JPH07107031B2 - Novel squarylium compound and method for producing the same - Google Patents
Novel squarylium compound and method for producing the sameInfo
- Publication number
- JPH07107031B2 JPH07107031B2 JP62305862A JP30586287A JPH07107031B2 JP H07107031 B2 JPH07107031 B2 JP H07107031B2 JP 62305862 A JP62305862 A JP 62305862A JP 30586287 A JP30586287 A JP 30586287A JP H07107031 B2 JPH07107031 B2 JP H07107031B2
- Authority
- JP
- Japan
- Prior art keywords
- represented
- formula
- structural formula
- derivative
- squarylium compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
- G03G5/0611—Squaric acid
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
Landscapes
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、新規なスクアリリウム化合物及びその製造方
法に関する。TECHNICAL FIELD The present invention relates to a novel squarylium compound and a method for producing the same.
従来の技術 従来、電子写真感光体に使用する感光材料については種
々のものが知られているが、近年有機系感光材料を用い
た電子写真感光体が注目され、種々検討されている。有
機系の光導電材料としては、ビスアゾ系顔料、トリスア
ゾ系顔料、フタロシアニン系顔料、シアニン類、ピリリ
ウム類等が知られており、又、近年ある種のスクアリリ
ウム化合物が優れた光導電特性を示し、電子写真感光材
料として使用できることが報告されている（例えば特開
昭60−136542号公報、同60−142946号公報、同60−1429
47号公報、同61−10540号公報、同62−450号公報等参
照）。2. Description of the Related Art Conventionally, various photosensitive materials used for electrophotographic photosensitive members have been known, but in recent years, electrophotographic photosensitive members using an organic photosensitive material have attracted attention and various studies have been made. As the organic photoconductive material, bisazo-based pigments, trisazo-based pigments, phthalocyanine-based pigments, cyanines, pyryliums and the like are known, and in recent years, some squarylium compounds exhibit excellent photoconductive properties, It has been reported that it can be used as an electrophotographic light-sensitive material (for example, JP-A-60-136542, JP-A-60-142946, and JP-A-60-1429).
47, 61-10540, 62-450, etc.).
発明が解決しようとする問題点 従来提案されている種々の有機化合物は、電子写真感光
体において、電荷発生剤として利用できるが、更に他の
優れた電荷発生剤を提供することが望まれている。Problems to be Solved by the Invention Various conventionally proposed organic compounds can be used as charge generating agents in electrophotographic photoreceptors, but it is desired to provide further excellent charge generating agents. .
本発明者等は、一群のスクアリリウム化合物について検
討した結果、以下に示す新規なスクアリリウム化合物が
電荷発生剤として有用であることを見出だし、本発明を
完成するに至った。As a result of examining a group of squarylium compounds, the present inventors have found that the following novel squarylium compounds are useful as a charge generating agent, and have completed the present invention.
したがって、本発明の目的は、電子写真感光体の電荷発
生剤として有用な新規なスクアリリウム化合物及びその
製造方法を提供することにある。Therefore, an object of the present invention is to provide a novel squarylium compound useful as a charge generating agent for an electrophotographic photoreceptor and a method for producing the same.
問題点を解決するための手段 本発明の新規なスクアリリウム化合物は、下記一般式
（Ｉ）で示される。Means for Solving Problems The novel squarylium compound of the present invention is represented by the following general formula (I).
（式中、Ｘは水素原子、メチル基、フッ素原子又は水酸
基を表わす） 上記一般式（Ｉ）で示されるスクアリリウム化合物は、
次のようにして製造される。 (In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group.) The squarylium compound represented by the general formula (I) is
It is manufactured as follows.
まず、下記構造式（II） で示される3,4−ジクロロ−３−シクロブテン−1,2−ジ
オンと、下記構造式（III） で示される3,5−ジフルオロ−N,N−ジメチルアニリンと
を反応させて、下記構造式（IV） で示されるクロロシクロブテンジオン誘導体を合成し、
次いで該クロロシクロブテンジオン誘導体を加水分解し
て、下記構造式（Ｖ） で示されるヒロドキシシクロブテンジオン誘導体を合成
し、該ヒロドキシシクロブテンジオン誘導体を下記一般
式（VI） （式中、Ｘは水素原子、メチル基、フッ素原子又は水酸
基を表わす） で示されるアニリン誘導体と反応させることによって製
造することができる。First, the following structural formula (II) 3,4-dichloro-3-cyclobutene-1,2-dione represented by the following structural formula (III) By reacting with 3,5-difluoro-N, N-dimethylaniline represented by the following structural formula (IV) A chlorocyclobutenedione derivative represented by
Then, the chlorocyclobutenedione derivative is hydrolyzed to give the following structural formula (V): A hydroxycyclobutenedione derivative represented by the following formula is synthesized, and the hydroxycyclobutenedione derivative is represented by the following general formula (VI): (In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group).
