# Patent

## Title
Charge-transfer material and process for producing the same, electron-transfer agent, photoreceptor for electrophotography and organic electroluminescence element using said charge-transfer material

## Abstract

A photosensitive layer contains an electron-transfer agent that makes use of a compound represented by the following general formula (1):




wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This is a divisional of U.S. Ser. No. 10/673,405 filed Sep. 30, 2003 now abandoned, which is a continuation of International Application No. PCT/JP02/02965 filed Mar. 27, 2002. The entire disclosure of the prior application is herein incorporated by reference in its entirety.


BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to a technical field involving the use of electron-transfer materials, and more particularly, to a novel electron-transfer compound as well as to a process for producing such a compound. The present invention further relates to an electron-transfer agent containing such a compound, and also, to an electrophotographic photoreceptor and an organic electroluminescence element containing such an agent.
2. Description of Related Art
Photocopiers, laser printers and other electrophotographic apparatuses are equipped with an electrophotographic photoreceptor. In the early days of development of photocopiers and laser printers, inorganic film was used in the photosensitive layer of the electrophotographic photoreceptors. Such inorganic film was formed of inorganic materials such as selenium, selenium-tellurium, selenium-arsenic and amorphous silicon.
As demand increases for inexpensive, environmentally less harmful electrophotographic photoreceptors, the photoreceptors incorporating organic film have become widely used and have replaced those with conventional photosensitive layers formed of inorganic film. The photosensitive layers formed of organic film are generally divided into two structurally different types: single-layered and multi-layered.
The single-layered photosensitive layer comprises a single layer of charge-transfer medium in which a charge-generation material has been dispersed. The single layer serves both to generate electrical charge and to transport charge. In comparison, the multi-layered photosensitive layer is formed as a multi-layered film comprising a charge-generation layer (CGL) and a charge-transfer layer (CTL) that are laminated on top of one another. The two layers have different functions with the charge-generation layer generating electrical charge and the charge-transfer layer transferring the generated charge.
While both types of the photosensitive layers are in use today, each requires a charge-transfer material with a high mobility in order to increase sensitivity.
The organic photosensitive layers are also divided into two different types, namely, positive charge photosensitive layers and negative charge photosensitive layers, based on the polarity they can be charged as well. Most of the known charge-transfer materials that have high mobility and are in practical use today are hole-drift type charge-transfer materials. Accordingly, the photoreceptors used in commercial electrophotographic products employ a negative charge photosensitive layer.
When these photosensitive layers are negatively charged by means of corona discharge phenomena, significant amounts of ozone are produced, causing many problems such as pollution of indoor environments and accelerated deterioration of the electrophotographic photoreceptor.
In order to avoid these problems occurring during the negative charging process, conventional electrophotographic apparatuses employ ozone filters or a special ozone-free charging technique. These approaches, however, bring about new problems, such as resulting in an undesirably large construction of the apparatus or complex electrophotography process. Further, none of these approaches has ever provided a practical solution.
As a result, the positive charge photoreceptors, which produce little ozone, are demanded in the marketplace as an effective countermeasure to the above-described problems, and to this end, a highly mobile electron-transfer material must be developed that can be used in the positive charge photosensitive layer.
Negative charge photoreceptors are better suited for use in color printers because of available toners. Also, by constructing the photosensitive layer as a single layer in a negative charge photoreceptor, the time required for the coating process, and thus the production cost, can be reduced. Constructing such a photosensitive layer, however, requires an electron-transfer material with even higher mobility, and no material has ever been found to have a sufficiently high electron mobility to provide such characteristics.
Therefore, a highly mobile electron-transfer material is as important in the negative charge photoreceptor as it is in the positive charge photoreceptor. Much effort has been made to find such material. The electron-transfer materials for use in the positive charge photoreceptor that are known to date include trinitrofluorenon (TNF), tetracyanoethylene, tetracyanoquinodimethane (TCNQ), quinone, diphenoquinone, naphthoquinone, anthraquinone, and derivatives thereof. Most of these electron-transfer materials, however, have a poor compatibility with binder resins so that it is difficult to uniformly disperse these materials in a photosensitive layer at a high concentration. Thus, the amount of the electron-transfer material contained in the photosensitive layer tends to be too small to provide sufficient electrical characteristics.
Unlike other electron-transfer materials, diphenoquinone compounds are known to have an exceptionally high compatibility with resins as well as a high electron mobility. On the other hand, diphenoquinone compounds tend to exhibit a strong color due to the long conjugated system within the molecule, and when used to form a photosensitive layer, diphenoquinone compounds absorb light that would otherwise reach the charge-generation material. As a result, the sensitivity of the photosensitive layer is decreased. Further, these compounds generate electrically stable radicals due to the symmetrical structure of their molecule skeletons. The radicals form electrical traps to hinder movement of electrons in a low electric field. Not only does this result in a reduced luminescence efficiency, and thus a reduced brightness of organic electroluminescence elements, but it also results in a high residual potential in the photosensitive layer of the photoreceptor.
One example of the electron-transfer material that has overcome the problem of reduced electron mobility in low electric fields is a compound described in Japanese Patent Laid-Open Publication No. Hei 9-34141, which has the structure shown by the following chemical formula 24:




The compound has a conjugated system involving three double bonds between an oxygen atom and a dicyanomethylene group within its molecular skeleton. Because of this relatively short conjugated system, the compound is capable of coloring only faintly and is thus less likely to absorb light.

Also, the dicyanomethylene group attached to one end of the quinone structure serves to keep the lives of the radicals produced during the movement of electrons short. As a result, the radicals are less likely to form traps even in a low electric field. However, movement of electrons is more restricted in this compound than in diphenoquinone compounds since its short conjugated system permits electrons to move within the molecule only over relatively short distances.
In practice, electrophotographic photoreceptors using the above compound are less than satisfactory when compared to the commercially available negative charge electrophotographic photoreceptors in terms of sensitivity and residual potential.
It is thus necessary for a practically useful electron-transfer material to meet two contradictory requirements: it must have a reduced ability to color and it must ensure a large degree of electron movement within the molecule. The former requirement is met by a short conjugated system in the chemical structure, whereas the latter is met by a long conjugated system provided by a larger molecular skeleton. A strong demand exists for a molecular structure that, aside from meeting these requirements, does not produce stable radicals.
SUMMARY OF THE INVENTION
The present invention has been devised to address the above-identified problems associated with the conventional art. It is thus an objective of the present invention to provide a novel useful electron-transfer material that can be dispersed in a photosensitive layer at a high concentration and has a high electron mobility. It is also an objective of the present invention to provide an electrophotographic photoreceptor with an improved sensitivity and residual potential, as well as to provide an organic electroluminescence element with a high luminescence efficiency.
In the search for a way to solve the above-described problems, the present inventors have found that a compound can be provided that has a novel molecular skeleton in which a quinone ring is connected via a double bond to a ring structure having an active methylene, as well as a production process of such a compound, a novel electron-transfer material, and an electrophotographic photoreceptor and an organic electroluminescence element containing such an electron-transfer material. The discovery ultimately led the present inventors to bring the present invention to completion.
Having been devised based on the above-described findings, the present invention provides a compound represented by the following general formula (1):




wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (1′) that replaces the general formula (1) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.




BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an IR spectrum of a compound represented by the chemical formula (7).
FIG. 2 is a 1H-NMR spectrum of the compound represented by the chemical formula (7).
FIG. 3 is an IR spectrum of a compound represented by the chemical formula (8).
FIG. 4 is a 1H-NMR spectrum of the compound represented by the chemical formula (8).
FIG. 5 is an IR spectrum of a compound represented by the chemical formula (9).
FIG. 6 is a 1H-NMR spectrum of the compound represented by the chemical formula (9).
FIG. 7 is an IR spectrum of a compound represented by the chemical formula (10).
FIG. 8 is a 1H-NMR spectrum of the compound represented by the chemical formula (10).
FIG. 9 is an IR spectrum of a compound represented by the chemical formula (11).
FIG. 10 is a 1H-NMR spectrum of the compound represented by the chemical formula (11).
FIG. 11 is an IR spectrum of a compound represented by the chemical formula (12).
FIG. 12 is a 1H-NMR spectrum of the compound represented by the chemical formula (12).
FIG. 13 is an IR spectrum of a compound represented by the chemical formula (13).
FIG. 14 is a 1H-NMR spectrum of the compound represented by the chemical formula (13).
FIG. 15 is an IR spectrum of a compound represented by the chemical formula (14).
FIG. 16 is a 1H-NMR spectrum of the compound represented by the chemical formula (14).
FIG. 17 is an IR spectrum of a compound represented by the chemical formula (15).
FIG. 18 is a 1H-NMR spectrum of the compound represented by the chemical formula (15).
FIG. 19 is an IR spectrum of a compound represented by the chemical formula (16).
FIG. 20 is a 1H-NMR spectrum of the compound represented by the chemical formula (16).
FIG. 21 is a cross-sectional view showing one example of a multi-layered electrophotographic photoreceptor.
FIG. 22 is a cross-sectional view showing one example of a single-layered electrophotographic photoreceptor.
FIG. 23 is a cross-sectional view showing one example of an organic electroluminescence element.
FIG. 24 is an IR spectrum of a compound represented by the chemical formula (29).
FIG. 25 is a 1H-NMR spectrum of the compound represented by the chemical formula (29).
FIG. 26 is an IR spectrum of a compound represented by the chemical formula (30).
FIG. 27 is a 1H-NMR spectrum of the compound represented by the chemical formula (30).
FIG. 28 is an IR spectrum of a compound represented by the chemical formula (31).
FIG. 29 is a 1H-NMR spectrum of the compound represented by the chemical formula (31).
FIG. 30 is an IR spectrum of a compound represented by the chemical formula (32).
FIG. 31 is a 1H-NMR spectrum of the compound represented by the chemical formula (32).
FIG. 32 is an IR spectrum of a compound represented by the chemical formula (33).
FIG. 33 is a 1H-NMR spectrum of the compound represented by the chemical formula (33).
FIG. 34 is an IR spectrum of a compound represented by the chemical formula (34).
FIG. 35 is a 1H-NMR spectrum of the compound represented by the chemical formula (34).
FIG. 36 is an IR spectrum of a compound represented by the chemical formula (35).
FIG. 37 is a 1H-NMR spectrum of the compound represented by the chemical formula (35).
FIG. 38 is an IR spectrum of a compound represented by the chemical formula (36).
FIG. 39 is a 1H-NMR spectrum of the compound represented by the chemical formula (36).
FIG. 40 is an IR spectrum of a compound represented by the chemical formula (37).
FIG. 41 is a 1H-NMR spectrum of the compound represented by the chemical formula (37).
FIG. 42 is an IR spectrum of a compound represented by the chemical formula (38).
FIG. 43 is a 1H-NMR spectrum of the compound represented by the chemical formula (38).
FIG. 44 is an IR spectrum of a compound represented by the chemical formula (39).
FIG. 45 is a 1H-NMR spectrum of the compound represented by the chemical formula (39).
FIG. 46 is an IR spectrum of a compound represented by the chemical formula (40).
FIG. 47 is a 1H-NMR spectrum of the compound represented by the chemical formula (40).
FIG. 48 is an IR spectrum of a compound represented by the chemical formula (41).
FIG. 49 is a 1H-NMR spectrum of the compound represented by the chemical formula (41).
FIG. 50 is an IR spectrum of a compound represented by the chemical formula (42).
FIG. 51 is a 1H-NMR spectrum of the compound represented by the chemical formula (42).
FIG. 52 is an IR spectrum of a compound represented by the chemical formula (43).
FIG. 53 is a 1H-NMR spectrum of the compound represented by the chemical formula (43).
FIG. 54 is an IR spectrum of a compound represented by the chemical formula (45).
FIG. 55 is a 1H-NMR spectrum of the compound represented by the chemical formula (45).
FIG. 56 is an IR spectrum of a compound represented by the chemical formula (46).
FIG. 57 is a 1H-NMR spectrum of the compound represented by the chemical formula (46).
FIG. 58 is an IR spectrum of a compound represented by the chemical formula (47).
FIG. 59 is a 1H-NMR spectrum of the compound represented by the chemical formula (47).
FIG. 60 is an IR spectrum of a compound represented by the chemical formula (48).
FIG. 61 is a 1H-NMR spectrum of the compound represented by the chemical formula (48).
FIG. 62 is an IR spectrum of a compound represented by the chemical formula (49).
FIG. 63 is a 1H-NMR spectrum of the compound represented by the chemical formula (49).
FIG. 64 is an IR spectrum of a compound represented by the chemical formula (50).
FIG. 65 is a 1H-NMR spectrum of the compound represented by the chemical formula (50).
FIG. 66 is an IR spectrum of a compound represented by the chemical formula (51).
FIG. 67 is a 1H-NMR spectrum of the compound represented by the chemical formula (51).
FIG. 68 is an IR spectrum of a compound represented by the chemical formula (52).
FIG. 69 is a 1H-NMR spectrum of the compound represented by the chemical formula (52).
FIG. 70 is an IR spectrum of a compound represented by the chemical formula (53).
FIG. 71 is a 1H-NMR spectrum of the compound represented by the chemical formula (53).
FIG. 72 is an IR spectrum of a compound represented by the chemical formula (54).
FIG. 73 is a 1H-NMR spectrum of the compound represented by the chemical formula (54).
FIG. 74 is an IR spectrum of a compound represented by the chemical formula (55).
FIG. 75 is a 1H-NMR spectrum of the compound represented by the chemical formula (55).
FIG. 76 is an IR spectrum of a compound represented by the chemical formula (56).
FIG. 77 is a 1H-NMR spectrum of the compound represented by the chemical formula (56).
FIG. 78 is an IR spectrum of a compound represented by the chemical formula (57).
FIG. 79 is a 1H-NMR spectrum of the compound represented by the chemical formula (57).
FIG. 80 is an IR spectrum of a compound represented by the chemical formula (58).
FIG. 81 is a 1H-NMR spectrum of the compound represented by the chemical formula (58).
FIG. 82 is an IR spectrum of a compound represented by the chemical formula (59).
FIG. 83 is a 1H-NMR spectrum of the compound represented by the chemical formula (59).
FIG. 84 is an IR spectrum of a compound represented by the chemical formula (60).
FIG. 85 is a 1H-NMR spectrum of the compound represented by the chemical formula (60).



Throughout the figures, the reference numeral 1 denotes an electroconductive substrate; the reference numeral 2 denotes a charge-generation layer; the reference numeral 3 denotes a charge-transfer layer; the reference numeral 4 denotes a photosensitive layer; the reference numerals 11 and 12 each denote an electrophotographic photoreceptor; the reference numeral 21 denotes an organic electroluminescence element; the reference numeral 22 denotes a first electrode; the reference numeral 25 denotes a luminescent layer; and the reference numeral 26 denotes a second electrode.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The ring structure represented by W exhibits strong acidity and thus strong electron acceptability. Given this, the present inventors have designed a novel molecular skeleton in which the ring represented by W is connected via a double bond to a quinone ring, which is generally known to exhibit a strong electron acceptability. The dipole moment of this molecular skeleton must be large enough so that the generation of stable radicals, as in the case of diphenoquinone, is prevented.
The dipole moment of the molecular skeleton can readily be calculated by the molecular orbital method to be compared. Specifically, the molecular skeleton has a dipole moment (debye) of 0.001 or larger, preferably 0.01 or larger, and more preferably 0.1 or larger as determined by MOPAC/AM1 using the molecular skeleton bearing no substituents. In this manner, the resulting radicals have relatively short lives and are thus less likely to form electric traps. As a result, electron transfer can take place even in a low electric field, and the electron mobility is significantly enhanced in a strong electric field, as is the efficiency of electron movement.
The two interconnected ring structures, namely, the 6-membered ring and the ring represented by W, make the molecular skeleton of the above-described compound larger than that of the compound of the formula (24). This ensures a larger distance along which electrons can travel and thus facilitates movement of electrons within the molecule. As a result, the compound exhibits a high electron mobility.
In contrast to diphenoquinone compounds, asymmetric configuration of its conjugated system ensures the above compound's weak ability to exhibit color, so that it hardly absorbs light. Furthermore, the ring represented by W attached to one end of the quinone ring makes its molecular structure asymmetric. This facilitates the compatibility of the compound with resin, so that it can be dispersed in resin at a high concentration. These functions can readily be varied as desired by using different combinations of substituents. In this manner, it is possible to optimize the compatibility with resin or control the speed or the amount of electron movement.
In a preferred embodiment, the present invention provides a compound represented by the following general formula (2):




wherein R1 and R3 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (2′) that replaces the general formula (2) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

Introduction of at least one alkyl group having 1 to 6 carbon atoms or at least one phenyl group into the substituents R1 and R3 can provide the molecular skeleton with the effect to push out electrons. In this manner, the polarization of the molecule, and thus the electron mobility within the molecule, is increased. The substituents that exhibit high compatibility with resin may be used in combination.
In a particularly preferred embodiment, the present invention provides a compound represented by the following general formula (3):




wherein X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (3′) that replaces the general formula (3) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

Introduction of the bulky t-Bu group into the quinone ring can increase the compatibility with resin and provide the molecular skeleton with the effect to push out electrons. In this manner, the polarization of the molecule is increased and a compound with significantly increased electron mobility is obtained.
The present invention provides a compound represented by the following general formula (4):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur.

