# Patent

## Title
Organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives

## Abstract

The invention relates to an organic electroluminescent device which contains 2,5-diaminoterephthalic acid derivatives of formula 1a as emitter substances in one or several emitter layers in a pure or doped manner. The ring A is a triple unsaturated benzene ring wherein R4′ and R8′ are zero or ring A is a double unsaturated ring respectively provided with a double bond in the 1,2 position and 4,5 position, and wherein R10 is a nitrile radical —CN or a radical C(═X1)—X2R1, R11 is a nitrile radical —CN or a radical —C(═X3)—X4R5, X1 and X3 are oxygen, sulfur or imino, X2 and X4 are oxygen, sulfur or optionally substituted amino, R1–R8, R4′ and R8′ are H, C1–20-alkyl, aryl, heteroaryl, R4 and R8 can be halogen, nitro, cyanogen or amino, R2–R4, R6–R8, R4′ and R8′ can be trifluoromethyl or pentafluorophenyl, and wherein certain radicals can form a saturated or unsaturated ring. The devices are characterized by narrow emission bands, low driver voltages, high photometric efficiency and high thermal stability within a broad spectral range

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application is a national stage of PCT/DE02/03110 filed Aug. 21, 2002, and based upon DE 101 41 266.5 filed Aug. 21, 2001 under the International Convention.
FIELD OF THE INVENTION
The present invention relates to a new organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives. Said derivatives are emitter substances for organic light-emitting diodes (OLED).
BACKGROUND TO THE INVENTION
Organic light-emitting diodes, which have long been known, use the electroluminescence of certain organic compounds. An OLED's structure and the tasks of its individual layers are exemplified in FIG. 1:
A layer sequence of organic substances is arranged between two electrodes, of which at least one must be translucent, each organic substance having a specific function within the device.

    1. The cathode consists of a base metal or an alloy (e.g. aluminium or calcium) and has the function of injecting electrons;
    2. The buffer layer consists of certain metal salts or the oxides thereof, e.g. LiF, and has the function of improving the electron injection into the layer 3;
    3. The electron conductor can e.g. consist of Alq3 (tris-(8-hydroxychinolinato)-aluminium) and conducts the electrons from the cathode to the emitting layer or the hole conductor inside the device;
    4. The hole conductor mainly consists of triphenylamine derivatives; several hole conductor layers can be provided whose characteristics are adapted to the device and whose function is to transport the holes to the emitting layer;
    5. The anode consists of ITO which injects the holes into the hole transport layer;
    6. The substrate consists of a transparent material, e.g. glass.


An arrangement of the type described above emits green light generated due to the excitation of Alq3 by the excitons formed from the holes and electrons.
However, such a simple arrangement has several drawbacks:

    1. Alq3 only emits light in the green spectral range;
    2. The emission band of Alq3 is too broad.


Said drawbacks can in part be eliminated by doping. This means that one or more substances are co-evaporated during the diode's production process. In general, these substances are contained in the Alq3 layer in an amount ranging up to a few percent. Said co-evaporation process is difficult to control.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the layered structure of an organic light-emitting diode.
FIG. 2 shows an embodiment of the layered structure of an organic light-emitting diode of the present invention.



SUMMARY AND DETAILED DESCRIPTION OF THE INVENTION
The invention relates to new emitter substances which eliminate the known drawbacks of Alq3 both as an emitter substance and a host material for dopants. As a consequence, Alq3 is generally required as an electron conductor only. The new emitter substances are characterized by:

    1. narrower emission bands;
    2. the devices cover a broad spectral range due to the fact that different substances are used, either in layers separated from one another or in mixed layers;
    3. low driver voltages;
    4. high photometric efficiency (low power consumption);
    5. high luminance (emission intensity);
    6. high thermal stability.


For the purposes of the invention, the term “device” relates to an arrangement in which the substrate and layers are arranged on top of one another according to FIG. 1 or 2, but which has not yet been incorporated into a light-emitting diode. Such an inventive device can in principle have the structure shown in FIG. 1 or 2. In said devices, the 2,5-diaminoterephthalic acid derivatives can be co-evaporated either alone or conjointly with other compounds, optionally even with known compounds, to obtain emitters. These emitters are used in combination with known hole conductors.
The object of the invention is to provide new organic electroluminescent devices using improved emitter substances.
According to the invention, the organic electroluminescent device contains 2,5-diaminoterephthalic acid derivatives of the following formula 1a in one or several emitter layers in a pure or doped form in a device




wherein the ring A is a triply unsaturated benzene ring wherein R4′ and R8′ are omitted, or the ring A is a doubly unsaturated ring having a double bond in the 1,2-position and in the 4,5-position, and
wherein R10 represents a nitrile radical —CN or a radical —C(═X1)—X2R1,
R11 is a nitrile radical —CN or a radical —C(═X3)—X4R5,
wherein
X1 and X3 can be the same or different atoms or groups, such as oxygen, sulphur, imino, preferably oxygen;
X2 and X4 can be the same or different atoms or groups, such as oxygen, sulphur, amino, wherein the amino nitrogen can be substituted with alkyl having 1 to 20 C-atoms, preferably C1 to C8, or with aryl, e.g. phenyl, naphthyl, or with heteroaryl, e.g. cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl, oxazolyl;
R1 to R8, R4′ and R8′ can be the same or different substituents, such as hydrogen, alkyl having 1 to 20 atoms, preferably C1 to C8; aryl, e.g. phenyl, naphthyl, as well as heteroaryl, e.g. cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl, oxazolyl, and the aforesaid radicals can be substituted singly or doubly with atoms or groups, e.g. di-C1–C3-amino or alkoxy with alkyl radicals C1 to C10, preferably C1–C4; C1–C4 alkyl, cyano, fluorine, chlorine, bromine or iodine as well as phenyl;
R4 and R8 can also be the same or different substituents, such as halogen, nitro, cyano or amino;
R2 to R4, R6 to R8, R4′ and R8′ can also be trifluoromethyl or pentafluorophenyl,
and wherein the following radicals can form a saturated or unsaturated ring
X1 and X2, R1 and R2, R2 and X2, R2 and R3, R3 and R4, R4 and X3, X3 and X4, R5 and X4, R6 and X4, R6 and R7, R7 and R8, R8 and X1, R3 and R4′, R7 and R8 ′, R4 and R4′, and R8 and R8′, to which rings further rings can be fused.
It is preferred that R2, R3, R6 and R7 be trifluoromethyl or pentafluorophenyl, R4 and R8 be halogen, nitro, cyano or amino, and the other substituents have the meaning indicated above.
It is particularly preferred that R4 and R8 be trifluoromethyl or pentafluorophenyl, and the other substituents have the meaning indicated above.
As regards spelling in the following text, R1-8 means R1 to R8; X2,4 means X2 and X4; R4′,8′ means R4′ and R8′.
The invention also relates to new 2,5-diaminoterephthalic acid derivatives of the formula 19




wherein X1 is O and X2 is O or N; R2 and R6 are methylene (—CH2—) which can be substituted with trifluoromethyl, R3 and R7 are the same or different, H, C1–C8 alkyl, aryl or heteroaryl, and R4 and R8 are the same or different, H, alkyl, aryl or trifluoromethyl. It is particularly preferred that alkyl be C1–C4 alkyl, aryl be phenyl or naphthyl, and heteroaryl be pyridyl, thienyl or furyl.
In general, it is preferred that substituents arranged opposite one another, such as X1 and X3, X2 and X4, R1 and R5, R2 and R6, R3 and R7, R4 and R8, R4′ and R8′, and R10 and R11, are the same, i.e. not different, in all structures according to the invention.
The electroluminescent devices according to the invention preferably contain 2 to 3 different substances which are mixed with one another in one device.
Now, preferred structures will be listed, wherein in the structures 1




    X1 and X2 can be members of a ring provided X1=N and there is no substituent R1 in case X2≠N;






    X2 and R1 can be members of a ring provided X2=N;






    X2 and R2 can be members of a ring provided X2=N;






    R2 and R3 can be members of a ring;






    R3 and R4 can be members of a ring;






    R4 and X3 can be members of a ring provided X3=N;






    X3 and X4 can be members of a ring provided X3=N and there is no substituent R1 in case X4≠N;






    X4 and R5 can be members of a ring provided X4=N;






    X4 and R6 can be members of a ring provided X4=N;






    R6 and R7 can be members of a ring;






R7 and R8 can be members of a ring;




    R8 and X1 can be members of a ring provided X1=N;






wherein symmetric combinations of the aforesaid structural types are preferred

    X1 and X2 as well as X3 and X4 can be members of a ring provided X1,3=N and there is no substituent R1,5 in case X2,4≠N;






    X2 and R1 can be members of a ring provided X2,4=N;






    X2 and R2 as well as X4 and R6 can be members of a ring provided X2,4=N;






    R2 and R3 as well as R6 and R7 can be members of a ring;






R3 and R4 as well as R7 and R8 can be members of a ring;




    R4 and X3 as well as R8 and X1 can be members of a ring provided X1,3=N;






and wherein in the structure 2





X1 and X2 can be members of a ring provided X1=N and there is no substituent R1 in case X2≠N;




X2 and R1 can be members of a ring provided X2=N;




X2 and R2 can be members of a ring provided X2=N;




    R2 and R3 can be members of a ring;






    R3 and R4 can be members of a ring;






    R4 and R4′ can be members of a ring;