上記の製造法において、各工程の反応は、公知の類似の
反応に準じて実施することができる。In the above production method, the reaction in each step can be carried out according to a known similar reaction.
即ち、まず、3,4−ジクロロ−３−シクロブテン−1,2−
ジオンを前記構造式（III）で示される3,5−ジフルオロ
−N,N−ジメチルアニリンと反応させるが、この反応
は、それ等を、適当な溶剤、例えば塩化メチレン、四塩
化炭素、クロロホルム等のハロゲン化炭化水素、ニトロ
ベンゼン、エチルエーテル、アセトニトリル等の通常の
フリーデルクラフツ反応溶媒に溶解し、所望ならば触
媒、例えば三フッ化硼素エチルエーテル錯体、塩化アル
ミニウム、塩化アンチモン、塩化鉄（II）又は（II
I）、塩化チタン（IV）、塩化錫（IV）、塩化ビスマス
（IV）、塩化亜鉛（II）、塩化水銀等の存在下、０〜40
℃において撹拌することによって行なうことができる。That is, first, 3,4-dichloro-3-cyclobutene-1,2-
The dione is reacted with 3,5-difluoro-N, N-dimethylaniline represented by the structural formula (III), which reaction is performed using a suitable solvent such as methylene chloride, carbon tetrachloride, chloroform and the like. Soluble in conventional Friedel-Crafts reaction solvents such as halogenated hydrocarbons, nitrobenzene, ethyl ether, acetonitrile, etc., and if desired, catalysts such as boron trifluoride ethyl ether complex, aluminum chloride, antimony chloride, iron (II) chloride Or (II
I), titanium chloride (IV), tin chloride (IV), bismuth chloride (IV), zinc chloride (II), mercury chloride, etc.
It can be carried out by stirring at ℃.
合成されたクロロシクロブテンジオン誘導体は、続いて
加水分解されるが、加水分解は、適当な酸、例えば酢酸
を含む水中で、加熱することによって実施される。The synthesized chlorocyclobutenedione derivative is subsequently hydrolyzed, the hydrolysis being carried out by heating in water with a suitable acid, for example acetic acid.
続いて、加水分解によって得られたヒドロキシシクロブ
テンジオン誘導体を前記一般式（VI）で示されるアニリ
ン誘導体と反応させるが、アニリン誘導体としては、N,
N−ジメチルアニリン、３−メチル−N,N−ジメチルアニ
リン、３−フルオロ−N,N−ジメチルアニリン及び３−
ヒドロキシ−N,N−ジメチルアニリンが使用される。Subsequently, the hydroxycyclobutenedione derivative obtained by hydrolysis is reacted with the aniline derivative represented by the general formula (VI).
N-dimethylaniline, 3-methyl-N, N-dimethylaniline, 3-fluoro-N, N-dimethylaniline and 3-
Hydroxy-N, N-dimethylaniline is used.
その反応は、これ等の化合物を適当な溶剤、例えば、ｎ
−ブチルアルコール、ｎ−ヘプチルアルコール等の炭素
数４〜８の脂肪族アルコール、またはこれとベンゼン、
トルエン等の芳香族炭化水素との混合溶媒中で加熱する
ことによって行なうことができる。The reaction involves reacting these compounds with a suitable solvent, for example n.
-Butyl alcohol, n-heptyl alcohol, and other aliphatic alcohols having 4 to 8 carbon atoms, or benzene,
It can be performed by heating in a mixed solvent with an aromatic hydrocarbon such as toluene.
本発明のスクアリリウム化合物は、電子写真感光体の電
荷発生剤として有用である。例えば、感光層が電荷発生
層と電荷輸送層とに機能分離された積層構造を有する場
合において、上記スクアリリウム化合物を成膜性の樹脂
と共に用いて電荷発生層を形成することができる。The squarylium compound of the present invention is useful as a charge generating agent for an electrophotographic photoreceptor. For example, when the photosensitive layer has a laminated structure in which the charge generation layer and the charge transport layer are functionally separated, the squarylium compound can be used together with a film-forming resin to form the charge generation layer.
