R3
R4








































D-625
H
Phenyl
H
H


















 


D-626
H
Phenyl
H
H


















 


D-627
H
Phenyl
H
H


















 


D-628
H
Phenyl
H
H


















 


D-629
H
Phenyl
H
H


















 


D-630
H
Phenyl
H
H


















 


D-631
H
Phenyl
H
H


















 


D-632
H
Phenyl
H
H


















 


D-633
H
Phenyl
H
H


















 


D-634
H
Phenyl
H
H


















 


D-635
H
Phenyl
H
H


















 


D-636
H
Phenyl
H
H









































TABLE 54







R1
R2
R3
R4








































D-637
H
Phenyl
H
H


















 


D-638
H
Phenyl
H
H


















 


D-639
H
Phenyl
H
H


















 


D-640
H
Phenyl
H
H


















 


D-641
H
Phenyl
H
H


















 


D-642
H
Phenyl
H
H


















 


D-643
H
Phenyl
H
H


















 


D-644
H
Phenyl
H
H


















 


D-645
H
Phenyl
H
H


















 


D-646
H
Phenyl
H
H


















 


D-647
H
Phenyl
H
H


















 


D-648
H
Phenyl
H
H









































TABLE 55







R1
R2
R3
R4








































D-649
H
Phenyl
H
H


















 


D-650
H
Phenyl
H
H


















 


D-651
H
Phenyl
H
H


















 


D-652
H
Phenyl
H
H


















 


D-653
H
Phenyl
H
H


















 


D-654
H
Phenyl
H
H


















 


D-655
H
Phenyl
H
H


















 


D-656
H
Phenyl
H
H


















 


D-657
H
Phenyl
H
H


















 


D-658
H
Phenyl
H
H


















 


D-659
H
Phenyl
H
H


















 


D-660
H
Phenyl
H
H









































TABLE 56







R1
R2
R3
R4








































D-661
H
Phenyl
H
H


















 


D-662
H
Phenyl
H
H


















 


D-663
H
Phenyl
H
H


















 


D-664
H
Phenyl
H
H


















 


D-665
H
Phenyl
H
H


















 


D-666
H
Phenyl
H
H


















 


D-667
H
Phenyl
H
H


















 


D-668
H
Phenyl
H
H


















 


D-669
H
Phenyl
H
H


















 


D-670
H
Phenyl
H
H


















 


D-671
H
Phenyl
H
H


















 


D-672
H
Phenyl
H
H









































TABLE 57







R1
R2
R3
R4








































D-673
H
Methyl
H
Methyl


















 


D-674
H
Methyl
H
Methyl


















 


D-675
H
Methyl
H
Methyl


















 


D-676
H
Methyl
H
Methyl


















 


D-677
H
Methyl
H
Methyl


















 


D-678
H
Methyl
H
Methyl


















 


D-679
H
Methyl
H
Methyl


















 


D-680
H
Methyl
H
Methyl


















 


D-681
H
Methyl
H
Methyl


















 


D-682
H
Methyl
H
Methyl


















 


D-683
H
Methyl
H
Methyl


















 


D-684
H
Methyl
H
Methyl









































TABLE 58







R1
R2
R3
R4








































D-685
H
Methyl
H
Methyl


















 


D-686
H
Methyl
H
Methyl


















 


D-687
H
Methyl
H
Methyl


















 


D-688
H
Methyl
H
Methyl


















 


D-689
H
Methyl
H
Methyl


















 


D-690
H
Methyl
H
Methyl


















 


D-691
H
Methyl
H
Methyl


















 


D-692
H
Methyl
H
Methyl


















 


D-693
H
Methyl
H
Methyl


















 


D-694
H
Methyl
H
Methyl


















 


D-695
H
Methyl
H
Methyl


















 


D-696
H
Methyl
H
Methyl









































TABLE 59







R1
R2
R3
R4








































D-697
H
Methyl
H
Methyl


















 


D-698
H
Methyl
H
Methyl


















 


D-699
H
Methyl
H
Methyl


















 


D-700
H
Methyl
H
Methyl


















 


D-701
H
Methyl
H
Methyl


















 


D-702
H
Methyl
H
Methyl


















 


D-703
H
Methyl
H
Methyl


















 


D-704
H
Methyl
H
Methyl


















 


D-705
H
Methyl
H
Methyl


















 


D-706
H
Methyl
H
Methyl


















 


D-707
H
Methyl
H
Methyl


















 


D-708
H
Methyl
H
Methyl









































TABLE 60







R1
R2
R3
R4








































D-709
H
Methyl
H
Methyl


















 


D-710
H
Methyl
H
Methyl


















 


D-711
H
Methyl
H
Methyl


















 


D-712
H
Methyl
H
Methyl


















 


D-713
H
Methyl
H
Methyl


















 


D-714
H
Methyl
H
Methyl


















 


D-715
H
Methyl
H
Methyl


















 


D-716
H
Methyl
H
Methyl


















 


D-717
H
Methyl
H
Methyl


















 


D-718
H
Methyl
H
Methyl


















 


D-719
H
Methyl
H
Methyl


















 


D-720
H
Methyl
H
Methyl









































TABLE 61







R1
R2
R3
R4








































D-721
H
Isopropyl
H
Isopropyl


















 


D-722
H
Isopropyl
H
Isopropyl


















 


D-723
H
Isopropyl
H
Isopropyl


















 


D-724
H
Isopropyl
H
Isopropyl


















 


D-725
H
Isopropyl
H
Isopropyl


















 


D-726
H
Isopropyl
H
Isopropyl


















 


D-727
H
Isopropyl
H
Isopropyl


















 


D-728
H
Isopropyl
H
Isopropyl


















 


D-729
H
Isopropyl
H
Isopropyl


















 


D-730
H
Isopropyl
H
Isopropyl


















 


D-731
H
Isopropyl
H
Isopropyl


















 


D-732
H
Isopropyl
H
Isopropyl








































TABLE 62






   R1
   R2
   R3
   R4























D-733
H
Isopropyl
H
Isopropyl


















 


D-734
H
Isopropyl
H
Isopropyl


















 


D-735
H
Isopropyl
H
Isopropyl


















 


D-736
H
Isopropyl
H
Isopropyl


















 


D-737
H
Isopropyl
H
Isopropyl


















 


D-738
H
Isopropyl
H
Isopropyl


















 


D-739
H
Isopropyl
H
Isopropyl


















 


D-740
H
Isopropyl
H
Isopropyl


















 


D-741
H
Isopropyl
H
Isopropyl


















 


D-742
H
Isopropyl
H
Isopropyl


















 


D-743
H
Isopropyl
H
Isopropyl


















 


D-744
H
Isopropyl
H
Isopropyl








































TABLE 63






   R1
   R2
   R3
   R4























D-745
H
Isopropyl
H
Isopropyl


















 


D-746
H
Isopropyl
H
Isopropyl


















 


D-747
H
Isopropyl
H
Isopropyl


















 


D-748
H
Isopropyl
H
Isopropyl


















 


D-749
H
Isopropyl
H
Isopropyl


















 


D-750
H
Isopropyl
H
Isopropyl


















 


D-751
H
Isopropyl
H
Isopropyl


















 


D-752
H
Isopropyl
H
Isopropyl


















 


D-753
H
Isopropyl
H
Isopropyl


















 


D-754
H
Isopropyl
H
Isopropyl


















 


D-755
H
Isopropyl
H
Isopropyl


















 


D-756
H
Isopropyl
H
Isopropyl








































TABLE 64






   R1
   R2
   R3
   R4























D-757
H
Isopropyl
H
Isopropyl


















 


D-758
H
Isopropyl
H
Isopropyl


















 


D-759
H
Isopropyl
H
Isopropyl


















 


D-760
H
Isopropyl
H
Isopropyl


















 


D-761
H
Isopropyl
H
Isopropyl


















 


D-762
H
Isopropyl
H
Isopropyl


















 


D-763
H
Isopropyl
H
Isopropyl


















 


D-764
H
Isopropyl
H
Isopropyl


















 


D-765
H
Isopropyl
H
Isopropyl


















 


D-766
H
Isopropyl
H
Isopropyl


















 


D-767
H
Isopropyl
H
Isopropyl


















 


D-768
H
Isopropyl
H
Isopropyl








































TABLE 65






   R1
   R2
   R3
   R4























D-769
Cyclohexyl
H
H
H


















 


D-770
Cyclohexyl
H
H
H


















 


D-771
Cyclohexyl
H
H
H


















 


D-772
Cyclohexyl
H
H
H


















 


D-773
Cyclohexyl
H
H
H


















 


D-774
Cyclohexyl
H
H
H


















 


D-775
Cyclohexyl
H
H
H


















 


D-776
Cyclohexyl
H
H
H


















 


D-777
Cyclohexyl
H
H
H


















 


D-778
Cyclohexyl
H
H
H


















 


D-779
Cyclohexyl
H
H
H


















 


D-780
Cyclohexyl
H
H
H








































TABLE 66






   R1
   R2
   R3
   R4























D-781
Cyclohexyl
H
H
H


















 