By introducing a phenyl, thienyl, or furil group, each being an aromatic 6 π electron system, into the substituent R5 in the general formula (4) above, the molecular skeleton can be stabilized.
The present invention provides a compound represented by the following general formula (5):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur.

The present invention provides a compound represented by the following general formula (6):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur.

The present invention provides a compound represented by the following general formula (44):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur.

The present invention provides a compound represented by the following chemical formula (7):




The present invention provides a compound represented by the following chemical formula (8):




The present invention provides a compound represented by the following chemical formula (9):




The present invention provides a compound represented by the following chemical formula (10):




The present invention provides a compound represented by the following chemical formula (11):




The present invention provides a compound represented by the following chemical formula (12):




The present invention provides a compound represented by the following chemical formula (13):




The present invention provides a compound represented by the following chemical formula (14):




The present invention provides a compound represented by the following chemical formula (15):




The present invention provides a compound represented by the following chemical formula (16):




The present invention provides a compound represented by the following chemical formula (29):




The present invention provides a compound represented by the following chemical formula (30):




The present invention provides a compound represented by the following chemical formula (31):




The present invention provides a compound represented by the following chemical formula (32):




The present invention provides a compound represented by the following chemical formula (33):




The present invention provides a compound represented by the following chemical formula (34):




The present invention provides a compound represented by the following chemical formula (35):




The present invention provides a compound represented by the following chemical formula (36):




The present invention provides a compound represented by the following chemical formula (37):




The present invention provides a compound represented by the following chemical formula (38):




The present invention provides a compound represented by the following chemical formula (39):




The present invention provides a compound represented by the following chemical formula (40):




The present invention provides a compound represented by the following chemical formula (41):




The present invention provides a compound represented by the following chemical formula (42):




The present invention provides a compound represented by the following chemical formula (43):




The present invention provides a compound represented by the following chemical formula (45):




The present invention provides a compound represented by the following chemical formula (46):




The present invention provides a compound represented by the following chemical formula (47):




The present invention provides a compound represented by the following chemical formula (48):




The present invention provides a compound represented by the following chemical formula (49):




The present invention provides a compound represented by the following chemical formula (50):




The present invention provides a compound represented by the following chemical formula (51):




The present invention provides a compound represented by the following chemical formula (52):




The present invention provides a compound represented by the following chemical formula (53):




The present invention provides a compound represented by the following chemical formula (54):




The present invention provides a compound represented by the following chemical formula (55):




The present invention provides a compound represented by the following chemical formula (56):




The present invention provides a compound represented by the following chemical formula (57):




The present invention provides a compound represented by the following chemical formula (58):




The present invention provides a compound represented by the following chemical formula (59):




The present invention provides a compound represented by the following chemical formula (60):




In each of the chemical formulae (7) through (16), (29) through (43), and (45) through (60), t-Bu represents a tertiary butyl group ((CH3)3C—), n-Bu represents a straight-chained butyl group (CH3CH2CH2CH2—), Me represents a methyl group (CH3—), n-Pr represents a straight chained propyl group (CH3CH2CH2—), and i-Pr represents an isopropyl group ((CH3)2CH—).
The present invention provides a process for producing a compound represented by the following general formula (1):




wherein R1 to R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (1′) that replaces the general formula (1) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring, the process involving the step of reacting in the presence of a base catalyst a benzoquinone compound represented by the following general formula (17):





wherein R1 to R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2, with a compound having an active methylene represented by the following general formula (18):





wherein the compound is a 4- to 8-membered ring; Y is oxygen or sulfur; and Z is a structure that has 2 or more atoms and forms a part of the ring. In this manner, the electron-transfer compound can be readily produced. A solvent which is inert against benzoquinone compound and the compound having an active methylene may be added along with the base catalyst to adjust the reaction rate.

The present invention provides a process for producing a compound represented by the following general formula (2):




wherein R1 and R3 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (2′) that replaces the general formula (2) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring, the process involving the step of reacting in the presence of a base catalyst a benzoquinone compound represented by the following general formula (19):





wherein R1 and R3 are each independently selected from the group consisting of hydrogen, alkyl with 1 to 6 carbon atoms, and phenyl; and

X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2, with a compound having an active methylene represented by the following general formula (18):





wherein the compound is a 4- to 8-membered ring; Y is oxygen or sulfur; and Z is a structure having 2 or more atoms and forms a part of the ring.

The present invention provides a process for producing a compound represented by the following general formula (3):




wherein X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (3′) that replaces the general formula (3) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms apart of the ring, the process involving the step of reacting in the presence of a base catalyst a benzoquinone compound represented by the following general formula (20):





wherein X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2, with a compound having an active methylene represented by the following general formula (18):





wherein the compound is a 4- to 8-membered ring; Y is oxygen or sulfur; and Z is a structure having 2 or more atoms and forms a part of the ring.

The present invention provides a process for producing a compound represented by the following general formula (4):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur, the process involving the step of reacting in the presence of a base catalyst a benzoquinone compound represented by the following general formula (17):





wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2, with a compound having an active methylene represented by the following general formula (21):





wherein R5 and R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and Y is oxygen or sulfur.

The present invention provides a process for producing a compound represented by the following general formula (5):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur, the process involving the step of reacting in the presence of a base catalyst a benzoquinone compound represented by the following general formula (17):





wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2, with a compound having an active methylene represented by the following general formula (22):





wherein R5 and R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and Y is oxygen or sulfur.

The present invention provides a process for producing a compound represented by the following general formula (6):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur, the process involving the step of reacting in the presence of a base catalyst a benzoquinone compound represented by the following general formula (17):





wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2, with a compound having an active methylene represented by the following general formula (23):





wherein R5 and R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur.

The present invention provides a process for producing a compound represented by the following general formula (44):




wherein R1 through R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur, the process involving the step of reacting in the presence of a base catalyst a benzoquinone compound represented by the following general formula (17):





wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2, with a compound having an active methylene represented by the following general formula (61):





wherein R5 and R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and Y is oxygen or sulfur.

The present invention provides a process for producing a compound in which the benzoquinone compound is reacted with the compound having an active methylene in the presence of the base catalyst and one or a mixture of two or more solvents selected from the group consisting of water, alcohol, and saturated aliphatic hydrocarbon solvent.
The present invention provides a process for producing a compound in which the benzoquinone compound is reacted with the compound having an active methylene in the presence of the base catalyst and a solvent that needs to be used in amounts of 50 ml or more to dissolve 1 g of the compound of the general formulae (1) through (6) and (44).
The present invention provides an electron-transfer agent comprising a resin containing as a charge-transfer material a compound represented by the following general formula (1):




wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (1′) that replaces the general formula (1) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

The present invention provides an electron-transfer agent comprising a resin containing as a charge-transfer material a compound represented by the following general formula (2):




wherein R1 and R3 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring having the structure shown in the following general formula (2′) that replaces the general formula (2) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

The present invention provides an electron-transfer agent comprising a resin containing as a charge-transfer material a compound represented by the following general formula (3):




wherein X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (3′) that replaces the general formula (3) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

The present invention provides an electrophotographic photoreceptor comprising an electroconductive substrate having at least a photosensitive layer disposed thereon, wherein the photosensitive layer contains as a charge-transfer material a compound represented by the following general formula (1):




wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (1′) that replaces the general formula (1) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

As described above, the use of the compound, which has a high electron mobility and high compatibility with resin, makes it possible to provide highly sensitive electrophotographic photoreceptors.
The present invention provides an electrophotographic photoreceptor, comprising an electroconductive substrate having at least one photosensitive layer disposed thereon, wherein the photosensitive layer contains as a charge-transfer material a compound represented by the following general formula (2):




wherein R1 and R3 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (2′) that replaces the general formula (2) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

As described above, the use of the compound, which has a high electron mobility and high compatibility with resin, makes it possible to provide electrophotographic photoreceptors with even higher sensitivity.
The present invention provides an electrophotographic photoreceptor comprising an electroconductive substrate having at least a photosensitive layer disposed thereon, wherein the photosensitive layer contains as a charge-transfer material a compound represented by the following general formula (3):




wherein X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (3′) that is to replace the general formula (3) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

As described above, the use of the compound, which has a high electron mobility and high compatibility with resin, makes it possible to provide extremely sensitive electrophotographic photoreceptors.
The present invention provides an organic electroluminescence element including an organic film that can at least emit light and is disposed between a pair of electrodes, wherein the organic film contains a compound represented by the following general formula (1):




wherein R1 to R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (1′) that replaces the general formula (1) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

The present invention provides an organic electroluminescence element including an organic film that can at least emit light and is arranged between a pair of electrodes, wherein the organic film contains a compound represented by the following general formula (2):




wherein R1 and R3 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (2′) that replaces the general formula (2) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

The present invention provides an organic electroluminescence element including an organic film that can at least emit light and is arranged between a pair of electrodes, wherein the organic film contains a compound represented by the following general formula (3):




wherein X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (3′) that replaces the general formula (3) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

The substituent represented by W in the general formulae (1) through (3) above does not include those represented by the following general formula (28):




wherein R′ is selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid.

As described above, not only does the compound of the present invention exhibit a high electron mobility, but it also makes it possible to design a proper molecular structure depending on functions required for the material for an electrophotographic photoreceptor or organic electroluminescence element that makes use of electron-transfer materials.
In cases where the substituents R1 through R6 in the above general formulae (1) through (6) and (44) are each selected from alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid, these substituents may be modified by other substituents. The modified substituents are also encompassed by the scope of the present invention. Among the substituents R1 through R6, R1 and R2 may link together to form a ring, as may R3 and R4.
The substituents R1 through R6 may be different from one another, or two or more of the substituents R1 through R6 may be identical to one another.
The substituent W, a 4- to 8-membered cyclic compound shown in the general formulae (1) through (3), may condense with other cyclic compounds and may form a fused ring. These fused rings are also encompassed by the scope of the present invention. The present invention further encompasses the case where the structure Z includes one or more of heteroatoms, the case where the structure Z consists only of carbon atoms, and the case where the structure Z is modified by a substituent.
Preferred embodiments of electron-transfer compounds, processes for producing the electron-transfer compounds, and electron-transfer agents of the present invention, as well as application examples thereof, will now be described in detail with reference to Tables A through AC mentioned below.
1. Description of Compounds
An electron-transfer compound in accordance with the present invention has a novel molecular skeleton in which an active methylene group of a cyclic compound that bears the active methylene is attached to a quinone ring via a double bond. The structure of the compound is shown by the following general formula (1):




wherein R1 through R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and W is a 4- to 8-membered ring and has the structure shown in the following general formula (1′) that replaces the general formula (1) above:





wherein Y is oxygen or sulfur, and Z is a structure that has 2 or more atoms and forms a part of the ring.

While specific examples of the electron-transfer compound are described below, they are not intended to limit the scope of the invention in any way. Tables A(1) through A(18) list structures of the compounds shown by the general formulae (101) through (314), each having six substituents, R1 through R6, whereas Tables A(19) through A(26) list structures of the compounds shown by the general formulae (315) through (423), each having five substituents, R1 through R5.
Table B is a list showing substituents S1 through S23, which can be independently used as the substituents R1 through R6, or R1 through R5, in the general formulae (101) through (423).
Tables C(1) through C(6) each show possible combinations of the six substituents R1 through R6 for the compounds of the general formulae (101) through (314), whereas Tables C(7) through C(11) each show possible combinations of the five substituents R1 through R5 for the compounds of the general formulae (315) through (423).
2. Description of Production Process
A production process in accordance with the present invention involves reacting a benzoquinone compound with a compound having an active methylene in the presence of a base catalyst. The benzoquinone compound for use in the process of the present invention has the structure represented by the following general formula (17):




wherein R1 to R4 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2.

Preferably, R2 and R4 each are a hydrogen atom in the general formula (17), as shown by the following general formula (19):




wherein R1 and R3 are each independently selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, and phenyl; and X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2.

Preferably, R1 and R3 in the general formula (19) each are a t-Bu group, as shown by the following general formula (20):




wherein X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2.

The compound having an active methylene for use in the process of the present invention has the structure represented by the following general formula (18):




wherein the compound is a 4- to 8-membered ring; Y is oxygen or sulfur; and Z is a structure that has 2 or more atoms and forms a part of the ring. Preferably, the compound having an active methylene of the general formula (18) is a compound represented by the following general formula (21):





wherein R5 and R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and Y is oxygen or sulfur.

It is also preferred that the compound having an active methylene of the general formula (18) be a compound represented by the following general formula (22):




wherein R5 and R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; and Y is oxygen or sulfur.

It is also preferred that the compound having an active methylene of the general formula (18) be a compound represented by the following general formula (23):




wherein R5 and R6 are each independently selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl, aryl, heterocyclic ring, ester, alkoxy, aralkyl, allyl, amide, amino, acyl, alkenyl, alkynyl, carboxyl, carbonyl, and carboxylic acid; X is selected from the group consisting of oxygen, sulfur, and ═C(CN)2; and Y is oxygen or sulfur.

Examples of organic base catalysts that can serve as the base catalyst for use in the process of the present invention include primary amines, such as methylamine, ethylamine, propylamine, and butylamine; secondary amines, such as dimethylamine, diethylamine, methylethylamine, dipropylamine, and dibutylamine; tertiary amines, such as trimethylamine, dimethylethylamine, methyldiethylamine, dimethylpropylamine, triethylamine, methylethylpropylamine, diethylpropylamine, dipropylmethylamine, ethyldipropylamine, and tributylamine; cyclic amines, such as pyridine, 2,6-dimethylpyridine, quinoline, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5 -diazabicyclo[4.3.0]non-5-ene, and 1,4-diazabicyclo[2.2.2]octane; metal alkoxides, such as sodium methoxide, potassium methoxide, and butyl lithium; and metal amides, such as sodium amide and potassium amide.
Examples of inorganic base catalysts that can serve as the base catalyst for use in the present invention include basic gases such as ammonia, alkali metals such as sodium, potassium and lithium, metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, metal salts such as sodium carbonate and potassium carbonate. Among these bases, those having a base dissociation constant greater than that of pyridine are preferred since they can accelerate the reaction significantly. The base catalyst may be used as a mixture of two or more base catalysts.
The base catalyst may be used together with an inert solvent. Examples of the inert solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol and ethylene glycol, saturated aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and cycloheptane, aromatic hydrocarbons such as benzene, toluene and xylene, chloride-containing hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, ethers such as diethylether, diisopropylether, tetrahydrofuran (THF), dioxane and methoxyethanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate, and N-methylpyrrolidone. These inert solvents may be used independently or as a mixture of two or more solvents.
While the reaction may proceed at low temperatures depending on the type of the base catalyst used, it is preferably carried out at room temperature or above to reduce the reaction time. The reaction system may be heated or cooled depending on the conditions of the reaction. While it depends on the type of the materials used, the reaction may require stirring so that it can take place, or in some cases the reaction may proceed by simply allowing the mixture of the materials to stand still.
3. Description of Electron-Transfer Agent
An electron-transfer agent of the present invention comprises a resin and the electron-transfer compound. Examples of the resin for use in the electron-transfer agent include polycarbonate resin, styrene resin, acrylic resin, styrene-acrylic resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin, chlorinated polyether, vinyl chloride-vinyl acetate resin, polyester resin, nylon resin, vinyl acetate resin, furan resin, nitrile resin, alkyd resin, polyacetal resin, polymethylpentene resin, polyamide resin, polyurethane resin, epoxy resin, polyarylate resin, diarylate resin, polysulfone resin, polyethersulfone resin, polyarylsulfone resin, silicone resin, ketone resin, polyvinylbutyral resin, polyether resin, phenol resin, EVA (ethylene-vinyl acetate copolymer) resin, ACS (acrylonitrile-chlorinated polyethylene-styrene)resin, ABS (acrylonitrile-butadiene-styrene) resin, polyimide resin and epoxyarylate.
These resins may be used independently, as a copolymer of these resins or as a mixture of two or more resins.
Preferably, the resins with different molecular weights may be mixed together in order to enhance the hardness and wear-resistance.
The electron-transfer agent of the present invention contains the resin and the compound of the general formula (1), and the compound is dispersed in the resin.
When the preferred compound of the general formula (2) is used, it enhances the electron mobility, whereas when the particularly preferred compound of the general formula (3) is used, it enhances the electron mobility and the compatibility with the resin. In addition, these electron-transfer agents may be used as high-performance materials in various applications, including electrophotographic photoreceptors, electroconductive agents, charge-controlling agents, EL elements, photoelectric conversion elements, sensitizing agents for photochemical reactions, and high electroconductivity materials using charge-transfer complexes.
4. Description of Application Examples
a. Description of Electrophotographic Photoreceptor
An electrophotographic photoreceptor of the present invention includes an electroconductive substrate and a photosensitive layer disposed thereon. The photosensitive layer contains the electron-transfer compound as a charge-transfer material.
An exemplary electrophotographic photoreceptor of the present invention is denoted by reference numeral 11 in FIG. 21 and by reference numeral 12 in FIG. 22. The electrophotographic photoreceptor 11 is of a multi-layered type, whereas the electrophotographic photoreceptor 12 is of a single-layered type. The electrophotographic photoreceptors 11 and 12 each show one embodiment in which organic film containing the compound of the present invention is used in a photosensitive layer.
Referring to FIG. 21, the electrophotographic photoreceptor 11 includes a cylindrical electroconductive substrate 1. A charge-generation layer 2 and a charge-transfer layer 3 are disposed on the electroconductive substrate 1 in this order. The charge-generation layer 2 and the charge-transfer layer 3 together form a photosensitive layer 4.
The charge-generation layer 2 as shown in FIG. 21 includes at least a charge-generation material and may be formed by depositing the charge-generation material, by making use of a binder resin, on the electroconductive substrate 1 as a foundation.
Although the charge-generation layer 2 may be formed by using various methods, including conventional methods, it is preferably formed by dispersing or dissolving, along with the binder resin, the charge-generation material into a proper solvent so as to make a coating solution, coating the electroconductive substrate 1, which serves as a foundation, with the coating solution, and then drying the coating. Alternatively, the charge-generation layer 2 may be formed by vacuum-depositing the charge-generation material on the substrate.
The charge-transfer layer 3 includes at least a charge-transfer material, which will be described later, and may be formed by, for example, depositing the charge-transfer material, by making use of a binder resin, on the charge-generation layer 2 as the foundation for the charge-transfer layer 3. Although the charge-transfer layer 3 may be formed by using various methods, including conventional methods, it is typically formed by dispersing or dissolving, along with the binder resin, the charge-transfer material into a proper solvent so as to make a coating solution, coating the charge-generation layer 2, which serves as a foundation, with the coating solution, and then drying the coating.
Referring now to FIG. 22, one example of the single-layered electrophotographic photoreceptor is denoted by reference numeral 12. With the same numerals assigned to the same components as those in the electrophotographic photoreceptor 11 of the first example, the electrophotographic photoreceptor 12 includes a single-layered photosensitive layer 4 formed on the electroconductive substrate 1. The photosensitive layer 4 contains the charge-generation material and the charge-transfer material.
Although the photosensitive layer 4 may be formed by using various methods, including conventional methods, it is preferably formed by dispersing or dissolving, along with the binder resin, the charge-generation material into a proper solvent and then dissolving the charge-transfer material so as to make a coating solution, coating the electroconductive substrate 1, which serves as a foundation, with the coating solution, and then drying the coating. The charge-generation material and the charge-transfer material will be described later.
The electroconductive substrate 1 for use in the present invention may be formed of various electroconductive materials and may be of any material and shape. For example, it may be a metal article of a metal or an alloy of metals, including aluminum, magnesium, brass, stainless steel, nickel, chromium, titanium, gold, silver, copper, tin, platinum, molybdenum and indium; it may be a plastic plate or film with an electroconductive material, such as the aforementioned metal or carbon, vapor-deposited or plated thereon to impart conductivity; or it may be an electroconductive glass plate coated with tin oxide, indium oxide, aluminum iodide or copper iodide.
Cylindrical aluminum tubes are commonly used, and may or may not be surface-treated by aluminum-anodizing. A resin layer may be deposited on the surface of the aluminum tube, or on the anodized aluminum layer in the case of the surface-treated tube.
The resin layer is provided for the purposes of enhancing adhesion, serving as a barrier to prevent electric current from flowing from the substrate, and covering surface defects of the substrate. Various types of resin can be used in the resin layer, including polyethylene resin, acrylic resin, epoxy resin, polycarbonate resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, polyvinylbutyral resin, polyamide resin and nylon resin.
The resin layer may be formed solely of a single resin, or it may be formed of a mixture of two or more resins or in conjunction with the aluminum-anodizing treatment. Further, metal compounds, metal oxides, carbon, silica, resin powder and other materials may be dispersed in the resin layer. In addition, various pigments, electron acceptors and electron donors may be added in order to improve characteristics of the resin layer.
Examples of the charge-generation material for use in the present invention include selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, phthalocyanine pigments, monoazo pigments, trisazo pigments, polyazo pigments, indigo pigments, toluidine pigments, pyrazoline pigments, perylene pigments, quinacridone pigments and pyrylium salts. Among these, disazo pigments and phthalocyanine pigments are particularly preferred in order to obtain a high sensitivity because they are highly compatible with the compound of the present invention.
Of the phthalocyanine pigments, particularly preferred are oxytitanium phthalocyanine, copper phthalocyanine, metal-free phthalocyanine, hydroxygallium phthalocyanine, and diol adducts of oxytitanium phthalocyanine, each of which shows high absorption at longer wavelengths. These charge-generation materials may be used independently or as a mixture of two or more materials in order to obtain optimum wavelengths at which the photosensitivity peaks or has increased sensitivity.
Examples of the binder resins that can be used to form the photosensitive layer 4 include polycarbonate resin, styrene resin, acrylic resin, styrene-acrylic resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin, chlorinated polyether, vinyl chloride-vinyl acetate resin, polyester resin, nylon resin, vinyl acetate resin, furan resin, nitrile resin, alkyd resin, polyacetal resin, polymethylpentene resin, polyamide resin, polyurethane resin, epoxy resin, polyarylate resin, diarylate resin, polysulfone resin, polyethersulfone resin, polyarylsulfone resin, silicone resin, ketone resin, polyvinylbutyral resin, polyether resin, phenol resin, EVA (ethylene-vinyl acetate copolymer) resin, ACS (acrylonitrile-chlorinated polyethylene-styrene)resin, ABS (acrylonitrile-butadiene-styrene) resin, polyimide resin and epoxy arylate.
These resins may be used independently or as a mixture or a copolymer of two or more resins. Preferably, the resins with different molecular weights may be mixed together in order to enhance the hardness and wear-resistance. The binder resin can be used in each of the charge-generation layer 2 and the charge-transfer layer 3 in the multi-layered photoreceptor shown in FIG. 21.
Examples of the solvent for use in the coating solution include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, aromatic hydrocarbons such as toluene and xylene, chloride-containing hydrocarbons such as dichloromethane, dichloroethane, chloroform, and chlorobenzene, ethers such as dimethylether, diethylether, tetrahydrofuran (THF) and methoxyethanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate, N,N-dimethylformamide and dimethylsulfoxide. These solvents may be used independently or as a mixture of two or more solvents.
In the electrophotographic photoreceptor of the present invention, the photosensitive layer 4 contains as a charge-transfer material the compound of the general formula (1). The compound is preferable since it has a high electron mobility, has reduced ability to exhibit colors and can be dispersed in the photosensitive layer at a high concentration. When the preferred compound of the general formula (2) is used, it enhances the electron mobility, whereas when the particularly preferred compound of the general formula (3) is used, it also enhances the compatibility with the resin.
Other charge-transfer materials may also be added to the electrophotographic photoreceptor of the present invention. In such a case, the sensitivity is increased and the residual potential is decreased, with the result that characteristics of the electrophotographic photoreceptor of the present invention are improved.
An electroconductive high molecular compound as a charge-transfer material may be added to the electrophotographic photoreceptor for the purpose of improving the characteristics of the photoreceptor. Examples of the electroconductive polymer include polyvinylcarbazole, halogenated polyvinylcarbazole, polyvinylpyrene, polyvinylindoloquinoxaline, polyvinylbenzothiophene, polyvinylanthracene, polyvinylacridine, polyvinylpyrazoline, polyacetylene, polythiophene, polypyrrole, polyphenylene, polyphenylene vinylene, polyisothianaphtene, polyaniline, polydiacetylene, polyheptadiene, polypyridinediyl, polyquinoline, polyphenylenesulfide, polyferrocenylene, polyperinaphthylene, and polyphthalocyanine.
Low molecular compounds may also be used for this purpose, including trinitrofluorenon, tetracyanoethylene, tetracyanoquinodimethane, quinone, diphenoquinone, naphthoquinone, anthraquinone and derivatives thereof, polycyclic aromatic compounds such as anthracene, pyrene and phenanthrene, nitrogen-containing heterocyclic compounds such as indole, carbazole and imidazole, fluorenone, fluorene, oxadiazole, oxazole, pyrazoline, hydrazone, triphenylmethane, triphenylamine, enamine, stilbene and butadiene compounds.
Also used are polymeric solid electrolytes obtained by doping polymers, such as polyethyleneoxide, polypropyleneoxide, polyacrylonitrile, poly methacrylic acid, with metal ions such as Li ions. Further, an organic electron-transfer complex may also be used that consists of an electron donor compound and an electron acceptor compound as represented by tetrathiafulvalene-tetracyanoquinodimethane. These compounds may be added independently or as a mixture of two or more compounds to obtain desired photosensitive characteristics.
In order to improve photosensitive characteristics, durability or mechanical properties of the photoreceptor of the present invention, antioxidants, UV-absorbing agents, radical scavengers, softeners, hardeners or cross-linking agents may be added to the coating solution for producing the photoreceptor of the present invention, provided that these agents do not affect the characteristics of the electrophotographic photoreceptor.
The finished appearance of the photoreceptor and the life of the coating solution are improved by further adding dispersion stabilizers, anti-settling agents, anti-flooding agents, leveling agents, anti-foaming agents, thickeners and flatting agents.
In addition, a surface-protection layer may be provided on the photosensitive layer 4. The surface-protection layer may be organic film formed of epoxy resin, melamine resin, polyvinylformal resin, polycarbonate resin, fluororesin, polyurethane resin or silicone resin, or it may be film formed of siloxane structure resulting from hydrolysis of silane coupling agents. In this manner, the durability of the photoreceptor is enhanced. The surface-protection layer may serve to improve functions other than the durability.
b. Description of Organic Electroluminescence Elements
An organic electroluminescence element of the present invention includes a pair of electrodes and a layer disposed between the electrodes, and containing at least one luminescent substance. The electroluminescence element contains the compound represented by the general formula (1) as a compound to impart the electron mobility.
An organic electroluminescence element is an element in which a single layer or multiple layers of organic film (luminescent layer) are disposed between a pair of electrodes.
Referring to FIG. 23, an exemplary organic electroluminescence element is denoted by reference numeral 21. The organic electroluminescence element 21 includes a glass substrate 23, a first electrode (ITO electrode) 22 formed of indium-tin oxide (ITO) and deposited on one surface of the glass substrate 23, a luminescent layer 25 closely arranged on one surface of the first electrode 22, and a second electrode 26 closely arranged on a surface of the luminescent layer 25 that is opposite the first electrode 22.
The luminescent layer 25 contains a luminescent material and may further contain a hole-transfer material for transporting holes injected from the anode (the first electrode 22) to the luminescent material or an electron-transfer material for transporting electrons moving from the cathode (the second electrode 26) to the luminescent material. The luminescent material may have the ability to move holes or electrons.
When the luminescent layer has a multi-layered structure, the organic electroluminescence element may include a luminescent layer, an electron-transfer layer, and a hole-transfer layer that are laminated on top of one another between the pair of electrodes.
The order of laminating the layers can be changed depending on the purpose of the element.
Examples of the luminescent material include anthracene, naphthalene, phenanthlene, pyrene, tetracene, coronene, chrysene, fluoresceine, perylene, phthaloperylene, naphthaloperylene, perynone, phthaloperynone, naphthaloperynone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldadine, bis-benzoxazoline, bis-styrile, pyrazine, cyclopentadiene, metal complexes of quinoline, metal complexes of aminoquinoline, metal complexes of benzoquinoline, imine, diphenylethylene, vinylanthracene, diaminocarbazole, triphenylamine, benzidine-type triphenylamine, styrileamine-type triphenylamine, diaamine-type triphenylaminepyran, thiopyran, polymethine, merocyanine, imidazole-chelated oxynoid compounds, metal complexes of porphyrin, phthalocyanine complexes, rare earth metal complexes, quinacridone, rubrene, and fluorescent dyes for use in dye laser and in brightening.
Examples of the hole-transfer material include phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyaryl alkanes, stilbene, butadiene, amine, diamine, triphenylamine, indole, carbazole, triphenylmethane, enamine and their derivatives, and polyvinyl carbazole, polysilane and polymeric materials such as electroconductive polymers.
Aside from the electron-transfer compounds of the present invention, examples of the electron-transfer material include quinolinol complexes, fluorenon, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthraquinodimethane, anthrone, and derivatives thereof.
Examples of the electroconductive material for use in the anode include carbon, aluminum, brass, stainless steel, chromium, titanium, copper, tin, molybdenum, indium, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, and alloys thereof, metal oxides for use in ITO substrate and NESA substrate, such as tin oxide, indium oxide, aluminum iodide and copper iodide, and organic electroconductive resins, such as polythiophene and polypyrrole.
Examples of the electroconductive material for use in the cathode include, but are not limited to, magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum and alloys thereof. Typical examples of the alloy include, but are not limited to, magnesium/silver, magnesium/indium, and lithium/aluminum.
The ratio of the alloy is controlled by the temperature, atmosphere, and degree of vacuum of the evaporation source so that a proper ratio is selected. When necessary, each of the anode and the cathode may be formed as a layered structure consisting of two or more layers.
5. Examples
Production examples of the compounds in accordance with the present invention and examples of the electron-transfer agents will now be described in detail, as will the electrophotographic photoreceptors and the organic electroluminescence elements as application examples.
First, examples of one production process of the compound represented by the general formula (1) is described.
PRODUCTION EXAMPLE 1
A mixture of 0.44 g (2 mmols) of 2,6-di-tert-butylbenzoquinone, which served as a benzoquinone compound, 0.23 g (2 mmols) of a pyrazolone compound having an active methylene, and 2 mL pyridine, which served as a base catalyst, was stirred at room temperature to allow the reaction to proceed. The reaction mixture was concentrated and was purified through silica gel column chromatography (developing solvent=hexane:ethyl acetate=10:1) to obtain 2,6-di-tert-butyl-4-(1,3-dimethyl-5-oxo-4-pyrazolilidene)-2,5-cyclohexadiene-1-one, the compound represented by the formula (7), at a yield of 36%. This reaction is shown by the following chemical equation (25):