実施例 以下、本発明の実施例を示す。Examples Examples of the present invention will be shown below.
実施例１ 3,4−ジクロロ−３−シクロブテン−1,2−ジオン3.64g
（24.1ミリモル）、3,5−ジフルオロ−N,N−ジメチルア
ニリン7.54g（48.0ミリモル）及び三フッ化硼素エチル
エーテル錯体7.2g（48.0ミリモル）を塩化メチレン15ml
に溶解し、室温で24時間撹拌して反応を行なった。反応
終了後、反応混合物を希塩酸、次いで水で洗浄し、カラ
ムクロマトグラフィーを用いて分離精製を行ない、前記
構造式（IV）で示されるクロロシクロブテンジオン誘導
体2.31g（収率35％）を得た。（融点:189〜190℃） 得られたクロロシクロブテンジオン誘導体2.01g（7.4ミ
リモル）に酢酸10ml及び水5mlを加え、２時間加熱還流
させた後、放冷し、析出する沈澱物を濾別し、前記構造
式（Ｖ）で示されるヒドロキシシクロブテンジオン誘導
体1.61g（収率85％）を得た。（融点:223℃（分解）） 得られたヒドロキシシクロブテンジオン誘導体1.50g
（5.92ミリモル）と３−ヒドロキシ−N,N−ジメチルア
ニリン0.82g（6.1ミリモル）をブタノール60ml中で５時
間加熱撹拌した後、析出物を濾別して青緑色結晶を得
た。これをメタノール及びジエチルエーテルで洗浄した
後乾燥して、下記構造式で示されるスクアリリウム化合
物1.98g（収率90％）を得た。融点m.p.＝302℃（分
解）。Example 1 3,4-dichloro-3-cyclobutene-1,2-dione 3.64 g
(24.1 mmol), 3,5-difluoro-N, N-dimethylaniline 7.54 g (48.0 mmol) and boron trifluoride ethyl ether complex 7.2 g (48.0 mmol) in methylene chloride 15 ml.
And was stirred at room temperature for 24 hours to carry out the reaction. After completion of the reaction, the reaction mixture was washed with diluted hydrochloric acid and then with water, and separated and purified by column chromatography to obtain 2.31 g (yield 35%) of the chlorocyclobutenedione derivative represented by the structural formula (IV). It was (Melting point: 189-190 ° C) To 2.01 g (7.4 mmol) of the obtained chlorocyclobutenedione derivative was added 10 ml of acetic acid and 5 ml of water, and the mixture was heated under reflux for 2 hours and allowed to cool, and the precipitated precipitate was separated by filtration. Then, 1.61 g (yield 85%) of the hydroxycyclobutenedione derivative represented by the structural formula (V) was obtained. (Melting point: 223 ° C (decomposition)) Obtained hydroxycyclobutenedione derivative 1.50 g
(5.92 mmol) and 0.82 g (6.1 mmol) of 3-hydroxy-N, N-dimethylaniline were heated and stirred in 60 ml of butanol for 5 hours, and the precipitate was separated by filtration to obtain blue-green crystals. This was washed with methanol and diethyl ether and then dried to obtain 1.98 g (yield 90%) of a squarylium compound represented by the following structural formula. Melting point mp = 302 ° C (decomposition).
この化合物の赤外吸収スペクトルは第１図に示す通りで
あり、紫外吸収スペクトル（最大）は、UV（CH2Cl2）:6
14nmであった。又、元素分析値は、C20H18F2N2O3とし
て、次の通りであった。 The infrared absorption spectrum of this compound is as shown in FIG. 1, and the ultraviolet absorption spectrum (maximum) is UV (CH 2 Cl 2 ): 6.
It was 14 nm. Further, the elemental analysis values were as follows, assuming C 20 H 18 F 2 N 2 O 3 .
計算値（％） 実測値（％） Ｃ 64.51 64.54 Ｈ 4.87 4.97 Ｎ 7.52 7.50 実施例２〜４ 実施例１におけると同様にして前記構造式（Ｖ）で示さ
れるヒドロキシシクロブテンジオン誘導体を製造し、こ
れをN,N−ジメチルアニリン、３−メトキシ−N,N−ジメ
チルアニリン又は３−フルオロ−N,N−ジメチルアニリ
ンと同様に反応させ、第１表に示されるスクアリリウム
化合物を製造した。これ等の紫外吸収スペクトル（最
大）も第１表に示す。Calculated value (%) Measured value (%) C 64.51 64.54 H 4.87 4.97 N 7.52 7.50 Examples 2 to 4 The hydroxycyclobutenedione derivative represented by the structural formula (V) was prepared in the same manner as in Example 1, This was reacted in the same manner as N, N-dimethylaniline, 3-methoxy-N, N-dimethylaniline or 3-fluoro-N, N-dimethylaniline to produce the squarylium compounds shown in Table 1. The ultraviolet absorption spectra (maximum) of these are also shown in Table 1.