D-782
Cyclohexyl
H
H
H


















 


D-783
Cyclohexyl
H
H
H


















 


D-784
Cyclohexyl
H
H
H


















 


D-785
Cyclohexyl
H
H
H


















 


D-786
Cyclohexyl
H
H
H


















 


D-787
Cyclohexyl
H
H
H


















 


D-788
Cyclohexyl
H
H
H


















 


D-789
Cyclohexyl
H
H
H


















 


D-790
Cyclohexyl
H
H
H


















 


D-791
Cyclohexyl
H
H
H


















 


D-792
Cyclohexyl
H
H
H








































TABLE 67






   R1
   R2
   R3
   R4























D-793
Cyclohexyl
H
Cyclohexyl
H


















 


D-794
Cyclohexyl
H
Cyclohexyl
H


















 


D-795
Cyclohexyl
H
Cyclohexyl
H


















 


D-796
Cyclohexyl
H
Cyclohexyl
H


















 


D-797
Cyclohexyl
H
Cyclohexyl
H


















 


D-798
Cyclohexyl
H
Cyclohexyl
H


















 


D-799
Cyclohexyl
H
Cyclohexyl
H


















 


D-800
Cyclohexyl
H
Cyclohexyl
H


















 


D-801
Cyclohexyl
H
Cyclohexyl
H


















 


D-802
Cyclohexyl
H
Cyclohexyl
H


















 


D-803
Cyclohexyl
H
Cyclohexyl
H


















 


D-804
Cyclohexyl
H
Cyclohexyl
H








































TABLE 68






   R1
   R2
   R3
   R4























D-805
Cyclohexyl
H
Cyclohexyl
H


















 


D-806
Cyclohexyl
H
Cyclohexyl
H


















 


D-807
Cyclohexyl
H
Cyclohexyl
H


















 


D-808
Cyclohexyl
H
Cyclohexyl
H


















 


D-809
Cyclohexyl
H
Cyclohexyl
H


















 


D-810
Cyclohexyl
H
Cyclohexyl
H


















 


D-811
Cyclohexyl
H
Cyclohexyl
H


















 


D-812
Cyclohexyl
H
Cyclohexyl
H


















 


D-813
Cyclohexyl
H
Cyclohexyl
H


















 


D-814
Cyclohexyl
H
Cyclohexyl
H


















 


D-815
Cyclohexyl
H
Cyclohexyl
H


















 


D-816
Cyclohexyl
H
Cyclohexyl
H








































TABLE 69






   R1
   R2
   R3
   R4























D-817
4-t-butylphemyl
H
H
H


















 


D-818
4-t-butylphemyl
H
H
H


















 


D-819
4-t-butylphemyl
H
H
H


















 


D-820
4-t-butylphemyl
H
H
H


















 


D-821
4-t-butylphemyl
H
H
H


















 


D-822
4-t-butylphemyl
H
H
H


















 


D-823
4-trimethylsilylphenyl
H
H
H


















 


D-824
4-trimethylsilylphenyl
H
H
H


















 


D-825
4-trimethylsilylphenyl
H
H
H


















 


D-826
4-trimethylsilylphenyl
H
H
H


















 


D-827
4-trimethylsilylphenyl
H
H
H


















 


D-828
4-trimethylsilylphenyl
H
H
H








































TABLE 70






   R1
   R2
   R3
   R4























D-829
4-cyanophenyl
H
H
H


















 


D-830
4-cyanophenyl
H
H
H


















 


D-831
4-cyanophenyl
H
H
H


















 


D-832
4-cyanophenyl
H
H
H


















 


D-833
4-cyanophenyl
H
H
H


















 


D-834
4-cyanophenyl
H
H
H


















 


D-835
4-trifluoromethylphenyl
H
H
H


















 


D-836
4-trifluoromethylphenyl
H
H
H


















 


D-837
4-trifluoromethylphenyl
H
H
H


















 


D-838
4-trifluoromethylphenyl
H
H
H


















 


D-839
4-trifluoromethylphenyl
H
H
H


















 


D-840
4-trifluoromethylphenyl
H
H
H








































TABLE 71






   R1
   R2
   R3
   R4























D-841
2-quinolyl
H
H
H


















D-842
2-quinolyl
H
H
H


















D-843
2-quinolyl
H
H
H


















D-844
2-quinolyl
H
H
H


















D-845
2-quinolyl
H
H
H


















D-846
2-quinolyl
H
H
H


















D-847
3-isoquinolyl
H
H
H


















D-848
3-isoquinolyl
H
H
H


















D-849
3-isoquinolyl
H
H
H


















D-850
3-isoquinolyl
H
H
H


















D-851
3-isoquinolyl
H
H
H


















D-852
3-isoquinolyl
H
H
H








































TABLE 72






   R1
   R2
   R3
   R4























D-853
1-adamanthyl
H
H
H


















 


D-854
1-adamanthyl
H
H
H


















 


D-855
1-pyrenyl
H
H
H


















 


D-856
1-pyrenyl
H
H
H


















 


D-857
1-pyrenyl
H
H
H


















 


D-858
1-pyrenyl
H
H
H


















 


D-859
1-pyrenyl
H
H
H


















 


D-860
1-pyrenyl
H
H
H


















 


D-861
1-pyrenyl
H
H
H


















 


D-862
1-pyrenyl
H
H
H


















 


D-863
1-pyrenyl
H
H
H


















 


D-864
1-pyrenyl
H
H
H








































TABLE 73






   R1
   R2
   R3
   R4























D-865
H
Cyclohexyl
H
H


















 


D-866
H
Cyclohexyl
H
H


















 


D-867
H
Cyclohexyl
H
H


















 


D-868
H
Cyclohexyl
H
H


















 


D-869
H
Cyclohexyl
H
H


















 


D-870
H
Cyclohexyl
H
H


















 


D-871
H
Cyclohexyl
H
H


















 


D-872
H
Cyclohexyl
H
H


















 


D-873
H
Cyclohexyl
H
H


















 


D-874
H
Cyclohexyl
H
H


















 


D-875
H
Cyclohexyl
H
H


















 


D-876
H
Cyclohexyl
H
H








































TABLE 74






   R1
   R2
   R3
   R4























D-877
H
Cyclohexyl
H
H


















 


D-878
H
Cyclohexyl
H
H


















 


D-879
H
Cyclohexyl
H
H


















 


D-880
H
Cyclohexyl
H
H


















 


D-881
H
Cyclohexyl
H
H


















 


D-882
H
Cyclohexyl
H
H


















 


D-883
H
Cyclohexyl
H
H


















 


D-884
H
Cyclohexyl
H
H


















 


D-885
H
Cyclohexyl
H
H


















 


D-886
H
Cyclohexyl
H
H


















 


D-887
H
Cyclohexyl
H
H


















 


D-888
H
Cyclohexyl
H
H







































TABLE 75





   R1
   R2
   R3
   R4























H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H


















 


H
Cyclohexyl
H
H








































TABLE 76






   R1
   R2
   R3
   R4























D-901
H
Cyclohexyl
H
H


















 


D-902
H
Cyclohexyl
H
H


















 


D-903
H
Cyclohexyl
H
H


















 


D-904
H
Cyclohexyl
H
H


















 


D-905
H
Cyclohexyl
H
H


















 


D-906
H
Cyclohexyl
H
H


















 


D-907
H
Cyclohexyl
H
H


















 


D-908
H
Cyclohexyl
H
H


















 


D-909
H
Cyclohexyl
H
H


















 


D-910
H
Cyclohexyl
H
H


















 


D-911
H
Cyclohexyl
H
H


















 


D-912
H
Cyclohexyl
H
H








































TABLE 77






   R1
   R2
   R3
   R4























D-913
Methyl
H
Isopropyl
H


















 


D-914
Methyl
H
Isopropyl
H


















 


D-915
Methyl
H
Isopropyl
H


















 


D-916
Methyl
H
Isopropyl
H


















 


D-917
Methyl
H
Isopropyl
H


















 


D-918
Methyl
H
Isopropyl
H


















 


D-919
Methyl
H
Isopropyl
H


















 


D-920
Methyl
H
Isopropyl
H


















 


D-921
Methyl
H
Isopropyl
H


















 


D-922
Methyl
H
Isopropyl
H


















 


D-923
Methyl
H
Isopropyl
H


















 


D-924
Methyl
H
Isopropyl
H








































TABLE 78






   R1
   R2
   R3
   R4























D-925
Methyl
H
Isopropyl
H


















 


D-926
Methyl
H
Isopropyl
H


















 


D-927
Methyl
H
Isopropyl
H


















 


D-928
Methyl
H
Isopropyl
H


















 


D-929
Methyl
H
Isopropyl
H


















 


D-930
Methyl
H
Isopropyl
H


















 


D-931
Methyl
H
Isopropyl
H


















 


D-932
Methyl
H
Isopropyl
H


















 


D-933
Methyl
H
Isopropyl
H


















 