    R4 and X3 can be members of a ring provided X3=N;






    X3 and X4 can be members of a ring provided X3=N and there is no substituent R5 in case X4≠N;






X4 and R5 can be members of a ring provided X4=N;




    X4 and R6 can be members of a ring provided X4=N;






    R6 and R7 can be members of a ring;






    R7 and R8 can be members of a ring;






    R8 and R8′ can be members of a ring;






    R8 and X1 can be members of a ring provided X1=N;






wherein symmetric combinations of the aforesaid structural types are preferred

    X1 and R2 as well as X3 and X4 can be members of a ring provided X1,3=N and there is no substituent R1,5 in case X2,4≠N;






    X2 and R1 can be members of a ring provided X2,4=N;






    X2 and R2 as well as X4 and R6 can be members of a ring provided there is no substituent R1,5 in case X2,4≠N;






    R2 and R3 as well as R6 and R7 can be members of a ring;






    R3 and R4′ as well as R7 and R8′ can be members of a ring;






    R4 and R4′ as well as R8 and R8′ can be members of a ring;






    R4 and X3 as well as R8 and X1 can be members of a ring provided X1,3=N;






and wherein in the structures 3





    R2 and R3 can be members of a ring;






    R3 and R4 can be members of a ring;






    R6 and R7 can be members of a ring;






    R7 and R8 can be members of a ring;






    R2 and R3 as well as R6 and R7 can be members of a ring;






    R3 and R4 as well as R7 and R8 can be members of a ring;






and wherein in the structures 4





    R2 and R3 can be members of a ring;






    R3 and R4′ can be members of a ring;






    R4 and R4′ can be members of a ring;






    R6 and R7 can be members of a ring;






    R7 and R8′ can be members of a ring;






    R8 and R8′ can be members of a ring;






    R2 and R3 as well as R6 and R7 can be members of a ring;






    R3 and R4′ as well as R7 and R8′ can be members of a ring;






    R4 and R4′ as well as R8 and R8′ can be members of a ring;






The emitter substances of formula 1, i.e. derivatives of 2,5-diaminoterephthalic acid, can be obtained by reacting esters of cyclohexane-2,5-dione-1,4-dicarboxylic acid with primary anilines or amines, subsequent oxidation and, optionally, further modification. Said derivatives can be processed into cyclized derivatives in a manner known per se, as shown e.g. in Formula Diagrams I and II.








The compounds of formula 3 can be produced by reacting the respective 2,5-diaminoterephthalic acid amides with dehydrating agents.
In order to produce the compounds of formula 4, wherein R4 and R8 as well as R4′ and R8′ are not H, the esters of 2,5-diaminocyclohexane-1,4-dicarboxylic acid are converted into hydrazides and reacted with potassium hexacyanoferrate(III) in order to obtain aldehydes. These 2,5-diaminocyclohexane-1,4-dicarbaldehydes can be converted into oximes which are reacted with formic acid in order to obtain the compounds of formula 4.
Examples of the new emitters according to formula 1 are listed in Table 1:







TABLE 1





2,5-diaminoterephthalic acid derivatives



















Substance
X1
X2
R3
R1








1.0


 





1.1
O
O




—CH3


 





1.2
O
O




—CH3


 





1.3
O
O




—CH3


 





1.4
O
O




—CH3


 





1.5
O
O




—C2H5


 





1.6
O
O




—CH3


 





1.7
O
O




—CH3


 





1.8
O
O




—CH3


 





1.9
O
O




—CH3


 





1.10
O
O




—CH3


 





1.11
O
O




—CH3


 





1.12
O
O




—CH3


 





1.13
O
O




—CH3


 





1.14
O
O




—CH3


 





1.15
O
O




—CH3


 





1.16
O
O




—CH3


 





1.17
O
O




—CH3


 





1.18
O
O




—CH3


 





1.19
O
O




—CH3


 





1.20
O
O




—CH3


 





1.21
O
O




—CH3


 





1.22
O
O




—CH3


 





1.23
O
O




—CH3


 





1.24
O
O




—CH3


 





1.25
O
O
—C4H9
—CH3


 





1.26
O
O




—CH3


 





1.27
O
O




—CH3


 





1.28
O
O




—CH3


 





1.29
O
O




—CH3


 





1.30
O
O




—CH3


 





1.31
O
O




—CH3


 





1.32
O
O




—CH3


 





1.33
O
O




—CH3


 





1.34
O
O




—CH3


 





1.35
O
O




—CH3


 





1.36
O
O




—CH3


 





1.37
O
O




—CH3


 





1.38
O
O




—CH3


 





1.39
O
O




—CH3


 





1.40
O
O




—CH3


 





1.41
O
O




—CH3


 





1.42
O
O




—CH3


 





1.43
O
O




—CH3


 


1.44
O
O




—CH3


 


1.45
O
O




—CH3


 


1.46
O
O




—CH3


 


1.47
O
O




—CH3


 


1.48
O
O




—CH3


 


1.49
O
O




—CH3


 


1.50
O
O




—CH3


 


1.51
O
O




—CH3


 


1.52
O
O




—CH3


 


1.53
O
O




—CH3


 


1.54
O
O




—CH3


 


1.55
O
O

—CH3


 


1.56
O
O




—CH3


 


1.57
O
O




—CH3


 


1.58
O
O




—CH3


 


1.59
O
O




—CH3


 


1.60
O
O




—CH3


 


1.61
O
O




—CH3


 


1.62
O
O




—CH3


 


1.63
O
O




—CH3


 


1.64
O
O




—CH3


 


1.65
O
O




—CH3


 


1.67
O
O




—CH3


 


1.68
O
O




—CH3


 


1.69
O
O




—CH3


 


1.70






—CH3


 


1.71
O
N










 


1.72
O
N










 


1.73
O
O




—CH3


 


1.74
O
O




—CH3


 


1.75
O
O




—CH3


 





17.0


 










17.1








—CH3


 


17.2








—CH3


 


17.3








—


 


17.4








—


 





5.0


 


5.1














 





11.0


 











11.1
O
O




—CH3














Substance
R2
R4
X4
X3








1.0


 





1.1
H
H
O
O


 





1.2
—CH3
H
O
O


 





1.3
H
H
O
O


 





1.4
H
H
O
O


 





1.5
H
H
O
O


 





1.6
H
H
O
O


 





1.7
H
H
O
O


 





1.8
H
H
O
O


 





1.9
H
H
O
O


 





1.10
H
H
O
O


 





1.11
H
H
O
O


 





1.12
H
H
O
O


 





1.13
H
H
O
O


 





1.14
H
H
O
O


 





1.15
H
H
O
O


 





1.16
H
H
O
O


 





1.17
H
H
O
O


 





1.18
H
H
O
O


 





1.19
—CH3
H
O
O


 





1.20
H
H
O
O


 





1.21
H
H
O
O


 





1.22
H
H
O
O


 





1.23
H
H
O
O


 





1.24
H
H
O
O


 





1.25
H
H
O
O


 





1.26
H
H
O
O


 





1.27
H
H
O
O


 





1.28
H
H
O
O


 





1.29
—CH3
H
O
O


 





1.30
H
H
O
O


 





1.31
—CH3
H
O
O


 





1.32
—CH3
H
O
O


 





1.33
—CH3
H
O
O


 





1.34




H
O
O


 





1.35
H
H
O
O


 





1.36
—CH3
H
O
O


 





1.37
H
H
O
O


 





1.38




H
O
O


 





1.39




H
O
O


 





1.40




H
O
O


 





1.41




H
O
O


 





1.42




H
O
O


 





1.43
H
H
O
O


 


1.44
—CH3
H
O
O


 


1.45
—CH3
H
O
O


 


1.46
—CH3
H
O
O


 


1.47
—CH3
H
O
O


 


1.48
—CH3
H
O
O


 


1.49
—CH3
H
O
O


 


1.50
—CF3
H
O
O


 


1.51
—CF3
H
O
O


 


1.52
—CF3
H
O
O


 


1.53
—CF3
H
O
O


 


1.54
—CF3
H
O
O


 


1.55
—CF3
H
O
O


 


1.56




H
O
O


 


1.57




H
O
O


 


1.58




H
O
O


 


1.59




H
O
O


 


1.60




H
O
O


 


1.61




H
O
O


 


1.62




H
O
O


 


1.63




H
O
O


 


1.64




H
O
O


 


1.65
—CH3
H
O
O


 


1.67




H
O
O


 


1.68




H
O
O


 


1.69




H
O
O


 


1.70




H
O
O


 


1.71
H
H
N
O


 


1.72




H
N
O


 


1.73
—CH3




O
O


 


1.74








O
O


 


1.75








O
O


 





17.0


 










17.1
—CH3
H






 


17.2
—CH3
H






 


17.3
—CH3
H






 


17.4
—CH3
H






 














5.0


 


5.1
—CH3
H
O
O


 





11.0


 










11.1
—CH3
H

















Substance
R8
R5
R6








1.0


 





1.1
H
—CH3
H


 





1.2
H
—CH3
—CH3


 





1.3
H
—CH3
H


 





1.4
H
—CH3
H


 





1.5
H
—C2H5
H


 





1.6
H
—CH3
H


 





1.7
H
—CH3
H


 





1.8
H
—CH3
H


 





1.9
H
—CH3
H


 





1.10
H
—CH3
H


 





1.11
H
—CH3
H


 





1.12
H
—CH3
H


 





