JPH0558966A - N-phenyl-n-(3-aminophenyl)-1-pyrenylamine derivative, n-phenyl-n-(3-nitrophenyl)-1-pyrenylamine derivative and their production - Google Patents

Abstract

PURPOSE:To provide a new compound having excellent electrophotographic characteristics and useful as a photoconductive material. CONSTITUTION:The compound of formula I [R is H or (substituted)alkyl, alkoxy or phenyl], e.g. N-(4-methylphenyl)-N-(3-aminophenyl)-1-pyrenylamine. The compound can be produced by reacting a 3-nitrodiphenylamine derivative of formula II with a halogenated pyrene of formula III (X is Br or I) and reducing the resultant new nitro compound of formula IV. The compound is extremely useful as a photo-conductive material for the sensitive material of electrophotography. It can be optically or chemically sensitized by a sensitizer such as dye and Lewis acid. It is also useful as a charge-transfer substance for a function- separated sensitive material containing organic or inorganic pigment as a charge-generation substance.

Description

Detailed Description of the Invention

[0001]

This invention relates to N-phenyl-N- (3-aminophenyl) -1-, which is useful as an organic photoconductor.
The present invention relates to a pyrenylamine derivative, an N-phenyl-N- (3-nitrophenyl) -1-pyrenylamine derivative useful as an intermediate raw material for producing the same, and a method for producing them.

[0002]

2. Description of the Related Art Conventionally, as an organic photoconductive material for a photoconductor used in an electrophotographic system, for example, poly-N is used.
-Vinylcarbazole, triphenylamine compound (U.S. Pat. No. 3,180,730), benzidine compound (U.S. Pat. No. 3,265,496, JP-B-39-115)
No. 46, JP-A No. 53-27033, etc.) have been proposed.

The term "electrophotographic system" as used herein generally means that a photoconductive photoconductor is first charged in a dark place by, for example, corona discharge, and then imagewise exposure is performed to selectively discharge the charge in the exposed area. This is one of the image forming methods in which an electrostatic latent image is obtained by making the latent image portion visible by a developing means using toner or the like to form an image.
The basic characteristics required for a photoreceptor in such an electrophotographic system are as follows: 1) being charged to an appropriate potential in a dark place, 2) little discharge of charges in a dark place, and 3) irradiation with light. To discharge the electric charges more quickly.

However, the conventional photoconductive organic material does not always satisfy these requirements.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a novel N-phenyl-N- (3-aminophenyl)-, which satisfies all the above basic electrophotographic characteristics and is useful as a photoconductive material. 1-Pyrenylamine derivative, and N-phenyl-N-, useful as an intermediate raw material for producing the same
(3-nitrophenyl) -1-pyrenylamine derivative,
And to provide a method for manufacturing them.

[0006]

According to the present invention, the following chemical formula 1

[Chemical 1] (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-aminophenyl)- 1-pyrenylamine derivatives are provided, and

[Chemical 2] (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-nitrophenyl)- A 1-pyrenylamine derivative is provided, and further,

[Chemical 3] (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) And a 3-nitrodiphenylamine derivative and the following chemical formula 4

[Chemical 4] (X represents bromine or iodine) 1-
The following chemical formula 2 characterized by reacting with halogenopyrene

[Chemical 2] (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-nitrophenyl)- A method for producing a 1-pyrenylamine derivative is provided, and further,

[Chemical 2] (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-nitrophenyl)- The following chemical formula 1 characterized by reducing a 1-pyrenylamine derivative

[Chemical 1] (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-aminophenyl)- A method for producing a 1-pyrenylamine derivative is provided.

As described above, N-phenyl-N- (3-aminophenyl) -1 represented by the above chemical formula 1 of the present invention.
The -pyrenylamine derivative is a novel compound useful as a photoconductive material, and the compound is the corresponding N-phenyl-N- (3-nitrophenyl) represented by the above chemical formula 2.
It can be produced by reducing a -1-pyrenylamine derivative. Then, N represented by the above Chemical Formula 2
The -phenyl-N- (3-nitrophenyl) -1-pyrenylamine derivative is also a novel compound and corresponds to
A 3-nitro-diphenylamine derivative represented by
It can be produced by reacting with 1-halogenopyrene represented by Chemical Formula 4 above.

The 3-nitro-diphenylamine derivative represented by the chemical formula 3 and the 1-halogenopyrene represented by the chemical formula 4 are reacted to produce N-phenyl-N- (3-nitrophenyl) represented by the chemical formula 2. In order to produce a -1-pyrenylamine derivative, copper powder, copper oxide, copper halide, or the like, and an alkaline substance in an amount sufficient to neutralize hydrogen halide generated during the condensation reaction are added to the raw material mixture, In the presence of a solvent or without a solvent, under a nitrogen atmosphere,
It can be produced by reacting at a temperature of about 150 to 250 ° C.

In this case, examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. Further, as a reaction solvent, nitrobenzene, dichlorobenzene, quinoline, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-
Examples thereof include imidazolidinone.

Next, the N-phenyl-N- (3-nitrophenyl) represented by the above chemical formula 2 thus obtained
Examples of the reduction reaction from the -1-pyrenylamine derivative to the N-phenyl-N- (3-aminophenyl) -1-pyrenylamine derivative represented by Chemical Formula 1 include a hydrogenation method. In this case, platinum oxide, Raney-nickel, or platinum, palladium, rhodium, ruthenium supported on activated carbon, alumina, or barium sulfate is used as the catalyst. In operation, the reaction system is a closed system, the gas phase part is replaced with hydrogen gas at 1 atm, and the reaction is performed by vigorously stirring. Hydrogen gas is supplied through a pressure reducing valve to which hydrogen gas is supplied according to the absorbed amount. Since the absorption stops when the theoretical amount of hydrogen gas is absorbed, the reaction is terminated. In this case, the reaction temperature may be room temperature, but may be heated if the absorption of hydrogen gas is slow. As the reaction solvent, methanol, ethanol, propanol, tetrahydrofuran, dioxane, ethyl acetate, N, N-dimethylformamide or the like can be used.

Other reduction reactions include iron-hydrochloric acid,
A method of heating in an organic solvent using stannic chloride-hydrochloric acid or the like as a reducing agent can be mentioned. In this case, the reaction temperature is preferably 70 to 120 ° C., and the reaction is about 0.5 to
It will be completed in 3 hours. When an iron-hydrochloric acid reducing agent is used, it is preferably performed in N, N-dimethylformamide.

The pyrenylamine derivatives represented by the above Chemical Formulas 1 and 2 and the 3-nitro-diphenylamine derivative represented by the above Chemical Formula 3, which is the starting compound thereof, of the R group in the Chemical Formulas 1, 2 and 3 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group,
A lower alkyl group such as a butyl group, and an alkoxy group include a lower alkoxy group such as a methoxy group, an ethoxy group and a propoxy group. Furthermore, examples of the substituent in the alkyl group include a phenyl group, a halogen atom, an alkoxy group, and an aryloxy group, and examples of the substituent in the phenyl group include a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group). , A butyl group), a lower alkoxy group (eg, a methoxy group, an ethoxy group, a propoxy group, etc.) and a halogen atom (eg, bromine, chlorine etc.).

The novel N- represented by the above chemical formula 1 of the present invention
The phenyl-N- (3-aminophenyl) -1-pyrenylamine derivative is extremely useful as a photoconductive material in an electrophotographic photoreceptor, and is optically or chemically treated with a sensitizer such as a dye or a Lewis acid. Be sensitized to. Further, this is particularly useful as a charge transporting substance in a so-called function-separated type photoreceptor, which uses an organic pigment or an inorganic pigment as a charge generating substance.

Examples of the sensitizer include triarylmethane dyes such as methyl violet and crystal violet, xanthine dyes such as rose bengal, erythrosine and rhodamine, thiazine dyes such as methylene blue, and 2,4,7-trinitro-9. -Fluorenone, 2,
4-dinitro-9-fluorenone etc. are mentioned.

Examples of organic pigments include azo pigments such as CI Pigment Blue 25 (CI No. 21180), CI Pigment Red 41 (CI No. 21200), CI Pigment Red 3 (CI No. 45210), and CI Pigment Blue. 16 (CI
No. 74100) and the like, phthalocyanine-based pigments, such as CI BAT Brown 5 (CI No. 73410) and SI BAT Die (CI No. 73030), and perylene-based pigments such as Argos Scarlet B and Indanthren Scarlet R. .. Further, inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide and α-silicon can also be used.

[0016]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 Preparation of N- (4-methylphenyl) -N- (3-nitrophenyl) -1-pyrenylamine 4-methyl-3'-nitrodiphenylamine 10.04
g (44 mmol), 1-iodopyrene 17.33 g
(53 mmol), potassium carbonate 12.16 g copper powder 2.
90 ml of nitrobenzene was added to 80 g, and the mixture was stirred at 210 ° C. for 7.5 hours while azeotropically dehydrating with an ester tube under a nitrogen stream. After cooling to room temperature, nitrobenzene was distilled off from the filtrate filtered through Celite under reduced pressure, the residue was extracted with chloroform, washed with water, then dried over magnesium sulfate, and further concentrated under reduced pressure to give a dark brown color. An oily substance was obtained.
This is treated with a silica gel column [eluent: toluene / n-
Hexane (2/3) vol] and recrystallization from a toluene-ethanol mixed solvent to give N- (4-methylphenyl) -N- (3-nitrophenyl) represented by the following chemical formula 5 as orange-yellow needle crystals. 11.47 g (yield 60.8%) of -1-pyrenylamine was obtained.

[Chemical 5] The melting point of the obtained compound was 180.0 to 182.0 ° C., and its elemental analysis value was C ₂₉ H ₂₀ N ₂ O ₂ as follows. The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG.

Example 2 Preparation of N- (4-methylphenyl) -N- (3-aminophenyl) -1-pyrenylamine N- (4-methylphenyl) -N- (3-nitrophenyl) -1-pyrenylamine 12.11 g was dissolved in 120 ml of tetrahydrofuran, 1.21 g of 5% palladium-carbon was added thereto, and the mixture was hydrogenated at room temperature under a hydrogen atmosphere of 1 atm with a shaking hydrogenation apparatus. After completion of hydrogenation, the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure to give an orange oily substance. This was stirred under reflux with n-hexane to give a yellow powder shown below.
N- (4-methylphenyl) -N- (3-
Aminophenyl) -1-pyrenylamine 10.82 g
(Yield 96.1%) was obtained.

[Chemical 6] The melting point of the obtained compound was 153.0 to 158.0 ° C. The elemental analysis thereof were as follows as C ₂₉ H ₂₂ N _2. The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG.

[0019]

EFFECT OF THE INVENTION N- represented by Chemical Formula 1 according to the present invention
The phenyl-N- (3-aminophenyl) -1-pyrenylamine derivative is novel and effectively functions as a photoconductive material as described above, and is optically or chemically active by a sensitizer such as a dye or a Lewis acid. Therefore, it is suitable for use as a charge transport material in a photosensitive layer of an electrophotographic photoreceptor, and in particular, a charge generation layer and a charge transport layer are divided into two layers, that is, a charge in a so-called function separation type photosensitive layer. It is useful as a transport material. Further, N-phenyl-N- (3-nitrophenyl)-represented by the above Chemical Formula 2 of the present invention.
The 1-pyrenylamine derivative is a novel and useful intermediate raw material for the N-phenyl-N- (3-aminophenyl) -1-pyrenylamine derivative. And these novel pyrenylamine derivatives can be produced by the production method of the present invention.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum chart of N- (4-methylphenyl) -N- (3-nitrophenyl) -1-pyrenylamine of the present invention obtained in Example 1 (KBr tablet method).

2] Infrared absorption spectrum of N- (4-methylphenyl) -N- (3-aminophenyl) -1-pyrenylamine of the present invention obtained in Example 2 (KBr tableting method)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Adachi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (4)

[Claims] 1. The following chemical formula 1 (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-aminophenyl)- 1-pyrenylamine derivative. 2. The following chemical formula 2 (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-nitrophenyl)- 1-pyrenylamine derivative. 3. The following chemical formula 3 (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group) and a 3-nitrodiphenylamine derivative represented by the following chemical formula 4 (X represents bromine or iodine) 1-
The following chemical formula 2 characterized by reacting with halogenopyrene (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-nitrophenyl)- Process for producing 1-pyrenylamine derivative. 4. The following chemical formula 2 (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-nitrophenyl)- The following chemical formula 1 characterized by reducing a 1-pyrenylamine derivative (R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group.) N-phenyl-N- (3-aminophenyl)- Process for producing 1-pyrenylamine derivative.