JP2534061B2 - 1,3-Pentadiene derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel 1,3-pentadiene derivative useful as an organic photoconductive material for electrophotography and a fluorescent whitening agent, and a method for producing the same.

[Prior art]

Conventionally, many materials such as poly-N-vinylcarbazole have been proposed as organic photoconductive materials for photoreceptors used in electrophotography.

The term "electrophotographic method" as used herein generally refers to photoconductively charging a photoconductor by first charging it in a dark place by, for example, corona discharge, and then performing imagewise exposure 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 and the latent image portion is visualized 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) charging to an appropriate potential in a dark place, 2) little discharge of charges in a dark place, and 3) irradiation with light. Immediately discharging the electric charge is included. However, the conventional photoconductive organic material does not always satisfy these requirements.

On the other hand, selenium and zinc oxide are known as photoconductive inorganic materials, and among them, selenium is widely used in practice.
However, recently, from the viewpoint of electrophotographic process, various requirements for a photoreceptor, that is, in addition to the basic electrophotographic characteristics described above as an example, a belt-shaped photoreceptor having a flexible shape is required. Is becoming popular. However, in the case of selenium, it is generally difficult to produce such a shape.

〔Purpose〕

The object of the present invention is to satisfy all the basic electrophotographic characteristics,
Moreover, it is a novel and useful photoconductive material with excellent flexibility.
It is intended to provide a 1,3-pentadiene derivative and a method for producing the same.

〔Constitution〕

According to the present invention, as the first invention, a compound represented by the general formula (I) ACH = CH ₂ CH ₂ -A (I) 9-anthryl group, carbazolyl group, N-alkylcarbazolyl group, N-alkylphenothiazinyl group, R ₁ : hydrogen atom, lower alkyl group, lower alkoxy group, R ₂ , R ₃ : alkyl group (provided that R ₂ And R ₃ are simultaneously methyl groups), a phenyl group, an alkyl group-substituted phenyl group, an alkoxy group-substituted phenyl group or an aralkyl group].

Further, as a second invention, a compound represented by the general formula (II) YCH _{2 3} Y (II) [wherein Y: ^{_{-PO (OR 4) 2 Z -}} : a halogen ion R _4: in 1,3-propylene derivative of the general formula represented by a lower alkyl group] (III) A-CHO (III ) [wherein, A: 9-anthryl group, carbazolyl group, N-alkylcarbazolyl group, N-alkylphenothiazinyl group, R ₁ : hydrogen atom, lower alkyl group, lower alkoxy group, R ₂ , R ₃ : alkyl group (provided that R ₂ And R ₃ simultaneously represent a methyl group), a phenyl group, an alkyl group-substituted phenyl group, an alkoxy group-substituted phenyl group or an aralkyl group]. ) ACH = CH ₂ CH ₂ -A (I) [wherein A: 9-anthryl group, carbazolyl group, N-alkylcarbazolyl group, N-alkylphenothiazinyl group, R ₁ : hydrogen atom, lower alkyl group, lower alkoxy group, R ₂ , R ₃ : alkyl group (provided that R ₂ And R ₃ simultaneously represent a methyl group), a phenyl group, an alkyl group-substituted phenyl group, an alkoxy group-substituted phenyl group or an aralkyl group].

The 1,3-type compound represented by the general formula (I) obtained in the present invention
The pentadiene derivative is a new substance, which is
It is synthesized by reacting the 1,3-propylene derivative represented by the general formula (II) with the aldehyde compound represented by the general formula (III), preferably in the presence of a basic catalyst.

In this case, examples of the basic catalyst include potassium hydroxide, sodium amide and sodium methylate, potassium methylate, and alcoholates such as potassium-t-butoxide. The reaction solvent is methanol,
Examples thereof include ethanol, propanol, toluene, xylene, dioxane, N, N-dimethylformamide, dimethylsulfoxide and tetrahydrofuran.

The reaction temperature is 1) the stability of the solvent used with respect to the basic catalyst, 2) the reactivity of the condensation components (the compounds of the general formulas (II) and (III)), 3) the condensing agent of the base catalyst in the solvent. The reactivity can be selected in a wide range. For example, when using polar solvents, it is
The temperature is 100 ° C, preferably room temperature to 80 ° C. However, even higher temperatures may be used when shortening the reaction time or using condensing agents with low activity.

In the present invention, the above general formula (II) used as a raw material
The 1,3-propylene derivative represented by, for example, 1,3-
It can be easily produced by reacting a dihalopropylene compound with a trialkyl phosphite or triphenylphosphine directly or by heating in an organic solvent such as toluene, xylene or dimethylformamide.

Examples of the novel 1,3-pentadiene derivative of the present invention thus obtained are as follows.

The novel 1,3-pentadiene derivative obtained in the present invention is extremely useful as a photoconductive material in an electrophotographic photoreceptor, and is optically or chemically enhanced by a sensitizer such as a dye or a Lewis acid. It is felt. Further, this is particularly useful as a charge carrier substance in a so-called function-separated type photoreceptor having an organic pigment or an inorganic pigment as a charge generating substance.

Examples of the sensitizer include methyl violet,
Triarylmethane dyes such as crystal violet,
Xanthine dyes such as rose bengal, erythrosine and rhodamine B, thiazine dyes such as methylene blue, 2,4,7
-Trinitro-9-fluorenone, 2,4-dinitro-9
-Such as fluorenone.

As an organic pigment, CI Pigment Blue 25
(CI No.21180), Sea Pigment Red 41 (CI N
o.21200), CI Pigment Red 3 (CI No.4521
0) and other azo pigments, CI Pigment Blue 16 (CI
No.74100) and other phthalocyanine pigments, CIVAT BROWN 5 (CI No.73410), CIVAT Die (CI
No.73030) and the like, and indigo-based pigments such as Argos scarlet B and indense scarlet R. Further, inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide and α-silicon can also be used.

〔effect〕

The novel 1,3 represented by the general formula (I) according to the present invention
-The pendadiene derivative 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 preferably used as a charge-carrying substance for a photosensitive layer of an electrophotographic photoreceptor, and particularly useful as a charge-carrying substance 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.

In addition, the production method of the present invention can be said to be an industrially extremely advantageous production method because raw materials are easily available and the reaction operation is simple.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 55.0 g (0.075 mol) of trimethylene-1,3-bis (triphenylphosphonium) dibromide and 41.4 g (0.15 mol) of 4-N, N-diphenylaminobenzaldehyde were dissolved in 300 ml of toluene and heated at 10 ° C or lower. 15.4 g (0.22 mol) of potassium methylate powder are added in small portions. After the addition, the internal temperature is kept at 15 to 18 ° C for 4 hours while stirring. (The reaction is carried out in a nitrogen stream.) The reaction solution was diluted with 120 ml of water, and the product was extracted with toluene. Part of the toluene is distilled off,
It was purified by column chromatography (support: silica gel, developing agent: n-hexane / toluene). The obtained crystals were recrystallized with a toluene-n-hexane mixed solvent to give white crystals 1.
5-bis (4-N, N-diphenylaminophenyl) -1,3
15.8 g (yield 38%) of pentadiene was obtained. Melting point is 104.5 ~
It was 105.5 ° C.

Elemental analysis was as follows for C ₄₁ H ₃₄ N ₂ .

C% H% N% Calculated value 88.77 6.18 5.50 Measured value 88.76 6.10 5.43 Examples 2 to 9 In Example 1, except that the aldehyde shown in Table 1 below was used in place of 4-N, N-diphenylaminobenzaldecht. A new 1,3-pentadiene derivative was obtained in the same manner as in Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 209/86 C07D 209/86 279/22 279/22 // C09B 23/00 C09B 23/00 H G03G 5/06 313 G03G 5/06 313 320 320 320 (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Company Limited (72) Inventor Nobuo Suzuki 3-chome Kamiya, Kita-ku, Tokyo 7-6 Hodogaya Chemical Co., Ltd. Central Research Laboratory Tokyo Branch Room (72) Inventor Takayuki Sakai 3-7-6 Kamiya, Kita-ku, Tokyo Hodogaya Chemical Co., Ltd. Central Research Laboratory Tokyo Branch Room (72) Invention Susumu Suzuka 3-7-6 Kamiya, Kita-ku, Tokyo Hodogaya Chemical Industry Co., Ltd. Central Research Laboratory Tokyo Branch Room

Claims (2)

(57) [Claims] 1. A general formula (I) ACH = CH ₂ CH ₂ -A (I) [wherein A: 9-anthryl group, carbazolyl group, N-alkylcarbazolyl group, N-alkylphenothiazinyl group, R ₁ : hydrogen atom, lower alkyl group, lower alkoxy group, R ₂ , R ₃ : alkyl group (provided that R ₂ And R ₃ are simultaneously methyl groups), a phenyl group, an alkyl group-substituted phenyl group, an alkoxy group-substituted phenyl group or an aralkyl group]. 2. A general formula (II) YCH _{2 3} Y (II) [wherein Y: ^{_{-PO (OR 4) 2 Z -}} : a halogen ion R _4: in 1,3-propylene derivative of the general formula represented by a lower alkyl group] (III) A-CHO (III ) [wherein, A: 9-anthryl group, carbazolyl group, N-alkylcarbazolyl group, N-alkylphenothiazinyl group, R ₁ : hydrogen atom, lower alkyl group, lower alkoxy group, R ₂ , R ₃ : alkyl group (provided that R ₂ And R ₃ at the same time except for a methyl group), a phenyl group, an alkyl group-substituted phenyl group, an alkoxy group-substituted phenyl group or an aralkyl group]. ) ACH = CH ₂ CH ₂ -A (I) [wherein A: 9-anthryl group, carbazolyl group, N-alkylcarbazolyl group, N-alkylphenothiazinyl group, R ₁ : hydrogen atom, lower alkyl group, lower alkoxy group, R ₂ , R ₃ : alkyl group (provided that R ₂ And R ₃ are simultaneously a methyl group), a phenyl group, an alkyl group-substituted phenyl group, an alkoxy group-substituted phenyl group or an aralkyl group].