D-934
Methyl
H
Isopropyl
H


















 


D-935
Methyl
H
Isopropyl
H


















 


D-936
Methyl
H
Isopropyl
H








































TABLE 79






   R1
   R2
   R3
   R4























D-937
t-bytyl
H
Isopropyl
H


















 


D-938
t-bytyl
H
Isopropyl
H


















 


D-939
t-bytyl
H
Isopropyl
H


















 


D-940
t-bytyl
H
Isopropyl
H


















 


D-941
t-bytyl
H
Isopropyl
H


















 


D-942
t-bytyl
H
Isopropyl
H


















 


D-943
t-bytyl
H
Isopropyl
H


















 


D-944
t-bytyl
H
Isopropyl
H


















 


D-945
t-bytyl
H
Isopropyl
H


















 


D-946
t-bytyl
H
Isopropyl
H


















 


D-947
t-bytyl
H
Isopropyl
H


















 


D-948
t-bytyl
H
Isopropyl
H








































TABLE 80






   R1
   R2
   R3
   R4























D-949
t-bytyl
H
Isopropyl
H


















 


D-950
t-bytyl
H
Isopropyl
H


















 


D-951
t-bytyl
H
Isopropyl
H


















 


D-952
t-bytyl
H
Isopropyl
H


















 


D-953
t-bytyl
H
Isopropyl
H


















 


D-954
t-bytyl
H
Isopropyl
H


















 


D-955
t-bytyl
H
Isopropyl
H


















 


D-956
t-bytyl
H
Isopropyl
H


















 


D-957
t-bytyl
H
Isopropyl
H


















 


D-958
t-bytyl
H
Isopropyl
H


















 


D-959
t-bytyl
H
Isopropyl
H


















 


D-960
t-bytyl
H
Isopropyl
H








































TABLE 81





No
R5
R6
R7
R8
A5
A6
A7
A8







D-961
—H
—H
—H
—H
—Me
—Me
—Me
—Me


 


D-962
—H
—H
—H
—H
—Me




—Me






 


D-963
—H
—H
—H
—H


















 


D-964
—H
—H
—H
—H




—Me




—Me


 


D-965
—H
—H
—H
—H


















 


D-966
—Me
—H
—Me
—H


















 


D-967
—Me
—Me
—Me
—Me


















 


D-968




—H




—H
—Me




—Me






 


D-969
—H
—Me
—H
—Me


















 


D970




—H




—H








































TABLE 82





No
R5
R6
R7
R8
A5
A6
A7
A8







D-971
—H
—H
—H
—H
—Me




—Me






 


D-972
—H
—H
—H
—H


















 


D-973
—H
—H
—H
—H
—Me




—Me






 


D-974
—H
—H
—H
—H


















 


D-975
—H
—H
—H
—H


















 


D-976
—H
—H
—H
—H


















 


D-977
—H
—H
—H
—H


















 


D-978
—Me
—H
—Me
—H
—Me




—Me






 


D-979
—Me
—Me
—Me
Me


















 


D-980
—Me
—H
—Me
—H








































TABLE 83





No
R5
R6
R7
R8
A5
A6
A7
A8







D-981
—H
—H
—H
—H
—Me




—Me






 


D-982
—H
—H
—H
—H


















 


D-983
—H
—H
—H
—H
—Me




—Me






 


D-984
—H
—H
—H
—H


















 


D-985
—H
—H
—H
—H


















 


D-986
—H
—H
—H
—H


















 


D-987
—H
—H
—H
—H


















 


D-988
—Me
—H
—Me
—H
—Me




—Me






 


D-989
—H
—H
—H
—H


















 


D-990
—H
—H
—H
—H








































TABLE 84





No
R5
R6
R7
R8
A5
A6
A7
A8







D-991
—H
—H
—H
—H


















 


D-992
—H
—H
—H
—H


















 


D-993
—H
—H
—H
—H


















 


D-994
—H
—H
—H
—H


















 


D-995
—H
—H
—H
—H


















 


D-996
—H
—H
—H
—H


















 


D-997
—H
—H
—H
—H


















 


D-998
—H
—H
—H
—H


















 


D-999
—H
—H
—H
—H


















 


D-1000
—Me
—H
—H
—H








































TABLE 85





No
R5
R6
R7
R8
A5
A6
A7
A8







D-1001
—H
—H
—H
—H


















 


D-1002
—H
—H
—H
—H


















 


D-1003
—H
—H
—H
—H


















 


D-1004
—H
—H
—H
—H


















 


D-1005
—H
—H
—H
—H


















 


D-1006
—H
—H
—H
—H


















 


D-1007
—H
—H
—H
—H


















 


D-1008
—H
—H
—H
—H


















 


D-1009
—H
—H
—H
—H


















 


D-1010
—Me
—H
—Me
—H








































TABLE 86





No
R5
R6
R7
R8
A5
A6
A7
A8







D-1011
—H
—H
—H
—H


















 


D-1012
—H
—H
—H
—H


















 


D-1013
—H
—H
—H
—H


















 


D-1014
—H
—H
—H
—H


















 


D-1015
—H
—H
—H
—H


















 


D-1016
—H
—H
—H
—H


















 


D-1017
—H
—H
—H
—H


















 


D-1018
—H
—H
—H
—H


















 


D-1019
—H
—H
—H
—H


















 


D-1020
—Me
—H
—Me
—H








































TABLE 87





No
R5
R6
R7
R8
A5
A6
A7
A8







D-1021
—H
—H
—H
—H


















 


D-1022
—H
—H
—H
—H


















 


D-1023
—H
—H
—H
—H


















 


D-1024
—H
—H
—H
—H


















 


D-1025
—H
—H
—H
—H


















 


D-1026
—H
—H
—H
—H


















 


D-1027
—H
—H
—H
—H


















 


D-1028
Me
—H
Me
—H


















 


D-1029
—H
—H
—H
—H


















 


D-1030
—H
—H
—H
—H








































TABLE 88





No
R5
R6
R7
R8
A5
A6
A7
A8







D-1031
—H
—H
—H
—H


















 


D-1032
—H
—H
—H
—H


















 


D-1033
—H
—H
—H
—H


















 


D-1034
—H
—H
—H
—H


















 


D-1035
—H
—H
—H
—H


















 


D-1036
—H
—H
—H
—H


















 


D-1037
—H
—H
—H
—H


















 


D-1038
—H
—H
—H
—H


















 


D-1039
—H
—H
—H
—H


















 


D-1040
—Me
—H
—Me
—H








































TABLE 89





No
R5
R6
R7
R8
A5
A6
A7
A8







D-1041
—H
—H
—H
—H


















 


D-1042
—H
—H
—H
—H


















 


D-1043
—H
—H
—H
—H


















 


D-1044
—H
—H
—H
—H


















 


D-1045
—H
—H
—H
—H


















 


D-1046
—H
—H
—H
—H


















 


D-1047
—H
—H
—H
—H


















 


D-1048
Me
—H
Me
—H


















 


D-1049
—H
—H
—H
—H


















 


D-1050
—H
—H
—H
—H

























In the aromatic amine derivative of the present invention, since the aryl group (in particular, a benzene ring), the alkyl group, the cycroalkyl group or the heterocyclic group is connected to a diaminocrysene structure as a light emission center, an association between the compounds is prevented, resulting in a prolonged lifetime thereof. Moreover, because coupling a bulky substituent to the chrysene backbone structure increases a steric repulsion against the amine structure, the lifetime prolongs further.
Further, the aromatic amine derivatives have a strong fluorescence in a solid state, and are excellent in an electric field light emission, which leads to a fluorescent quantum efficiency as high as 0.3 or more. In addition, the aromatic amine derivatives of the present invention exhibit not only excellent capabilities of injecting and transporting holes from the metal electrode or organic thin film layers, but also excellent capabilities of injecting and transporting electrons from the metal electrode or organic thin film layers and, therefore, are usefully employable as light emitting materials, particularly doping materials for organic EL devices. Besides, the aromatic amine derivatives of the present invention may be used together with other hole transporting materials, electron transporting materials or doping materials.
The organic EL device of the present invention comprises one or plural organic thin film layers sandwiched between an anode and a cathode. In the case of one layer type, a light emitting layer as the organic thin film layer is sandwiched between the anode and cathode. The light emitting layer contains the light emitting material and may further contain a hole injecting material and an electron injecting material in order to transport holes injected from the anode or electrons injected from the cathode to the light emitting material. The aromatic amine derivatives of the present invention have an enhanced light emitting property and excellent hole injecting capability and hole transporting capability as well as excellent electron injecting capability and electron transporting capability and, therefore, can be employed as a light emitting material or a doping material in the light emitting layer.
In the organic EL device of the present invention, the light emitting layer contains the aromatic amine derivative of the present invention in an amount of preferably 0.1 to 20% by weight and more preferably 1 to 10% by weight. Further, the aromatic amine derivatives of the present invention exhibit not only an extremely high fluorescent quantum efficiency but also high hole transporting capability and electron transporting capability, and further are capable of forming a uniform thin film, so that the light emitting layer may be formed from the aromatic amine derivatives only.
On the other hand, in the case where the organic EL device of the present invention comprises two or more organic thin film layers having at least the light emitting layer which are sandwiched between the cathode and anode, the organic thin film layers preferably include an organic layer containing the aromatic amine derivative of the present invention as an essential component which is provided between the anode and the light emitting layer. Such an organic layer may be a hole injecting layer, a hole transporting layer, etc.
Further, in a case where the aromatic amine derivative of the present invention is employed as a doping material, it is preferable that at least one kind selected from the group consisting of anthracene derivatives of a following general formula (3), anthracene derivatives of a following general formula (4) and pyrene derivatives of a following general formula (5) is employed as a host material.




In the general formula (3), X1 and X2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 50 ring carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 50 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring carbon atoms or a halogen atom; e and f each independently represents an integer of 0 to 4; when e or f is 2 or greater, X1 and X2 may be the same with or different from each other.
Ar1 and Ar2 each independently represents a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 50 ring carbon atoms; at least one of Ar1 or Ar2 represents a substituted or unsubstituted aryl group with a condensed ring and having 10 to 50 ring carbon atoms; and m represents an integer of 1 to 3. When m is 2 or greater, a group within the above parentheses: [ ] may be the same with or different from each other.
Specific examples and substituents of the X1, X2, Ar1 and Ar2 are the same as those explained about the foregoing general formula (1).




In the general formula (4), X1 to X3 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 50 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring carbon atoms or a halogen atom; e, f, and g each independently represents an integer of 0 to 4. When e, f, or g is 2 or greater, X1, X2 and X3 may be the same with or different from each other.
Ar1 represents a substituted or unsubstituted aryl group with a condensed ring and having 10 to 50 ring carbon atoms and Ar3 represents a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms; n represents an integer of 1 to 3. When n is 2 or greater, a group within the above parentheses: [ ] may be the same with or different from each other.
Specific examples and substituents of the X1 to X3, Ar1 and Ar3 are the same as those explained about the foregoing general formula (1).
Specific examples of anthracene derivative represented by the general formulae (3) and (4) will be illustrated below, though not particularly limited thereto.



















In the general formula (5), Ar5 and Ar6 each represents a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;

    L1 and L2 each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenylene group, a substituted or unsubstituted fluorenylene group or a substituted or unsubstituted dibenzosilolylene group;
    s represents an integer of 0 to 2, p represents an integer of 1 to 4, q represents an integer of 0 to 2 and r represents an integer of 0 to 4; and
    L1 or Ar5 bonds to any one of 1 to 5 position of pyrene, also L2 or Ar6 bonds to any one of 6 to 10 position thereof,
    however, when p+r is an even number, Ar5, Ar6, L1 and L2 satisfy a following requirement (1) or a requirement (2):
    (1) Ar5≠Ar6 and/or L1≠L2 (wherein ≠means that each group has a different structure)
    (2) when Ar5=Ar6 and L1=L2 
    (2-1) s≠q and/or p≠r, or
    (2-2) when s=q, and p=r,
    (2-2-1) both L1 and L2 or pyrene each bond respectively to different positions of Ar5 and Ar6, or
    (2-2-2) both L1 and L2 or pyrene each bonds respectively to the same position of Ar5 and Ar6, excluding a case where both L1 and L2 or both Ar5 and Ar6 bond to 1 and 6 positions thereof, or 2 and 7 positions thereof.


Specific examples and substituents of the Ar5, Ar6, L1 and L2 are the same as those explained about the foregoing general formula (1).
Specific examples of the pyrene derivative represented by the general formula (5) will be illustrated below, though not particularly limited thereto.
















