JPH107630A - Amine compound containing hydroxyl group and its production intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new amine compound containing a hydroxyl group, effectively acting as a photoconductive material and useful as an electron- transporting material in a photosensitive photoreceptor layer of an electrophotography and a production intermediate for a polycarbonate resin, polyester resin, etc. SOLUTION: This new amine compound containing a hydroxyl group is represented by formula I [R1 and R2 are each H, a (substituted) alkyl or a (substituted) aryl; Ar1 to Ar3 and Ar6 are each an arylene; Ar4 , Ar5 and Ar<7> are each a (substituted) aryl or a (substituted) heterocyclic group], e.g. 1,4-bis( 2-[4-( N-[4-(2,2-diphenylvinyl)phenyl]-N-(4-hydroxyphenyl)}amino)phenyl]-1- phenyl}vinyl)-benzene. The compound of formula I is obtained by performing an ether cleavage reaction or an ester cleavage reaction of a compound of formula II [R10 is a (substituted) alkyl or an acyl].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydroxyl group-containing amine compound which is useful as an organic photoconductive material for electrophotography and also as an intermediate for producing various materials derived from a hydroxyl group, and an intermediate for producing the same. And a useful amine compound.

[0002]

2. Description of the Related Art Conventionally, as an organic photoconductive material of a photoreceptor used in an electrophotographic system, for example, poly N
-Vinyl carbazole, triphenylamine compound (U.S. Pat. No. 3,180,730), benzidine compound (U.S. Pat. No. 3,265,496, JP-B-39-11546, JP-A-53-1). 27033
Many proposals have been made.

[0003] The "electrophotographic method" referred to here generally means that a photoconductive photoreceptor is first charged in a dark place, for example, by corona discharge, and then imagewise exposed to selectively charge the exposed portion. This is one of image forming methods in which an electrostatic latent image is obtained by discharging the latent image, and the latent image portion is visualized by a developing unit using toner or the like to form an image. The basic characteristics required of the photoreceptor in such an electrophotographic system include: 1) being charged to an appropriate potential in a dark place, 2) being less discharged in a dark place, and 3) being irradiated with light. To discharge the electric charge more quickly.

In recent years, polymer photoconductive materials (US Pat. No. 4,801,517, US Pat. No. 4,80) have been developed in order to further improve the mechanical strength of a photoreceptor.
No. 6,443, U.S. Pat. No. 4,806,444, JP-A-3-221522, JP-A-4-4-1.
No. 1627) has been proposed. However, conventional low-molecular or high-molecular photoconductive materials do not always satisfy the above requirements.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photoconductive material which satisfies all basic electrophotographic properties, and also as an intermediate for producing various materials derived from hydroxyl groups. Another object of the present invention is to provide a novel hydroxyl-containing amine compound which is useful as well as a novel amine compound which is useful as an intermediate for producing the same.

[0006]

According to the present invention, the following general formulas (1), (2), (3), (4), (5),
A hydroxyl group-containing amine compound (including an ether group or ester group-containing amine compound) represented by (6), (7), (8) and (9) is provided.

[0007]

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[0008]

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[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

Embedded image In the formula, R ₁ and R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. A
r ₁ , Ar ₂ , Ar ₃ and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R
₉ represents a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
a, b, c, and g are integers from 1 to 4, and d, e, and f are 1
Is an integer of up to 5. R ₁₀ represents a halogen atom, a substituted or unsubstituted alkyl group or an acyl group.

Hereinafter, the hydroxyl group-containing amine compound of the present invention and the ether group or ester group-containing amine compound as an intermediate for the production thereof will be described in more detail. The general formulas (1), (2), (3), (4), (5),
Specific examples of the amine compounds represented by (6), (7), (8), and (9) when R _{1 to} R ₉ are a substituted or unsubstituted alkyl group include the following. Can be. A C ₁ -C ₅ linear or branched alkyl group which further contains a fluorine atom, a cyano group, a phenyl group or a phenyl group substituted with a halogen atom or a C ₁ -C ₅ alkyl group; It may be. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n
-Butyl group, i-butyl group, trifluoromethyl group, 2
-Cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like.

