JP2761830B2 - Novel 9,10-bis (N, N-diarylamino) phenanthrene derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 9,10-bis (N, N-diarylamino) phenanthrene derivative useful as an organic photoconductive material for use in a charge transport layer of an electrophotographic photosensitive member, and a method for producing the same. Is provided.

[0002]

2. Description of the Related Art The electrophotographic method invented by Carlson (US Pat. No. 2,297,691) is one of image forming methods and is also called xerography. The principle is that the photoreceptor is first charged by corona discharge, then exposed to a light image to convert it to an electrostatic latent image, then colored toner is applied and developed, and the resulting toner image is transferred to paper. There are features. The characteristics required of such an electrophotographic photoreceptor are: 1) it can be sufficiently charged at a corona receiving potential in a dark place; 2) it has a high ability to hold a charged position; 3) its surface charge is quickly lost by light irradiation. And the like.

Conventionally, inorganic photoconductive materials such as selenium, cadmium sulfide, and zinc oxide have been used as photoconductive materials for electrophotography. These inorganic photoconductive materials have advantages such as high safety and high printing durability, but have some disadvantages, for example, high production cost, poor workability,
In addition, toxicity problems have been pointed out.

In order to solve these problems, research on an electrophotographic photosensitive member using an organic photoconductive material has been actively conducted in recent years. Organic photoconductive materials have many advantages, such as light weight, variety of shapes, low cost, and no pollution, and many organic compounds have been proposed. For example, hydrazone derivatives (US Pat. No. 3,717,462, JP-A-54-59,143, US Pat. No. 4,150,9)
No. 87), triarylpyrazoline derivatives (US Pat. No. 3,837,851, US Pat. No. 3,180,729)
), Diarylalkane derivatives (US Pat. No. 3,82
0,989, JP-A-51-93,224, JP-A-5-93,224
5-108,667), arylamine derivatives (U.S. Pat. No. 3,180,730, JP-A-55-1444.2).
No. 50, JP-A-56-119,132) and stilbene derivatives (JP-A-58-190,953, JP-A-59-195,658) and the like are known. But,
In the electrophotographic photoreceptor using these compounds in the charge transport layer as an organic photoconductive material, at present, the chargeability, sensitivity and residual potential are not always satisfactory.
It has been desired to develop a charge transport material having an excellent charge transport function and which can be used for a long time.

[0005]

In view of such a situation, the present inventors have made intensive studies on organic photoconductors having excellent usability in order to solve the problems of the prior art. Useful novel 9,10-bis (N, N-diarylamino) phenanthrene derivatives and a method for producing the same have been found, and the present invention has been completed.

[0006]

That is, the present invention provides a 9,10-bis (N, N-diarylamino) phenanthrene derivative represented by the following general formula (1) and a method for producing the same. Things.

[0007]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R
₆ , R ₇ and R ₈ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. However, R ₅ , R ₆ , R ₇ and R ₈ must not be simultaneously hydrogen atoms. The 9,10-bis (N, N-diarylamino) phenanthrene derivative represented by the general formula (1) obtained in the present invention is a novel compound. To explain the embodiment of the present invention in more detail, a basic reaction for obtaining a 9,10-bis (N, N-diarylamino) phenanthrene derivative is represented by the following reaction formula (A).

[0009]

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[0010]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R
₆ , R ₇ and R ₈ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. However, R ₅ , R ₆ , R ₇ and R ₈ must not be simultaneously hydrogen atoms. X represents a halogen atom.

That is, a 9,10-phenanthrenequinone derivative represented by the general formula (3) obtained by a known method [J. Chem. Soc. , 1429 (197
1). Chem. Soc. Chem. Comm. ,
397 (1978)] and an aniline derivative represented by the general formula (2) in the presence of an acid catalyst to form a diimine derivative represented by the general formula (4), and then reduced,
The diamine derivative represented by the general formula (5) is obtained, and the halobenzene derivative represented by the general formula (5) is reacted with the halobenzene derivative represented by the general formula (6) in the presence of a base and a catalyst. The triarylamine derivative represented by 1) can be synthesized in high yield.

The general formulas (1), (2), (3),
In (4), (5) and (6), R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group; a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Alkoxy groups such as groups; and halogen atoms such as chlorine, bromine and iodine. X is a halogen atom such as chlorine, bromine and iodine.

Examples of the acid catalyst used for the synthesis (Formula 6) of the diimine derivative represented by the general formula (4) include organic sulfuric acid such as concentrated sulfuric acid and P-toluenesulfonic acid;
Also, for example, polyphosphoric acid, TiCl ₄ , ZnCl ₂ , A
Lewis acids such as lCl ₃ , SnCl ₄ , BF ₃
For example, a polymer carrier to which a sulfonic acid group is bonded, such as polystyrenesulfonic acid and Nafion, may be mentioned. The amount used is 2 to 5.0 times the mol of the raw material, preferably 3.0 to 5.0 times.
3.5 molar times is appropriate.

The reducing agent used in the synthesis of the diamine derivative represented by the general formula (5) is, for example, H ₂ / P
t, H ₂ / Pd, H ₂ / Ni, LiAlH ₄ , NaBH
₄ , Zn, Sn and the like. The amount used is 4 to 10.0 times mol, preferably 5 to 6 times mol of the raw material. In the case where the aniline derivative represented by the general formula (2) used in Chemical formula 6 has a P-position electron donating group such as P-toluidine and has high activity, the product is expected to have the general formula (4) The compound was not the compound shown, but a compound represented by the general formula (5) in which reduction was further advanced. In such a case, the reduction reaction operation corresponding to Chemical formula 7 can be omitted.

As the base used in the synthesis of the 9,10-bis (N, N-diarylamino) phenanthrene derivative represented by the general formula (1) (Chem. 7), for example, potassium carbonate, lithium hydroxide, sodium hydroxide , Potassium hydroxide, inorganic bases such as pyridine, picoline, triethylamine, N, N-dimethylaniline,
N-methylpyrrolidine, 1,5-diazabicyclo [4.
3.0] nonene-5 (DBN), 1,5-diazabicyclo [5.4.0] undecene-5 (DBU), 1,4-
Organic bases such as diazabicyclo [2.2.0] octane (DBCO) can be mentioned. Examples of the catalyst include copper powder, copper oxide, cuprous chloride, copper sulfate, copper acetate and the like. The solvent may or may not be used. When used, the solvent dissolves the diamine derivative represented by the general formula (5) and the halobenzene derivative represented by the general formula (6), which are the raw materials, to facilitate the reaction. Anything can be allowed to proceed,
For example, aromatic hydrocarbons such as toluene and xylene and nitrobenzene, dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide,
N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (H
Aprotic polar solvents such as MPA) are preferred. The reaction temperature to be applied can be appropriately selected so that the production rate of the target compound represented by the general formula (1) becomes the best, and 8
0 to 300 ° C, particularly preferably 150 to 260 ° C.
The reaction may be performed under normal pressure, but may be performed under pressure to accelerate the reaction and shorten the reaction time.

The novel 9,10-bis (N, N-diarylamino) phenanthrene derivative obtained by the present invention is useful as a function-separated electrophotographic photosensitive member using an organic or inorganic pigment as a charge generating substance. It can be used for an electrophotographic apparatus and a facsimile provided with the electrophotographic photosensitive member.

[0018]

When the novel 9,10-bis (N, N-diarylamino) phenanthrene derivative represented by the general formula (1) according to the present invention is used as a charge transporting material for an electrophotographic photoreceptor, the chargeability is improved. It is characterized by excellent initial characteristics such as sensitivity, residual potential, etc., and has no characteristic deterioration in repeated use against corona discharge or visible light, and is particularly excellent in light resistance, which is a practical requirement. We are satisfied with performance enough.

[0019]

The present invention will be described in more detail with reference to the following Examples, which, however, do not limit the present invention. [Example 1] N, N'-di (4-methylphenyl)-
N, N'-di (4-n-butylphenyl) -2-methyl-9,10-diaminophenanthrene (Compound No.
Synthesis of 1) 5.7 g of 2-methyl-9,10-phenanthrenequinone and pn-butylaniline in 114 ml of toluene.
After adding 7 g and 11 ml of pyridine, the mixture was cooled to 10 ° C. or lower, and a solution of 14.9 g of titanium tetrachloride dissolved in 17 ml of toluene was added dropwise. After the completion of the dropwise addition, the reaction was carried out at 20 ° C. for 8 hours. After completion of the reaction, 220 ml of water and 5
7 ml was added, and after liquid separation, the organic layer was concentrated under reduced pressure.
Ethanol (57 ml) was added to the concentrated solution, and after heating under reflux, the internal temperature was cooled to room temperature and filtered, and N, N'-
Di (4-n-butylanilino) -2-methyl-9,10
5.1 g of phenanthrene (41% yield) was obtained. 132-133 ° C Next, 15.9 g of p-iodotoluene and potassium carbonate 6.
A mixture of 7 g, 0.1 g of copper sulfate and 5.9 g of N, N'-di (4-n-butylanilino) -2-methyl-9,10-phenanthrene was heated at 210 ° C. for 18 hours under a nitrogen stream. 40 ml of water and 40 m of chloroform were added to the reaction mixture.
l, and the mixture was separated. The residue obtained by concentrating the chloroform layer under reduced pressure was recrystallized from n-hexane. 2.6 g (yield 32%, N in Table 1)
o. 1 compound) was obtained. Melting point: 153 to 154 ° C

Example 2 N, N'-di (4-methylphenyl) -N, N'-di (4-n-pentylphenyl-2,3-dimethyl-9,10-diaminophenanthrene (compound No. Synthesis of 2) 1,2-Naphthoquinone 25 in 200 ml of chloroform
g, 2,3-dimethyl-1,3-butadiene 17.4 g
After heating and refluxing for 23 hours, the reaction was cooled to room temperature, filtered, washed with 100 ml of ethyl acetate, and the crystals were washed with 5.5 g of brown 2,3-dimethyl-9,10-phenanthrenequinone (yield 15%). %). 5.5 g of 2,3-dimethyl-9,10-phenanthrenequinone, 15.4 g of pn-pentylaniline and 11 ml of pyridine were added to 109 ml of toluene, and after cooling to 10 ° C. or lower, 13.4 g of titanium tetrachloride was added to toluene. A solution dissolved in 54 ml was added dropwise. After the completion of the dropwise addition, the reaction was carried out at 20 ° C. for 8 hours. After completion of the reaction, 220 ml of water and 57 ml of ethyl acetate were added. After liquid separation, the organic layer was concentrated under reduced pressure. Ethanol (57 ml) was added to the concentrate, and after heating under reflux, the internal temperature was cooled to room temperature and filtered, and N, N'-di (4-n-pentylanilino) -2,3-dimethyl-9 as a pale yellow powder was obtained. And 10-phenanthrene (7 g, yield 58%). Melting point 118-1
19 ° C. Next, 21.3 g of p-iodotoluene and potassium carbonate 7.
A mixture of 4 g, copper sulfate 0.2 g, and N, N'-di (4-n-pentylanilino) -2,3-dimethyl-9,10-phenanthrene 7 g was heated at 210 ° C. for 18 hours under a nitrogen stream. did. 40 ml of water and 40 ml of chloroform were added to the reaction mixture.
After the separation of the chloroform layer, the residue obtained by concentrating the chloroform layer under reduced pressure was recrystallized from n-hexane. 4.3 g (46% yield, No. 2 compound in Table 1) was obtained. 83-84 ° C

Example 3 N, N'-di (4-methylphenyl) -N, N'-di (4-n-pentylphenyl-2,3,6,7-tetramethyl-9,10- Synthesis of diaminophenanthrene [Compound No. 7] 600 ml of benzene, 73.9 g of 2,3-dimethyl-1,3-butadiene, 60 g of 2,3-dihydroxybenzoic acid, and 186 g of manganese dioxide were added to an autoclave.
After reacting at 110 ° C. for 26 hours, the mixture was filtered, the filtrate was concentrated and purified by column, and 6.6 g of red crystals of 2,3,6,7-tetramethyl-9,10-phenanthrenequinone (6.6 g in yield). 4%). 2,3,6,7 in 107 ml of toluene
-Tetramethyl-9,10-phenanthrenequinone 6
g, pn-pentylaniline 14.8 g, pyridine 1
Add 1 ml and cool to 10 ° C or less.
A solution of 3.2 g dissolved in 53 ml of toluene was added dropwise.
After the completion of the dropwise addition, the reaction was carried out at 20 ° C. for 8 hours. After completion of the reaction, 220 ml of water and 57 ml of ethyl acetate were added,
After liquid separation, the organic layer was concentrated under reduced pressure. Ethanol (57 ml) was added to the concentrate, and after heating under reflux, the internal temperature was cooled to room temperature and filtered, and N, N'-di (4-n-pentylanilino) -2,3,6,7 as a pale yellow powder was obtained. -8.4 g (66% yield) of tetramethylphenanthrene was obtained. Melting point 192-1
93 ° C. Next, 18.9 g of p-iodotoluene and potassium carbonate 8.
A mixture of 0 g, copper sulfate 0.2 g, and N, N'-di (4-n-pentylanilino) -2,3,6,7-tetramethylphenanthrene 9 g was heated at 210 ° C. for 18 hours under a nitrogen stream. did. 45 ml of water and 45 ml of chloroform were added to the reaction mixture.
After the separation of the chloroform layer, the residue obtained by concentrating the chloroform layer under reduced pressure was recrystallized from n-hexane. 3.4 g (yield 32%, compound No. 7 in Table 1) was obtained. 166-167 ° C

The structure and properties of the novel 9,10-bis (N, N-diarylamino) phenanthrene derivative represented by the general formula (1) synthesized by the method of the present invention are shown in Table A below.

[0023]

[Table 1]

Application Example 1 Application Example 2 2 parts of a bisazo compound represented by Chemical Formula 8 as a charge generating substance and a polyester resin [manufactured by Toyobo Co., Ltd .:
Trade name Byron 200] 2 parts in tetrahydrofuran 10
Part, and pulverized and mixed in a ball mill for 10 hours. The obtained photoconductive composition is applied on a laminated film of a 5 μm-thick aluminum foil and a polyester film, and dried to generate a charge of about 0.5 μm in thickness. A sample of the film having a layer was prepared. Next, 3 parts of a polycarbonate resin (trade name: Panlite K-1300, manufactured by Teijin Limited) and 15 parts of tetrahydrofuran were charged with the compound No. of Example 1 as a charge transport material. 1 was dissolved in 2 parts, and this solution was applied on the charge generation layer using an applicator, and the thickness was about 15 μm.
To form an electrophotographic photoreceptor having a two-layered photosensitive layer. The photoreceptor sample thus obtained was charged by performing a corona discharge of -5 KV for 10 seconds using an electrostatic copying paper tester (EPA-8100, manufactured by Kawaguchi Electric Works), and then darkened for 10 seconds. After attenuating, the surface potential V ₀ (volt) at this time was measured, and then a 2854K tungsten lamp was irradiated to determine the time (sec) until the surface potential became 1/2 of V ₀ , and the sensitivity (half-exposure) The amount E _1/2 ) was measured. The result is V ₀ = −
698, E _1/2 = 2.3 lux · sec.

[0025]

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[Application Examples 2 to 4] Compound No. 1 of Application Example 1
A two-layer photoconductor was prepared in the same manner as in Application Example 1, except that 1 was replaced with each of the 9,10-bis (N, N-diarylamino) phenanthrene derivatives shown in Table A above.
In the same manner as in Application Example 1, the surface potential V ₀ due to negative charging and the half-life exposure amount E _1/2 were measured. The results are shown in Table-B below.

[0027]

[Table 2]

[Comparative Example]
Example of application except that 4-methyl-N- (4-methylphenyl) -N-phenyl-benzeneamine of Example 1 was replaced with a 9,10-bis (N, N-diarylamino) phenanthrene derivative shown in Table-A In the same manner as in Example 1, a two-layer photoreceptor was prepared, and in the same manner as in Application Example 1, the surface potential V ₀ due to negative charging and the half-exposure amount E _1/2 were measured. Table-
B. It was recognized that the comparative compound of Chemical formula 9 had poor chargeability and low electrophotographic sensitivity as compared with the compound of the present invention.

[0029]

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Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 251/24 C07C 251/24 // G03G 5/06 314 G03G 5/06 314B (72) Inventor Kazunori Kikuchi 5-2 Higashi-Yawata, Hiratsuka-shi, Kanagawa Prefecture -3 Sankyo Chemical Co., Ltd. Synthetic Chemistry Laboratory (56) Reference JP-A-5-39248 (JP, A) JP-A 5-155825 (JP, A) JP-A 5-150481 (JP, A) Kaihei 7-120949 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 211/61 C07C 209/10 C07C 209/52 C07C 213/02 C07C 217/90 C07C 251/24 G03G 5/06 314 CA (STN)

Claims (2)

(57) [Claims] 1. The method according to claim 1, wherein the compound represented by the following general formula (1) is:
Bis (N, N-diarylamino) phenanthrene derivatives. Embedded image In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. However,
R ₅ , R ₆ , R ₇ and R ₈ must not be simultaneously hydrogen atoms. 2. An aniline derivative represented by the following general formula (2) is reacted with a 9,10-phenanthrenequinone derivative represented by the following general formula (3) to give a diimine represented by the following general formula (4). After the derivative, the following general formula (5)
2. A novel diamine derivative represented by the general formula (1) according to claim 1, wherein the derivative is converted into a diamine derivative represented by the following general formula (6) and reacted with a halobenzene derivative represented by the following general formula (6). A method for producing a 10-bis (N, N-diarylamino) phenanthrene derivative. Embedded image Embedded image Embedded image In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. However,
R ₅ , R ₆ , R ₇ and R ₈ must not be simultaneously hydrogen atoms. X represents a halogen atom.