Examples of the organic EL device of a multilayer type include those having multilayer structures such as (an anode/a hole injecting layer/a light emitting layer/a cathode), (an anode/a light emitting layer/an electron injecting layer/a cathode) and (an anode/a hole injecting layer/a light emitting layer/an electron injecting layer/a cathode).
The multilayers may also optionally contain, in addition to the aromatic amine derivatives of the present invention, conventionally known materials such as light emitting materials, doping materials, hole injecting materials and electron injecting materials according to requirements. The organic EL device having such a multilayer structure can be prevented from suffering from deterioration in luminance and lifetime due to quenching. If required, the light emitting materials, doping materials, hole injecting materials and electron injecting materials may be used in combination with each other. The use of the doping materials enables the resultant device to be improved in luminance of light emission and efficiency of light emission, and further emit a red color light or a blue color light. Further, in the organic EL device of the present invention, the hole injecting layer, the light emitting layer and the electron injecting layer may respectively have a multilayer structure including two or more layers. In these cases, a layer injecting holes from the electrode is called as a hole injecting layer, and a layer for accepting the holes from the hole injecting layer and transporting the holes to the light emitting layer is called as a hole transporting layer. Also, a layer injecting electrons the electrode is called as an electron injecting layer, and a layer transporting for accepting the electrons from the electron injecting layer and transporting the electrons to the light emitting layer is called as an electron transporting layer. Those respective layers may be selectively used according to various factors such as energy level of the materials used, heat resistance, and adhesion to the organic thin film layers or the metal electrodes.
Examples of the host material or the doping material besides the foregoing general formulae (3) to (5) employable for the light emitting layer together with the aromatic amine derivative of the present invention include condensed mass aromatic compound such as naphthalene, phenanthrene, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenyl cyclopentadiene, fluorene, spiro fluorene, 9,10-diphenylanthracene, 9,10-bis(phenyl-ethynyl)anthracene, 1,4-bis(9′-ethynyl anthracenyl)benzene and those derivatives; organometallic complex such as tris(8-quinolinolat)aluminium, bis-(2-methyl-8-quinolinolat)-4-(phenylphenolinat)aluminum, etc.; triarylamine derivative, styryl amine derivative, stilbene derivative, coumarine derivative, pyran derivative, oxazone derivative, benzothiazole derivative, benzoxazole derivative, benzimidazole derivative, pyrazine derivative, cinnamate ester derivative, diketo pyrrolopyrrole derivative, acridone derivative, quinacridon derivative, etc.; though not particularly limited thereto.
The hole injecting material is preferably made of compounds which have a good hole transporting capability as well as excellent capabilities of accepting holes injected from the anode and injecting the holes into the light emitting layer or light emitting material, prevent excited particles produced in the light emitting layer from moving into the electron injecting layer or electron injecting material, and exhibit an excellent capability of forming a thin film. Specific examples of the hole injecting material include phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazole thione, pyrazoline, pyrazolone, tetrahydroimidazole, hydrazone, acyl hydrazone, polyaryl alkanes, stilbene, butadiene, benzidine-type triphenyl amine, styryl amine-type triphenyl amine, diamine-type triphenyl amine and derivatives thereof, as well as polyvinyl carbazoles, polysilanes, and high molecular materials such as electro-conductive polymers, though not particularly limited thereto.
Among those hole injecting materials usable in the organic EL device of the present invention, more effective hole injecting materials are aromatic tertiary amine derivatives and phthalocyanine derivatives.
Specific examples of the aromatic tertiary amine derivatives include triphenyl amine, tritolyl amine, tolyldiphenyl amine, N,N′-diphenyl-N,N′-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine, N,N,N′,N′-(4-methylphenyl)-1,1′-phenyl-4,4′-diamine, N,N,N′,N′-(4-methylphenyl)-1,1′-biphenyl-4,4′-diamine, N,N′-diphenyl-N,N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N,N′-(methylphenyl)-N,N′-(4-n-butylphenyl)-phenanthrene-9,10-diamine, N,N-bis(4-di-4-tolylaminophenyl)-4-phenyl-cylcohexane, and oligomers and polymers having these aromatic tertiary amine skeletons, though not particularly limited thereto.
Specific examples of the phthalocyanine (Pc) derivatives include phthalocyanine derivatives such as H2Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl2SiPc, (HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O—GaPc, as well as naphthalocyanine derivatives, though not particularly limited thereto.
Also, in the organic EL device of the present invention, between the light emitting layer and the anode, there is preferably formed a layer such as the above hole transporting layer or hole injecting layer containing those aromatic tertiary amine derivatives and/or phthalocyanine derivatives,.
The electron injecting material is preferably made of compounds which have a good electron transporting capability as well as excellent capabilities of accepting electrons injected from the cathode and injecting the electrons into the light emitting layer or light emitting material, prevent excited particles produced in the light emitting layer from moving into the hole injecting layer, and exhibit an excellent capability of forming a thin film. Specific examples of the electron injecting material include fluorenone, anthraquinodimethane, diphenoquinone, thiopyrane dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and derivatives thereof, though not particularly limited thereto. Further, an electron accepting substance and an electron donating substance may be added to the hole injecting material and the electron injecting material, respectively, for enhanced sensitization thereof.
In the organic EL device of the present invention, among these electron injecting materials, more effective electron injecting materials are metal complex compounds and five-member ring derivatives having a nitrogen atom.
Specific examples of the metal complex compounds include 8-hydroxyquinolinatolithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, though not particularly limited thereto.
The five-member ring derivatives having a nitrogen atom are preferably derivatives of oxazole, thiazole, oxadiazole, thiadiazole or triazole. Specific examples of the nitrogen-containing five-member ring derivatives include 2,5-bis(1-phenyl)-1,3,4-oxazole, dimethyl POPOP, 2,5-bis(1-phenyl)-1,3,4-thiazole, 2,5-bis(1-phenyl)-1,3,4-oxadiazole, 2-(4′-tert-butylphenyl)-5-(4′′-biphenyl)-1,3,4-oxadiazole, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole, 1,4-bis[2-(5-phenyloxadiazolyl)]benzene, 1,4-bis[2-(5-phenyloxadiazolyl)-4-tert-butylbenzene], 2-(4′-tert-butylphenyl)-5-(4′′-biphenyl)-1,3,4-thiadiazole, 2,5-bis(1-naphthyl)-1,3,4-thiadiazole, 1,4-bis[2-(5-phenylthiadiazolyl)]benzene, 2-(4′-tert-butylphenyl)-5-(4′′-biphenyl)-1,3,4-triazole, 2,5-bis(1-naphthyl)-1,3,4-triazole, and 1,4-bis[2-(5-phenyltriazolyl)]benzene, though not particularly limited thereto.
In the organic EL device of the present invention, the light emitting layer may also optionally contain, in addition to the aromatic amine derivatives represented by the general formula (1), at least one material selected from the group consisting of light emitting materials, doping materials, hole injecting materials and electron injecting materials. The organic EL device of the present invention may be further provided with a protective layer on a surface thereof, or the whole part thereof may be protected with silicone oil, resins, etc., in order to enhance stability thereof against temperature, humidity, atmosphere, etc.
The anode of the organic EL device according to the present invention may be suitably made of an electro-conductive material having a work function more than 4 eV. Examples of the electro-conductive material for the anode include carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium and alloys thereof, metal oxides such as tin oxide and indium oxide which are used for ITO substrates or NESA substrates, and organic electro-conductive resins such as polythiophene and polypyrrole. The cathode of the organic EL device according to the present invention may be suitably made of an electro-conductive material having a work function of 4 eV or less. Examples of the electro-conductive material for the cathode include magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, lithium fluoride and alloys thereof, though not particularly limited thereto. Typical examples of the alloys include alloys of magnesium and silver, alloys of magnesium and indium, and alloys of lithium and aluminum, though not particularly limited thereto. The ratio between the constituting metals in the alloys may be controlled and appropriately determined depending upon temperature of vapor deposition sources, atmosphere, vacuum degree, etc. The anode and cathode may be constituted of two or more layers, if required.
At least one surface of the organic EL device of the present invention preferably exhibits a sufficient transparency in a wavelength range of light emitted therefrom in order to enhance an efficiency of light emission thereof. Further, the substrate for the device is also preferably transparent. The transparent electrode is formed using the above electro-conductive material by vapor deposition method, sputtering method, etc., so as to ensure a desirable transparency thereof. The electrode disposed on a light emitting surface of the device preferably has a light transmittance of 10% or greater. The substrate is not particularly limited as long as it suitably has a good mechanical and thermal strength as well as a good transparency. Examples of the substrate include glass substrates and transparent resin films. Specific examples of the transparent resin films include films made of polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylons, polyether ether ketones, polysulfones, polyether sulfones, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluororethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyesters, polycarbonates, polyurethanes, polyimides, polyether imides and polypropylene.
The respective layers of the organic EL device of the present invention may be formed by either a dry film-forming process such as vacuum deposition, sputtering, plasma and ion-plating, or a wet film-forming process such as spin-coating, dipping and flow-coating. The thickness of the respective layers is not particularly limited, but should be adjusted to an appropriate range. When the thickness is too large, a large electric voltage must be applied to the device in order to achieve a predetermined light output, resulting in a poor efficiency of light emission. On the other hand, when the thickness is too small, pinholes tend to be formed in the layers, thereby failing to obtain a sufficient luminance of light emission even upon applying an electric field thereto. The suitable thickness of the respective layers is usually in the range of from 5 nm to 10 μm and preferably from 10 nm to 0.2 μm.
In the wet film-forming process, materials constituting the respective layers are dissolved or dispersed in a suitable solvent such as ethanol, chloroform, tetrahydrofuran and dioxane to form a thin film thereof The solvent used for forming the respective layers is not particularly limited. Also, suitable resins or additives may be added to the respective organic thin film layers for the purposes of improving a film-forming property, preventing formation of pinholes in the resultant film, etc. Examples of the resins usable for the above purposes include insulating resins such as polystyrene, polycarbonates, polyarylates, polyesters, polyamides, polyurethanes, polysulfones, polymethyl methacrylate, polymethyl acrylate and celluloses as well as copolymers thereof, photoconductive resins such as poly-N-vinyl carbazole and polysilanes, and electro-conductive resins such as polythiophene and polypyrrole. Examples of the additives include antioxidants, ultraviolet absorbers and plasticizers.
The organic EL device of the present invention is suitably applied to, for example, planar light-emitting members such as a wall-hanging type television flat panel displays or so, light sources for copiers, printers, back light for liquid crystal displays and, measuring instruments, display panels, marker light, etc. Further, the material of the present invention can be used not only for organic EL devices but also in other applications such as electronic photographic members, photoelectric converter elements, solar cells, image sensors, etc.
EXAMPLE
The present invention will be described in more detail by reference to the following examples.
Synthesis Example 1
Synthesis of Chemical Compound (4)
(1-1) Synthesis of 2-bromo-6-methylnaphthalene
Under an atmospheric argon gas flow, trifluoromethane sulfonic acid-6-bromo-2-naphthyl ester in an amount of 32 g (90 mmol), dichloro(diphenylphosphinoferrocene)palladium in an amount of 3.6 g (5% by mol), lithium bromide in an amount of 7.8 g (90 mmol) and desiccated tetrahydrofuran in an amount of 100 milliliter were placed into a three neck flask with cooling pipe and having a capacity of 500 milliliter, and then, the resultant solution was cooled down to −20° C. After slowly dripping methylmagnesiumbromide in an amount of 90 milliliter (90 mmol, 1 mol/liter (tetrahydrofuran)) into the flask, the resultant solution was stirred under heating at the temperature of 80° C. for 4 hours. After the reaction terminated, adding dilute hydrochloric acid in an amount of 100 milliliter into the reacted solution, an organic layer was separated and washed with the use of sodium bicarbonate solution and sodium chloride solution, followed by drying with the use of magnesium sulfate. After removing the solvent by distillation by means of a rotary evaporator, the resultant crude product was refined by means of column chromatography (silicagel, hexane/dichloromethane=90/10), and as a result, 9.4 g of aimed compound (white crystal) was obtained (yield: 47%).
(1-2) Synthesis of 2-(6-methyl-2-naphthyl)benzaldehyde
Under an atmospheric argon gas flow, 2-bromo-6-methylnaphthalene in an amount of 6.6 g (30 mmol), 2-formylphenylboronic acid in an amount of 5.4 g (36 mmol), (tetrakistriphenylphosphine)palladium in an amount of 0.7 g (0.6 mmol), 2N sodium carbonate aqueous solution in an amount of 45 milliliter and dimethoxyethane in an amount of 90 milliliter were placed into a three neck flask with a cooling pipe and having a capacity of 500 milliliter, and the resultant solution was refluxed under heating for 8 hours. After the reaction terminated, adding water in an amount of 100 milliliter into the reacted solution, an organic layer was separated and washed with the use of sodium chloride solution, followed by drying with the use of magnesium sulfate. After removing the solvent by distillation by means of a rotary evaporator, the resultant crude product was refined by means of column chromatography (silicagel, hexane/dichloromethane=60/40), and as a result, 6.7 g of aimed compound (white crystal) was obtained (yield: 91%).
(1-3) Synthesis of 2-((2-methoxyvinyl)phenyl)-6-methylnaphthalene
Under an atmospheric argon gas flow, 2-(6-methyl-2-naphthyl)benzaldehyde in an amount of 13.7 g (55 mmol), (methoxymethyl)triphenylphosphoniumchloride in an amount of 21 g (61 mmol), t butoxy potassium in an amount of 7.5 g (67 mmol) and desiccated tetrahydrofuran in an amount of 250 milliliter were placed into a three neck flask with a cooling pipe and having a capacity of 500 milliliter, and the resultant solution was stirred at the room temperature for a night. After the reaction terminated, adding water in an amount of 100 milliliter into the reacted solution, an organic layer was separated, followed by drying with the use of magnesium sulfate. After removing the solvent by distillation by means of a rotary evaporator, the resultant crude product was refined by means of column chromatography (silicagel, hexane/dichloromethane=10/90), and as a result, 12.8 g of aimed compound (white crystal) was obtained (yield: 84%).
(1-4) Synthesis of 2-methylchrysene
Under an atmospheric argon gas flow, 2-((2-methoxyvinyl)phenyl)-6-methylnaphthalene in an amount of 12.8 g (46 mmol), several drops of methyl acid, and desiccated dichloromethane in an amount of 100 milliliter were placed into a three necked-flask equipped with a cooling pipe and having a capacity of 500 milliliter, and the resultant solution was stirred at the room temperature for 8 hours. After the reaction terminated, adding sodium bicarbonate solution in an amount of 100 milliliter into the reacted solution, crystals were separated by filtration. The resultant crude product was washed with the use of water and methanol, and then, it was vacuum dried at the temperature of 50° C. for 8 hours, and as a result, 8.2 g of aimed compound (white crystal) was obtained (yield: 73%).
(1-5) Synthesis of 2-methyl-6,12-dibromochrysene
Under an atmospheric argon gas flow, 2-methylchrysene in an amount of 8.2 g (34 mmol), N-bromosuccinimide in an amount of 14.5 g (81 mmol) and N,N-dimethylformamide in an amount of 400 milliliter were placed into a three neck flask with a cooling pipe and having a capacity of 1 liter, and the resultant solution was stirred at the room temperature for one night. After the reaction terminated, adding water in an amount of 300 milliliter into the reacted solution, crystals were separated by filtration. The resultant crude product was washed with the use of water and methanol, and then, it was re-crystallized in 100 milliliter of toluene, and as a result, 8.8 g of aimed compound (white crystal) was obtained (yield: 65%).
(1-6) Synthesis of Chemical Compound (4)
Under an atmospheric argon gas flow, 2-methyl-6,12-dibromochrysene in an amount of 4.0 g (10 mmol), bis(3,4-dimethylphenyl)amine in an amount of 5.6 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-necked flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 5.8 g of pale yellow powders were obtained. The pale yellow powders were identified as Compound (4) from the result in accordance with Field Desorption Mass Spectrum (FD-MS) measurement (yield: 85%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (4) is shown in FIG. 1. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (4) among the toluene solvent were 400 nm and 456 nm respectively.
Synthesis Example 2
Synthesis of Compound (9)
(2-1) Synthesis of 2-isopropyl-6,12-dibromochrysene
An aimed compound was obtained in a similar manner as Synthesis Example 1 from the step (1-1) to the step (1-5) except that isopropylmagnesium bromide was employed instead of methylmagnesium bromide in the step (1-1).
(2-2) Synthesis of Compound (9)
Under an atmospheric argon gas flow, 2-isopropyl-6,12-dibromochrysene in an amount of 4.2 g (10 mmol), 4-isopropylphenyl-p-tolyl amine in an amount of 5.6 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-necked flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 6.4 g of pale yellow powders were obtained. The obtained product was identified to be Compound (9) in accordance with FD-MS measurement (yield: 90%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (9) is shown in FIG. 2. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (9) among the toluene solvent were 407 nm and 453 nm respectively.
Synthesis Example 3
Synthesis of Chemical Compound (20)
(3-1) Synthesis of 2-bromo-6-isopropylnaphthalene
Under an atmospheric argon gas flow, trifluoromethane sulfonic acid-6-bromo-2-naphthyl ester in an amount of 32 g (90 mmol), dichloro(diphenylphosphinoferrocene)palladium in an amount of 3.6 g (5% by mol), lithium bromide in an amount of 7.8 g (90 mmol) and desiccated tetrahydrofuran in an amount of 100 milliliter were placed into three necked-flask equipped with cooling pipe and having a capacity of 500 milliliter, and then, the resultant solution was cooled down to −20° C. After slowly dripping isopropylmagnesiumbromide in an amount of 90 milliliter (90 mmol, 1 mol/liter (tetrahydrofuran)) into the flask, the resultant solution was stirred under heating at the temperature of 80° C. for 4 hours. After the reaction terminated, adding dilute hydrochloric acid in an amount of 100 milliliter into the reacted solution, an organic layer was separated and washed with the use of sodium bicarbonate solution and sodium chloride solution, followed by drying with the use of magnesium sulfate. After removing the solvent by distillation by means of a rotary evaporator, the resultant crude product was refined by means of column chromatography (silicagel, hexane/dichloromethane=90/10), and as a result, 9.4 g of aimed compound (white crystal) was obtained (yield: 33%).
(3-2) Synthesis of 6-isopropylnaphthalene-2-boronic acid
Under an atmospheric argon gas flow, 2-bromo-6-isopropylnaphthalene in an amount of 9.4 g (38 mmol), desiccated ether in an amount of 100 milliliter and desiccated toluen in an amount of 50 milliliter were placed into a three necked-flask equipped with cooling pipe and having a capacity of 500 milliliter, and then, the resultant solution was cooled down to −40° C. After slowly dripping n-butyllithium in an amount of 25 milliliter (40 mmol, 1.58M (n-hexane)) into the flask, the resultant solution was stirred at a temperature of −20° C. for 2 hours. Subsequently, the solution was cooled down to −40° C. and then, slowly dripping boronic acid triisopropylester in an amount of 26 milliliter (114 mmol), the resultant solution was stirred at the room temperature for one night. After the reaction terminated, adding dilute hydrochloric acid in an amount of 100 milliliter into the reacted solution, an organic layer was separated and washed with the use of sodium chloride solution, followed by drying with the use of magnesium sulfate. After removing the solvent by distillation by means of a rotary evaporator, the resultant crude product was washed with the use of 100 milliliter of toluene and as a result, 5.0 g of an aimed compound (white crystal) was obtained (yield: 63%).
(3-3) Synthesis of 5-isopropyl-2-(6-isopropyl-2-naphthyl)benzaldehyde
Under an atmospheric argon gas flow, 2-hydroxy-5-isopropylbenzaldehyde in an amount of 4.4 g (27 mmol), trifluoromethane sulfonic acid anhydride in an amount of 11.2 g (40 mmol), pyridine in an amount of 6 milliliter (80 mmol) and dichloromethane in an amount of 100 milliliter were placed into a three necked-flask equipped with a cooling pipe and having a capacity of 500 milliliter, and the resultant solution was stirred at the room temperature for 2 hours. After the reaction terminated, the resultant was separated by filtration, and after washing the resultant crude product with the use of hexane and dichloromethane, the resultant solution was vacuum dried at a temperature of 50° C. for 8 hours and as a result, 6.0 g of 2-formyl-4-isopropylphenyltrifluoromethanesulfonate (white crystal) was obtained (yield: 75%). Subsequently, under an atmospheric argon gas flow, 2-formyl-4-isopropylphenyl trifluoromethanesulfonate in an amount of 5.9 g (20 mmol), 6-isopropylnaphthalene-2-boronic acid in an amount of 4.7 g (22 mmol), (tetrakistriphenylphosphine)palladium in an amount of 1.1 g (1 mmol), 2N sodium carbonate aqueous solution in an amount of 30 milliliter and dimethoxyethane in an amount of 40 milliliter were placed into a three necked-flask equipped with a cooling pipe and having a capacity of 500 milliliter, and the resultant solution was refluxed under heating for 8 hours. After the reaction terminated, adding water in an amount of 100 milliliter into the reacted solution, an organic layer was separated and washed with the use of sodium chloride solution, followed by drying with the use of magnesium sulfate. After removing the solvent by distillation by means of a rotary evaporator, the resultant crude product was refined by means of column chromatography (silicagel, hexane/dichloromethane=60/40), and as a result, 4.4 g of an aimed compound (white crystal) was obtained (yield: 70%).
(3-4) Synthesis of 2-isopropyl-6-(4-isopropyl-2-(2-methoxyvinyl)phenyl)naphthalene
Under an atmospheric argon gas flow, 5-isopropyl-2-(6-isopropyl-2-naphthyl)benzaldehyde in an amount of 4.4 g (14 mmol), (methoxymethyl)triphenylphosphoniumchloride in an amount of 5.1 g (15 mmol), t-butoxypotassium in an amount of 1.7 g (15 mmol) and desiccated tetrahydrofuran in an amount of 100 milliliter were placed into a three-necked flask equipped with a cooling pipe and having a capacity of 500 milliliter, and the resultant solution was stirred under heating at the room temperature for one night. After the reaction terminated, adding water in an amount of 100 milliliter into the reacted solution, an organic layer was separated, followed by drying with the use of magnesium sulfate. After removing the solvent by distillation by means of a rotary evaporator, the resultant crude product was refined by means of column chromatography (silicagel, hexane/dichloromethane=10/90), and as a result, 4.3 g of an aimed compound (white crystal) was obtained (yield: 90%).
(3-5) Synthesis of 2,8-diisopropyl chrysene
Under an atmospheric argon gas flow, 2-isopropyl-6-(4-isopropyl-2-(2-methoxy vinyl)phenyl)naphthalene in an amount of 4.3 g (12 mmol), several drops of methyl acid, and desiccated dichloromethane in an amount of 50 milliliter were placed into a three necked-flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred at the room temperature for 8 hours. After the reaction terminated, adding sodium bicarbonate solution in an amount of 100 milliliter into the reacted solution, crystals were separated by filtration. The resultant crude product was washed with the use of water and methanol, and then, it was vacuum dried at the temperature of 50° C. for 8 hours, and as a result, 3.5 g of an aimed compound (white crystal) was obtained (yield: 90%).
(3-6) Synthesis of 2,8-diisopropyl-6,12-dibromochrysene
Under an atmospheric argon gas flow, 2,8-diisopropyl chrysene in an amount of 3.5 g (12 mmol), N-bromosuccinimide in an amount of 5.3 g (30 mmol) and N,N-dimethylformamide in an amount of 20 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 500 milliliter, and the resultant solution was stirred at the room temperature for one night. After the reaction terminated, adding water in an amount of 300 milliliter into the reacted solution, crystals were separated by filtration. The resultant crude product was washed with the use of water and methanol, and then, it was re-crystallized in 100 milliliter of toluene, and as a result, 4.7 g of an aimed compound (white crystal) was obtained (yield: 80%).
(3-7) Synthesis of Chemical Compound (20)
Under an atmospheric argon gas flow, 2,8-diisopropyl-6,12-dibromochrysene in an amount of 4.7 g (10 mmol), 4-isopropylphenyl-p-tolyl amine in an amount of 5.6 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 6.6 g of pale yellow powders were obtained. The obtained product was identified to be Compound (20) in accordance with FD-MS measurement (yield: 88%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (20) is shown in FIG. 3. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (20) among the toluene solvent were 407 nm and 450 nm respectively.
Synthesis Example 4
Synthesis of Compound (23)
(4-1) Synthesis of 2-t-butyl-8-isopropyl-6,12-dibromochrysene
An aimed compound was obtained in a similar manner as Synthesis Example 3 from the step (3-1) to the step (3-6) except that 2-hydroxy-5-t-butyl benzaldehyde was employed instead of 2-hydroxy-5-isopropyl benzaldehyde in the step (3-3).
(4-2) Synthesis of Compound (23)
Under an atmospheric argon gas flow, 2-t-butyl-8-isopropyl-6,12-dibromo chrysene in an amount of 4.8 g (10 mmol), bis(3,4-dimethylphenyl)amine in an amount of 5.6 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluen and 100 milliliter of methanol, and as a result, 6.9 g of pale yellow powders were obtained. The obtained product was identified to be Compound (23) in accordance with FD-MS measurement (yield: 90%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (23) is shown in FIG. 4. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (23) among the toluene solvent were 409 nm and 453 nm respectively.
Synthesis Example 5
Synthesis of Compound (25)
Under an atmospheric argon gas flow, 2-isopropyl-6,12-dibromo chrysene obtained in the step (2-1) in Synthesis Example 2 in an amount of 4.2 g (10 mmol), bis(3,4-dimethylphenyl)amine in an amount of 6.3 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine in an amount of 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluen and 100 milliliter of methanol, and as a result, 6.8 g of pale yellow powders were obtained. The obtained product was identified to be Compound (25) in accordance with FD-MS measurement (yield: 88%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (25) is shown in FIG. 5. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (25) among the toluene solvent were 415 nm and 459 nm respectively.
Synthesis Example 6
Synthesis of Compound (39)
Under an atmospheric argon gas flow, 2-isopropyl-6,12-dibromo chrysene obtained in the step (2-1) in Synthesis Example 2 in an amount of 4.2 g (10 mmol), di(2-naphthyl)amine in an amount of 6.7 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine in an amount of 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 6.8 g of pale yellow powders were obtained. The obtained product was identified to be Compound (39) in accordance with FD-MS measurement (yield: 85%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (39) is shown in FIG. 6. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (39) among the toluene solvent were 408 nm and 452 nm respectively.
Synthesis Example 7
Synthesis of Compound (57)
(7-1) Synthesis of 2-t-butyl-6,12-dibromochrysene
An aimed compound was obtained in a similar manner as Synthesis Example 1 from the step (1-1) to the step (1-5) except that t-butyl magnesium bromide was employed instead of methyl magnesium bromide in the step (1-1).
(7-2) Synthesis of Chemical Compound (57)
Under an atmospheric argon gas flow, 2-t-butyl-6,12-dibromochrysene in an amount of 4.4 g (10 mmol), bis(3,4-dimethylphenyl)amine in an amount of 5.6 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 6.5 g of pale yellow powders were obtained. The obtained product was identified to be Compound (57) in accordance with FD-MS measurement (yield: 90%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (57) is shown in FIG. 7. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (57) among the toluene solvent were 410 nm and 456 nm respectively.
Synthesis Example 8
Synthesis of Compound (95)
Under an atmospheric argon gas flow, 2-methyl-6,12-dibromochrysene obtained in the step (1-5) in Synthesis Example 1 in an amount of 4.0 g (10 mmol), di(4-cyclohexylphenyl)amine in an amount of 8.3 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 6.3 g of pale yellow powders were obtained. The obtained product was identified to be Compound (95) in accordance with FD-MS measurement yield: 70%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (95) is shown in FIG. 8. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (95) among the toluene solvent were 406 nm and 454 nm respectively.
Synthesis Example 9
Synthesis of Compound (D-973)
Under an atmospheric argon gas flow, 6,12-dibromochrysene in an amount of 3.8 g (10 mmol), N-methylaniline in an amount of 2.7 g (25 mmol, palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-necked flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 2.2 g of white powders were obtained. The obtained product was identified to be Compound (D-973) in accordance with FD-MS measurement (yield: 50%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (D-973) is shown in FIG. 9. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (D-973) among the toluene solvent were 373 nm and 440 nm respectively.
Synthesis Example 10
Synthesis of Compound (D-974)
Under an atmospheric argon gas flow, 6,12-dibromochrysene in an amount of 3.8 g (10 mmol), N-isopropylaniline in an amount of 3.4 g (25 mmol, palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 2.0 g of pale yellow powders were obtained. The obtained product was identified to be Compound (C-974) in accordance with FD-MS measurement (yield: 40%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (D-974) is shown in FIG. 10. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (D-974) among the toluene solvent were 362 nm and 436 nm respectively.
Synthesis Example 11
Synthesis of Compound (D-998)
Under an atmospheric argon gas flow, 6,12-dibromochrysene in an amount of 3.8 g (10 mmol), N-(4-isopropylphenyl)pyridine-3-amine in an amount of 5.3 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 4.2 g of pale yellow powders were obtained. The obtained product was identified to be Compound (D-998) in accordance with FD-MS measurement (yield: 65%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (D-998) is shown in FIG. 11. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (D-998) among the toluene solvent were 393 nm and 444 nm respectively.
Synthesis Example 12
Synthesis of Compound (D-1000)
Under an atmospheric argon gas flow, 2-methyl-6,12-dibromochrysene in an amount of 3.9 g (10 mmol), N-(4-isopropylphenyl)pyridine-3-amine in an amount of 5.3 g (25 mmol), palladium acetate in an amount of 0.03 g (1.5% by mol), tri-t-butylphosphine 0.06 g (3% by mol), t-butoxy sodium in an amount of 2.4 g (25 mmol) and desiccated toluene in an amount of 100 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100° C. for one night. After the reaction terminated, precipitated crystals were separated by filtration and washed with the use of 50 milliliter of toluene and 100 milliliter of methanol, and as a result, 5.3 g of pale yellow powders were obtained. The obtained product was identified to be Compound (D-1000) in accordance with FD-MS measurement (yield: 80%).
Measurement by means of DRX-500 (Trade name; produced by Brucker Optics Inc.) was carried out using dimethylene chloride as a solvent and a result of 1H-NMR spectrum about the resultant Compound (D-1000) is shown in FIG. 12. Further, the maximum absorption wavelength and the maximum fluorescence wavelength of Compound (D-1000) among the toluene solvent were 385 nm and 440 nm respectively.
Example 1
A 120 nm-thick transparent electrode made of indium oxide was formed on a glass substrate having a size of 25 mm×75 mm×1.1 mm. The glass substrate with the transparent electrode was cleaned by irradiation of Ultra Violet ray and ozone. The thus cleaned glass substrate with the transparent electrode was mounted to a vacuum vapor deposition apparatus.
First, N′,N′′-bis[4-(diphenylamino)phenyl]-N′,N′′-diphenylbiphenyl-4,4′-diamine was vapor-deposited to form a hole injecting layer having a thickness of 60 nm, and then N,N,N′,N′-tetrakis(4-biphenyl)-4,4′-bendizine was vapor deposited on the hole injecting layer to form a hole transporting layer having a thickness of 20 nm. Then, 10,10′-bis[1,1′,4′,1′′]terphenyl-2-yl-9,9′-bianthracenyl and the above Compound (9) were simultaneously vapor deposited at a weight ratio of 40:2 on the hole transporting layer to form a light emitting layer having a thickness of 40 nm.
Next, tris(8-hydroxyquinolinato)aluminum was vapor-deposited on the light emitting layer to form an electron injecting layer having a thickness of 10 nm. Then, tris(8-hydroxyquinolinato)aluminum and lithium was vapor-deposited at a weight ratio of 10:0.3 on the electron injecting layer to form a layer having a thickness of 10 nm, and further aluminum was vapor-deposited thereon to form an aluminum layer having a thickness of 150 nm. The aluminum layer functioned as a cathode. Thus, an organic EL device was fabricated.
As a result of subjecting the thus obtained organic EL device to a test by passing electric current, it was confirmed that a blue light with a luminance of 602 cd/m2 (peak wavelength of light emission: 464 nm) and current efficiency of 6.0 cd/A was emitted at a voltage of 6.0 V and a current density of 10 mA/cm2. Further, as a result of subjecting the device to a continuous test by passing DC electric current starting at an initial luminance of 500 cd/m2, it was confirmed that the half lifetime thereof was 18900 hours.
Example 2
An organic EL device was fabricated in accordance with the same procedures as those conducted in Example 1 except that Compound (9) was replaced with Compound (23).
As a result of subjecting the thus obtained organic EL device to a test by passing electric current, it was confirmed that a blue light with a luminance of 664 cd/m2 (peak wavelength of light emission: 462 nm) and current efficiency of 6.6 cd/A was emitted at a voltage of 6.5 V and a current density of 10 mA/cm2. Further, as a result of subjecting the device to a continuous test by passing DC electric current starting at an initial luminance of 500 cd/m2, it was confirmed that the half lifetime thereof was 16000 hours.
Example 3
An organic EL device was fabricated in accordance with the same procedures as those conducted in Example 1 except that 10,10′-bis[1,1′,4′,1′]terphenyl-2-yl-9,9′-bianthracenyl was replaced with 10-(3-(naphthalen-1-yl)phenyl)-9-(naphthalen-2-yl)anthracene.
As a result of subjecting the thus obtained organic EL device to a test by passing electric current, it was confirmed that a blue light with a luminance of 631 cd/m2 (peak wavelength of light emission: 464 nm) and current efficiency of 6.3 cd/A was emitted at a voltage of 6.5 V and a current density of 10 mA/cm2. Further, as a result of subjecting the device to a continuous test by passing DC electric current starting at an initial luminance of 500 cd/m2, it was confirmed that the half lifetime thereof was 20000 hours or longer.
Example 4
An organic EL device was fabricated in accordance with the same procedures as those conducted in Example 3 except that Compound (9) was replaced with Compound (23) for the doping material.
As a result of subjecting the thus obtained organic EL device to a test by passing electric current, it was confirmed that a blue light with a luminance of 710 cd/m2 (peak wavelength of light emission: 465 nm) and current efficiency of 7.1 cd/A was emitted at a voltage of 6.5 V and a current density of 10 mA/cm2. Further, as a result of subjecting the device to a continuous test by passing DC electric current starting at an initial luminance of 500 cd/m2, it was confirmed that the half lifetime thereof was 20000 hours or longer.
Example 5
An organic EL device was fabricated in accordance with the same procedures as those conducted in Example 3 except that Compound (9) was replaced with Compound (25) for the doping material.
As a result of subjecting the thus obtained organic EL device to a test by passing electric current, it was confirmed that a blue light with a luminance of 793 cd/m2 (peak wavelength of light emission: 469 nm) and current efficiency of 7.9 cd/A was emitted at a voltage of 6.5 V and a current density of 10 mA/cm2. Further, as a result of subjecting the device to a continuous test by passing DC electric current starting at an initial luminance of 500 cd/m2, it was confirmed that the half lifetime thereof was 20000 hours or longer.
Example 6
An organic EL device was fabricated in accordance with the same procedures as those conducted in Example 3 except that Compound (9) was replaced with Compound (10) for the doping material.
As a result of subjecting the thus obtained organic EL device to a test by passing electric current, it was confirmed that a blue light with a luminance of 782 cd/m2 (peak wavelength of light emission: 468 nm) and current efficiency of 7.8 cd/A was emitted at a voltage of 6.5 V and a current density of 10 mA/cm2. Further, as a result of subjecting the device to a continuous test by passing DC electric current starting at an initial luminance of 500 cd/m2, it was confirmed that the half lifetime thereof was 20000 hours or longer.
Comparative Example 1
An organic EL device was fabricated in accordance with the same procedures as those conducted in Example 1 except that Compound (9) was replaced with 6,12-bis(4-isopropylphenyl-p-tolylamino)chrysene.
As a result of subjecting the thus obtained organic EL device to a test by passing electric current, it was confirmed that a blue light with a luminance of 594 cd/m2 (peak wavelength of light emission: 462 nm) and current efficiency of 5.9 cd/A was emitted at a voltage of 6.3 V and a current density of 10 mA/cm2. Further, as a result of subjecting the device to a continuous test by passing DC electric current starting at an initial luminance of 500 cd/m2, it was confirmed that the half lifetime thereof was 4590 hours.
From the above-mentioned result, it is apparent that when any substituent does not bond to diaminochrysene backbone structure, half lifetime shortens because of an association between compounds each other.
INDUSTRIAL APPLICABILITY
The organic EL device using the aromatic amine derivative according to the present invention can exhibit a practically sufficient luminance of light emission even upon applying a low voltage thereto, and has an enhanced efficiency of light emission and the device is free from deterioration in properties even after being used for a long period of time and, therefore, has a long lifetime. Resultantly, the EL device is useful as a flat panel light emitting member for a wall-hanging type television or as a light source of backlight and the like for display devices.