PRODUCTION EXAMPLE 2
The experiment was carried out in the same manner as in Example 1, except that the base catalyst, pyridine, was replaced by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The product was obtained at a yield of 35%.
PRODUCTION EXAMPLE 3
The experiment was carried out in the same manner as in Example 1, except that the base catalyst, pyridine, was replaced by trimethylamine. The product was obtained at a yield of 32%.
PRODUCTION EXAMPLE 4
The experiment was carried out in the same manner as in Example 1, except that the base catalyst, pyridine, was replaced by 2,6-dimethylpyridine. The product was obtained at a yield of 35%.
PRODUCTION EXAMPLE 5
The experiment was carried out in the same manner as in Example 1, except that the base catalyst, pyridine, was replaced by tributylamine. The product was obtained at a yield of 30%.
PRODUCTION EXAMPLE 6
The experiment was carried out in the same manner as in Example 1, except that 20 ml ethanol was added as an inert solvent and the base catalyst, pyridine, was replaced by sodium hydroxide. The product was obtained at a yield of 30%.
PRODUCTION EXAMPLES 7 THROUGH 15
Different compounds were used as a compound having an active methylene group. The reaction temperature, reaction time, and yield are shown in Table D(1) for each compound. The structure formula and the name of the compound are shown in Tables D(2) and D(3) for each of the compounds of the formulae (8) through (16) obtained in respective Production Examples.
The melting point and the results of the elemental analysis are shown in Table E for each of the compounds of the formulae (7) through (16) obtained in Production Example 1 and respective Production Examples 7 through 15.
The IR and NMR charts are shown in FIGS. 1 through 20 for each of the compounds of the formulae (7) through (16) obtained in Production Example 1 and in Production Examples 7 through 15.
For IR spectrography, samples were prepared by using the potassium bromide (KBr)-pellet method. For NMR spectrography, deuterated chloroform was used as the sample solvent, and measurements were taken at a frequency of 60 MHz. The horizontal and the vertical axes of the NMR chart indicate chemical shifts and the intensity, respectively.
Comparative Production Example
The experiment was carried out in the same manner as in Example 1, except that the basic solvent, triethylamine, was not used. The reaction did not take place and no product was obtained.
Next, examples of the manner by which the electron mobility of the electron-transfer agent of the present invention was measured are described in conjunction with comparative examples.
EXAMPLE 1
5 g of oxytitanium phthalocyanine was dry-milled together with 50 ml of glass beads for 100 hours on a paint shaker. 50 mL of n-propanol and 5 g of polyvinylbutyral were then added, and the mixture was wet-milled for 1 hour. 100 mL of methyl ethyl ketone solvent was then added to the milled product, and the product was dispersed into the solvent for 10 hours. The resulting dispersion solution was applied to an aluminum-laminated PET film with a bar-coater and was dried to form a 0.5 μm-thick charge-generation layer.
Next, a coating solution was prepared consisting of 8 parts by weight of the compound of the formula (7), 10 parts by weight of polycarbonate and 100 parts by weight of tetrahydrofuran (THF). The coating solution was applied with a bar-coater and was then dried at 80° C. for 1 hour to form a 10 μm-thick charge-transfer layer. Gold was vapor-deposited onto the charge-transfer layer to a thickness of 0.04 μm (40 nm) as an opposed electrode. The electron mobility was measured by applying an electric field to the film and irradiating the film with a laser pulse.
EXAMPLES 2 THROUGH 10
The electron mobility was measured in the same manner as in Example 1 above, except that the compound represented by the formula (7) was replaced by the compound represented by the formula (8) through (16).
COMPARATIVE EXAMPLE 1
The electron mobility was measured in the same manner as in Example 1 above, except that the compound represented by the formula (7) was replaced by the compound represented by the formula (24).
Results
The electron mobilities measured at an electric field of 3.0×105 V/cm are shown in Table F.
As can be seen from Table F, the electron mobility was 1×10−8 (cm2/V·sec) or higher in each of Examples 1 through 10 and was in each case higher than the electron mobility obtained in Comparative Example 1 (1×10−9 (cm2/V·sec)).
While application examples of the present invention are described below with reference to comparative examples, they are not intended to limit the scope of the invention in any way.
Examples of Organic Electroluminescence Elements
APPLICATION EXAMPLE 1
The compound represented by the formula (7) and tris(8-hydroxyquinolinol) aluminum complex were dissolved in chloroform at a ratio of 3:1. The solution was applied by spin-coating to a cleaned glass plate having an ITO electrode to form a 0.07 μm-thick luminescent layer. A 10:1 alloy of magnesium and silver was vapor-deposited onto the luminescent layer to form a 0.2 μm-thick electrode and thus obtain an organic electroluminescence element as shown in FIG. 23.
APPLICATION EXAMPLES 2 THROUGH 10
In each Application Example, an organic electroluminescence element was obtained by replacing the compound of the chemical formula (7) of Application Example 1 with each of the compounds of the chemical formulae (8) through (16). The amount of luminescence that each of the organic electroluminescence elements obtained in Application Examples 1 through 10 emitted when applied a direct current at 5V was shown in Table G.
As can be seen from Table G, the amount of luminescence was 60 (cd/m2) or larger and was sufficiently high in each of Application Examples 1 through 10.
Examples of Electrophotographic Photoreceptors for use in Photocopiers
APPLICATION EXAMPLE 11
10 parts by weight of polycarbonate as a binder resin and 80 parts by weight of THF as a solvent were mixed with 1 part by weight of a dis-azo pigment as a charge-generation material shown by the following chemical formula (26):




The mixture was kneaded for dispersal for 10 hours in a sand mill. As charge-transfer materials, 9 parts by weight of a triphenyldiamine compound shown by the following chemical formula (27):





and 2 parts by weight of the compound shown by the formula (7) were dissolved in the mixture to form a coating solution. An aluminum drum as an electroconductive substrate 1 was dipped in this coating solution to apply coating. The drum was then dried at 80° C. for 1 hour to form a 20 μm-thick photosensitive layer 4 that served both to generate charge and to transport charge. In this manner, a single-layered electrophotographic photoreceptor 12 was prepared.

APPLICATION EXAMPLES 12 THROUGH 20
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 11 with each of the compounds of the chemical formulae (8) through (16).
COMPARATIVE EXAMPLE 2
A single-layered electrophotographic photoreceptor was prepared in the same manner as in Example 11, except that the compound represented by the formula (7) was replaced by the compound represented by the formula (24).
Examples of Electrophotographic Photoreceptors for use in Printers
APPLICATION EXAMPLE 21
5 g of oxytitanium phthalocyanine was dry-milled together with 50 ml of glass beads for 100 hours on a paint shaker. 50 mL of n-propanol and 5 g of polyvinylbutyral were then added and the mixture was wet-milled for 1 hour. 100 mL of methyl ethyl ketone solvent was then added to the milled product, and the product was dispersed into the solvent for 10 hours. An aluminum drum as the electroconductive substrate 1 was dipped in the resulting dispersion solution to apply coating. The coating was then dried to form a 0.2 μm-thick charge-generation layer 2.
Next, a coating solution was prepared consisting of 8 parts by weight of the compound of the formula (7), 10 parts by weight of polycarbonate and 100 parts by weight of tetrahydrofuran (THF). The drum with the charge-generation layer 2 formed thereon was dipped in the coating solution to apply coating. The coating was then dried at 80° C. for 1 hour to form a 20 μm-thick charge-transfer layer 3. In this manner, a multi-layered electrophotographic photoreceptor was obtained.
APPLICATION EXAMPLES 22 THROUGH 30
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 21 with each of the compounds of the chemical formulae (8) through (16).
COMPARATIVE EXAMPLE 3
A multi-layered electrophotographic photoreceptor was prepared in the same manner as in Application Example 21 above, except that the compound represented by the formula (7) was replaced by the compound represented by the formula (24).
APPLICATION EXAMPLE 31
A mixture of 1 part by weight of oxytitanium phthalocyanine as a charge-generation material, 10 parts by weight of polycarbonate as a binder resin, and 80 parts by weight of THF as a solvent was kneaded for dispersal for 10 hours in a sand mill. As charge-transfer materials, 9 parts by weight of triphenyldiamine compound shown by the formula (26) and 2 parts by weight of the compound shown by the formula (7) were dissolved in the mixture to form a coating solution. An aluminum drum as an electroconductive substrate 1 was dipped in this coating solution to apply coating. The drum was then dried at 80° C. for 1 hour to form a 20 μm-thick photosensitive layer 4 that served both to generate charge and to transport charge. In this manner, a single-layered electrophotographic photoreceptor was manufactured.
APPLICATION EXAMPLES 32 THROUGH 40
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 31 with each of the compounds of the chemical formulae (8) through (16).
COMPARATIVE EXAMPLE 4
A single-layered electrophotographic photoreceptor was prepared in the same manner as in Example 31, except that the compound represented by the formula (7) was replaced by the compound represented by the formula (24)
APPLICATION EXAMPLE 41
A mixture of 1 part by weight of oxytitanium phthalocyanine as a charge-generation material, 10 parts by weight of polycarbonate as a binder resin, and 80 parts by weight of THF as a solvent was kneaded for dispersal for 10 hours in a sand mill. As charge-transfer materials, 1 part by weight of triphenyldiamine compound shown by the formula (26) and 9 parts by weight of the compound shown by the formula (7) were dissolved in the mixture to form a coating solution. An aluminum drum as an electroconductive substrate 1 was dipped in this coating solution to apply coating. The drum was then dried at 80° C. for 1 hour to form a 20 μm-thick photosensitive layer 4 that served both to generate charge and to transport charge. In this manner, a single-layered electrophotographic photosensitive layer was obtained.
APPLICATION EXAMPLES 42 THROUGH 50
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 41 with each of the compounds of the formulae (8) through (16).
COMPARATIVE EXAMPLE 5
A single-layered electrophotographic photoreceptor was prepared in the same manner as in Application Example 41, except that the compound represented by the formula (7) was replaced by the compound represented by the formula (24).
Conditions for Measurement
A corona discharger was adjusted to generate a corona discharge current of 17 μA. The electrophotographic photoreceptors prepared in Application Examples 11 through 40 and Comparative Examples 2 through 4 were positively charged by the corona discharge in a dark environment and each photoreceptor was measured for the charged electric potential. The photoreceptors were then exposed to white light, and the exposure E/50 (lux·sec) at which the surface potential of each electrophotographic photoreceptor decreased by half, from 700V down to 350V, was measured. This half decay exposure reflects the sensitivity of the electrophotographic photoreceptor: the smaller the half decay exposure, the higher the sensitivity.
Results
The results of the measurement for Application Examples 11 through 20 and Comparative Example 2 are as shown in Table H below.
The results for Application Examples 11 through 20 and Comparative Example 2 were obtained for positively charged, single-layered photoreceptors for use in photocopiers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (7) through (16), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24). Also, the chargeability of the photoreceptor is enhanced.
The results of the measurement for Application Examples 21 through 30 and Comparative Example 3 are as shown in Table I.
The results for Application Examples 21 through 30 and Comparative Example 3 were obtained for positively charged, multi-layered photoreceptors for use in printers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (7) through (16), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
The results of the measurement for Application Examples 31 through 40 and Comparative Example 4 are as shown in Table J.
The results for Application Examples 31 through 40 and Comparative Example 4 were obtained for positively charged, single-layered photoreceptors for use in printers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (7) through (16), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
Next, a corona discharger was adjusted to generate a corona discharge current of 17 μA. The electrophotographic photoreceptors prepared in Application Examples 41 through 50 and Comparative Example 5 were negatively charged by the corona discharge in a dark environment and each photoreceptor was measured for the charged electric potential. The photoreceptors were then exposed to white light, and the exposure E/50 (lux·sec) at which the absolute value of the surface potential of each electrophotographic photoreceptor decreased by half, from −700V up to −350V, was measured. The results are shown in Table K. The half decay exposure reflects the sensitivity of the electrophotographic photoreceptor: the smaller the half decay exposure, the higher the sensitivity.
The results for Application Examples 41 through 50 and Comparative Example 5 were obtained for negatively charged, single-layered photoreceptors for use in printers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (7) through (16), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
While a description has been given of examples of electrophotographic photoreceptors in which the organic film is used as the photosensitive layer, these examples are illustrative rather than restrictive and do not limit the scope of the invention in any way. For example, the present invention also encompasses within its scope an electrophotographic photoreceptor in which the above-described organic film is used as a foundation layer disposed between the photosensitive layer and the electroconductive substrate. Although organic film for use as the foundation layer needs to have a proper conductivity, the organic film containing the compound represented by the general formula (1) has a high electron mobility and is thus suitable for this purpose so that a highly sensitive electrophotographic photoreceptor can be obtained through the use of such organic film.
Alternatively, the organic film may be used as a protection layer formed over the photosensitive layer. To summarize, the present invention encompasses within its scope any electrophotographic photoreceptor incorporating organic film that contains the compound represented by the general formula (1).
While cases have been described in which a benzoquinone compound is reacted with a compound incorporating an active methylene in the presence of a base catalyst alone, the present invention also encompasses other cases. According to the present invention, the yield of the desired product can be increased by carrying out the reaction using, along with the base catalyst, a solvent that can hardly dissolve the desired product. As used herein, the term “desired product” refers to any of the compounds represented by the general formulae (1) through (6) and (44).
When the reaction is carried out by using the base catalyst alone, a side reaction takes place by which the compound having an active methylene further adds to the desired product that has resulted from the reaction of the benzoquinone compound with the compound having an active methylene. As a result, by-products are produced.
When the benzoquinone compound reacts with the active methylene using a solvent that can hardly dissolve the desired product (inert solvent), along with the base catalyst, the resulting desired product is removed from the reaction system by crystallizing it with the help of the solvent that can hardly dissolve the desired product.
As a result, the further addition of the compound having an active methylene to the desired product can be prevented.
It is believed that by allowing the reaction to proceed in the solvent that can hardly dissolve the desired product, the side reaction can be suppressed so that the yield of the desired product is increased.
Preferably, the solvent is an alcohol solvent, such as methanol, ethanol and butanol, a saturated aliphatic hydrocarbon, such as heptane and hexane, or water. These solvents may be used independently or as a mixture of two or more solvents. Of these, water, methanol, ethanol, and butanol are particularly preferred because of their cost performance and low solubility against the desired product.
The solvent for use with the base catalyst (inert solvent) is not limited to alcohols, saturated aliphatic hydrocarbons or water. The solvent may be any solvent that requires 50 ml or more to dissolve 1 g of the desired product and may be used independently or as a mixture of two or more solvents.
Other examples of the production process of the compound of the present invention will now be described in detail.
PRODUCTION EXAMPLE 16
A mixture of 0.44 g (2 mmols) of 2,6-di-tert-butylbenzoquinone, which served as a benzoquinone compound, 0.35 g (2 mmols) of methylphenylpyrazolone, which served as a compound having an active methylene, 0.5 mL pyridine, which served as a base catalyst, and 4 mL water was allowed to undergo reaction for 5 hours at 45° C. while being stirred. Subsequently, the reaction mixture was added to 4 mL water and the mixture was filtrated. The resulting crystals were washed with 8 mL methanol and were then recrystallized with a mixture of chloroform and methanol. As a result, 0.63 g of 2,6-di-tert-butyl-4-(3-methyl-1-phenyl-5-oxo-4-pyrazolidene)-2,5-cyclohexadiene-1-one was obtained. The yield of the product was 84%.
PRODUCTION EXAMPLE 17
The process was carried out in the same manner as in Production Example 16, except that 1 ml pyridine and 2 ml water were used. The product was obtained at a yield of 65%.
PRODUCTION EXAMPLE 18
The process was carried out in the same manner as in Production Example 16, except that 1 ml pyridine and 4 ml water were used. The product was obtained at a yield of 75%.
PRODUCTION EXAMPLE 19
The process was carried out in the same manner as in Production Example 16, except that methanol was used in place of water. The product was produced at a yield of 62%.
PRODUCTION EXAMPLE 20
The process was carried out in the same manner as in Production Example 16, except that hexane was used in place of water. The product was produced at a yield of 51%.
PRODUCTION EXAMPLE 21
The process was carried out in the same manner as in Production Example 16, except that 2 ml chloroform was used in place of water. The product was produced at a yield of 34%.
PRODUCTION EXAMPLE 22
The process was carried out in the same manner as in Production Example 16, except that 2 ml toluene was used in place of water. The product was produced at a yield of 35%.
The comparisons between each of Production Examples 16 through 20 and Production Example 7 indicate that while each process can produce the same compound represented by the formula (8), higher yields of 84%, 65%, 75%, 62%, and 51% were achieved in Production Examples 16, 17, 18, 19, and 20, respectively, as compared to the 32% yield in Production Example 7. In comparison, the yields obtained in Production Examples 21 and 22 with the use of chloroform and toluene were comparable to that of Production Example 7, with no apparent increase in the yield.
PRODUCTION EXAMPLES 23 THROUGH 37
Different compounds were used as a compound having an active methylene group. The reaction temperature, reaction time, and yield are shown in Tables L(1) and L(2) for each compound. The structure formula and the name of the compound are shown in Tables M(1) through. M(3) for each of the compounds of the formulae (29) through (43) obtained in respective Production Examples.
The melting point and the results of the elemental analysis are shown in Table N for each of the compounds of the formulae (29) through (43) obtained in Production Examples 23 through 37.
The IR and NMR charts are shown in FIGS. 24 through 53 for each of the compounds of the formulae (29) through (43) obtained in Production Examples 23 through 37.
Next, the examples of measuring the electron mobility of the electron transfer agent of the present invention are described in conjunction with comparative examples.
EXAMPLES 11 THROUGH 25
The electron mobility was measured in the same manner as in Example 1 above, except that the compound represented by the formula (7) was replaced by the compound represented by the formulae (29) through (43).
Results
The electron mobilities measured at an electric field of 3.0×105 V/cm are shown in Table O.
As can be seen from Table O, the electron mobility was 1×10−8 (cm2/V·sec) or higher in each of Examples 11 through 25 and was in each case higher than the electron mobility obtained in Comparative Example 1 (1×10−9 (cm2/V·sec)).
Examples of Electrophotographic Photoreceptors for Use in Printers
APPLICATION EXAMPLES 51 THROUGH 65
In each Application Example, an organic electroluminescence element was obtained by replacing the compound of the chemical formula (7) of Application Example 1 with each of the compounds of the chemical formulae (29) through (43). The amount of luminescence that each of the organic electroluminescence elements obtained, in Application Examples 51 through 65 emitted when applied a direct current at 5V, is shown in Table P.
As can be seen from Table P, the amount of luminescence was 60 (cd/m2) or larger and was sufficiently high in each of Application Examples 51 through 65.
Examples of Electrophotographic Photoreceptors for Use in Photocopiers
APPLICATION EXAMPLES 66 THROUGH 80
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 11 with each of the compounds of the chemical formulae (29) through (43).
Examples of Electrophotographic Photoreceptors for Use in Printers
APPLICATION EXAMPLES 81 THROUGH 95
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 21 with each of the compounds of the chemical formulae (29) through (43).
APPLICATION EXAMPLES 96 THROUGH 110
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 31 with each of the compounds of the chemical formulae (29) through (43).
APPLICATION EXAMPLES 111 THROUGH 125
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 41 with each of the compounds of the formulae (29) through (43).
Conditions for Measurement
A corona discharger was adjusted to generate a corona discharge current of 17 μA. The electrophotographic photoreceptors prepared in Application Examples 66 through 110 were positively charged by the corona discharge in a dark environment and each photoreceptor was measured for the charged electric potential. The photoreceptors were then exposed to white light, and the exposure E/50 (lux·sec) at which the surface potential of each electrophotographic photoreceptor decreased by half, from 700V down to 350V, was measured. This half decay exposure reflects the sensitivity of the electrophotographic photoreceptor.
Results
The results of the measurement for Application Examples 66 through 80 are shown in Table Q below together with the results of Comparative Example 2.
The results for Application Examples 66 through 80 and Comparative Example 2 were obtained for positively charged, single-layered photoreceptors for use in photocopiers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (29) through (43), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24). Also, the chargeability of the photoreceptor is enhanced.
The results of the measurement for Application Examples 81 through 95 are shown in Table R below together with the results of Comparative Example 3.
The results for Application Examples 81 through 95 and Comparative Example 3 were obtained for positively charged, multi-layered photoreceptors for use in printers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (29) through (43), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
The results of the measurement for Application Examples 96 through 110 are shown in Table S below together with the results of Comparative Example 4.
The results for Application Examples 96 through 110 and Comparative Example 4 were obtained for positively charged, single-layered photoreceptors for use in printers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (29) through (43), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
Next, a corona discharger was adjusted to generate a corona discharge current of 17 μA. The electrophotographic photoreceptors prepared in Application Examples 111 through 125 were negatively charged by the corona discharge in a dark environment and each photoreceptor was measured for the charged electric potential. The photoreceptors were then exposed to white light, and the exposure E/50 (lux·sec) at which the absolute value of the surface potential of each electrophotographic photoreceptor decreased by half, from −700V up to −350V, was measured. The results are shown in Table T. The half decay exposure reflects the sensitivity of the electrophotographic photoreceptor.
The results for Application Examples 111 through 125 and Comparative Example 5 were obtained for negatively charged, single-layered photoreceptors for use in printers. The comparisons between each Application Example and Comparative Example suggest that through the use of the electron-transfer materials of the chemical formulae (29) through (43), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
Other examples of the production process of the compound of the present invention will now be described in detail.
PRODUCTION EXAMPLE 38
A mixture of 0.88 g (4 mmols) of 2,6-di-tert-butylbenzoquinone, which served as a benzoquinone compound, 0.75 g (4 mmols) of 3-methyl-1-p-tolyl-5-pyrazolone, which served as a cyclic compound having an active methylene, and 4 mL pyridine, which served as a base catalyst, was allowed to undergo reaction for 20 hours at 25° C. while being stirred. Subsequently, the reaction mixture was concentrated and was purified through column chromatography (hexane:ethyl acetate=10:1). As a result, 0.83 g of the compound shown by the chemical formula (45) is obtained as the desired product (yield=53%).
PRODUCTION EXAMPLES 39 THROUGH 53
Different compounds were used as a compound having an active methylene group. The reaction temperature, reaction time, and yield are shown in Tables U(1) and U(2) for each compound. The structure formula and the name of the compound are shown in Tables V(1) through V(3) for each of the compounds of the formulae (45) through (60) obtained in respective Production Examples.
The melting point and the results of the elemental analysis are shown in Table W for each of the compounds of the formulae (45) through (60) obtained in Production Examples 38 through 53.
The IR and NMR spectra are shown in FIGS. 54 through 85 for each of the compounds of the formulae (45) through (60) obtained in Production Examples 38 through 53.
EXAMPLES 26 THROUGH 41
The electron mobility was measured in the same manner as in Example 1 above, except that the compound represented by the formula (7) was replaced by the compound represented by the formulae (45) through (60).
Results
The electron mobilities measured at an electric field of 3.0×105 V/cm are shown in Table X.
As can be seen from Table X, the electron mobility was 1×10−8 (cm2/V·sec) or higher in each of Examples 26 through 41 and was in each case higher than the electron mobility obtained in Comparative Example 1.
Production Examples of Organic Electroluminescence Elements
APPLICATION EXAMPLES 126 THROUGH 141
Each of the organic electroluminescence elements of Application Examples 126 through 141 was obtained by replacing the compound of the chemical formula (7) of Application Example 1 with each of the compounds of the chemical formulae (45) through (60). The amount of luminescence that each of the organic electroluminescence elements obtained, in Application Examples 126 through 141 emitted when applied a direct current at 5V, is shown in Table Y
As can be seen from Table Y, the amount of luminescence was 60 (cd/m2) or higher and was sufficiently high in each of Application Examples 126 through 141.
Production Examples of Electrophotographic Photoreceptors for Use in Photocopiers
APPLICATION EXAMPLES 142 THROUGH 157
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) with each of the compounds of the chemical formulae (45) through (60).
Production Examples of Electrophotographic Photoreceptors for Use in Printers
APPLICATION EXAMPLES 158 THROUGH 173
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 21 with Each of the Compounds of the Chemical Formulae (45) Through (60).
APPLICATION EXAMPLES 174 THROUGH 189
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 31 with each of the compounds of the chemical formulae (45) through (60). Application Examples 190 through 205
In each Application Example, an electrophotographic photoreceptor was obtained by replacing the compound of the chemical formula (7) of Application Example 41 with each of the compounds of the formulae (45) through (60).
Conditions for Measurement
A corona discharger was adjusted to generate a corona discharge current of 17 μA. The electrophotographic photoreceptors prepared in Application Examples 142 through 157, 158 through 173, and 174 through 189 were each positively charged by the corona discharge in a dark environment and each photoreceptor was measured for the charged electric potential. The photoreceptors were then exposed to white light, and the exposure E/50 (lux·sec) at which the surface potential of each electrophotographic photoreceptor decreased by half, from 700V down to 350V, was measured. This half decay exposure reflects the sensitivity of the electrophotographic photoreceptor.
Results
The results of the measurement for Application Examples 142 through 157 and the results for Comparative Example 2 are as shown in Table Z.
The results for Application Examples 142 through 157 and Comparative Example 2 were obtained for positively charged, single-layered photoreceptors for use in photocopiers. The comparisons between each of Application Examples 142 through 157 and Comparative Example 2 suggest that through the use of the electron-transfer materials of the chemical formulae (45) through (60), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24). Also, the chargeability of the photoreceptor is enhanced.
The results of the measurement for Application Examples 158 through 173 and Application Example 3 are as shown in Table AA below.
The results for Application Examples 158 through 173 and Comparative Example 3 were obtained for positively charged, multi-layered photoreceptors for use in printers. The comparisons between each of Application Examples 158 through 173 and Comparative Example 3 suggest that through the use of the electron-transfer materials of the chemical formulae (45) through (60), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
The results of the measurement for Application Examples 174 through 189 and Comparative Example 4 are as shown in Table AB below.
The results for Application Examples 174 through 189 and Comparative Example 4 were obtained for positively charged, single-layered photoreceptors for use in printers. The comparisons between each of Application Examples 174 through 189 and Comparative Example 4 suggest that through the use of the electron-transfer materials of the chemical formulae (45) through (60), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
Next, a corona discharger was adjusted to generate a corona discharge current of 17 μA. The electrophotographic photoreceptors prepared in Application Examples 190 through 205 were each negatively charged by the corona discharge in a dark environment and each photoreceptor was measured for the charged electric potential. The photoreceptors were then exposed to white light, and the exposure E/50 (lux·sec) at which the absolute value of the surface potential of each electrophotographic photoreceptor decreased by half, from −700V up to −350V, was measured. The results are shown in Table AC. The half decay exposure reflects the sensitivity of the electrophotographic photoreceptor.
The results for Application Examples 190 through 205 and Comparative Example 5 were obtained for negatively charged, single-layered photoreceptors for use in printers. The comparisons between each of Application Examples 190 through 205 and Comparative Example 5 suggest that through the use of the electron-transfer materials of the chemical formulae (45) through (60), a photoreceptor can be obtained that has a higher sensitivity than the photoreceptor using the compound of the formula (24).
As set forth, the electron-transfer compounds of the present invention have a structure in which two ring structures, a quinone ring and a ring structure incorporating an active methylene group, are connected with each other via a double bond and therefore have a large molecular skeleton that permits a large distance for electron movement within the molecule. Accordingly, the compounds of the present invention show a high electron mobility to allow electrons to move freely within the molecule and thus are capable of coloring only faintly, which helps reduce the light absorption. Asymmetrical molecular structure of the compounds of the present invention contributes to their high compatibility with resins.
The present invention also provides a simple process for producing the electron-transfer compounds that makes use of a base catalyst. Also, an efficient electron-transfer agent can be obtained by mixing the electron-transfer compound with a proper resin. Further, a highly sensitive photosensitive layer can be obtained by using the electron-transfer compound in electrophotographic photoreceptors.
The high compatibility of the electron-transfer compound with binder resins makes it possible to disperse the compound in the photosensitive layer uniformly and abundantly. In this regard, the incident light is not prevented from passing through to the charge-generation material because of the ability of the electron-transfer compound to color only faintly. As a result, a highly sensitive electrophotographic photoreceptor is obtained. Such an electrophotographic photoreceptor can be used to serve both as the positive charge type and as the negative charge type.
Moreover, the electron-transfer compounds of the present invention can be used as an electron-transfer material for use in organic electroluminescence elements. The present invention permits selection of substituents that can provide the characteristics required of the electron-transfer compound for serving as a particular high-performance material and permits designing a desired molecular structure for the electron-transfer compound.







TABLE A1







A list of general formulas (substituents R1~R6)










No.
General formula







101







 



102







 



103







 



104







 



105







 



106







 



107







 



108







 



109







 



110







 



111







 



112







 



113







 



114





















TABLE A2







A list of general formulas (substituents R1~R6)










No.
General formula







115







 



116







 



117







 



118







 



119







 



120







 



121







 



122







 



123







 



124







 



125







 



126







 



127







 



128





















TABLE A3







A list of general formulas (substituents R1~R6)










No.
General formula







129







 



130







 



131







 



132







 



133







 



134







 



135







 



136







 



137







 



138







 



139







 



140







 



141







 



142





















TABLE A4







A list of general formulas (substituents R1~R6)










No.
General formula







143







 



144







 



145







 



146







 



147







 



148







 



149







 



150







 



151







 



152







 



153







 



154







 



155







 



156





















TABLE A5







A list of general formulas (substituents R1~R6)










No.
General formula







157







 



158







 



159







 



160







 



161







 



162







 



163







 



164







 



165







 



166







 



167







 



168







 



169







 



170





















TABLE A6







A list of general formulas (substituents R1~R6)










No.
General formula







171







 



172







 



173







 



174







 



175







 



176







 



177







 



178







 



179







 



180







 



181







 



182







 



183







 



184





















TABLE A7







A list of general formulas (substituents R1~R6)










No.
General formula







185







 



186







 



187







 



188







 



189







 



190







 



191







 



192







 



193







 



194







 



195







 



196







 



197







 



198





















TABLE A8







A list of general formulas (substituents R1~R6)










No.
General formula







199







 



200







 



201







 



202







 



203







 



204







 



205







 



206







 



207







 



208







 



209







 



210







 



211







 



212





















TABLE A9







A list of general formulas (substituents R1~R6)










No.
General formula







213







 



214







 



215







 



216







 



217







 



218







 



219







 



220







 



221







 



222







 



223







 



224







 



225







 



226





















TABLE A10







A list of general formulas (substituents R1~R6)










No.
General formula







227







 



228







 



229







 



230







 



231







 



232







 



233







 



234







 



235







 



236







 



237







 



238







 



239







 



240





















TABLE A11







A list of general formulas (substituents R1~R6)










No.
General formula







241







 



242







 



243







 



244







 



245







 



246







 



247







 



248







 



249







 



250







 



251







 



252







 



253







 



254





















TABLE A12







A list of general formulas (substituents R1~R6)










No.
General formula







255







 



256







 



257







 



258







 



259







 



260







 



261







 



262







 



263







 



264







 



265







 



266







 



267







 



268





















TABLE A13







A list of general formulas (substituents R1~R6)










No.
General formula







269







 



270







 



271







 



272







 



273







 



274







 



275







 



276







 



277







 



278







 



279







 



280







 



281







 



282





















TABLE A14







A list of general formulas (substituents R1~R6)










No.
General formula







283







 



284







 



285







 



286







 



287







 



288







 



289







 



290







 



291







 



292







 



293







 



294





















TABLE A15







A list of general formulas (substituents R1~R6)










No.
General formula







295







 



296







 



297







 



298







 



299







 



300





















TABLE A16







A list of general formulas (substituents R1~R6)










No.
General formula







301







 



302







 



303







 



304







 



305







 



306





















TABLE A17







A list of general formulas (substituents R1~R6)










No.
General formula







307







 



308







 



309







 



310







 



311







 



312





















TABLE A18







A list of general formulas (substituents R1~R6)










No.
General formula







313







 



314





















TABLE A19







A list of general formulas (substituents R1~R5)










No.
General formula







315







 



316







 



317







 



318







 



319







 



320







 



321







 



322







 



323







 



324







 



325







 



326







 



327







 



328





















TABLE A20







A list of general formulas (substituents R1~R5)










No.
General formula







329







 



330







 



331







 



332







 



333







 



334







 



335







 



336







 



337







 



338







 



339







 



340







 



341







 



342





















TABLE A21







A list of general formulas (substituents R1~R5)










No.
General formula







343







 



344







 



345







 



346







 



347







 



348







 



349







 



350







 



351







 



352







 



353







 



354







 



355







 



356





















TABLE A22







A list of general formulas (substituents R1~R5)










No.
General formula







357







 



358







 



359







 



360







 



361







 



362







 



363







 



364







 



365







 



366







 



367







 



368







 



369







 



370





















TABLE A23







A list of general formulas (substituents R1~R5)










No.
General formula







371







 



372







 



373







 



374







 



375







 



376







 



378







 



379







 



380







 



381







 



382







 



383







 



384







 



385





















TABLE A24







A list of general formulas (substituents R1~R5)










No.
General formula







386







 



387







 



388







 



389







 



390







 



391







 



392







 



393







 



394







 



395







 



396







 



397







 



398







 



399





















TABLE A25







A list of general formulas (substituents R1~R5)










No.
General formula







400







 



401







 



402







 



403







 



404







 



405







 



406







 



407







 



408







 



409







 



410







 



411







 



412







 



413





















TABLE A26







A list of general formulas (substituents R1~R5)










No.
General formula







414







 



415







 



416







 



417







 



418







 



419







 



420







 



421







 



422







 



423





















TABLE B







A list of substituents










Substituent's No
substituent







S1 
—H



S2 
—CH3



S3 
-t-Bu



S4 
—OCH3



S5 
—CF3



S6 
—NO2



S7 
—CO2CH3



S8 
—CH═CH—CH═CH2



S9 
—C2H5



S10
—Cl



 



S11







 



S12







 



S13







 



S14







 



S15







 



S16







 



S17







 



S18







 



S19







 



S20







 



S21







 



S22







 



S23





















TABLE C1







A list of compounds (substituents R1~R6)














R1
R2
R3
R4
R5
R6







S3
S1
S3
S1
S11
S11



S3
S2
S3
S1
S11
S11



S3
S2
S3
S2
S11
S11



S3
S1
S12
S1
S11
S11



S3
S2
S12
S1
S11
S11



S3
S2
S12
S2
S11
S11



S3
S1
S13
S1
S11
S11



S3
S2
S13
S1
S11
S11



S3
S2
S13
S2
S11
S11



S3
S11
S3
S2
S11
S11



S3
S1
S3
S1
S11
S13



S3
S1
S3
S1
S11
S12



S3
S2
S3
S1
S11
S13



S3
S2
S3
S1
S11
S12



S3
S1
S12
S1
S11
S13



S3
S1
S13
S1
S11
S12



S3
S2
S12
S1
S11
S13



S3
S2
S13
S1
S11
S12



S3
S1
S3
S1
S12
S13



S3
S1
S3
S1
S13
S12



S3
S2
S3
S1
S12
S13



S3
S2
S3
S1
S13
S12



S3
S1
S13
S1
S12
S13



S3
S1
S12
S1
S13
S13



S3
S2
S12
S1
S12
S13



S3
S2
S13
S1
S13
S12



S3
S1
S3
S1
S3
S18



S3
S1
S3
S1
S14
S15



S3
S1
S3
S1
S15
S14



S3
S1
S3
S1
S17
S13



S3
S1
S3
S1
S16
S12



S3
S1
S3
S1
S12
S11



S3
S1
S3
S1
S12
S13



S3
S1
S3
S1
S13
S11



S3
S1
S3
S1
S13
S12



S3
S2
S3
S1
S12
S11



S3
S2
S3
S1
S13
S11



S3
S1
S4
S2
S11
S13



S3
S6
S7
S4
S2
S12



S3
S10
S11
S6
S19
S16



S3
S2
S20
S10
S7
S11

















TABLE C2







A list of compounds (substituents R1~R6)














R1
R2
R3
R4
R5
R6







S3
S3
S3
S3
S3
S18



S3
S20
S2
S11
S16
S3



S3
S11
S10
S7
S5
S13



S3
S7
S6
S1
S20
S15



S3
S4
S1
S20
S18
S20



S12
S1
S3
S1
S11
S13



S12
S1
S3
S1
S3
S18



S12
S2
S3
S1
S11
S13



S12
S1
S3
S1
S14
S15



S12
S1
S3
S1
S15
S14



S12
S1
S3
S1
S17
S13



S12
S1
S3
S1
S16
S12



S12
S1
S3
S1
S12
S11



S12
S1
S3
S1
S12
S13



S12
S1
S3
S1
S13
S11



S12
S1
S3
S1
S13
S12



S12
S1
S12
S1
S12
S11



S12
S1
S13
S1
S12
S13



S12
S1
S13
S1
S13
S11



S12
S1
S12
S1
S13
S12



S12
S1
S4
S2
S11
S13



S12
S6
S7
S4
S2
S12



S12
S10
S11
S6
S19
S16



S12
S2
S20
S10
S7
S11



S12
S3
S3
S3
S3
S18



S12
S20
S2
S11
S16
S3



S12
S11
S10
S7
S5
S13



S12
S7
S6
S1
S20
S15



S12
S4
S1
S20
S18
S20



S13
S1
S3
S1
S11
S13



S13
S1
S3
S1
S3
S18



S13
S2
S3
S1
S11
S13



S13
S1
S3
S1
S14
S15



S13
S1
S3
S1
S15
S14



S13
S1
S3
S1
S17
S13



S13
S1
S3
S1
S16
S12



S13
S1
S3
S1
S12
S11



S13
S1
S3
S1
S12
S13



S13
S1
S3
S1
S13
S11



S13
S1
S3
S1
S13
S12



S13
S2
S13
S1
S12
S11

















TABLE C3







A list of compounds (substituents R1~R6)














R1
R2
R3
R4
R5
R6







S13
S1
S12
S1
S12
S13



S13
S2
S12
S1
S13
S11



S13
S1
S13
S1
S13
S12



S13
S1
S4
S2
S11
S13



S13
S6
S7
S4
S2
S12



S13
S10
S11
S6
S19
S16



S13
S2
S20
S10
S7
S11



S13
S3
S3
S3
S3
S18



S13
S20
S2
S11
S16
S3



S13
S11
S10
S7
S5
S13



S13
S7
S6
S1
S20
S15



S13
S4
S1
S20
S18
S20



S11
S1
S2
S20
S7
S11



S11
S6
S20
S7
S3
S18



S11
S1
S12
S2
S11
S13



S11
S10
S3
S1
S16
S3



S11
S2
S1
S6
S5
S13



S11
S3
S10
S2
S20
S15



S11
S20
S6
S4
S18
S20



S11
S11
S11
S11
S11
S13



S11
S7
S4
S10
S2
S12



S11
S4
S7
S3
S19
S16



S11
S1
S11
S1
S11
S13



S11
S2
S11
S1
S11
S13



S11
S1
S11
S1
S11
S12



S11
S2
S11
S1
S11
S12



S11
S1
S12
S1
S11
S13



S11
S2
S12
S1
S11
S13



S11
S1
S12
S1
S11
S12



S11
S2
S12
S1
S11
S12



S11
S1
S13
S1
S11
S13



S11
S2
S13
S1
S11
S13



S11
S1
S13
S1
S11
S12



S11
S2
S13
S1
S11
S12



S11
S1
S11
S1
S14
S15



S11
S1
S11
S1
S12
S11



S11
S1
S11
S1
S13
S11



S11
S2
S11
S1
S12
S11



S11
S2
S11
S1
S13
S11



S11
S1
S11
S1
S13
S13



S11
S1
S11
S1
S13
S12

















TABLE C4







A list of compounds (substituents R1~R6)














R1
R2
R3
R4
R5
R6







S11
S1
S11
S1
S12
S13



S11
S1
S11
S1
S13
S13



S11
S1
S12
S1
S12
S11



S11
S1
S12
S1
S13
S11



S11
S2
S12
S1
S12
S11



S11
S2
S12
S1
S13
S11



S11
S1
S12
S1
S12
S12



S11
S1
S12
S1
S13
S12



S11
S1
S12
S1
S12
S13



S11
S1
S12
S1
S13
S13



S11
S1
S13
S1
S12
S11



S11
S1
S13
S1
S13
S11



S11
S2
S13
S1
S12
S11



S11
S2
S13
S1
S13
S11



S11
S1
S13
S1
S12
S12



S11
S1
S13
S1
S13
S12



S11
S1
S13
S1
S12
S13



S11
S1
S13
S1
S13
S13



S11
S11
S11
S1
S11
S13



S11
S1
S7
S1
S11
S13



S15
S1
S15
S1
S11
S13



S17
S1
S11
S1
S11
S13



S11
S1
S11
S1
S12
S11



S11
S1
S11
S1
S13
S11



S13
S1
S13
S1
S11
S13



S8
S1
S2
S1
S11
S13













S21
S8
S1
S11
S13



S21
S8
S1
S12
S11



S21
S3
S1
S11
S13












S21
S21
S11
S13



S22
S21
S11
S12













S23
S9
S1
S11
S13














S2
S2
S2
S1
S14
S15



S2
S2
S2
S1
S11
S13



S2
S1
S11
S7
S20
S15



S2
S1
S11
S7
S12
S11



S2
S6
S4
S1
S18
S20



S2
S10
S7
S20
S5
S13



S2
S2
S2
S2
S2
S12



S2
S3
S20
S4
S19
S16



S2
S3
S20
S4
S13
S11

















TABLE C5







A list of compounds (substituents R1~R6)














R1
R2
R3
R4
R5
R6







S2
S3
S13
S4
S13
S11



S2
S20
S3
S6
S11
S13



S2
S11
S1
S10
S3
S18



S2
S7
S10
S3
S16
S3



S2
S4
S6
S11
S7
S11



S20
S1
S7
S10
S16
S3



S20
S6
S22
S3
S7
S22



S20
S10
S4
S22
S3
S18



S20
S2
S3
S7
S18
S20



S20
S3
S2
S1
S5
S13



S20
S20
S20
S20
S20
S15



S20
S20
S20
S20
S12
S11



S20
S11
S6
S2
S19
S16



S20
S11
S6
S2
S13
S11



S20
S7
S1
S4
S11
S13



S20
S4
S10
S6
S2
S12



S1
S1
S1
S1
S19
S16



S1
S1
S1
S1
S13
S11



S1
S6
S10
S20
S11
S13



S1
S10
S6
S7
S2
S12



S1
S2
S11
S4
S16
S3



S1
S3
S4
S6
S7
S11



S1
S20
S7
S2
S3
S18



S1
S11
S2
S3
S18
S20



S1
S7
S20
S11
S5
S13



S1
S4
S3
S10
S20
S15



S1
S4
S3
S10
S12
S11



S6
S1
S10
S4
S3
S18



S6
S6
S6
S6
S16
S3



S6
S10
S1
S2
S7
S11



S6
S2
S4
S3
S20
S15



S6
S2
S4
S3
S12
S11



S6
S3
S7
S11
S18
S20



S6
S20
S11
S10
S5
S13



S6
S11
S20
S1
S2
S12



S6
S7
S3
S20
S19
S16



S6
S7
S3
S20
S13
S11



S6
S4
S2
S7
S11
S13



S10
S1
S6
S3
S5
S13



S10
S6
S1
S11
S20
S15



S10
S6
S1
S11
S12
S11

















TABLE C6







A list of compounds (substituents R1~R6)














R1
R2
R3
R4
R5
R6







S10
S10
S10
S10
S18
S20



S10
S2
S7
S1
S11
S13



S10
S3
S11
S20
S2
S12



S10
S20
S4
S7
S19
S16



S10
S20
S4
S7
S13
S11



S10
S11
S3
S4
S7
S11



S10
S7
S2
S6
S3
S18



S10
S4
S20
S2
S16
S3



S7
S1
S20
S6
S18
S20



S7
S6
S3
S2
S5
S13



S7
S10
S2
S4
S20
S15



S7
S10
S2
S4
S12
S11



S7
S2
S10
S11
S19
S16



S7
S2
S10
S11
S13
S11



S7
S3
S6
S10
S11
S13



S7
S20
S1
S3
S2
S12



S7
S11
S4
S20
S16
S3



S7
S7
S7
S7
S7
S11



S7
S4
S11
S1
S3
S18



S4
S1
S3
S11
S2
S12



S4
S6
S2
S10
S19
S16



S4
S6
S2
S10
S13
S11



S4
S10
S20
S3
S11
S13



S4
S2
S6
S20
S3
S18



S4
S3
S1
S7
S16
S3



S4
S20
S10
S1
S7
S11



S4
S11
S7
S6
S20
S15



S4
S11
S7
S6
S12
S11



S4
S7
S11
S2
S18
S20



S4
S4
S4
S4
S5
S13

















TABLE C7







A list of compounds (substituents R1~R6)













R1
R2
R3
R4
R5







S3
S1
S3
S1
S11



S3
S1
S12
S1
S11



S3
S1
S13
S1
S11



S3
S1
S3
S1
S3



S3
S2
S3
S1
S11



S3
S2
S12
S1
S11



S3
S2
S13
S1
S11



S3
S1
S3
S1
S14



S3
S1
S3
S1
S15



S3
S1
S3
S1
S17



S3
S1
S3
S1
S16



S3
S1
S3
S1
S12



S3
S1
S3
S1
S13



S3
S2
S3
S1
S12



S3
S2
S3
S1
S13



S3
S1
S4
S2
S11



S3
S6
S7
S4
S2



S3
S10
S11
S6
S19



S3
S2
S20
S10
S7



S3
S3
S3
S3
S3



S3
S20
S2
S11
S16



S3
S11
S10
S7
S4



S3
S7
S6
S1
S20



S3
S4
S1
S20
S15



S12
S1
S3
S1
S11



S12
S1
S3
S1
S3



S12
S2
S3
S1
S11



S12
S1
S12
S1
S11



S12
S1
S13
S1
S11



S12
S1
S12
S1
S3



S12
S1
S13
S1
S3



S12
S2
S12
S1
S11



S12
S2
S13
S1
S11



S12
S1
S3
S1
S14



S12
S1
S3
S1
S15



S12
S1
S3
S1
S17



S12
S1
S3
S1
S16



S12
S1
S3
S1
S12



S12
S1
S3
S1
S13



S12
S1
S12
S1
S12



S12
S1
S13
S1
S13

















TABLE C8







A list of compounds (substituents R1~R5)













R1
R2
R3
R4
R5







S12
S1
S12
S1
S13



S12
S1
S13
S1
S12



S12
S1
S4
S2
S11



S12
S6
S7
S4
S2



S12
S10
S11
S6
S19



S12
S2
S20
S10
S7



S12
S3
S3
S3
S3



S12
S20
S2
S11
S16



S12
S11
S10
S7
S4



S12
S7
S6
S1
S20



S12
S4
S1
S20
S15



S13
S1
S3
S1
S11



S13
S1
S3
S1
S3



S13
S2
S3
S1
S11



S13
S1
S12
S1
S11



S13
S1
S12
S1
S3



S13
S2
S12
S1
S11



S13
S1
S13
S1
S11



S13
S1
S13
S1
S3



S13
S2
S13
S1
S11



S13
S1
S3
S1
S14



S13
S1
S3
S1
S15



S13
S1
S3
S1
S17



S13
S1
S3
S1
S16



S13
S1
S3
S1
S12



S13
S1
S3
S1
S13



S13
S1
S12
S1
S12



S13
S1
S12
S1
S13



S13
S1
S13
S1
S12



S13
S1
S13
S1
S13



S13
S1
S4
S2
S11



S13
S6
S7
S4
S2



S13
S10
S11
S6
S19



S13
S2
S20
S10
S7



S13
S3
S3
S3
S3



S13
S20
S2
S11
S16



S13
S11
S10
S7
S4



S13
S7
S6
S1
S20



S13
S4
S1
S20
S15



S11
S1
S2
S20
S7



S11
S6
S20
S7
S3

















TABLE C9







A list of compounds (substituents R1~R5)













R1
R2
R3
R4
R5







S11
S1
S12
S2
S11



S11
S10
S3
S1
S16



S11
S2
S1
S6
S4



S11
S3
S10
S2
S20



S11
S20
S6
S4
S15



S11
S11
S11
S11
S11



S11
S7
S4
S10
S2



S11
S4
S7
S3
S19



S11
S1
S11
S1
S11



S11
S2
S11
S1
S11



S11
S1
S11
S1
S14



S11
S1
S11
S1
S12



S11
S1
S11
S1
S13



S11
S1
S12
S1
S11



S11
S2
S12
S1
S11



S11
S1
S12
S1
S14



S11
S1
S12
S1
S12



S11
S1
S12
S1
S13



S11
S1
S13
S1
S11



S11
S2
S13
S1
S11



S11
S1
S13
S1
S14



S11
S1
S13
S1
S12



S11
S1
S13
S1
S13



S11
S11
S11
S1
S11



S11
S1
S7
S1
S11



S15
S1
S15
S1
S11



S17
S1
S11
S1
S11



S11
S1
S11
S1
S12



S11
S1
S11
S1
S13



S13
S1
S13
S1
S11



S8
S1
S2
S1
S11













S21

S8
S1
S11



S21

S8
S1
S12



S21

S3
S1
S11













S21

S21

S11



S22

S21

S11













S23

S9
S1
S11













S2
S2
S2
S1
S14



S2
S2
S2
S1
S11



S2
S1
S11
S7
S20



S2
S1
S11
S7
S12

















TABLE C10







A list of compounds (substituents R1~R5)













R1
R2
R3
R4
R5







S2
S6
S4
S1
S15



S2
S10
S7
S20
S4



S2
S2
S2
S2
S2



S2
S3
S20
S4
S19



S2
S3
S20
S4
S13



S2
S3
S13
S4
S13



S2
S20
S3
S6
S11



S2
S11
S1
S10
S3



S2
S7
S10
S3
S16



S2
S4
S6
S11
S7



S20
S1
S7
S10
S16



S20
S6
S11
S3
S7



S20
S10
S4
S11
S3



S20
S2
S3
S7
S15



S20
S3
S2
S1
S4



S20
S20
S20
S20
S20



S20
S20
S20
S20
S12



S20
S11
S6
S2
S19



S20
S11
S6
S2
S13



S20
S7
S1
S4
S11



S20
S4
S10
S6
S2



S1
S1
S1
S1
S19



S1
S1
S1
S1
S13



S1
S6
S10
S20
S11



S1
S10
S6
S7
S2



S1
S2
S11
S4
S16



S1
S3
S4
S6
S7



S1
S20
S7
S2
S3



S1
S11
S2
S3
S15



S1
S7
S20
S11
S4



S1
S4
S3
S10
S20



S1
S4
S3
S10
S12



S6
S1
S10
S4
S3



S6
S6
S6
S6
S16



S6
S10
S1
S2
S7



S6
S2
S4
S3
S20



S6
S2
S4
S3
S12



S6
S3
S7
S11
S15



S6
S20
S11
S10
S4



S6
S11
S20
S1
S2



S6
S7
S3
S20
S19

















TABLE C11







A list of compounds (substituents R1~R5)













R1
R2
R3
R4
R5







S6
S7
S3
S20
S13



S6
S4
S2
S7
S11



S10
S1
S6
S3
S4



S10
S6
S1
S11
S20



S10
S6
S1
S11
S12



S10
S10
S10
S10
S15



S10
S2
S7
S1
S11



S10
S3
S11
S20
S2



S10
S20
S4
S7
S19



S10
S20
S4
S7
S13



S10
S11
S3
S4
S7



S10
S7
S2
S6
S3



S10
S4
S20
S2
S16



S7
S1
S20
S6
S15



S7
S6
S3
S2
S4



S7
S10
S2
S4
S20



S7
S10
S2
S4
S12



S7
S2
S10
S11
S19



S7
S2
S10
S11
S13



S7
S3
S6
S10
S11



S7
S20
S1
S3
S2



S7
S11
S4
S20
S16



S7
S7
S7
S7
S7



S7
S4
S11
S1
S3



S4
S1
S3
S11
S2



S4
S6
S2
S10
S19



S4
S6
S2
S10
S13



S4
S10
S20
S3
S11



S4
S2
S6
S20
S3



S4
S3
S1
S7
S16



S4
S20
S10
S1
S7



S4
S11
S7
S6
S20



S4
S11
S7
S6
S12



S4
S7
S11
S2
S15



S4
S4
S4
S4
S4

















TABLE D1







Synthesis examples obtained in production examples 7~15











Reaction Temperature




Reaction Time


Production Example
A compound having an active methylene
Yield (%)












7




20° C.20 hours32


 


8




20° C.20 hours67


 


9




20° C.20 hours63


 


10




45° C.3.5 hours 41


 


11




20° C.20 hours37


 


12




20° C.20 hours37


 


13




45° C. 8 hours30


 


14




20° C.20 hours55


 


15




20° C.30 minute10
















TABLE D2







Compounds obtained in production examples 7–15









Production Example
Compound
Name of compound












7




2,6-Di-tert-butyl-4-(3-methyl-1-phenyl-5-oxo-4-pyrazolilidene)-2,5-cyclohexadiene-1-one


 


8




2,6-Di-tert-butyl-4-[3-methyl-1-(4-chlorophenyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


9




2,6-Di-tert-butyt-4-[3-methyl-1-(4-bromophenyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


10




2,6-Di-tert-butyl-4-(3-trifluoro-methyl-1-phenyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


11




2,6-Di-tert-butyt-4-[3-(2-furanyl)-1-phenyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one
















TABLE D3







Compounds obtained in Production Examples









Production Example
Compound
Name of compound





12




2,6-Di-tert-butyl-4-[3-(2-thienyl)-1-phenyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


13




1,3-Bis-3-(2,6-di-tert-butyl-1-oxo-2,5-cyclohexadiene-4-ylidene)-1-phenyl-5-oxo-4-pyrazolylbenzene


 


14




2,6-Di-tert-butyl-4-(2,2-dimethyl-1,3-dioxane-4,6-dione-5-ylidene)-2,5-cyclohexadiene-1-one


 


15




2,6-Di-tert-butyl-4-(1,3-diethyl-2-thioxo-4,6-dioxo-5-pyrimidinylidene)-2,5-cyclohexadiene-1-one
















TABLE E







The melting point and the results of the element analysis for each compounds of the


formulae (7)~(16)









Results of the element analysis










Compound
Melting Point(° C.)
Calculated Value(%)
Observed Valve(%)





 (7)
135.6~136.4
C: 72.58, H: 8.33, N: 8.91
C: 72.32, H: 8.45, N: 8.71


 (8)
165.7~166.0
C: 76.56, H: 7.50, N: 7.44
C: 76.66, H: 7.67, N: 7.70


 (9)
214.4~215.1
C: 70.15, H: 6.62, N: 6.82
C: 70.35, H: 6.48, N: 6.61


(10)
212.6~213.3
C: 63.30, H: 5.98, N: 6.15
C: 63.41, H: 5.88, N: 6.03


(11)
159.0~159.5
C: 66.96, H: 5.85, N: 6.51
C: 67.11, H: 5.78, N: 6.34


(12)
200.5~201.0
C: 75.68, H: 6.59, N: 6.54
C: 75.47, H: 6.79, N: 6.83


(13)
227.5~228.1
C: 72.94, H: 6.35, N: 6.30
C: 72.82, H: 6.21, N: 6.45


(14)
316.9~317.5
C: 78.17, H: 6.81, N: 7.01
C: 78.23, H: 6.63, N: 6.88



(Decomposition)


(15)
153.8~154.5
C: 69.34, H: 7.56
C: 69.27, H: 7.66


(16)
127.3~128.2
C: 65.64, H: 7.51, N: 6.96
C: 65.71, H: 7.39, N: 6.81
















TABLE F







Measurement results of Electron Mobilites for Example and


Comparative Example










Example
Electron Mobilites(cm2/V · sec)







Example 1
2 × 10−8



Example 2
6 × 10−8



Example 3
1 × 10−8



Example 4
1 × 10−8



Example 5
6 × 10−8



Example 6
3 × 10−8



Example 7
6 × 10−8



Example 8
1 × 10−8



Example 9
1 × 10−8



Example 10
4 × 10−8



Comparative Example 1
1 × 10−9

















TABLE G







The amount of luminescence of the organic electro luminescence


Elements obtained in Application Examples 1~10










Example
The amount of luminescence (cd/m2)














Application Example 1
100



Application Example 2
120



Application Example 3
60



Application Example 4
60



Application Example 5
110



Application Example 6
90



Application Example 7
100



Application Example 8
80



Application Example 9
80



Application Example 10
100

















TABLE H







Electrical Potential and Half-decay exposure for


Application Examples 11~20 and Comparative Example 2










Electrical Potential
Half-decay exposure


Example
(V)
(Lux · sec)





Application Example 11
640
3.4


Application Example 12
670
2.9


Application Example 13
620
4.8


Application Example 14
630
4.7


Application Example 15
660
3.3


Application Example 16
650
4.0


Application Example 17
650
3.6


Application Example 18
630
4.2


Application Example 19
620
4.3


Application Example 20
640
3.9


Comparative Example 2
580
6.1
















TABLE I







Electrical Potential and Half-decay exposure for


Application Examples 21~30 and Comparative Example 3










Electrical Potential
Half-decay exposure


Example
(V)
(Lux · sec)





Application Example 21
580
1.8


Application Example 22
590
1.4


Application Example 23
540
2.3


Application Example 24
560
2.0


Application Example 25
570
1.5


Application Example 26
550
1.9


Application Example 27
570
1.6


Application Example 28
550
1.9


Application Example 29
580
2.1


Application Example 30
560
1.7


Comparative Example 3
550
2.8
















TABLE J







Electrical Potential and Half-decay exposure for Application


Examples 31~40 and Comparative Example 4












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)







Application Example 31
530
2.0



Application Example 32
550
1.8



Application Example 33
520
2.3



Application Example 34
550
2.2



Application Example 35
570
1.7



Application Example 36
540
1.8



Application Example 37
530
1.9



Application Example 38
540
2.2



Application Example 39
550
2.1



Application Example 40
560
2.0



Comparative Example 4
540
3.0

















TABLE K







Electrical Potential and Half-decay exposure for Application


Example 41~50 and Comparative Example 5












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)







Application Example 41
−600
1.5



Application Example 42
−590
1.2



Application Example 43
−610
2.0



Application Example 44
−600
2.1



Application Example 45
−580
1.3



Application Example 46
−600
1.6



Application Example 47
−590
1.2



Application Example 48
−610
1.9



Application Example 49
−600
2.0



Application Example 50
−570
1.8



Comparative Example 5
−620
3.5

















TABLE L1







Synthesis examples obtained in production examples 23~31











Reaction Temperature


Production

Reaction Time


Example
A compound having an active methylene
Yield (%)












23




2520 hours49


 


24




2516 hours20


 


25




2020 hours64


 


26




2520 hours50


 


27




50 6 hours 5


 


28




50 6 hours 2


 


29




70 3 hours 9


 


30




2520 hours44


 


31




2520 hours39
















TABLE L2







Synthesis examples obtained in production examples 32~37











Reaction Temperature


Production

Reaction Time


Example
A compound having an active methylene
Yield (%)












32




2520 hours30


 


33




2520 hours49


 


34




2520 hours28


 


35




2520 hours38


 


36




2520 hours41


 


37




2520 hours36
















TABLE Ml







Compounds obtained in production examples 23~27









Production




Example
Compound
Name of compound












23
Formula (29)



2,6-Di-tert-butyl-4-[1-phenyl-3-(4-trifluoromethylphenyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


24
Formula (30)



2,6-Di-tert-butyl-4-[3-(2-furanyl)-1-(1-naphthyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


25
Formula (31)



2,6-Di-tert-butyl-4-[1-(2-benzothiazolyl)-3-methyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


26
Formula (32)



2,6-Di-tert-butyl-4-(1-phenyl-3-propyl-5-oxo-4-pyrazolilidene)-2,5-cyclohexadiene-1-one


 


27
Formula (33)



2,6-Di-tert-butyl-4-[1-tert-butyl-3-(2-thienyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one
















TABLE M2







Compounds obtained in production examples 28~33









Production




Example
Compound
Name of compound












28
Formula (34)



2,6-Di-tert-butyl-4-[1-tert-butyl-3-(2-furanyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


29
Formula (35)



2,6-Di-tert-butyl-4-(1-tert-butyl-3-trifluoromethyl-5-oxo-4-pyrazolilidene)-2,5-cyclohexadiene-1-one


 


30
Formula (36)



2,6-Di-tert-butyl-4-(3-iso-propyl-1-phenyl-5-oxo-4-pyrazolilidene)-2,5-cyclohexadiene-1-one


 


31
Formula (37)



2,6-Di-tert-butyl-4-(3-butyl-1-phenyl-5-oxo-4-pyrazolili-dene)-2,5-cyclohexadiene-1-one


 


32
Formula (38)



2,6-Di-tert-butyl-4-[3-methyl-1-(2-methylphenyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


33
Formula (39)



2,6-Di-tert-butyl-4-[1-(2-methylphenyl)-3-propyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one
















TABLE M3







Compounds obtained in production examples 34~37









Production




Example
Compound
Name of compound












34
Formula (40)



2,6-Di-tert-butyl-4-[1-(2-methylphenyl)-3-(2-thienyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


35
Formula (41)



2,6-Di-tert-butyl-4-[3-(2-furanyl)-1-(2-methylphenyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


36
Formula (42)



2,6-Di-tert-butyl-4-[3-(2-furanyl)-1-(4-iso-propylphenyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


37
Formula (43)



2,6-Di-tert-butyl-4-[3-propyl-1-(4-iso-propylphenyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one
















TABLE N







The melting point and the results of the element analysis for


each compounds of the formulae (29)~(43)









Results of the element analysis











Melting Point
Calculated Value
Observed Value


Compound
(° C.)
(%)
(%)





(29)
261.0~262.9
C: 71.13, H: 5.77, N: 5.53
C: 71.34, H: 5.42, N: 5.32


(30)
175.0~175.5
C: 77.80, H: 6.32, N: 5.85
C: 77.67, H: 6.12, N: 5.65


(31)
260.9~261.7
C: 69.26, H: 6.28, N: 9.69
C: 69.07, H: 6.48, N: 9.71


(32)
155.4~156.1
C: 77.19, H: 7.97, N: 6.92
C: 77.23, H: 7.82, N: 6.67


(33)
179.9~180.6
C: 70.72, H: 7.60, N: 6.60
C: 70.58, H: 7.48, N: 6.55


(34)
153.7~154.4
C: 73.50, H: 7.90, N: 6.86
C: 73.24, H: 7.95, N: 6.77


(35)
130.7~131.4
C: 64.37, H: 7.12, N: 6.82
C: 64.49, H: 7.02, N: 6.93


(36)
166.4~167.1
C: 77.19, H: 7.97, N: 6.92
C: 77.35, H: 7.86, N: 6.83


(37)
149.6~150.2
C: 77.48, H: 8.19, N: 6.69
C: 77.63, H: 8.35, N: 6.65


(38)
68.0~70.0
C: 76.89, H: 7.74, N: 7.17
C: 76.65, H: 7.57, N: 7.01


(39)
87.1~87.9
C: 77.48, H: 8.19, N: 6.69
C: 77.62, H: 8.34, N: 6.82


(40)
170.0~170.7
C: 73.33, H: 6.59, N: 6.11
C: 73.37, H: 6.67, N: 6.34


(41)
154.0~154.5
C: 75.99, H: 6.83, N: 6.33
C: 75.82, H: 6.97, N: 6.51


(42)
157.8~158.5
C: 76.57, H: 7.28, N: 5.95
C: 76.77, H: 7.12, N: 6.01


(43)
75.0~78.0
C: 77.99, H: 8.58, N: 6.27
C: 78.12, H: 8.45, N: 6.34
















TABLE O







Measurement results of Electron mobilities for example 11~25


and Comparative example










Example
Electron mobilities(cm2/V · sec)







Example 11
1 × 10−8



Example 12
3 × 10−8



Example 13
3 × 10−8



Example 14
1 × 10−7



Example 15
5 × 10−8



Example 16
2 × 10−7



Example 17
1 × 10−8



Example 18
1 × 10−7



Example 19
1 × 10−7



Example 20
8 × 10−8



Example 21
6 × 10−8



Example 22
2 × 10−7



Example 23
2 × 10−7



Example 24
4 × 10−8



Example 25
2 × 10−7



Comparative Example 1
1 × 10−9

















TABLE P







The amount of luminescence of the organic electro luminescence


elements obtained in Application Examples 51~65











The amount of



Example
luminescence (cd/m2)














Application example 51
60



Application example 52
100



Application example 53
90



Application example 54
140



Application example 55
110



Application example 56
150



Application example 57
80



Application example 58
130



Application example 59
150



Application example 60
130



Application example 61
120



Application example 62
130



Application example 63
120



Application example 64
70



Application example 65
130

















TABLE Q







Electrical Potential and half-decay exposure for Application


Examples 66~80 and Comparative Examples 2












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)







Application example 66
670
4.5



Application example 67
640
4.6



Application example 68
630
4.3



Application example 69
650
2.4



Application example 70
640
3.8



Application example 71
620
2.3



Application example 72
660
4.7



Application example 73
650
2.7



Application example 74
670
2.6



Application example 75
680
2.9



Application example 76
630
3.9



Application example 77
640
3.7



Application example 78
670
3.5



Application example 79
660
3.9



Application example 80
640
2.8



Comparative Example 2
580
6.1

















TABLE R







Electrical Potential and half-decay exposure for Application


Examples 81~95 and Comparative Examples 3












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)







Application Example 81
600
2.4



Application Example 82
570
2.3



Application Example 83
560
2.2



Application Example 84
570
1.3



Application Example 85
560
1.6



Application Example 86
590
1.2



Application Example 87
570
2.1



Application Example 88
580
1.4



Application Example 89
570
1.3



Application Example 90
590
1.5



Application Example 91
600
1.9



Application Example 92
560
1.7



Application Example 93
580
1.9



Application Example 94
580
2.3



Application Example 95
570
1.6



Comparative Example 3
550
2.8

















TABLE S







Electrical Potential and Half-decay exposure for Application


Example 96~110 and Comparative Example 4












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)







Application Example 96
560
2.2



Application Example 97
540
2.1



Application Example 98
530
2.2



Application Example 99
550
1.6



Application Example 100
530
2.2



Application Example 101
540
1.5



Application Example 102
520
2.3



Application Example 103
550
1.7



Application Example 104
530
1.6



Application Example 105
570
1.8



Application Example 106
560
2.0



Application Example 107
530
1.9



Application Example 108
570
1.9



Application Example 109
560
2.2



Application Example 110
540
1.6



Comparative Example 4
540
3.0

















TABLE T







Electrical Potential and Half-decay exposure for Application


Example 111~125 and Comparative Example 5












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)







Application Example 111
−610
2.1



Application Example 112
−580
1.9



Application Example 113
−580
1.7



Application Example 114
−590
1.1



Application Example 115
−570
1.6



Application Example 116
−580
1.0



Application Example 117
−560
2.2



Application Example 118
−600
1.2



Application Example 119
−580
1.1



Application Example 120
−620
1.3



Application Example 121
−610
1.7



Application Example 122
−580
1.5



Application Example 123
−600
1.4



Application Example 124
−590
1.9



Application Example 125
−570
1.3



Comparative Example 5
−620
3.5

















TABLE U1







Synthesis examples obtained in production 38~46











Reaction Temperature


Production
A compound having an active
Reaction Time


Example
methylene
Yield (%)












38




25° C.20 hours53


 


39




25° C.20 hours34


 


40




25° C.20 hours31


 


41




25° C.20 hours36


 


42




25° C.20 hours29


 


43




25° C.20 hours32


 


44




25° C.20 hours21


 


45




25° C.20 hours25


 


46




25° C.20 hours31
















TABLE U2







Synthesis examples obtained in production 47~53











Reaction Temperature


Production
A compound having an active
Reaction Time


Example
methylene
Yield (%)












47




20° C.  3 hours41


 


48




20° C.1.5 hours53


 


49




20° C. 20 hours30


 


50




20° C. 20 hours32


 


51




20° C. 20 hours18


 


52




20° C. 20 hours57


 


53




20° C. 20 hours36
















TABLE V1







Compounds obtained in production 38~43









Production




Example
Compound
Name of compound












38
Formula (45)



2,6-Di-tert-butyl-4-[1-(4-methylphenyl)-3-methyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


39
Formula (46)



2,6-Di-tert-butyl-4-[3-(4-methylphenyl)-1-propyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


40
Formula (47)



2,6-Di-tert-butyl-4-[1-(2-chlorophenyl)-3-methyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


41
Formula (48)



2,6-Di-tert-butyl-4-[1-(2-chlorophenyl)-3-propyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


42
Formula (49)



2,6-Di-tert-butyl-4-[1-(2-chlorophenyl)-3-(2-thienyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


43
Formula (50)



2,6-Di-tert-butyl-4-[1-(2-chlorophenyl)-3-(2-furanyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one
















TABLE V2







Compounds obtained in production 44~49









Production




Example
Compound
Name of compound












44
Formula (51)



2,6-Di-tert-butyl-4-[3-methyl-1-(2-pyridinyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


45
Formula (52)



2,6-Di-tert-butyl-4-[3-propyl-1-(2-pyridinyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


46
Formula (53)



2,6-Di-tert-butyl-4-[3-(2-furanyl)-1-(2-pyridinyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


47
Formula (54)



2,6-Di-tert-butyl-4-[1-(3-chlorophenyl)-3-methyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


48
Formula (55)



2,6-Di-tert-butyl-4-[1-(3-chlorophenyl)-3-propyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


49
Formula (56)



2,6-Di-tert-butyl-4-[1-(3-chlorophenyl)-3-(2-thienyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one
















TABLE V3







Compounds obtained in production 50~53









Production




Example
Compound
Name of compound












50
Formula (57)



2,6-Di-tert-butyl-4-[1-(2,5-dichlorophenyl)-3-propyl-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


51
Formula (58)



2,6-Di-tert-butyl-4-[1-(2,5-dichlorophenyl)-3-(2-thienyl)-5-oxo-4-pyrazolilidene]-2,5-cyclohexadiene-1-one


 


52
Formula (59)



2,6-Di-tert-butyl-4-(1,2-diphenyl-3,5-dioxo-4-pyrazolilidene)-2,5-cyclohexadiene-1-one


 


53
Formula (60)



2,6-Di-tert-butyl-4-(1,2-dimethyl-3,5-dioxo-4-pyrazolilidene)-2,5-cyclohexadiene-1-one
















TABLE W







The melting point and the results of the element analysis for each compounds of


the formulae(45)~(60)










Melting Point
Results of the element analysis










Compound
(° C.)
Calculated Value (%)
Observed Value (%)





(45)
188.6~189.2
C: 76.89, H: 7.74, N: 7.17
C: 76.68, H: 7.45, N: 7.22


(46)
154.6~155.0
C: 77.48, H: 8.19, N: 6.69
C: 77.67, H: 8.01, N: 6.59


(47)
71.7~72.4
C: 70.15, H: 6.62, N: 6.82
C: 70.22, H: 6.72, N: 6.70


(48)
116.8~117.5
C: 71.14, H: 7.12, N: 6.38
C: 71.18, H: 7.34, N: 6.48


(49)
179.0~179.3
C: 67.70, H: 5.68, N: 5.85
C: 67.56, H: 5.60, N: 5.92


(50)
178.8~179.3
C: 70.05, H: 5.88, N: 6.05
C: 70.20, H: 5.81, N: 6.00


(51)
193.2~193.8
C: 73.18, H: 7.21, N: 11.13
C: 73.30, H: 7.24, N: 11.24


(52)
138.4~139.1
C: 74.04, H: 7.70, N: 10.36
C: 74.24, H: 7.81, N: 10.26


(53)
222.5~222.9
C: 72.71, H: 6.34, N: 9.78
C: 72.62, H: 6.15, N: 9.82


(54)
162.9~163.5
C: 70.15, H: 6.62, N: 6.82
C: 70.31, H: 6.32, N: 6.68


(55)
165.8~166.3
C: 71.14, H: 7.12, N: 6.38
C: 71.26, H: 7.03, N: 6.42


(56)
179.7~181.2
C: 67.70, H: 5.68, N: 5.85
C: 67.81, H: 5.61, N: 5.78


(57)
131.5~132.1
C: 65.96, H: 6.39, N: 5.92
C: 65.83, H: 6.49, N: 5.81


(58)
137.6~138.9
C: 63.16, H: 5.10, N: 5.46
C: 63.33, H: 5.21, N: 5.34


(59)
174.8~175.8
C: 76.63, H: 6.65, N: 6.16
C: 76.68, H: 6.56, N: 6.19


(60)
162.8~164.0
C: 69.06, H: 7.93, N: 8.48
C: 69.15, H: 7.82, N: 8.28
















TABLE X







Measurement results of electron mobilities for example 26~41


and Comparative examples










Example
Electron Mobilities(cm2/V · sec)







Example 26
1 × 10−7



Example 27
1 × 10−7



Example 28
4 × 10−8



Example 29
7 × 10−7



Example 30
1 × 10−7



Example 31
2 × 10−7



Example 32
2 × 10−7



Example 33
1 × 10−7



Example 34
8 × 10−8



Example 35
2 × 10−8



Example 36
4 × 10−8



Example 37
4 × 10−8



Example 38
2 × 10−8



Example 39
1 × 10−7



Example 40
7 × 10−8



Example 41
6 × 10−8



Comparative examples 1
1 × 10−9

















TABLE Y







The amount of luminescence of the organic electro luminescence


elements obtained in Application Examples 126~141











The amount of



Example
luminescence (cd/m2)














Application Example 126
100



Application Example 127
110



Application Example 128
70



Application Example 129
150



Application Example 130
120



Application Example 131
120



Application Example 132
90



Application Example 133
120



Application Example 134
80



Application Example 135
70



Application Example 136
90



Application Example 137
80



Application Example 138
60



Application Example 139
120



Application Example 140
90



Application Example 141
100

















TABLE Z







Electrical potential and half-decay exposure for Application


Examples 142~157 and Comparative example 2












Electrical
Half-decay exposure



Example
potential (V)
(Lux · sec)







Application Example 142
650
3.5



Application Example 143
630
3.2



Application Example 144
620
4.5



Application Example 145
690
2.2



Application Example 146
640
3.4



Application Example 147
670
3.0



Application Example 148
650
3.0



Application Example 149
660
3.2



Application Example 150
680
4.3



Application Example 151
670
4.5



Application Example 152
680
4.2



Application Example 153
620
4.0



Application Example 154
650
4.6



Application Example 155
630
3.3



Application Example 156
650
4.4



Application Example 157
680
4.5



Comparative example 2
580
6.1

















TABLE AA







Electrical potential and half-decay exposure for Application


Example 158~173 and Comparative example 3












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)















Application Example 158
600
1.6



Application Example 159
540
1.3



Application Example 160
570
2.5



Application Example 161
600
1.1



Application Example 162
580
1.6



Application Example 163
610
1.3



Application Example 164
590
1.2



Application Example 165
580
1.3



Application Example 166
600
2.3



Application Example 167
570
2.4



Application Example 168
580
2.2



Application Example 169
560
2.1



Application Example 170
570
2.3



Application Example 171
590
1.4



Application Example 172
560
2.4



Application Example 173
580
2.5



Comparative example 3
550
2.8

















TABLE AB







Electrical potential and half-decay exposure for Application


Example 174~189 and Comparative example 4












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)















Application Example 174
550
2.2



Application Example 175
530
1.9



Application Example 176
540
2.4



Application Example 177
580
1.5



Application Example 178
530
1.8



Application Example 179
560
1.6



Application Example 180
550
1.6



Application Example 181
570
1.8



Application Example 182
540
2.6



Application Example 183
580
2.4



Application Example 184
570
2.0



Application Example 185
520
1.9



Application Example 186
560
2.1



Application Example 187
550
1.7



Application Example 188
590
2.3



Application Example 189
580
2.5



Comparative example 4
540
3.0

















TABLE AC







Electrical potential and half-decay exposure for Application


Example 190~205 and Comparative example 5












Electrical
Half-decay exposure



Example
Potential (V)
(Lux · sec)















Application Example 190
−590
1.9



Application Example 191
−570
1.8



Application Example 192
−560
2.3



Application Example 193
−600
1.1



Application Example 194
−570
1.6



Application Example 195
−590
1.5



Application Example 196
−550
1.7



Application Example 197
−590
1.6



Application Example 198
−580
1.9



Application Example 199
−590
2.1



Application Example 200
−570
1.9



Application Example 201
−560
2.0



Application Example 202
−580
2.3



Application Example 203
−570
1.7



Application Example 204
−620
2.0



Application Example 205
−610
2.1



Comparative Example 5
−620
3.5

## Claims

1. An electrophotographic photoreceptor comprising an electroconductive substrate having at least a photosensitive layer disposed thereon, wherein the photosensitive layer contains as a charge-transfer material a compound represented by the following general formula (4):




wherein X and Y are oxygen, R1 and R3 are tert-butyl, R2 and R4 are hydrogen, R5 is alkyl or aryl, R6 is aryl.

2. An electrophotographic photoreceptor comprising an electroconductive substrate having at least a photosensitive layer disposed thereon, wherein the photosensitive layer contains as a charge-transfer material a compound represented by the following general formula (4):




wherein X and Y are oxygen, R1 and R3 are tert-butyl, R2 and R4 are hydrogen, R5 is methyl, and R6 is selected from a group consisting of methyl, phenyl, para-chlorophenyl, para-bromophenyl, ortho-methylphenyl, para-methylphenyl, ortho-chlorophenyl, meta-chlorophenyl.

3. An electrophotographic photoreceptor comprising an electroconductive substrate having at least a photosensitive layer disposed thereon, wherein the photosensitive layer contains as a charge-transfer material a compound represented by the following general formula (4):




wherein X and Y are oxygen, R1 and R3 are tert-butyl, R2 and R4 are hydrogen, R5 is n-propyl, and R6 is selected from a group consisting of phenyl, ortho-methylphenyl, para-isopropylphenyl, para-methylphenyl, ortho-chlorophenyl, meta-chlorophenyl, and 2,5-dichlorophenyl.