1.13
H
—CH3
H


 





1.14
H
—CH3
H


 





1.15
H
—CH3
H


 





1.16
H
—CH3
H


 





1.17
H
—CH3
H


 





1.18
H
—CH3
H


 





1.19
H
—CH3
—CH3


 





1.20
H
—CH3
H


 





1.21
H
—CH3
H


 





1.22
H
—CH3
H


 





1.23
H
—CH3
H


 





1.24
H
—CH3
H


 





1.25
H
—CH3
H


 





1.26
H
—CH3
H


 





1.27
H
—CH3
H


 





1.28
H
—CH3
H


 





1.29
H
—CH3
—CH3


 





1.30
H
—CH3
H


 





1.31
H
—CH3
—CH3


 





1.32
H
—CH3
—CH3


 





1.33
H
—CH3
—CH3


 





1.34
H
—CH3






 





1.35
H
—CH3
H


 





1.36
H
—CH3
—CH3


 





1.37
H
—CH3
H


 





1.38
H
—CH3






 





1.39
H
—CH3






 





1.40
H
—CH3






 





1.41
H
—CH3






 





1.42
H
—CH3






 





1.43
H
—CH3
H


 


1.44
H
—CH3
—CH3


 


1.45
H
—CH3
—CH3


 


1.46
H
—CH3
—CH3


 


1.47
H
—CH3
—CH3


 


1.48
H
—CH3
—CH3


 


1.49
H
—CH3
—CH3


 


1.50
H
—CH3
—CF3


 


1.51
H
—CH3
—CF3


 


1.52
H
—CH3
—CF3


 


1.53
H
—CH3
—CF3


 


1.54
H
—CH3
—CF3


 


1.55
H
—CH3
—CF3


 


1.56
H
—CH3






 


1.57
H
—CH3






 


1.58
H
—CH3






 


1.59
H
—CH3






 


1.60
H
—CH3






 


1.61
H
—CH3






 


1.62
H
—CH3






 


1.63
H
—CH3






 


1.64
H
—CH3






 


1.65
H
—CH3
—CH3


 


1.67
H
—CH3






 


1.68
H
—CH3






 


1.69
H
—CH3






 


1.70
H
—CH3






 


1.71
H




H


 


1.72
H










 


1.73




—CH3
—CH3


 


1.74




—CH3






 


1.75




—CH3






 





17.0


 


17.1
H
—CH3
—CH3


 


17.2
H
—CH3
—CH3


 


17.3
H
—
—CH3


 


17.4
H
—
—CH3


 





5.0


 


5.1
H
—CH3
—CH3


 





11.0


 


11.1




—CH3
—CH3













Substance
R7










1.0



 






1.1







 






1.2







 






1.3







 






1.4







 






1.5







 






1.6







 






1.7







 






1.8







 






1.9







 






1.10







 






1.11







 






1.12







 






1.13







 






1.14







 






1.15







 






1.16







 






1.17







 






1.18







 






1.19







 






1.20







 






1.21







 






1.22







 






1.23




 






1.24







 






1.25
—C4H9



 






1.26







 






1.27







 






1.28







 






1.29







 






1.30







 






1.31







 






1.32







 






1.33







 






1.34







 






1.35







 






1.36







 






1.37







 






1.38







 






1.39







 






1.40







 






1.41







 






1.42







 






1.43







 



1.44







 



1.45







 



1.46







 



1.47







 



1.48







 



1.49







 



1.50







 



1.51







 



1.52







 



1.53







 



1.54







 



1.55




 



1.56







 



1.57







 



1.58







 



1.59







 



1.60







 



1.61







 



1.62







 



1.63







 



1.64







 



1.65







 



1.67







 



1.68







 



1.69







 



1.70







 



1.71







 



1.72







 



1.73







 



1.74







 



1.75







 






17.0



 



17.1







 



17.2







 



17.3







 



17.4







 






5.0



 



5.1







 






11.0



 



11.1


















Substance
X1
X2
R3








19.0


 





19.1
O
O






 





19.2
O
O






 





19.3
O
O






 





19.4
O
O






 





19.5
O
O






 





19.6
O
O






 





19.7
O
O






 





19.8
O
O






 





19.9
O
O






 





19.10
O
O






 





19.11
O
O






 





19.12
O
O






 


19.13
O
O






 


19.14
O
O






 


19.15
O
O






 


19.16
O
O






 


19.17
O
O






 





7.0


 


7.1
O
O






 


7.2
O
O






 





13.0


 


13.1
O
O






 


13.2
O
O






















Substance
R2
R1
R4
X4
X3
R8










19.0



 






19.1
—CH2—
—
H
O
O
H



 






19.2
—CH2—
—
H
O
O
H



 






19.3
—CH2—
—
H
O
O
H



 






19.4
—CH2—
—
H
O
O
H



 






19.5
—CH2—
—
H
O
O
H



 






19.6
—CH2—
—
H
O
O
H



 






19.7
—CH2—
—
H
O
O
H



 






19.8
—CH2—
—
H
O
O
H



 






19.9
—CH2—
—
H
O
O
H



 






19.10
—CH2—
—
H
O
O
H



 






19.11
—CH2—
—
H
O
O
H



 






19.12
—CH2—
—
H
O
O
H



 



19.13
—CH2—
—
H
O
O
H



 



19.14
—CH2—
—
H
O
O
H



 



19.15
—CF2—
—
H
O
O
H



 



19.16




—
H
O
O
H



 



19.17




—
H
O
O
H



 






7.0



 














7.1
—CH2—
H
O
O
H



 



7.2
—CH2—
H
N
O
H



 






13.0



 















13.1




—CH3
H
N
O
H



 



13.2




—CH3
H
N
O
H












Substance
R6
R5
R7










19.0



 






19.1
—CH2—
—







 






19.2
—CH2—
—







 






19.3
—CH2—
—







 






19.4
—CH2—
—







 






19.5
—CH2—
—







 






19.6
—CH2—
—







 






19.7
—CH2—
—







 






19.8
—CH2—
—







 






19.9
—CH2—
—







 






19.10
—CH2—
—







 






19.11
—CH2—
—







 






19.12
—CH2—
—







 



19.13
—CH2—
—







 



19.14
—CH2—
—







 



19.15
—CF2—
—







 



19.16




—







 



19.17




—







 






7.0



 



7.1
—CH3
—CH3







 



7.2




—CH3







 






13.0



 



13.1
—CH2—







 



13.2
—CH2—


























Substance
X1
R1
X2
R2
R3
R4
R5
X3
X4
R6
R7








20.0


 
















20.1
O
—CH3
O




H
—CH3
O
O






 


20.2
O
—CH3
O




H
—CH3
O
O






 


20.3
O
—CH3
O




H
—CH3
O
O






 


20.4
O
—CH3
O




H
—CH3
O
O






 





8.0


 

















8.1
O
—CH3
O




H
—CH3
O
O
—CH3






 


8.2
O
—CH3
O




H
—CH3
O
O










 


8.3
O
—CH3
O








—CH3
O
O





















Substance
R8










20.0



 



20.1
H



 



20.2
H



 



20.3
H



 



20.4
H



 






8.0



 



8.1
H



 



8.2
H



 



8.3
H























Substance
X1
X2
R3
R2
R1
R4
X4
X3
R8
R6
R5
R7








14.0


 


















14.1
O
—CH3
O
—CH3








—CH3
O
O




H


 


14.2
O
—CH3
O












—CH3
O
O




H



















Substance
R1
X2
X1
R4
R3
R2
R5
X4
X3








18.0


 














18.1




O
H




—CH3




O


 


18.2




O
H




—CH3




O


 


18.3




O
H




—CH3




O


 


18.4




O
H




—CH3




O


 





6.0


 















6.1




O
H




—CH3
—CH3
O
O


 


6.2




O
H








—CH3
O
O


 





12.0


 















12.1
—CH3
O
O
H




—CH3




O


 


12.2
—CH3
O
O
H












O


 





21.0


 















21.1
—CH3
O
O








—CH3
O
O


 





9.0


 


9.1
—CH3
O
O








—CH3
O
O


 














9.2
—CH3
O
O












O


 





15.0


 















15.1




O
H





—CH3
O
O















Substance
R8
R7
R6










18.0



 



18.1
H




—CH3



 



18.2
H




—CH3



 



18.3
H




—CH3



 



18.4
H




—CH3



 






6.0



 



6.1
H




—CH3



 



6.2
H











 






12.0



 



12.1
H




H



 



12.2
H




—CH3



 






21.0



 











21.1











 






9.0



 












9.1
H











 



9.2
H











 






15.0



 











15.1




























Substance
X2
R2
R3
R4
X3
R5
R6
X4
R7








22.0


 















22.1
O
—CH3








—CH3
—CH3
O






 





10.0


 


10.1
O
—CH3








—CH3
—CH3
O






 














10.2
O








—CH3
—CH3
O



 





16.0


 















16.1
O




H
O
—CH3
—CH3
O



















Substance
R8
X1
R1










22.0



 











22.1




—CH3



 






10.0



 












10.1
H
O
—CH3



 



10.2
H
O
—CH3



 






16.0



 











16.1




—CH3

















TABLE 2





2,5-diamino-3,6-dihydroterephthalic acid derivatives




















Substance
X1
X2
R3
R1
R2








2.0


 





2.1
O
O




—CH3
H


 





2.2
O
O




—CH3
—CH3


 





2.3
O
O




—CH3
H


 





2.4
O
O




—CH3
H


 





2.5
O
O




—C2H5
H


 





2.6
O
O




—CH3
H


 





2.7
O
O




—CH3
H


 





2.8
O
O




—CH3
H


 





2.9
O
O




—CH3
H


 





2.10
O
O




—CH3
H


 





2.11
O
O




—CH3
H


 





2.12
O
O




—CH3
H


 





2.13
O
O




—CH3
H


 





2.14
O
O




—CH3
H


 





2.15
O
O




—CH3
H


 





2.16
O
O




—CH3
H


 





2.17
O
O




—CH3
H


 





2.18
O
O




—CH3
H


 





2.19
O
O




—CH3
—CH3


 





2.20
O
O




—CH3
H


 





2.21
O
O




—CH3
H


 





2.22
O
O




—CH3
H


 





2.24
O
O




—CH3
H


 





2.25
O
O
—C4H9
—CH3
H


 





2.26
O
O




—CH3
H


 





2.27
O
O




—CH3
H


 





2.28
O
O




—CH3
H


 





2.29
O
O




—CH3
—CH3


 





2.30
O
O




—CH3
H


 





2.31
O
O




—CH3
—CH3


 





2.32
O
O




—CH3
—CH3


 





2.33
O
O




—CH3
—CH3


 





2.34
O
O




—CH3






 





2.35
O
O




—CH3
H


 





2.36
O
O




—CH3
—CH3


 





2.37
O
O




—CH3
H


 





2.38
O
O




—CH3






 





2.39
O
O




—CH3






 





2.40
O
O




—CH3






 





2.41
O
O




—CH3






 





2.42
O
O




—CH3






 





2.43
O
O




—CH3
H


 


2.44
O
O




—CH3
—CH3


 


2.45
O
O




—CH3
—CH3


 


2.46
O
O




—CH3






 


2.47
O
O




—CH3






 


2.48
O
O




—CH3
—CH3


 


2.49
O
O




—CH3
—CH3


 


2.50
O
O




—CH3
—CH3


 


2.51
O
O




—CH3
—CH3


 


2.52
O
O




—CH3
—CH3


 


2.53
O
O




—CH3
—CH3


 


2.54
O
O




—CH3
—CF3


 


2.55
O
O




—CH3
—CF3


 


2.56
O
O




—CH3
—CF3


 


2.57
O
O




—CH3
—CF3


 


2.58
O
O




—CH3
—CF3


 


2.59
O
O




—CH3
—CF3


 


2.60
O
O




—CH3






 


2.61
O
O




—CH3






 


2.62
O
O




—CH3






 


2.63
O
O




—CH3






 


2.64
O
O




—CH3






 


2.65
O
O




—CH3






 


2.66
O
O




—CH3






 


2.67
O
O




—CH3






 


2.68
O
O




—CH3






 


2.69
O
O




—CH3
—CH3


 


2.70
O
O




—CH3






 


2.71
O
O




—CH3






 


2.72
O
O




—CH3






 


2.73






—CH3






 


2.74
O
N








H


 


2.75
O
N














 


2.76
O
O




—CH3
—CH3


 


2.78
O
O




—CH3






 


2.79
O
O




—CH3





















Substance
R4′
R4′
X4
X3
R8
R8′
R5








2.0


 





2.1
H
H
O
O
H
H
—CH3


 





2.2
H
H
O
O
H
H
—CH3


 





2.3
H
H
O
O
H
H
—CH3


 





2.4
H
H
O
O
H
H
—CH3


 





2.5
H
H
O
O
H
H
—CH3


 





2.6
H
H
O
O
H
H
—CH3


 





2.7
H
H
O
O
H
H
—CH3


 





2.8
H
H
O
O
H
H
—CH3


 





2.9
H
H
O
O
H
H
—CH3


 





2.10
H
H
O
O
H
H
—CH3


 





2.11
H
H
O
O
H
H
—CH3


 





2.12
H
H
O
O
H
H
—CH3


 





2.13
H
H
O
O
H
H
—CH3


 





2.14
H
H
O
O
H
H
—CH3


 





2.15
H
H
O
O
H
H
—CH3


 





2.16
H
H
O
O
H
H
—CH3


 





2.17
H
H
O
O
H
H
—CH3


 





2.18
H
H
O
O
H
H
—CH3


 





2.19
H
H
O
O
H
H
—CH3


 





2.20
H
H
O
O
H
H
—CH3


 





2.21
H
H
O
O
H
H
—CH3


 





2.22
H
H
O
O
H
H
—CH3


 





2.24
H
H
O
O
H
H
—CH3


 





2.25
H
H
O
O
H
H
—CH3


 





2.26
H
H
O
O
H
H
—CH3


 





2.27
H
H
O
O
H
H
—CH3


 





2.28
H
H
O
O
H
H
—CH3


 





2.29
H
H
O
O
H
H
—CH3


 





2.30
H
H
O
O
H
H
—CH3


 





2.31
H
H
O
O
H
H
—CH3


 





2.32
H
H
O
O
H
H
—CH3


 





2.33
H
H
O
O
H
H
—CH3


 





2.34
H
H
O
O
H
H
—CH3


 





2.35
H
H
O
O
H
H
—CH3


 





2.36
H
H
O
O
H
H
—CH3


 





2.37
H
H
O
O
H
H
—CH3


 





2.38
H
H
O
O
H
H
—CH3


 





2.39
H
H
O
O
H
H
—CH3


 





2.40
H
H
O
O
H
H
—CH3


 





2.41
H
H
O
O
H
H
—CH3


 





2.42
H
H
O
O
H
H
—CH3


 





2.43
H
H
O
O
H
H
—CH3


 


2.44
F
F
O
O
F
F
—CH3


 


2.45
F
F
O
O
F
F
—CH3


 


2.46
F
F
O
O
F
F
—CH3


 


2.47
F
F
O
O
F
F
—CH3


 


2.48
H
H
O
O
H
H
—CH3


 


2.49
H
H
O
O
H
H
—CH3


 


2.50
H
H
O
O
H
H
—CH3


 


2.51
H
H
O
O
H
H
—CH3


 


2.52
H
H
O
O
H
H
—CH3


 


2.53
H
H
O
O
H
H
—CH3


 


2.54
H
H
O
O
H
H
—CH3


 


2.55
H
H
O
O
H
H
—CH3


 


2.56
H
H
O
O
H
H
—CH3


 


2.57
H
H
O
O
H
H
—CH3


 


2.58
H
H
O
O
H
H
—CH3


 


2.59
H
H
O
O
H
H
—CH3


 


2.60
H
H
O
O
H
H
—CH3


 


2.61
H
H
O
O
H
H
—CH3


 


2.62
H
H
O
O
H
H
—CH3


 


2.63
H
H
O
O
H
H
—CH3


 


2.64
H
H
O
O
H
H
—CH3


 


2.65
H
H
O
O
H
H
—CH3


 


2.66
H
H
O
O
H
H
—CH3


 


2.67
H
H
O
O
H
H
—CH3


 


2.68
H
H
O
O
H
H
—CH3


 


2.69
H
H
O
O
H
H
—CH3


 


2.70
H
H
O
O
H
H
—CH3


 


2.71
H
H
O
O
H
H
—CH3


 


2.72
H
H
O
O
H
H
—CH3


 


2.73
H
H
O
O
H
H
—CH3


 


2.74
H
H
N
O
H
H






 


2.75
H
H
N
O
H
H






 


2.76








O
O








—CH3


 


2.78








O
O








—CH3


 


2.79








O
O








—CH3














Substance
R6
R7










2.0



 






2.1
H







 






2.2
—CH3







 






2.3
H







 






2.4
H







 






2.5
H







 






2.6
H







 






2.7
H







 






2.8
H







 






2.9
H







 






2.10
H







 






2.11
H







 






2.12
H







 






2.13
H







 






2.14
H







 






2.15
H







 






2.16
H







 






2.17
H







 






2.18
H







 






2.19
—CH3







 






2.20
H







 






2.21
H







 






2.22
H







 






2.24
H







 






2.25
H
—C4H9



 






2.26
H







 






2.27
H







 






2.28
H







 






2.29
—CH3







 






2.30
H







 






2.31
—CH3







 






2.32
—CH3







 






2.33
—CH3







 






2.34











 






2.35
H







 






2.36
—CH3







 






2.37
H







 






2.38











 






2.39











 






2.40











 






2.41











 






2.42











 






2.43
H







 



2.44
—CH3







 



2.45
—CH3







 



2.46











 



2.47











 



2.48
—CH3







 



2.49
—CH3







 



2.50
—CH3







 



2.51
—CH3







 



2.52
—CH3







 



2.53
—CH3







 



2.54
—CF3







 



2.55
—CF3







 



2.56
—CF3







 



2.57
—CF3







 



2.58
—CF3







 



2.59
—CF3







 



2.60











 



2.61











 



2.62











 



2.63











 



2.64











 



2.65











 



2.66











 



2.67











 



2.68











 



2.69
—CH3







 



2.70











 



2.71











 



2.72











 



2.73











 



2.74
H







 



2.75











 



2.76
—CH3







 



2.78











 



2.79

























Substance
X1
X2
R3
R1
R2
R4








37.0


 












37.1








—CH3
—CH3
H


 


37.2












—CH3
H


 


37.3








—
—CH3
H


 


37.4








—
—CH3
H


 





23.0


 


23.1












—CH3
H


 





30.0


 













30.1
O
O




—CH3
—CH3
H


















Substance
X4
X3
R8
R5
R6
R7
R4′
R8′








37.0


 














37.1




H
—CH3
—CH3




H
H


 


37.2




H




—CH3




H
H


 


37.3




H
—
—CH3




H
H


 


37.4




H
—
—CH3




H
H


 





23.0


 















23.1
O
O
H
—CH3
—CH3




H
H


 





30.0


 














30.1








—CH3
—CH3




H






















Substance
X1
X2
R3
R2
R1
R4
X4
X3








39.0


 





39.1
O
O




—CH2—
—
H
O
O


 





39.2
O
O




—CH2—
—
H
O
O


 





39.3
O
O




—CH2—
—
H
O
O


 





39.4
O
O




—CH2—
—
H
O
O


 





39.5
O
O




—CH2—
—
H
O
O


 





39.6
O
O




—CH2—
—
H
O
O


 





39.7
O
O




—CH2—
—
H
O
O


 





39.8
O
O




—CH2—
—
H
O
O


 





39.9
O
O




—CH2—
—
H
O
O


 





39.10
O
O




—CH2—
—
H
O
O


 





39.11
O
O




—CH2—
—
H
O
O


 





39.12
O
O




—CH3—
—
H
O
O


 


39.13
O
O




—CH2—
—
H
O
O


 


39.14
O
O




—CH2—
—
H
O
O


 


39.15
O
O




—CF2—
—
H
O
O


 


39.16
O
O








—
H
O
O


 


39.17
O
O








—
H
O
O


 


39.18
O
O




—CH2—
—
H
O
O


 


39.19
O
O




—CH2—
—
H
O
O


 


39.20
O
O




—CF2—
—
H
O
O


 


39.21
O
O








—
H
O
O


 


39.22
O
O








—
H
O
O


 





25.0


 














25.1
O
O




—CH2—
H
O
O


 


25.2
O
O




—CH2—
H
N
O


 





32.0


 















32.1
O
O








—CH3
H
N
O


 


32.2
O
O








—CH3
H
N
O


















Substance
R8
R6
R5
R7
R4′
R8′










39.0



 






39.1
H
—CH2—
—




H
H



 






39.2
H
—CH2—
—




H
H



 






39.3
H
—CH2—
—




H
H



 






39.4
H
—CH2—
—




H
H



 






39.5
H
—CH2—
—




H
H



 






39.6
H
—CH2—
—




H
H



 






39.7
H
—CH2—
—




H
H



 






39.8
H
—CH2—
—




H
H



 






39.9
H
—CH2—
—




H
H



 






39.10
H
—CH2—
—




H
H



 






39.11
H
—CH2—
—




H
H



 






39.12
H
—CH2—
—




H
H



 



39.13
H
—CH2—
—




H
H



 



39.14
H
—CH2—
—




H
H



 



39.15
H
—CF2—
—




H
H



 



39.16
H




—




H
H



 



39.17
H




—




H
H



 



39.18
H
—CH2—
—




H
H



 



39.19
H
—CH2—
—




H
H



 



39.20
H
—CF2—
—




H
H



 



39.21
H




—




H
H



 



39.22
H




—




H
H



 






25.0



 



25.1
H
—CH3
—CH3




H
H



 



25.2
H




—CH3




H
H



 






32.0



 














32.1
H
—CH2—




H
H



 



32.2
H
—CH2—




H
H























Substance
X1
R1
X2
R2
R3
R4
R5
X3
X4
R6
R7
R8








40.0


 

















40.1
O
—CH3
O




H
—CH3
O
O




H


 


40.2
O
—CH3
O




H
—CH3
O
O




H


 


40.3
O
—CH3
O




H
—CH3
O
O




H


 


40.4
O
—CH3
O




H
—CH3
O
O




H


 





26.0


 


















26.1
O
—CH3
O




H
—CH3
O
O
—CH3




H


 


26.2
O
—CH3
O




H
—CH3
O
O








H


 


26.3
O
—CH3
O








—CH3
O
O








H














Substance
R4′
R8′










40.0



 



40.1
H
H



 



40.2
H
H



 



40.3
H
H



 



40.4
H
H



 






26.0



 



26.1
H
H



 



26.2
H
H



 



26.3




H

























Substance
X1
R1
X2
R4
R2
R3
R5
X3
X4
R6
R7
R8
R4′
R8′








33.0


 




















33.1
O
—CH3
O
—CH3








—CH3
O
O




H
—CH3
H


 


33.2
O
—CH3
O












—CH3
O
O




H




H
























Substance
R1
X2
X1
R4
R3
R2
R5
X4
X3
R8
R7
R6
R4′
R8′








38.0


 



















38.1




O
H




—CH3




O
H




—CH3
H
H


 


38.2




O
H




—CH3




O
H




—CH3
H
H


 


38.3




O
H




—CH3




O
H




—CH3
H
H


 


38.4




O
H




—CH3




O
H




—CH3
H
H


 





24.0


 




















24.1




O
H




—CH3
—CH3
O
O
H




—CH3
H
H


 


24.2




O
H








—CH3
O
O
H








H
H


 





31.0


 




















31.1
—CH3
O
O
H




—CH3




O
H




H
H
H


 


31.2
—CH3
O
O
H












O
H




—CH3
H
H
























Substance
R1
X2
X1
R4′
R3
R2
R5
X4
X3
R8′
R7
R6
R4
R8








41.0


 



















41.1
—CH3
O
O








—CH3
O
O








H
H


 





27.0


 




















27.1
—CH3
O
O








—CH3
O
O
H








H
H


 



















27.2
—CH3
O
O












O
H








H
H
























Substance
R1
X2
X1
R4
R3
R2
R5
X4
X3
R5
R7
R8′
R4′
R8








34.0


 



















34.1




O
H




—CH3
—CH3
O
O








H
H






















Substance
X2
R2
R3
R4
X3
R5
R6
X4
R7
R8
X1
R1








43.0


 

















43.1
O
—CH3








—CH3
—CH3
O








—CH3


 





29.0


 


















29.1
O
—CH3








—CH3
—CH3
O




H
O
—CH3


 

















29.2
O








—CH3
—CH3
O

H
O
—CH3


 





36.0


 

















36.1
O




H
O
—CH3
—CH3
O








—CH3














Substance
R4′
R8′










43.0



 



43.1
—CH3
—CH3



 






29.0



 



29.1
—CH3
—CH3



 



29.2
H
H



 






36.0



 



36.1
H
H

















TABLE 3





Substituted 2,5-diaminoterephthalic acid dinitriles





















Substance
R3
R2
R4
R8
R6
R7





















3.0


 






3.1




H
H
H
H






 






3.2




—CH3
H
H
—CH3






 






3.3




H
H
H
H






 






3.4




H
H
H
H






 






3.5




H
H
H
H






 






3.6




H
H
H
H






 






3.7




H
H
H
H






 






3.8




H
H
H
H






 






3.9




H
H
H
H






 






3.10




H
H
H
H






 






3.11




H
H
H
H






 






3.12




H
H
H
H






 






3.13




H
H
H
H






 






3.14




H
H
H
H






 






3.15




H
H
H
H






 






3.16




H
H
H
H






 






3.17




—CH3
H
H
—CH3






 






3.18




H
H
H
H






 






3.19




H
H
H
H






 






3.20




H
H
H
H






 






3.21




H
H
H
H






 






3.22
—C4H9
H
H
H
H
—C4H9


 






3.23




H
H
H
H






 






3.24




H
H
H
H






 






3.25




H
H
H
H






 






3.26




—CH3
H
H
—CH3






 






3.27




H
H
H
H






 






3.28




—CH3
H
H
—CH3






 






3.29




—CH3
H
H
—CH3






 






3.30




—CH3
H
H
—CH3






 






3.31








H
H










 






3.32




H
H
H
H






 






3.33




—CH3
H
H
—CH3






 






3.34




H
H
H
H






 






3.35








H
H










 






3.36








H
H










 






3.37








H
H










 






3.38








H
H










 






3.39








H
H










 






3.40




H
H
H
H






 



3.41




—CH3
H
H
—CH3






 



3.42




—CH3
H
H
—CH3






 



3.43




—CH3
H
H
—CH3






 



3.44




—CH3
H
H
—CH3






 



3.45




—CH3
H
H
—CH3






 



3.46




—CH3
H
H
—CH3






 



3.47




—CF3
H
H
—CF3






 



3.48




—CF3
H
H
—CF3






 



3.49




—CF3
H
H
—CF3






 



3.50




—CF3
H
H
—CF3






 



3.51




—CF3
H
H
—CF3






 



3.52




—CF3
H
H
—CF3






 



3.53








H
H










 



3.54








H
H










 



3.55








H
H










 



3.56








H
H










 



3.57








H
H










 



3.58








H
H










 



3.59








H
H










 



3.60








H
H










 



3.61








H
H










 



3.62




—CH3
H
H
—CH3






 



3.63








H
H










 



3.64








H
H










 



3.65








H
H










 



3.66








H
H










 



3.67




H
H
H
H






 



3.68








H
H










 



3.69




—CH3








—CH3






 



3.70


























 



3.71








































Substance
R2
R3
R4
R6
R7
R8



















48.0


 



48.1




H




H


 



48.2




H




H


 



48.3




H




H


 



48.4




H




H


 






44.0


 














44.1




H
—CH3




H


 



44.2




H








H


 



44.3
















H
















Substance
R8
R2
R3
R6
R7
R4




















46.0


 



46.1
H
—CH3








H


 



46.2
H












H
















Substance
R4
R3
R2
R8
R7
R6



















49.0


 



49.1


















 






45.0


 














45.1








H










 






47.0


 














47.1
H





























TABLE 4





Substituted 2,5-diamino-3,6-dihydroterephthalic acid dinitriles
























Substance

R3
R2
R4
R4′
R8
R8′
R6
R7









4.0


—CH3
—CH3
—CH3
—CH3


 






4.1




H
—CH3
—CH3
—CH3
—CH3
H






 






4.2




—CH3
—CH3
—CH3
—CH3
—CH3
—CH3






 






4.3




H
—CH3
—CH3
—CH3
—CH3
H

















Substance

R3
R2









4.4




H


 






4.5




H


 






4.6




H


 






4.7




H


 






4.8




H


 






4.9




H


 






4.10




H


 






4.11




H


 






4.12




H


 






4.13




H


 






4.14




H


 






4.15




H


 






4.16




H


 






4.17




—CH3


 






4.18




H


 






4.19




H


 






4.20




H


 






4.21




H


 






4.22
—C4H9
H


 






4.23




H


 






4.24




H


 






4.25




H


 






4.26




—CH3


 






4.27




H


 






4.28




—CH3


 






4.29




—CH3


 






4.30




—CH3


 






4.31










 











H


 






4.32




—CH3


 






4.33




H


 






4.34










 






4.35










 






4.36










 






4.37










 






4.38










 






4.39




H


 



4.40




—CH3


 



4.41




—CH3


 



4.42




—CH3


 



4.43




—CH3


 



4.44




—CH3


 



4.45




—CH3


 



4.46




—CF3


 



4.47




—CF3


 



4.48




—CF3


 



4.49




—CF3


 



4.50




—CF3


 



4.51




—CF3


 



4.52










 



4.53










 



4.54










 



4.55










 



4.56










 



4.57










 



4.58










 



4.59










 



4.60










 



4.61




—CH3


 



4.62










 



4.63










 



4.64










 



4.65










 



4.66




H


 



4.67










 



4.68




—CH3


 



4.69










 



4.70






















Substance

R4
R8
R6









4.4
—CH3
—CH3
H


 






4.5
—CH3
—CH3
H


 






4.6
—CH3
—CH3
H


 






4.7
—CH3
—CH3
H


 






4.8
—CH3
—CH3
H


 






4.9
—CH3
—CH3
H


 






4.10
—CH3
—CH3
H


 






4.11
—CH3
—CH3
H


 






4.12
—CH3
—CH3
H


 






4.13
—CH3
—CH3
H


 






4.14
—CH3
—CH3
H


 






4.15
—CH3
—CH3
H


 






4.16
—CH3
—CH3
H


 






4.17
—CH3
—CH3
—CH3


 






4.18
—CH3
—CH3
H


 






4.19
—CH3
—CH3
H


 






4.20
—CH3
—CH3
H


 






4.21
—CH3
—CH3
H


 






4.22
—CH3
—CH3
H


 






4.23
—CH3
—CH3
H


 






4.24
—CH3
—CH3
H


 






4.25
—CH3
—CH3
H


 






4.26
—CH3
—CH3
—CH3


 






4.27
—CH3
—CH3
H


 






4.28
—CH3
—CH3
—CH3


 






4.29
—CH3
—CH3
—CH3


 






4.30
—CH3
—CH3
—CH3


 






4.31
—CH3
—CH3






 







—CH3
—CH3
H


 






4.32
—CH3
—CH3
—CH3


 






4.33
—CH3
—CH3
H


 






4.34
—CH3
—CH3






 






4.35
—CH3
—CH3






 






4.36
—CH3
—CH3






 






4.37
—CH3
—CH3






 






4.38
—CH3
—CH3






 






4.39
—CH3
—CH3
H


 



4.40
—CH3
—CH3
—CH3



4.41
—CH3
—CH3
—CH3



4.42
—CH3
—CH3
—CH3



4.43
—CH3
—CH3
—CH3



4.44
—CH3
—CH3
—CH3



4.45
—CH3
—CH3
—CH3



4.46
—CH3
—CH3
—CF3



4.47
—CH3
—CH3
—CF3



4.48
—CH3
—CH3
—CF3



4.49
—CH3
—CH3
—CF3



4.50
—CH3
—CH3
—CF3



4.51
—CH3
—CH3
—CF3


 



4.52
—CH3
—CH3






 



4.53
—CH3
—CH3






 



4.54
—CH3
—CH3






 



4.55
—CH3
—CH3






 



4.56
—CH3
—CH3






 



4.57
—CH3
—CH3






 



4.58
—CH3
—CH3






 



4.59
—CH3
—CH3






 



4.60
—CH3
—CH3






 



4.61
—CH3
H
—CH3


 



4.62
—CH3
H






 



4.63
—CH3
H






 



4.64
—CH3
H






 



4.65
—CH3
H






 



4.66
—CH3
H
H


 



4.67
—CH3
H






 



4.68








—CH3


 



4.69














 



4.70




























Substance

R7
R4′
R8′











4.4




—CH3
—CH3



 







4.5




—CH3
—CH3



 







4.6




—CH3
—CH3



 







4.7




—CH3
—CH3



 







4.8




—CH3
—CH3



 







4.9




—CH3
—CH3



 







4.10




—CH3
—CH3



 







4.11




—CH3
—CH3



 







4.12




—CH3
—CH3



 







4.13




—CH3
—CH3



 







4.14




—CH3
—CH3



 







4.15




—CH3
—CH3



 







4.16




—CH3
—CH3



 







4.17




—CH3
—CH3



 







4.18




—CH3
—CH3



 







4.19




—CH3
—CH3



 







4.20




—CH3
—CH3



 







4.21




—CH3
—CH3



 







4.22
—C4H9
—CH3
—CH3



 







4.23




—CH3
—CH3



 







4.24




—CH3
—CH3



 







4.25




—CH3
—CH3



 







4.26




—CH3
—CH3



 







4.27




—CH3
—CH3



 







4.28




—CH3
—CH3



 







4.29




—CH3
—CH3



 







4.30




—CH3
—CH3



 







4.31




—CH3
—CH3



 












—CH3
—CH3



 







4.32




—CH3
—CH3



 







4.33




—CH3
—CH3



 







4.34




—CH3
—CH3



 







4.35




—CH3
—CH3



 







4.36




—CH3
—CH3



 







4.37




—CH3
—CH3



 







4.38




—CH3
—CH3



 







4.39




—CH3
—CH3



 




4.40




—CH3
—CH3



 




4.41




—CH3
—CH3



 




4.42




—CH3
—CH3



 




4.43




—CH3
—CH3



 




4.44




—CH3
—CH3



 




4.45




—CH3
—CH3



 




4.46




—CH3
—CH3



 




4.47




—CH3
—CH3



 




4.48




—CH3
—CH3



 




4.49




—CH3
—CH3



 




4.50




—CH3
—CH3



 




4.51




—CH3
—CH3



 




4.52




—CH3
—CH3



 




4.53




—CH3
—CH3



 




4.54




—CH3
—CH3



 




4.55




—CH3
—CH3



 




4.56




—CH3
—CH3



 




4.57




—CH3
—CH3



 




4.58




—CH3
—CH3



 




4.59




—CH3
—CH3



 




4.60




—CH3
—CH3



 




4.61




—CH3
—CH3



 




4.62




—CH3
—CH3



 




4.63




—CH3
—CH3



 




4.64




—CH3
—CH3



 




4.65




—CH3
—CH3



 




4.66




—CH3
—CH3



 




4.67




—CH3
—CH3



 




4.68




—CH3
—CH3



 




4.69




—CH3
—CH3



 




4.70




—CH3
—CH3




















Substance

R2
R3
R4
R6
R7
R8
R8′
R4′









56.0


 















56.1




—CH3




—CH3
—CH3
—CH3


 



56.2




—CH3




—CH3
—CH3
—CH3


 



56.3




—CH3




—CH3
—CH3
—CH3


 



56.4




—CH3




—CH3
—CH3
—CH3



















Substance

R2
R3
R6
R7
R8
R8′
R4
R4′









50.0


 
















50.1




—CH3




—CH3
—CH3
—CH3
—CH3


 



50.2












—CH3
—CH3
—CH3
—CH3


 



50.3
















—CH3




—CH3



















Substance

R8
R8′
R3
R6
R7
R4
R4′
R2









53.0


 
















53.1
—CH3
—CH3








—CH3
—CH3
—CH3


 



53.2
—CH3
—CH3








—CH3
—CH3























Substance

R4′
R3
R2
R8′
R7
R6
R4
R8









57.0


 















57.1
















—CH3
—CH3


 






51.0


 
















51.1








H








—CH3
—CH3



















Substance

R4
R4′
R3
R2
R6
R7
R8′
R8









54.0


 
















54.1
—CH3
—CH3
















—CH3



















Substance

R4
R4′
R3
R2
R6
R7
R8′
R8′









52.0


 


















52.1
















—CH3
—CH3


 






55.0


 


















55.1
—CH3
—CH3


















 






58.0


 


















58.1

































The new emitters are used in a device comprising or not comprising an electron transport layer, wherein the layers in a device can be arranged as shown in FIG. 2:

    1. The substrate consists of a transparent material, e.g. glass;
    2. The anode consists of ITO which injects the holes into the hole transport layer;
    3./4. The hole conductor mainly consists of triphenylamine derivatives; several hole conductor layers can be provided whose characteristics are adapted to the device;
    5. Between the hole conductor and the electron conductor, one or more emitter layers are arranged;
    6. The electron conductor can e.g. consist of Alq3 and conducts the electrons from the cathode to the emitting layer or the hole conductor inside the device;
    7. The buffer layer consists of certain metal salts or the oxides thereof, e.g. LiF, and improves the electron injection into the layer 6;
    8. The cathode consists of a base metal or an alloy (e.g. aluminium or calcium).


Typically, the emitter layers are 3–10 nm thick, preferably 4–6 nm. The emission wavelengths depend on the chemical structure in a characteristic manner, i.e. electronic and steric factors of the molecules obviously influence the wavelength of the emitted light and the performance achieved. The wavelengths of the examples listed in Table 2 range between 538 nm and 618 nm.
In order to achieve mixed colours, the new emitters of formulas 1.0–58.0 can be arranged on top of one another, either in the form of several layers each of which consists of an emitter material in its pure form (FIG. 2) or in the form of one or several layer(s) in which the emitter materials are provided in a mixed form.
The layers comprising the new emitters of formulas 1.0–58.0 can be doped with known emitter materials, as shown in FIG. 1.
The new emitters of formulas 1.0–58.0 can be used in devices comprising hole conductors known per se (59 and 60) and other components. Typical examples are shown in FIGS. 1 and 2.




4,4′,4′′-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine (1-NAPHDATA)





N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine (α-NPD)

The devices based on the new emitters can be produced in a manner known per se, i.e. by vacuum deposition at between 1 and 10−9 torrs.
Alternatively, the devices can be produced by solution coating, e.g. web coating or spin coating. Here, the new emitters of formulas 1.0–58.0 can be applied either as the pure substance or as a dopant contained in a suitable polymer.
Surprisingly, it has been found that particularly efficient devices can be produced using substances of the formula 1.0 which have been substituted with fluorine. A remarkably high photometric efficiency is observed in these cases. Using the substance 1.2, a device emitting a spectrally nearly pure green is obtained.
EXPERIMENTAL PART
The following examples are intended to illustrate the invention in more detail, but do by no means limit the same.
Example 1 (Substances 2.1, 2.3–2.5)




0.06 mol cyclohexane-2,5-dione-1,4-dicarboxylic acid diester is suspended in a mixture of 200 ml glacial acetic acid and 200 ml alcohol (corresponding to the ester component). In a nitrogen atmosphere, 0.135 mol of a primary amine or aniline is speedily added. The reaction mixture is refluxed for 5–8 hours while stirring thoroughly. Anilines which have been substituted with an acceptor require longer reaction times.
In the case of anilines, the crude product can be isolated by sucking off the cooled-down reaction mixture, thoroughly washing it with methanol and drying.
Aliphatic amines form highly soluble products, i.e. the solvent must be separated almost completely using a rotary evaporator. The crude product is added into methanol, thoroughly cooled, sucked off and dried.
Example 2 (Substances 1.1, 1.31.5)




The esters of dihydroterephthalic acid obtained in Example 1 are oxidized. Yields of up to 95% are achieved during isolation. In order to purify the separated crude product, it can be recrystallized from DMF, toluene, chloroform or methanol. The substances obtained are sublimable.
Example 3 (Substances 19.1–19.4)
The esters obtained according to Example 2 are saponified in mixtures of n-propanol and water. 0.01 mol terephthalic acid diester is suspended in approx. 50 ml n-propanol, and 50 ml water containing 0.03 mol potassium hydroxide is added. The suspension is refluxed until a clear solution is obtained. Once another 2 hours have passed, the liquid is sucked off. In order to neutralize the solution, approx. 5 ml glacial acetic acid is added dropwise. The acid obtained is washed with methanol and dried.
In order to produce the substances 19.1–19.4, 0.01 mol of the terephthalic acid obtained is refluxed for 2 hours in 100 ml glacial acetic acid to which 15 ml formaldehyde solution (37%) has been added.
The reaction products are separated and washed with methanol. They are recrystallized from acetonitrile or chloroform. The substances obtained can be purified by sublimation.
Example 4 (Substance 1.2)
In order to obtain compounds of this type, the respective terephthalic acid ester (Example 2) can be alkylated. 0.05 mol terephthalic acid ester is suspended in 350 ml anhydrous DMSO, and 18.63 g (0.131 mol) methyl iodide is added. 6.1 g (0.152 mol) 60% sodium hydride in paraffin is added in portions at a temperature ranging between 20 and 23° C. and while stirring throrougly. Once a reaction time of approx. 5 hours has passed, the colour of the solid constitutents has changed from orange to pure yellow. Now, approx. 200 ml methanol is added to the mixture, thereby considerably improving filterability.
The separated yellow reaction product is thoroughly washed with methanol and dried. A pure product is obtained by recrystallization from toluene.
Example 5 (Device: Substance 19.4)
A 55 nm thick layer of 4,4′,4′′-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine and another 5 nm thick layer of N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine were deposited onto a structured ITO glass substrate measuring 50×50 mm2. Onto these hole transport layers, 5 nm 1,6-bis(2,4-dimethoxyphenyl)-benzo[1,2-d;4,5-d′]-1,2,6,7-tetrahydro-bis[1,3]oxazine-4,9-dione (19.4) is deposited.
In addition, a 30 nm thick layer of tris-(8-hydroxychinolinato)-aluminium is now applied onto this emitter layer, followed by a very thin buffer layer (0.5 nm) of lithium fluoride and finally aluminium.
The arrangement was tested applying an adjustable voltage between 0 and 15 V. The device emits a wavelength of 578 nm (yellow). A luminance (emission intensity) of 100 cd/m2 was achieved at 5.0 V. The maximum luminance (emission intensity) achieved was 11,400 cd/m2.
Example 6 (Device: Substance 1.21)
A device was produced according to Example 5, into which a 5 nm thick layer of 2,5-bis-(N-(2,4-dimethoxyphenyl)amino)terephthalic acid diethyl ester was incorporated as emitter substance between the hole conductor and the electron conductor.
The device was also tested applying an adjustable voltage between 0 and 15 V. The device emits a wavelength of 618 nm (red). A luminance (emission intensity) of 100 cd/m2 was achieved at 9.5 V. The maximum luminance (emission intensity) achieved was 644 cd/m2.
Example 7 (Device: Substance 1.5)
The device has the same structure as those of Examples 5 and 6. The emitter substance used was 2,5-bis-(N-phenylamino)-terephthalic acid diethyl ester.
Once again, the device was tested applying an adjustable voltage between 0 and 15 V. The device emits a yellow light (578 mm). A luminance (emission intensity) of 100 cd/m2 was achieved at 5.6 V. The maximum luminance (emission intensity) recorded was 5,300 cd/m2.
Example 8 (Device: Substance 1.2)
Analogously to Examples 5–7 and according to the same structural principle, a 5 nm thick layer of N,N′-dimethyl-2,5-bis-(N-(2-fluorophenyl)-amino)terephthalic acid dimethyl ester was deposited onto the hole transport layers.
The arrangement (FIG. 2) was tested applying an adjustable voltage between 0 and 15 V. The device emits a green light (λmax=547 nm). A luminance (emission intensity) of 100 cd/m2 was achieved at 5.4 V. The maximum luminance (emission intensity) achieved was 17,700 cd/m2.

    1. The substrate consists of glass;
    2. The anode consists of ITO;
    3. 1-Naphdata is applied as hole conductor;
    4. Another hole conductor layer consists of α-NPD;
    5. One or several emitter layers are arranged between the hole conductor and the electron conductor;
    6. The electron conductor can e.g. consist of Alq3;
    7. The buffer layer consists of LiF;
    8. The cathode consists of a base metal or an alloy (e.g. aluminium or calcium).


Typically, the emitter layers are 3–10 nm thick, preferably 4–6 nm.
Photometric Parameters of Selected Emitter Substances













TABLE 2





#
1)V
2)nm
Colour
3)cd/m2
4)cd/A
5)lm/W





















 1.21
9.2
629
red-white
1980
0.12
0.07


 1.16*)
9.3
634
red-white
3990
0.14
0.10


 1.16
14.0
618
red
144
0.09
0.07


 1.30
5.6
612
orange-red
12100
2.17
2.27


19.4
5.0
578
yellow
11400
2.04
1.72


 1.5
5.6
578
yellow
5300
1.59
1.42


 1.4
8.0
577
yellow
1410
0.81
0.37


19.3
6.5
565
yellow-green
4530
0.72
0.49


 1.3
8.1
577
yellow-green
4330
2.77
1.52


19.7
10.2

yellow-green
474
0.26
0.10


 1.34
3.5
550
green
36500
1.00
9.21


 1.36
5.7
546
green
18100
6.60
4.34


 1.2
5.4
547
green
17700
7.70
4.93


 1.38
6.4
546
green
11300
4.62
2.47


19.2
6.6
564
green
6010
0.89
0.66


19.1
6.7
540
green
4680
3.05
1.70


19.6
8.6
545
green
2610
0.52
0.36


 1.29
11.1
564
green
1330
1.59
0.47


 1.1
7.1
538
green
1300
0.48
0.22


 1.33
10.3
563
green
1100
1.53
0.54


 1.31
10.8
566
green
754
1.60
0.53


19.8
13.4

green
273
1.20
0.70


19.11
14.4
532
green
144
0.03
0.01


19.5
>20.0
540
green
8
0.30
0.28


19.9
>15.0
544
green
64
0.58
0.13





1)voltage at 100 cd/m2


2)λmax of electroluminescence


3)max. luminance (emission intensity)


4)max. photometric efficiency


5)max. performance efficiency















TABLE 3





Table 3#
λmax (solid)
λem (solid)

















1.6

614


1.7

597


1.8

604


1.10

626


1.11

596


1.12

586


1.1

547


1.13

559


1.14

543


1.15

605


1.16
500
635


1.17

596


1.18

617


1.19
435
531


1.4

599


1.20

596


19.1
475
564


19.4
460
598


1.5
465
582


1.21
495
625


19.5

612


1.23

573


1.24

564


1.25

605


1.26

602


19.3

582


1.6

623


19.6

592


1.28

588


1.3

595


1.24

612


19.8
453
583


1.2

558


1.5
496
622





λmax: absorption maximum


λem: emission maximum


λell: maximum of electroluminescence













TABLE 4







Absorbance coefficients ε of selected emitter substances










#
λmax (nm)
ε (l · mol−1 cm−1)
Solvent













1.16
489
6000
CHCl3


1.5
469
6640
CHCl3


1.34
403
4744
NMP


19.6
452
5250
CHCl3


19.5
474
4670
CHCl3


19.7
433
5450
NMP


1.17
472
6410
CHCl3


1.15
486
5930
CHCl3


1.12
460
5930
CHCl3


1.11
481
6840
CHCl3


1.8
472
6450
CHCl3


1.7
474
6550
CHCl3


19.1
434
4700
NMP


1.30
493
5450
NMP


1.27
482
6800
CHCl3



















TABLE 5







Absorption maxima of selected




emitter substances in solution#
λmax (NMP)



















1.6
482



1.7
476



1.8
463



1.9
652



1.10
509



1.11
475



1.12
445



1.1
413



1.13
427



1.14
428



1.15
482



1.16
494



1.17
464



1.18
464



1.19
417



1.4
468



1.20
461



19.1
435



19.4
458



1.5
451



1.21
479



1.22
505



19.5
472



1.23
432



1.24
446



1.25
487



1.26
482



19.3
447



1.6
481



19.6
452



1.28
473



1.3
451



1.24
480



1.30
493



1.34
403



1.5
461



1.43
496




















TABLE 6







DSC values of selected




emitter substances#
DSC peak in ° C.



















19.3
260.0



1.6
269.1



1.7
171.3



1.8
227.8



1.11
192.1



1.12
172.2



1.15
232.0



1.17
166.5



19.1
325.7



1.16
183.3



1.34
254.7



19.1
325.7



1.27
182.5










Preparation and Measuring Conditions
a) Substrate: 125 nm ITO, approx. 13 Ω/sq and 85% tranmission, 50×50 mm2 glass substrate (1.1 mm thick polished soda-lime float glass with SiO2 layer and 8 individual ITO anodes (active surface area: 2×2 mm2))
Purified 2×20 min in an ultrasonic bath with Aceton selectopur and Methanol selectopur,

    3× snow jet cleaning (CO2 ice crystals)
    O2 plasma treatment (5 min at 450 W and 0.12 mbar)


b) Pressure (2–4)×10−5 mbar during deposition

    Aluminium oxide ceramic crucible
    Deposition rate: 0.06 nm/s
    Layer thickness checked using a piezoelectric microbalance measuring device


Change of mask and intermediate aeration of the deposition chamber, first with nitrogen and then with air

    Cathodes, 0.5 nm lithium fluoride (insulating) and 100 nm aluminium each


c) The device according to FIG. 2 was introduced in a glove box, the active OLED suface was positioned above calibrated Vλ silicon photodiodes in a darkened measuring device, and the anode (ITO-) and cathode (A1-) contacts were brought in contact with gilded spring electrodes
Programmable voltage supply (SMU) and digital multimeter for recording and processing the OLED curve in a PC via GPIB-BUS and LabView program
Voltage pulse operation (pulses lasting 1 s) between −10 V and +15 V (0.5 V increments): current density-voltage curve and luminance (emission intensity)-voltage curve as well as the calculated photometric efficiency values (in cd/A) and performance efficiency values (in 1 m/W) as a function of U
d) Wavelength of maximum by recording the electroluminescence spectrum using an Xdap diode array spectrometer

## Claims

1. A 2,5-diaminoterephthalic acid derivative of formula 19,



wherein X1 and X3 are O, X2 and X4, which can be the same or different, are O or N; R2 and R6 are methylene (—CH2—), which can be substituted with trifluoromethyl, R3 and R7 are the same or different, H, C1–C8 alkyl, aryl, or heteroaryl, and R4 and R8 are the same or different, H, alkyl, aryl or trifluoromethyl, and R1 and R5, which can be the same or different and are H, C1–C4 alkyl or phenyl with the proviso that R1 is absent if X2 is O and R5 is absent if X4 is O.

2. The derivative of claim 1, wherein alkyl is C1–C4 alkyl, aryl is phenyl or naphthyl, and heteroaryl is pyridyl, thienyl or furyl.

3. The derivative of claim 1, wherein alkyl is C1–C8 alkyl, aryl is phenyl or naphthyl, and heteroaryl is cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl or oxazolyl.

4. The derivative of claim 1, wherein R4 and R8 are trifluoromethyl, 2-fluorophenyl, 3-fluorophenyl, 4-flurophenyl, 2,4,-difluorophenyl, 2,6-difluorophenyl, 2,3,4,5-tetrafluorophenyl or pentafluorophenyl.

5. The derivitive of claim 1, wherein R4 and R8 are the same or different and are hydrogen, C1–C8 alkyl or phenyl.

6. The derivative of claim 1, wherein R4 and R8 are the same or different and are hydrogen, C1–C4 alkyl or phenyl.

7. The derivative of claim 6, wherein R1 and R8 are H.

8. The derivative of claim 1, wherein R1 and R5 are C1–C4 alkyl or phenyl, and X2 and X4 are nitrogen.

9. The derivative of claim 1, wherein X2 is N.

10. The derivative of claim 1, wherein X2 is O.

11. The derivative of claim 1, wherein R3 and R7 are 2-fluorophenyl, 3-fluorophenyl, 4-flurophenyl, 2,4,-difluorophenyl, 2,6-difluorophenyl, 2,3,4,5-tetrafluorophenyl or pentafluorophenyl.

12. The derivative of claim 1, wherein R3 and R7 are the same or different and are substituted or unsubstituted phenyl, said substituted phenyl being substituted singly or multiply with halogen, CN, C1–C4 alkyl, C1–C4 alkoxy, amino or phenyl.

13. The derivative of claim 12, wherein R3 and R7 are N,N-dimethyl-4-aminophenyl, and R4 and R8 are H.

14. The derivative of claim 12, wherein X2 and X4 are O, R3 and R7 are 4-cyanophenyl, and R4 and R8 are H.

15. The derivative of claim 1, wherein R3 and R7 are the same or different and are substituted or unsubstituted phenyl, said substituted phenyl being substituted singly or multiply with fluoro, chloro, CN, methyl, methoxy, trifluoromethyl, or phenyl.

16. The derivative of claim 1, wherein X2 and X4 are O, R3 and R7 are phenyl, and R4 and R8 are H.

17. The derivative of claim 1, wherein X2 and X4 are O, and R4 and R8 are H.

18. The derivative of claim 17, wherein R3 and R7 are substituted or unsubstituted α-naphthyl.

19. The derivative of claim 17, wherein R3 and R7 are substituted or unsubstituted β-naphthyl.

20. The derivative of claim 17, wherein R3 and R7 are substituted or unsubstituted phenyl.

21. The derivative of claim 20, wherein R3 and R7 are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with C1–C4 alkyl, C1–C4 alkoxy or a combination thereof.

22. The derivative of claim 21, wherein R3 and R7 are 2,4-dimethylphenyl.

23. The derivative of claim 1, wherein X2 and X4 are N.

24. The derivative of claim 23, wherein R1 and R5 are phenyl.

25. The derivative of claim 23, wherein R1 and R5 are C1–C 4 alkyl.

26. The derivative of claim 23, wherein R3 and R7 are substituted or unsubstituted α-naphthyl.

27. The derivative of claim 23, wherein R3 and R7 are substituted or unsubstituted β-naphthyl.

28. The derivative of claim 23, wherein R3 and R7 are substituted or unsubstituted phenyl.

29. The derivative of claim 28, wherein R3 and R7 are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with C1–C4 alkyl, C1–C4 alkoxy or a combination thereof.

30. The derivative of claim 28, wherein R3 and R7 are 2,4-dimethylphenyl.

31. The derivative of claim 28, wherein R3 and R7 are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with halogen, nitro, cyano, amino, C1–C8 alkyl or phenyl.

32. The derivative of claim 28, wherein R3 and R7 are the same or different and are substituted phenyl, said phenyl substituted singly or multiply with halogen, C1–C4 alkyl, trifluoromethyl, C1–C4 alkoxy or a combination thereof.

33. The derivative of claim 1, wherein R3 and R7 are the same or different and are C1–C4 alkyl, unsubstituted phenyl, or substituted phenyl.