## Claims

1. An aromatic amine derivative represented by the following general formula (1):




wherein A1 to A4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 50 ring carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 50 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 50 carbon atoms or a halogen atom;
a, b, c and d each independently represents an integer of 0 to 5, when a, b, c or d each is 2 or greater, A1 to A4 may be the same with or different from each other, and may bond each other to form a saturated or unsaturated ring; and further, a couple of A1 and A2, and a couple of A3 and A4 may bond each other to form a saturated or unsaturated ring;
R1 to R4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 20 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 ring carbon atoms or a substituted or unsubstituted silyl group having 3 to 50 carbon atoms; a couple of R1 and R2, and a couple of R3 and R4 may bond each other to form a saturated or unsaturated ring;
however, a case where all of R1 to R4 in the general formula (1) are hydrogen atoms is excluded.

2. The aromatic amine derivative according to claim 1, wherein at least one of R1 or R3 in the general formula (1) independently represents a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.

3. The aromatic amine derivative according to claim 1, wherein R1 and R3 in the general formula (1) each independently represents a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.

4. The aromatic amine derivative according to claim 1, wherein at least one of R2 or R4 in the general formula (1) independently represents a substituted or unsubstituted primary alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted secondary alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group having 1 to 50 ring carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms.

5. The aromatic amine derivative according to claim 1, wherein R1 to R4 in the general formula (1) each independently represents a hydrogen atom, a substituted or unsubstituted arylamino group having 5 to 20 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 ring carbon atoms or a substituted or unsubstituted silyl group having 3 to 50 carbon atoms.

6. The aromatic amine derivative according to claim 1, wherein A1 to A4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 12 ring carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 6 ring carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 18 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 18 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 6 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 20 carbon atoms or a halogen atom;
a, b, c and d each independently represents an integer of 0 to 2, when a, b, c or d each is 2 or greater, A1 to A4 may be the same with or different from each other, and may bond each other to form a saturated or unsaturated ring; and further, a couple of A1 and A2, and a couple of A3 and A4 may bond each other to form a saturated or unsaturated ring;
R1 to R4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 ring carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 12 ring carbon atoms, a substituted or unsubstituted arylamino group having 5 to 18 ring carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring carbon atoms or a substituted or unsubstituted silyl group having 3 to 20 carbon atoms; a couple of R1 and R2, and a couple of R3 and R4 may bond each other to form a saturated or unsaturated ring;
however, a case where all of R1 to R4 in the general formula (1) are hydrogen atoms is excluded.

7. The aromatic amine derivative according to claim 1, wherein the alkyl group represented by R2 and R4 in the general formula (1) are primary or secondary.

8. The aromatic amine derivative according to claim 1, wherein at least one of R1 or R3 in the general formula (1) represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group or a cyclohexyl group.

9. The aromatic amine derivative according to claim 1, wherein at least one of R2 or R4 in the general formula (1) represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group or a cyclohexyl group.

10. The aromatic amine derivative according to claim 1, which is represented by the following formula:

11. The aromatic amine derivative according to claim 1, which is represented by the following formula:

12. The aromatic amine derivative according to claim 1, which is represented by the following formula:

13. The aromatic amine derivative according to claim 1, which is represented by the following formula:

14. The aromatic amine derivative according to claim 1, which is represented by the following formula:

15. The aromatic amine derivative according to claim 1, which is represented by the following formula:

16. The aromatic amine derivative according to claim 1, which is represented by the following formula:

17. The aromatic amine derivative according to claim 1, which is represented by the following formula: