JPH10330333A - New trisubstituted ethylene compound having cycloheptanylidene structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound excellent in electric charge transportability and storage stability and used as a sensitizer for electrophotography and as a material for organic electroluminescent elements. SOLUTION: A compound of formula I [(A) is an o-arylene; R1 , R2 are each an alkyl, an aryl; Ar1 is an arylene; R3 , R4 are each a halogen, an alkyl, an aryl, etc.; (s), (m) are each 0-4], etc., a compound of formula II. The compound of formula I is obtained by subjecting a compound of formula III and a compound of formula IV to a double bond-forming reaction (Witting-Horner-Emmons reaction) in the presence of a base such as sodium or potassium alkoxide, sodium hydride or sodium amide in a solvent such as ethanol, toluene, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide preferably at a reaction temperature of -10 to 100 deg.C for a reaction time of 1-48 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a trisubstituted ethylene compound useful as a charge transporting agent for use in electrophotographic photoreceptors and organic electroluminescent (EL) devices.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been used as photoconductive materials for photoconductors used in electrophotography. Xerography, as already disclosed by Carlson in U.S. Pat. No. 2,297,691, involves coating a normally insulating material whose electrical resistance varies according to the dose received during image exposure. A photoconductive material made of a support is used. The photoconductive material is generally first given a uniform surface charge in the dark after a suitable period of dark adaptation. Next, it is exposed to a pattern of illumination that has the effect of reducing surface charge depending on the relative energy contained in the various parts of the illumination pattern. The surface charge or the electrostatic latent image remaining on the surface of the photosensitive layer in this manner is then brought into a visible image by contacting the surface with an appropriate electrophoretic display material.
Such an indicator substance, ie, a toner, whether contained in an insulating liquid or a dry carrier, can be deposited on the surface of the photosensitive layer according to the charge pattern. The attached display substance can be fixed by known means such as heat pressure and solvent vapor. And a second support (eg, paper,
Film, etc.). Similarly, the electrostatic latent image can be transferred to a second support and developed there. Electrophotography is one of image forming methods for forming an image in this way. The basic characteristics required of the photoreceptor in such an electrophotographic method include:
(1) Charging can be performed at an appropriate position in a dark place, (2) Dissipation of electric charge in a dark place is small, and (3) Electric charge can be quickly deviated by light irradiation. It is true that the conventionally used inorganic materials have many advantages as well as various disadvantages. For example, selenium, which is widely used at present, satisfies the above conditions (1) to (3), but the production conditions are difficult, the production cost is high, there is no flexibility, and the selenium is processed into a belt shape. However, there are disadvantages such as difficulty in carrying out the method, and sensitivity to heat and mechanical impacts, requiring careful handling. Cadmium sulfide and zinc oxide are used as photoreceptors by dispersing them in a resin as a binder.
Due to mechanical defects such as smoothness, hardness, tensile strength, and friction resistance, it cannot be used repeatedly as it is.

In recent years, electrophotographic photoreceptors using various organic substances have been proposed to eliminate the disadvantages of these inorganic substances, and some of them have been put to practical use. For example, a photoreceptor comprising poly-N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one (U.S. Pat.
No. 484,237), those obtained by sensitizing poly-N-vinylcarbazole with a pyrylium salt-based dye (JP-B-48-25).
No. 658), and a photoreceptor containing an organic pigment as a main component
7-37543), a photoreceptor containing a eutectic complex composed of a dye and a resin as a main component (JP-A-47-10735), and a photoreceptor containing a hydrazone-based compound as a main component (JP-A-57-735).
Nos. 101844 and 54-150128), and a photoreceptor containing an aromatic tertiary amine compound as a main component (Japanese Patent Publication No.
32372), and a photoreceptor containing a stilbene compound as a main component (JP-A-58-198043). These photoconductors have excellent properties,
Although it is considered to be of high value in practical use, considering the various requirements for the photoreceptor in electrophotography, it has not been possible to obtain anything that sufficiently satisfies these requirements. is there. Therefore, studies on electrophotographic photoreceptors using organic substances have been actively conducted at present, and recently published patent applications have disclosed novel hydrazone compounds (Japanese Patent Application Laid-Open No. 8-143550) and carbazole-based stilbene compounds. (JP-A-8-59615) and trisubstituted ethylene compounds (JP-A-63-225660,
JP-A-9-59256) and the like are disclosed.

[0004] Vanslike and Tan et al., For example, US Pat. Nos. 4,539,507 and 4,720,432.
Phenyl group in JP-A-5-234681.
The use of aromatic tertiary amines containing phenylene or biphenylene groups in the hole-injection / transport zone of internally bonded organic EL devices improves light output stability and thereby extends operating life. . Improvements in the aromatic tertiary amine used in this hole injection transport zone to further measure the stability of light output have been attempted by many researchers, and have been reported in many patent applications and academic literature. I have. For example, Japanese Journal of App for biphenyl tertiary amines
led Physics, 27, L269 (198
8), JP-A-59-194393, Appl. Phys
s. Lett. 66, 2679 (1995);
-234681, 7-331238, 8-48
Regarding tertiary amines of the Sudaburst series, such as Appl. Phys
s. Lett. 65,807 (1994), Tokiko 7-
No. 110940 and the like. However, the performance of the conventionally known compounds is not sufficient, and further improvement is desired.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel compound used for an electrophotographic photoreceptor, an organic electric field generating element and the like. A further object of the present invention is to provide a novel trisubstituted ethylene compound which is used for an electrophotographic photoreceptor and an organic electroluminescence (EL) device and has excellent charge transporting ability and storage stability.

[0006]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that a trisubstituted ethylene compound having a specific cycloheptanylidene structure in a molecule has a high charge transporting ability and storage stability. They have found that they are satisfied, and have made the present invention based on this finding.

That is, the present invention provides a trisubstituted ethylene compound represented by the general formula (I):

[0008]

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(Wherein (A) represents an o-arylene group; R ₁ and R ₂ represent an alkyl group or an aryl group; Ar ₁ represents an arylene group; R ₃ and R ₄ represent a halogen atom; , Aryl, alkoxy, aryloxy, dialkylamino, N-alkyl-N-arylamino or diarylamino groups, wherein s and m represent an integer of 0 to 4.). In the present invention, each group represented by (A), R ₁ , R ₂ , Ar ₁ , R ₃ and R ₄ in the general formula (I) is an unsubstituted group as apparent from the following description. It is meant to include not only those substituted with a substituent, but also those substituted with a substituent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Next, (A), Ar ₁ , R ₁ , R ₂ , R ₃ , R ₄ , s, m and n in the general formula (I) will be described.

(A) represents a substituted or unsubstituted o-arylene group. Specific examples thereof (shown as unsubstituted examples) include the following groups.

[0012]

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When (A) has a substituent, preferred substituents are the same as the substituents described in R ₃ and R ₄ described below.

Preferred (A) is a substituted or unsubstituted o
-Phenylene group, particularly preferably an unsubstituted or alkyl-substituted o-phenylene group.

Ar ₁ represents a substituted or unsubstituted arylene group. More specifically, Ar ₁ represents a substituted or unsubstituted phenylene, naphthylene, biphenylene or anthrylene group.

When Ar ₁ has a substituent, preferred substituents are the same as the substituents described later for R ₃ and R ₄ .

Preferred Ar ₁ is a substituted or unsubstituted phenylene group, particularly preferably an unsubstituted p-phenylene group.

R ₁ and R ₂ represent a substituted or unsubstituted alkyl or aryl group. The unsubstituted group is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 36 carbon atoms.

More specifically, methyl, ethyl, isopropyl, n-butyl, t-butyl, n-dodecyl,
Or an alkyl group such as cyclohexyl, or an aryl group such as phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, naphthacenyl, pentacenyl or pentaphenyl. When these groups have a substituent, the substituent is the same as the substituent which R ₃ and R ₄ described below may have. R ₁ and R ₂ may be bonded directly or indirectly via a methylene, ethylene or vinylene group to form a ring.

Preferred R ₁ and R ₂ are methyl, ethyl, isopropyl, benzyl, phenyl, 1-naphthyl or 2-naphthyl.

R ₃ and R ₄ represent a halogen atom, a substituted or unsubstituted alkyl, aryl, alkoxy, aryloxy, dialkylamino, N-alkyl-N-arylamino, or diarylamino group. A halogen atom of chlorine, bromine or iodine, an unsubstituted group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 36 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 36 carbon atoms. Aryloxy group, dialkylamino group having 2 to 20 carbon atoms, N-alkyl-N-arylamino group having 7 to 42 carbon atoms or 12 to carbon atoms
48 diarylamino groups.

More specifically, other than the halogen atom,
Alkyl groups such as methyl, ethyl, isopropyl, n-butyl, t-butyl, n-dodecyl, or cyclohexyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, naphthacenyl, aryl groups such as pentacenyl or pentaphenyl, methoxy,
Alkoxyl groups such as ethoxy, isopropoxy, n-hexyloxy, cyclohexyloxy, octyloxy, or dodecyloxy, aryloxy groups such as phenoxy, naphthoxy, anthracenoxy, or pentasenoxy, dimethylamino, diethylamino,
A dialkylamino group such as dibutylamino, dioctylamino or N-ethyl-N-butylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-isopropyl-N- (3-methylphenyl) An N-alkyl-N-arylamino group such as amino, N-methyl-N- (1-naphthyl) amino, or N-butyl-N- (1-naphthacenyl) amino, or diphenylamino, N-phenyl-N -(1-naphthyl) amino, N- (1-naphthyl) -N- (1-naphthyl) amino, N-phenyl-N- (1-anthracenyl) amino, or N- (1-anthracenyl) -N
A diarylamino group such as-(1-phenanthrenyl) amino;

When these groups have a substituent, the substituent may be a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group An arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, Examples include an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, an acyl group, a silyl group and an azolyl group.

R ₃ and R ₄ are preferably a halogen atom, an alkyl group, an alkoxy group, a dialkylamino group or a diarylamino group, and particularly preferably an alkyl group or a dialkylamino group.

S and m each represent an integer of 0 to 4, preferably 0 or 1.

Next, specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited to these.

[0027]

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[0028]

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[0029]

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[0030]

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Next, a method for synthesizing the compound of the present invention will be described below. A typical synthetic method is shown in (Scheme 1).

[0032]

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The double bond type reaction (synthesis of [ 3 ] by the reaction of [ 1 ] and [ 2 ]) in (Scheme 1) is Wit
Famous as the tig-Horner-Emmons reaction, the reaction is usually carried out in a solvent such as ethanol, triene, tetrahydrofuran, dimethylformamide, or dimethylsulfoxide using a base such as sodium or potassium alkoxide, sodium hydride or sodium amide. Reru ("New Experimental Chemistry Course" No. 14-
(I), p. 238, 1977, Maruzen Co., Ltd.).
The synthesis of [ 1 ] or [ 5 ] can be usually carried out by reacting the corresponding halide of chlorine, bromine or iodine with triethyl phosphite. The halide as the precursor of [ 5 ] can be synthesized via an alcohol obtained by reducing the metal hydride of [ 2 ]. The convertible group in the compound in the above scheme is a nitro group, an alkoxy group, an alkoxycarbonyl group or the like with respect to a functional group such as a hydroxyl group and a carboxyl group. The reaction between the compounds [ 1 ] and [ 2 ] is preferably performed in a molar ratio of the compounds [ 1 ] and [ 2 ] of 1:
0.5 to 1: 1.5, at a reaction temperature of -10 to 100 ° C,
The reaction can be performed for a reaction time of 1 to 48 hours, but is not limited thereto. The reaction between the compound [ 4 ] and the compound [ 5 ] is preferably performed at a molar ratio of 1: 0.5 between the compound [ 4 ] and the compound [ 5 ].
The reaction can be performed at a reaction temperature of -10 to 100 ° C for a reaction time of 0.5 to 48 hours, but is not limited thereto. Synthesis of [ 2 ] is Ber, Vol. 97,
1318 and 1329 (1964).

[0034]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Synthesis of Exemplified Compound (1)) 27.0 g (99.5 mmol) of diethyl 4-dimethylaminophenylmethylphosphonate and 26.0 g (101.4 mmol) of tribenzocycloheptatrienone were added to dimethyl sulfoxide ( DMSO) in 100 ml,
In it, 11.4 g of potassium t-butoxide (101.
6 mmol) and stirred at room temperature for about 20 hours. Water was added to the reaction solution, extracted with chloroform, and the extract concentrate was purified by silica gel chromatography to give 24.5 g of Exemplified Compound (1) as white crystals (yield: 68).
%) Could be obtained.

Example 2 (Synthesis of Exemplified Compound (3)) Diethyl 4-dibenzylaminophenylmethylphosphonate, tribenzocycloheptatrienone and potassium t-butoxide were reacted in DMSO in the same molar ratio as in Example 1. Exemplified compound (3) as white crystals in a yield of 70
% Could be obtained.

Example 3 (Synthesis of Exemplified Compound (4)) 27.3 g of 4-formyltriphenylamine (100 m
mol) and 31.4 g (95 mmol) of diethyl tribenzocycloheptatrien-9-ylphosphonate in DM
Potassium t-butoxide 1 in SO (300 ml) solution
1.0 g (98 mmol) was added, and the mixture was stirred at room temperature for about 24 hours. Water was added to the reaction solution, extraction was performed with chloroform, and the extract concentrate was separated and purified by silica gel chromatography to obtain 30.4 g (yield 66%) of Exemplified Compound (4) as white crystals. Was.

Example 4 (Synthesis of Exemplified Compound (6)) Diethyl 4- [bis (4-methylphenyl) amino] phenylmethylphosphonate 42.3 g (99.9 mmol)
l) and 2-methyltribenzocycloheptatrienone 2
5.7 g (95.1 mmol) in 300 ml of DMSO
Dissolved in potassium t-butoxide 11.2 g
(99.8 mmol), and the mixture was stirred at room temperature for about 20 hours. Water was added to the reaction solution, the mixture was extracted with chloroform, and the extract was concentrated and then separated and purified by silica gel chromatography to give 31.6 g of Exemplified Compound (6) as white crystals.
(63% yield).

Example 5 (Synthesis of Exemplified Compound (20)) 4- [5- (5H-dibenzo [b, f] azepinyl)]
29.0 g (97.5 mmol) of benzaldehyde and 32.2 g (97.5 mmol) of diethyl tribenzocycloheptatrien-9-yl phosphonate in DMSO (3
1 ml of potassium t-butoxide in the solution.
(98.2 mmol), and the mixture was stirred at room temperature for about 25 hours. Water was added to the reaction solution, extracted with chloroform, dried and concentrated, and the residue was separated and purified by silica gel chromatography to give Exemplified Compound (20) as white crystals.
1.0 g (yield 67%) was obtained.

[0040]

The novel tri-substituted ethylene compound having a cycloheptanylidene structure according to the present invention has excellent charge transporting ability and storage stability, and can be used as a material for an electrophotographic photosensitive member or an organic electroluminescent (EL) device. Is effective in improving their performance. In particular, the compound of the present invention gave a high-performance photoreceptor when used in an electrophotographic photoreceptor, and greatly improved its performance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 223/22 C07D 223/22 295/02 295/02 Z 295/06 295/06 Z 307/87 307/87 G03G 5/06 314 G03G 5/06 314 314Z H05B 33/22 H05B 33/22 // C09K 11/06 C09K 11/06 Z

Claims (1)

[Claims] 1. A trisubstituted ethylene compound represented by the general formula (I). Embedded image (Wherein (A) represents an o-arylene group; R ₁ and R ₂ represent an alkyl group or an aryl group; Ar ₁ represents an arylene group; R ₃ and R ₄ represent a halogen atom, alkyl, aryl, Represents an alkoxy, aryloxy, dialkylamino, N-alkyl-N-arylamino or diarylamino group, wherein s and m are 0
Represents an integer of 1 to 4. )