Further, the general formulas (1), (2),
In the amine compounds represented by (3), (4), (5), (6), (7), (8) and (9), Ar ₄ , A
Specific examples where r ₅ and Ar ₇ are a substituted or unsubstituted aryl group include the following.
Phenyl, naphthyl, biphenylyl, terphenylyl, pyrenyl, fluorenyl, 9,9-dimethyl-2-fluorenyl, azulenyl, anthryl, triphenylenyl, chrysenyl and the like;
These may have a lower alkyl group, a lower alkoxy group and a halogen atom as substituents. Further, a group represented by the following general formula (10) can be exemplified.

[0018]

Embedded image Wherein, X is -O -, - S -, - SO -, - SO 2 -, -
CO- and the following divalent groups are represented.

[0019]

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[0020]

Embedded image (Where R ₁₁ and R ₁₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, a substituted or unsubstituted aryl group, an amino group, a nitro group, a cyano group, and n is 1 to 12 represents an integer, and 1 represents an integer of 1 to 3.)

In the divalent group X in the general formula (10), specific examples of the substituted or unsubstituted alkyl group for R ₁₁ and R ₁₂ are the same as those defined for R _{1 to} R ₉ . Further, specific examples of the amino group include a group represented by the following general formula.

[0022]

Embedded image (R ₁₃ and R ₁₄ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) Here, in R ₁₃ and R ₁₄ , a substituted or unsubstituted alkyl group and a substituted or unsubstituted Specific examples of the aryl group include the definitions of R _{1 to} R ₉ , and Ar ₄ , Ar ₅ , and A
definition of r ₇ and is the same. R ₁₃ and R ₁₄ may form a ring together. Further, a ring may be formed together with a carbon atom on the aryl group. Specific examples of such a group include a piperidino group, a morpholino group, and a uroridyl group. Further, when R _{3 to} R ₁₀ are halogen atoms, and when R ₁ to R ₁₀
When R ₁₄ is a group having a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Further, the general formulas (1), (2),
(3), (4), (5), (6), (7), (8),
In the amine compound represented by (9), Ar ₄ , A
Specific examples of the substituted or unsubstituted heterocyclic group for r ₅ and Ar ₇ include a monovalent group derived from furan, thiophene, oxazole, pyridine, benzofuran, benzothiophene and the like, and these are lower alkyl groups, It may have a lower alkoxy group and a halogen atom as substituents. In addition, the general formulas (1), (2), (3),
In the amine compounds represented by (4), (5), (6), (7), (8), and (9), Ar ₁ , Ar ₂ , A
Specific examples of the arylene group for r ₃ and Ar ₆ include a divalent group derived from the aryl group.

The hydroxyl group-containing amine compound according to the present invention is a novel substance, and its production method will be described below.
That is, the compounds represented by the general formulas (1) to (8) are synthesized by a cleavage reaction of an ether or an ester of the compound represented by the following general formula (9).

[0025]

Embedded image In the formula, R ₁ and R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. A
r ₁ , Ar ₂ , Ar ₃ and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₁₀ represents a substituted or unsubstituted alkyl group or acyl group. (Same as above)

Specific examples of the ether cleavage reaction include a method using an acidic reagent and a method using a basic reagent.
Examples of the acidic reagent include hydrogen bromide, hydrogen iodide, trifluoroacetic acid, hydrochloride of pyridine, concentrated hydrochloric acid, magnesium iodide ethylate, aluminum chloride, aluminum bromide,
Boron tribromide, boron trichloride, boron triiodide, etc., as basic reagents, potassium hydroxide, sodium hydroxide, sodium, lithium, sodium iodide, lithium iodide, lithium diphenyl phosphide, sodium thiolate, etc. Can be mentioned. Acetic anhydride, dichloromethane, tetrahydrofuran (TH
F), N, N-dimethylformamide (DMF), pyridine, butanol, and the like. The reaction temperature depends on the reactivity of the reagent to be used.
Performed between 0 ° C.

The compound represented by the general formula (9) is
The synthesis scheme shown below, that is, W of a compound represented by the general formula (11) and a compound represented by the general formula (12)
It is synthesized by an ittig reaction or a modified Wittig reaction.

[0028]

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Here, specific examples of R ₁₅ include C ₁ -C ₅
Linear or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, n-
And a pentyl group. In the above reaction, preferably, a modified Witt shown in the synthesis scheme shown below is used.
By the ig reaction, the compound represented by the general formula (9) can be synthesized from the compound represented by the general formula (13) and the compound represented by the general formula (14) in high yield.

[0030]

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The reaction at this time may be a conventionally known method.
For example, a phosphonate compound and a formyl compound are dissolved in a polar solvent such as DMF, and potassium-
It can be easily synthesized by adding a strong base compound such as t-butylate or sodium methylate little by little. The compounds represented by the general formulas (13) and (14) are each synthesized by a conventionally known method. For example, in the synthesis of phosphonate compounds, Eur.
J. Med. Chem. (1993) 28 pp. 94
It is also synthesized by the method described in 3-948.

The hydroxyl group-containing amine compound of the present invention is extremely useful as a photoconductive material in an electrophotographic photosensitive member, and is sensitized optically or chemically by a sensitizer such as a dye or Lewis acid. Further, this is particularly useful as a so-called function-separated type charge transporting substance using 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, xanthene 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 and the like.

As organic pigments, azo pigments such as C.I. Pigment Blue 25 (CI No. 21180), C.I. Pigment Red 41 (CI. No. 21200), C.I. Pigment Red 3 (CI. No. 45210), and C.I. (CI N
o. Phthalocyanine-based pigments such as C.I. 74100), indigo-based pigments such as C-I-but Brown 5 (CI No. 73410), C.I. . In addition, inorganic substances such as selenium, selenium-tellurium, cadmium sulfide, and α-silicon can also be used.

It is also useful as an intermediate for producing various materials derived from hydroxyl groups, for example, polycarbonate resin, polyester resin, polyurethane resin, epoxy resin and the like.

[0036]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Example 1 4-Formyl-4'- represented by the following structural formula (15)
Methoxy-4 ″-(2,2-diphenylvinyl) triphenylamine 69.4 g (0.06 × 2 × 1.2 mo)
l) and 30.4 g (0.06 mol) of a bis (phosphonate) represented by the following structural formula (16) were added to DMF5
Dissolved in 00 ml. To this solution, add t-BuOK24.
2 g (0.06 x 2 x 1.2 x 1.25 mol) to 15
It was added while maintaining ２５25 ° C. After stirring for 3 hours to confirm the disappearance of the raw materials, the reaction product was poured into 2000 ml of water.
After extraction with ethyl acetate, purification was performed by silica gel column chromatography (developing solvent, toluene: n-hexane = 1: 1) to obtain 62.3 g of the desired product (17) (yield: 89.9).
%). This compound was amorphous.

[0038]

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[0039]

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[0040]

Embedded image FIG. 1 shows the infrared absorption spectrum and the results of elemental analysis.

[0041]

[Table 1]

Example 2 57.8 g of the compound (17) obtained in Example 1 (0.0
5 mol) and 30 g of sodium thioethylate (0.3
6 mol) was placed in 500 ml of dried DMF, and heated under reflux for 8 hours under a nitrogen stream. After cooling to room temperature,
The contents were poured into ice water and neutralized with concentrated hydrochloric acid. This was filtered, washed with water, and then subjected to silica gel column chromatography (developing solvent, toluene: ethyl acetate = 10: 1) to obtain 52.6 g (yield 93.3%) of a yellow powder.

[0043]

Embedded image This compound was amorphous. FIG. 2 shows the results of infrared absorption spectrum and elemental analysis of the obtained compound.

[0044]

[Table 2]

Application Example Application Example as Polymer Raw Material 5.64 g (0.005 mol) of the hydroxyl-containing amine compound (18) obtained in Example 2 was dissolved in 40 ml of dehydrated THF, and stirred under a nitrogen gas stream. While 1.52 g of triethylamine (0.0
After addition of polytetramethylene ether glycol bischloroformate (average molecular weight 25
0 from polytetramethylene ether glycol)
1.92 g (0.005 × 1.05 mol) of dry TH
What melt | dissolved in F10ml was dripped over 30 minutes under water cooling. After completion of the dropwise addition, the mixture was further stirred for 2 hours and then precipitated in methanol to obtain a crude product. This was repeatedly reprecipitated twice, and the precipitate was dried to obtain a polycarbonate resin having the following structural formula.

[0046]

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[0047]

As described above in detail and specifically, the present invention provides the novel hydroxyl-containing amine compound and the novel amine compound. The hydroxyl group-containing amine compound according to the present invention effectively functions as a photoconductive material as described above, and is sensitized optically or chemically by a sensitizer such as a dye or a Lewis acid. It is suitably used as a charge transporting material in a photosensitive layer of a photographic photosensitive member, and is particularly useful as a charge transporting material in a so-called function-separated type photosensitive layer in which a charge generating layer and a charge transporting layer are divided into two layers. It is also useful as an intermediate for the production of various materials derived from hydroxyl groups, for example, polycarbonate resins, polyester resins, polyurethane resins, epoxy resins and the like.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum (KBr tablet method) of an amine compound (Compound No. 17) of the present invention.

FIG. 2 is an infrared absorption spectrum (KBr tablet method) of the amine compound (Compound No. 18) of the present invention.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuki Nagai 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Akira Katayama 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Mitsutoshi Anzai 66-2 Horikawa-cho, Saiwai-ku, Kawasaki City, Kanagawa Prefecture Inside (72) Inventor Katsuhiro Morooka 66-2 Horikawacho, Saiwai-ku, Kawasaki City, Kanagawa Prefecture Hodani Chemical Industry Inside the corporation

Claims (9)

[Claims] 1. A hydroxyl group-containing amine compound represented by the following general formula (1). Embedded image In the formula, R ₁ and R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. A
r ₁ , Ar ₂ , Ar ₃ and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. 2. A hydroxyl group-containing amine compound represented by the following general formula (2). Embedded image In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. A
r ₁ , Ar ₂ , Ar ₃ and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. 3. A hydroxyl group-containing amine compound represented by the following general formula (3). Embedded image In the formula, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. 4. A hydroxyl group-containing amine compound represented by the following general formula (4). Embedded image In the formula, Ar ₂ , Ar ₃ , and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₃ represents a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a represents an integer of 1 to 4. 5. A hydroxyl group-containing amine compound represented by the following general formula (5). Embedded image In the formula, Ar ₆ represents an arylene group. Ar ₄ , Ar ₅ , A
r ₇ each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₃ ,
R ₄ and R ₅ represent a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a, b, and c represent an integer of 1 to 4. 6. A hydroxyl group-containing amine compound represented by the following general formula (6). Embedded image In the formula, Ar ₆ represents an arylene group. Ar ₄ and Ar ₅ are
Each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₃ , R ₄ , R ₅ ,
R ₆ represents a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a, b, and c represent an integer of 1 to 4. d represents an integer of 1 to 5. 7. A hydroxyl group-containing amine compound represented by the following general formula (7). Embedded image In the formula, Ar ₆ represents an arylene group. R ₃ , R ₄ , R ₅ , R
₆ , R ₇ and R ₈ represent a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a, b, and c represent an integer of 1 to 4. d,
e and f represent an integer of 1 to 5. 8. A hydroxyl group-containing amine compound represented by the following general formula (8). Embedded image In the formula, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ represent a halogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a, b, c,
g represents an integer of 1 to 4. d, e, and f represent an integer of 1 to 5. 9. An intermediate for producing a hydroxyl group-containing amine compound represented by the following general formula (9). Embedded image In the formula, R ₁ and R ₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. A
r ₁ , Ar ₂ , Ar ₃ and Ar ₆ each independently represent an arylene group. Ar ₄ , Ar ₅ and Ar ₇ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₁₀ represents a halogen atom, a substituted or unsubstituted alkyl group or an acyl group.