発明の効果 本発明のスクアリリウム化合物は、新規な化合物であ
り、電子写真感光体における電荷発生剤として有用な物
質であって、可視領域から近赤外領域までの広い範囲に
わたって感度を有する電子写真感光体を得ることができ
る。特に、電荷発生層と電荷輸送層とに機能分離された
積層構造を有する電子写真感光体において、電荷発生層
中に含有させると良好な感度のものが得られる。 EFFECTS OF THE INVENTION The squarylium compound of the present invention is a novel compound, is a substance useful as a charge generating agent in an electrophotographic photosensitive member, and has sensitivity in a wide range from the visible region to the near infrared region. You can get the body. In particular, in an electrophotographic photosensitive member having a laminated structure in which the charge generating layer and the charge transporting layer are functionally separated, when the electrophotographic photosensitive member is contained in the charge generating layer, excellent sensitivity can be obtained.
第１図は実施例１におけるスクアリリウム化合物の赤外
吸収スペクトル図である。FIG. 1 is an infrared absorption spectrum diagram of the squarylium compound in Example 1.
Claims (2)
基を表わす） で示されるスクアリリウム化合物。1. The following general formula (I): (In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group).
オンと、下記構造式（III） で示される3,5−ジフルオロ−N,N−ジメチルアニリンと
を反応させて、下記構造式（IV） で示されるクロロシクロブテンジオン誘導体を合成し、
次いで該クロロシクロブテンジオン誘導体を加水分解し
て、下記構造式（Ｖ） で示されるヒロドキシシクロブテンジオン誘導体を合成
し、該ヒロドキシシクロブテンジオン誘導体を下記一般
式（VI） （式中、Ｘは水素原子、メチル基、フッ素原子又は水酸
基を表わす） で示されるアニリン誘導体と反応させることを特徴とす
る下記一般式（Ｉ） （式中、Ｘは前記と同じ意味を表わす） で示されるスクアリリウム化合物の製造方法。2. The following structural formula (II) 3,4-dichloro-3-cyclobutene-1,2-dione represented by the following structural formula (III) By reacting with 3,5-difluoro-N, N-dimethylaniline represented by the following structural formula (IV) A chlorocyclobutenedione derivative represented by
Then, the chlorocyclobutenedione derivative is hydrolyzed to give the following structural formula (V): A hydroxycyclobutenedione derivative represented by the following formula is synthesized, and the hydroxycyclobutenedione derivative is represented by the following general formula (VI): (Wherein, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group) and is reacted with an aniline derivative represented by the following general formula (I) (In the formula, X has the same meaning as described above.) A method for producing a squarylium compound.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305862A JPH07107031B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
| US07/278,917 US5047589A (en) | 1987-12-04 | 1988-12-02 | Electrophotographic light-sensitive material containing squarylium compound |
| US07/623,697 US5169987A (en) | 1987-12-04 | 1990-12-07 | Squarlylium compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305862A JPH07107031B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01146847A JPH01146847A (en) | 1989-06-08 |
| JPH07107031B2 true JPH07107031B2 (en) | 1995-11-15 |
Family
ID=17950255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62305862A Expired - Fee Related JPH07107031B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07107031B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2871181B2 (en) * | 1991-07-09 | 1999-03-17 | ブラザー工業株式会社 | Photocurable composition |
| JP3141517B2 (en) | 1992-05-14 | 2001-03-05 | ブラザー工業株式会社 | Photocurable composition |
| US5488601A (en) * | 1992-10-26 | 1996-01-30 | Dai Nippon Printing Co., Ltd. | Photoelectric sensor, information recording system, and information recording method |
| JP3362745B2 (en) * | 1993-07-28 | 2003-01-07 | ブラザー工業株式会社 | Photosensitive microcapsule type toner |
-
1987
- 1987-12-04 JP JP62305862A patent/JPH07107031B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01146847A (en) | 1989-06-08 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |