JPS60169453A - 2,4-bis(2'-monosubstituted amino-4'-disubstituted aminophenyl)cyclobutenediylium-1,3-diolate - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R<1> and R<2> are alkyl. allyl, benzyl or aryl which may have substituent group or R<1> and R<2> may together with N form a 5- or 6-membered heterocyclic group; R<3> is -C(=O)-R<4> or -SO2-R<5> (R<4> and R<5> are alkyl or phenyl which may have substituent group)]. EXAMPLE:A charge generator of photosensitive material for electrophotography. It can be applied to a displaying material, sensor, or an optical recording medium such as optical disk. PREPARATION:The compound of formula I can be produced by reacting 2mol of the m-phenylenediamine derivative of formula II with 1mol of 3,4-dihydroxy-3- cyclobutene-1,2-dione in an organic solvent e.g. an alcohol such as methanol, ethanol, propanol, etc. or an aromatic hydrocarbon such as benzene, toluene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel λ, dags(,2'-7)substituted amino-ψ'-disubstituted aminophenyl)cycloptenediilium/,3-diolates. .

Cyclobutenediilium/3-diolates are generally known to exhibit a relatively large molecular extinction coefficient in a solution state. In addition, in the solution state it shows a very sharp absorption spectrum, while in the solid state (dispersed state) it shows a wide absorption spectrum, and some species also show good photoconductivity, such as electrophotography. It is used as a charge generating agent for photoreceptors.

The present inventors have discovered that such cycloptendiylium-7,
As a result of various studies on new compounds having a 3-diolate skeleton, it was found that compounds in which m-phenylenediamine derivatives were introduced into such a skeleton exhibited a larger molecular extinction coefficient than conventional compounds, and were also used as charge generating agents for electrophotographic photoreceptors. The present invention has been completed by learning that the present invention can be used advantageously as a method such as the following.

That is, the gist of the present invention is the general formula [I) - [wherein R' and R2 represent an alkyl group, an allyl group, a benzyl group, or an allyl group which may have a substituent, and R1 and R2 are They may be linked to each other to form a 5- or 6-membered heterocycle together with the nitrogen atom. Also, R3
is -6-R' or -8o2-R'(R' and R5
represents an alkyl group or a phenyl group which may have a substituent. ) is shown. It exists in the co-bis(co'-monoconverted aminoda'-disubstituted aminophenyl)cyclobutene'diylium-3-diolates represented by the following formula.

The present invention will be described below. The cyclobutene'diylium-7,3-diolates of the present invention are represented by the general formula CI).

In the formula, R1 and R2 are a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, which may have a substituent,
It represents an alkyl group such as an octyl group or a coethylhexyl group, an allyl group, a benzyl group, or an aryl group such as a phenyl group or a naphthyl group.

Examples of the above-mentioned substituents include a hydroxy group, a cyano group, an alkoxy group, a halogen atom, and examples of those having such substituents include a hydroxyethyl group, a cyanethyl group, a methoxyethyl group, Ethoxyethyl group, methoxypropyl group, chloroethyl group, p-
Examples include chlorobenzyl group and p-bromobenzyl group.

Further, R' and R2 are connected to each other and together with a nitrogen atom, a 5-negative ring or a 6-membered heterocycle, for example, a pyrrolidine ring,
A piperidine ring, a morpholine ring, etc. may be formed.

R3 represents a group represented by -8-R4 or -5o2-R', and R4 and R5 are alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and hexyl group that may have a substituent. or phenyl group.

Examples of the above-mentioned substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc. Examples of substituents having such substituents include trifluoromethyl groups, chloromethyl groups, p-dichloro Examples include phenyl group, tolyl group, methoxyphenyl group, p-nitrophenyl group, and the like.

The above-mentioned compound of the present invention is, for example, represented by the general formula [II] (wherein R
1, R1 and R3 have the same meanings as in the forepaw general formula [I]. ) of m-phenylenediamine derivatives in a comolar ratio expressed by methanol, ethanol, furopanol, butanol, pentanol, hexanol, etc., and aromatic hydrocarbons such as benzene, toluene, xylene, etc. 3. in an organic solvent or a mixed solvent thereof in a 7 molar ratio. Terdihydroxy
3-cyclobutene-/1,2-dione and 50℃~200℃
It is produced by reaction under temperature conditions of .degree. C., preferably go.degree.

The reaction product is usually obtained as a precipitate during the reaction, but may be dissolved in some cases.

In this case, after the reaction is complete, cool and add methanol or
It can be easily isolated as crystals by diluting with ethanol or the like.

The product is almost pure, but if desired, suspension recrystallization,
High purity can be obtained by known means such as column purification and sublimation.

The compound of the present invention thus obtained has an extremely high molecular extinction coefficient in a solution state, and has metallic luster in a solid state. Such compounds of the present invention are valuable as charge generating agents for electrophotographic photoreceptors, for example.
It is preferable to use a laser beam having a wavelength of b 00 nm to q o o nm as the light source.

In addition, the compound of the present invention is highly ionic and is subject to various environmental changes, such as the type of bath medium, dissolution temperature, pH, etc. when in a solution state, and when in a solid state. ,
Since it reacts extremely sensitively to crystal type, particle size, etc., and changes hue etc., it can also be applied to display materials, sensors, optical recording media such as optical disks, etc.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the Examples unless the spirit thereof is exceeded.

Example/ m-acetylamino-N, N-diethylaniline A;
t 9 and 3. Terdihydroxy-3-cyclobutene-/, cordion/, AI to n-butyl alcohol/2
Suspended in a mixed solvent of 0d and benzene gOml,
The reaction was carried out under reflux while removing the resulting water. After IO time, the reaction was stopped, allowed to cool, the precipitated crystals were collected, and heated suspension purification was carried out under reflux with methanol/θOml.
After washing with methanol and water and drying under reduced pressure, it has a metallic luster and a melting point of 2 as shown by the structural formula below! A green powder 3II of f/-, 2 °C was obtained.

〇- Elemental analysis values (as 028H34N404) were as follows.

Further, the results of infrared absorption spectrum measurement were as shown in FIG.

Furthermore, the visible absorption spectrum measurement results were as follows.

Concentration λ, /7 m-ethylcarbonylamino-N to N-diethylaniline
, N-diethylaniline was used to obtain a green powder.

〇- Elemental analysis values (as C26H1°N404) were as follows.

Moreover, the infrared absorption spectrum measurement results were as shown in FIG.

Furthermore, the visible absorption spectrum measurement results were as follows.

Concentration /, q3x10-6yz (cHcz3),
g, 7 x 10-6M/l (NMP*) thick absorption wavelength 47/nm, Ag/nm molecular extinction coefficient
lIoθooo, -〇〇o.

NMP*: N-methylpyrrolidone Example 3 m-benzoylamino-N,N- instead of m-acetylamino-N,N-diethylaniline in Example/
Example/Except that diethylaniline was used.
A shiny melting point shown by the following structural formula according to the method of 2.
23. ! ; -125°C blue-green powder was obtained.

- The elemental analysis value (as C38H38N404) was as follows.

Further, the results of infrared absorption spectrum measurement were as shown in FIG.

Furthermore, the measurement results of the absorption spectrum in the visible region were as shown in Shimo Kimiji.

Concentration /, 30 X / (f'M/l (OHOt,
) Maximum absorption wavelength: 6g0nrn Molecular extinction coefficient: 3g0000 m'(p) ) luenesulfonylamino-N,N-diethylaninon was used instead of m-acetylamino-N,N-dietheraniline in Example/. Except that: According to the method of implementation, a metallic luster with a melting point of 270-. A bronze-like powder having a temperature of 27/°C was obtained, and the elemental analysis values (as c38H4, N4o6s) were as follows.

Further, the infrared absorption spectrum measurement results were as shown in FIG.

Furthermore, the visible absorption spectrum measurement results were as follows.

Concentration -'/, tox 10-'wt (cHct3
) Maximum absorption wavelength i/nm Molecular extinction coefficient 3g, 2000 In Example 5, m-benzoylamino-N,N-dihydroxyethylaniline was used as a substitute for m-acetyl-N,N-diethylaniline. A bright melting point represented by the following structural formula: llIg-, l'19. ! A black-rimmed powder was obtained.

The elemental analysis values (as C38H3sN408) were as follows.

Further, the infrared absorption spectrum measurement results were as shown in FIG.

Furthermore, the visible absorption spectrum measurement results were as follows.

Concentration /, 6θ Table 7 also shows the maximum absorption wavelength values of each compound.

Reference Example An example will be shown in which the compound of the present invention described in Example 1 was used as a charge generating agent for an electrophotographic photoreceptor.

1 part by weight of the present compound and 1 part by weight of polyester (manufactured by Toyobo ■, trade name: Vylon 5oo) were added to 1 part by weight of pentoxone (trademark: Mitsubishi Kasei Ltd.), and dispersed with a sand grinder.

How thick is the dispersion of this compound? j Using a film applicator on the aluminum evaporated layer deposited on a 1m polyester film, the film thickness after drying is o, 3gytrt.
After applying it until it was dry, it was dried. 9 parts by weight of N-ethylcarbasol-3-aldehyde diphenylhydrazone and a methacrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trademark DIANAL BR-g,
A solution prepared by dissolving 10 parts by weight of toluene in 57 parts by weight was applied to a dry film thickness of 73 μm to form a charge transfer layer.

In this way, an electrophotographic photoreceptor having a two-layer photosensitive layer was obtained. Is this photoreceptor from g 00 nm?
It had sensitivity over a wide range of o o nm, and the white light sensitivity (E2) was 3.3 tux, sec, indicating good sensitivity.

The measurements were carried out using a measuring device model SP'12g manufactured by Kawaguchi Electric. First, the photoreceptor was charged by corona discharge at -A KV in a dark place, and then exposed to white light at an illuminance of s tuX, and the exposure amount required for the surface potential to attenuate to 4 of the initial surface potential was 1"/i). I met.

[Brief explanation of drawings]

Figures 1 to 5 are examples/~examples! FIG. 2 shows an infrared absorption spectrum diagram of the cyclobutyl/diylium/3-diolate of the present invention obtained in the above. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - Others/Continued from page 1 ■Int, CI, 4 Identification code: Office docket number 0 Inventor: Shinji Aramaki Kamoshi, Midori-ku, Yokohama City Inside the Pressure Research Institute 0 Inventor Michiyo Yokoyama Inside the Kamoshiin Research Institute, Midori-ku, Yokohama City

Claims (1)

[Claims] (1) General formula CI) 〇- [In the above formula, R' and R2 represent an alkyl group, an allyl group, a benzyl group, or an aryl group that may have a substituent, and R1 and R2 are connected to each other. may form an S-membered ring or a 6-membered heterocycle together with the nitrogen atom. R
3 is -6-R4 or -SO□-R5 (R4 and R8
represents an alkyl group or a phenyl group which may have a substituent. ) is shown. ], Derbis(co'-monosubstituted amino-q'-disubstituted aminophenyl)cyclobutyldiylium/, ? -diolates.