JPH0768195B2 - Novel cyclobutenedione derivative - Google Patents
Novel cyclobutenedione derivativeInfo
- Publication number
- JPH0768195B2 JPH0768195B2 JP30586687A JP30586687A JPH0768195B2 JP H0768195 B2 JPH0768195 B2 JP H0768195B2 JP 30586687 A JP30586687 A JP 30586687A JP 30586687 A JP30586687 A JP 30586687A JP H0768195 B2 JPH0768195 B2 JP H0768195B2
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- Prior art keywords
- formula
- derivative
- cyclobutenedione
- cyclobutenedione derivative
- compound
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- 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.)
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、電気写真感光材料、光ディスク用記録材料、
太陽電池、赤外線カットフィルターの分野で有用なスク
エアリリウム化合物の合成原料となる新規なシクロブテ
ンジオンに関する。TECHNICAL FIELD The present invention relates to an electrophotographic photosensitive material, a recording material for optical discs,
The present invention relates to a novel cyclobutenedione as a raw material for synthesizing a squarylium compound useful in the fields of solar cells and infrared cut filters.
従来の技術 近年、ある種のスクアリリウム化合物が優れた光導電性
を示し、電子写真感光材料その他の用途に使用できるこ
とが報告されている（例えば、特開昭60−136452号公
報、同60−142946号公報、同60−142947号公報、同61−
10540号公報、同62−450号公報参照）。2. Description of the Related Art Recently, it has been reported that certain squarylium compounds exhibit excellent photoconductivity and can be used in electrophotographic photosensitive materials and other applications (for example, JP-A-60-136452 and JP-A-60-142946). No. 60-142947, No. 61-2929
(See 10540 and 62-450).
これらのスクアリリウム化合物は、原料物質として、ジ
クロロブテンジオンを用いて合成される。These squarylium compounds are synthesized by using dichlorobutenedione as a raw material.
従来3,4−ジクロロ−３−シクロブテン1,2−ジオン（ス
クエアリック酸塩化物）は、下記反応式（１）及び
（２）で示させるように、ルイス酸触媒の存在下で芳香
族化合物と反応して、対応する３−アリール−４−クロ
ロ−３−シクロブテン１、２−ジオンを生成することが
知られている。Conventional 3,4-dichloro-3-cyclobutene 1,2-dione (squareric acid chloride) is an aromatic compound in the presence of a Lewis acid catalyst, as shown in the following reaction formulas (1) and (2). It is known to react with to form the corresponding 3-aryl-4-chloro-3-cyclobutene 1,2-dione.
これらの反応では、選択性に問題があり、特に（２）の
反応では、目的化合物（収率34％）のほかに、次式に示
される１、２−付加体（収率３％）が副成する。 In these reactions, there is a problem in selectivity. Especially in the reaction of (2), in addition to the target compound (yield 34%), 1,2-adduct (yield 3%) represented by the following formula is obtained. By-product.
発明が解決しようとする問題点 芳香族化合物として、N,N−ジメチルアニリン等の第三
級芳香族アミンを用いてスクエアリック酸塩化物とのフ
リーデルクラフツ反応を試みた例は、これまで報告され
ていない。 Problems to be Solved by the Invention Examples of attempting Friedel-Crafts reaction with squaric acid chloride by using a tertiary aromatic amine such as N, N-dimethylaniline as an aromatic compound have been reported so far. It has not been.
本発明者等は、一群の第三級芳香族アミンを用い、シク
ロブテンジオン誘導体を合成することについて検討した
結果、特定の第三級芳香族アミンを用いると、電子写真
感光材料その他の用途に使用できる新規なスクアリリウ
ム化合物を製造するための中間体となる新規なシクロブ
テンジオン誘導体が得られたことを見出だした。The present inventors have examined the synthesis of a cyclobutenedione derivative using a group of tertiary aromatic amines, and as a result, when a specific tertiary aromatic amine is used, it can be used in electrophotographic photosensitive materials and other applications. It has been found that new cyclobutenedione derivatives have been obtained which are intermediates for the production of new squarylium compounds which can be used.
したがって、本発明の目的は、電子写真感光材料その他
の用途に使用できる新規なスクアリリウム化合物を製造
するための中間体となり新規なシクロブテンジオン誘導
体を提供することにある。Therefore, an object of the present invention is to provide a novel cyclobutenedione derivative which serves as an intermediate for producing a novel squarylium compound that can be used in electrophotographic photosensitive materials and other applications.
問題点を解決するための手段 本発明の新規なシクロブテンジオン誘導体は、下記一般
式（Ｉ） （式中、R1、R2及びR3は、それぞれメチル基、エチル
基、プロピル基又はブチル基を表わし、Ｘは塩素原子又
は水酸基を表わす） で示される。Means for Solving Problems The novel cyclobutenedione derivative of the present invention has the following general formula (I): (In the formula, R 1 , R 2 and R 3 each represent a methyl group, an ethyl group, a propyl group or a butyl group, and X represents a chlorine atom or a hydroxyl group).
上記のシクロブテンジオン誘導体は、下記構造式（Ia）
及び（Ib）が含まれる。The above cyclobutenedione derivative has the following structural formula (Ia)
And (Ib) are included.
（式中、R1、R2及びR3は、それぞれ前記と同じ意味を表
わす） これ等の更に具体的な化合物としては、下記構造式のシ
クロブテンジオン誘導体を例示することができる。 (In the formula, R 1 , R 2 and R 3 have the same meanings as described above.) Specific examples of these compounds include cyclobutenedione derivatives having the following structural formula.
（式中、R1及びR2は、それぞれ前記と同じ意味を表わ
す） 上記一般式（Ｉ）で示されるシクロブテンジオン誘導体
は、次のようにして製造することができる。 (In the formula, R 1 and R 2 have the same meanings as described above.) The cyclobutenedione derivative represented by the general formula (I) can be produced as follows.
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、下記一般式（III） （式中、R1、R2及びR3は、それぞれ前記と同じ意味を表
わす） で示されるアニリン誘導体とを反応させてクロロシクロ
ブテンジオン誘導体を合成し、所望により、加水分解す
ることによって得ることができる。Structural formula (II) below 3,4-dichloro-3-cyclobutene-1,2-dione represented by the following general formula (III) (Wherein R 1 , R 2 and R 3 have the same meanings as described above) to obtain a chlorocyclobutenedione derivative, which is obtained by hydrolysis if desired. be able to.
上記の反応は、公知の類似の反応に準じて実施すること
ができる。The above reaction 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−
ジオンと一般式（III）で示されるアニリン誘導体とを
反応させる。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（III）、塩化チタン（IV）、塩化錫（I
V）、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
うことができる。That is, first, 3,4-dichloro-3-cyclobutene-1,2-
The dione is reacted with the aniline derivative represented by the general formula (III). This reaction is carried out by dissolving them in a suitable solvent, for example, a methylene chloride, carbon tetrachloride, a halogenated hydrocarbon such as chloroform, a conventional Friedel-Crafts reaction solvent such as nitrobenzene, ethyl ether, acetonitrile and the like, and if desired. Catalysts such as boron trifluoride ethyl ether complex, aluminum chloride, antimony chloride, iron (II) or (III) chloride, titanium (IV) chloride, tin chloride (I
V), bismuth (IV) chloride, zinc (II) chloride, mercury chloride, etc. in the presence of stirring at 0 to 40 ° C.
合成されたクロロシクロブテンジオン誘導体は、所望に
より加水分解されるが、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 optionally hydrolyzed, and the hydrolysis is carried out by heating in water containing a suitable acid such as acetic acid.
本発明のシクロブテンジオン誘導体は、電子写真感光材
料、光ディスク用記録材料、太陽電池、赤外線カットフ
ィルターの分野で有用なスクエアリリウム化合物の合成
原料として有用である。例えば、本発明のシクロブテン
ジオン誘導体を、下記一般式（IV）で示されるアニリン
誘導体と縮合させることにより、種々のスクアリリウム
化合物を製造することができる。INDUSTRIAL APPLICABILITY The cyclobutenedione derivative of the present invention is useful as a raw material for synthesizing a squarylium compound useful in the fields of electrophotographic photosensitive materials, recording materials for optical disks, solar cells, and infrared cut filters. For example, various cyclorylium compounds can be produced by condensing the cyclobutenedione derivative of the present invention with an aniline derivative represented by the following general formula (IV).
（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） 実施例 以下、本発明の実施例を示す。 (In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group.) 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1.93g
（12.8ミリモル）及び３−アセチルアミノ−Ｎ−,N−ジ
メチルアニリン4.52g（25.4ミリモル）を塩化メチレン2
0mlに溶解し、室温で２時間撹拌し、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、
下記構造式で示されるクロロシクロブテンジオン化合物
2.16g（収率58％）を得た。融点:mp＝218℃ 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）:4
34nmであった。又、元素分析値は、C14H13ClN2O3とし
て、次の通りであった。Example 1 3,4-dichloro-3-cyclobutene-1,2-dione 1.93 g
(12.8 mmol) and 4.52 g (25.4 mmol) of 3-acetylamino-N-, N-dimethylaniline in methylene chloride 2
It was dissolved in 0 ml and stirred at room temperature for 2 hours to carry out the reaction.
After completion of the reaction, the reaction mixture was washed with diluted hydrochloric acid and then with water,
Separation and purification using column chromatography,
Chlorocyclobutenedione compound represented by the following structural formula
2.16 g (yield 58%) was obtained. Melting point: mp = 218 ℃ 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 ): 4.
It was 34 nm. Moreover, the elemental analysis values were as follows, as C 14 H 13 ClN 2 O 3 .
計算値(%) 実測値(%) Ｃ 57.45 57.27 Ｈ 4.48 4.36 Ｎ 9.57 9.75 実施例２ 実施例１において得られたクロロシクロブテンジオン化
合物1.00g（3.42ミリモル）に酢酸10ml及び水1mlを加
え、10分間加熱還流させた後、放冷し、析出する沈澱物
を濾別し、下記構造式で示されるヒドロキシシクロブテ
ンジオン化合物0.86gを（収率92％）を得た。融点:mp＝
280℃（分解） この化合物の赤外吸収スペクトルは第２図に示す通りで
あり、紫外吸収スペクトル（最大）は、UV（CH2Cl2）:4
15nmであった。又、元素分析値は、C14H14N2O4として、
次の通りであった。Calculated value (%) Measured value (%) C 57.45 57.27 H 4.48 4.36 N 9.57 9.75 Example 2 To 1.00 g (3.42 mmol) of the chlorocyclobutenedione compound obtained in Example 1 was added 10 ml of acetic acid and 1 ml of water to give 10 After heating and refluxing for 1 minute, the mixture was allowed to cool and the precipitated precipitate was filtered off to obtain 0.86 g of hydroxycyclobutenedione compound represented by the following structural formula (yield 92%). Melting point: mp =
280 ℃ (decomposition) The infrared absorption spectrum of this compound is as shown in FIG. 2, and the ultraviolet absorption spectrum (maximum) is UV (CH 2 Cl 2 ): 4.
It was 15 nm. The elemental analysis value is C 14 H 14 N 2 O 4 ,
It was as follows.
計算値(%) 実測値(%) Ｃ 61.31 61.29 Ｈ 5.15 5.10 Ｎ 10.21 10.09 実施例３〜８ 目的化合物に対応する原料物質を選択し、実施例１にお
けると同様にして3,4−ジクロロ−３−シクロブテン−
1,2−ジオンと反応させ、第１表に示す化合物を製造し
た。これ等の化合物の紫外吸収スペクトル（最大）も又
第１表に示す。Calculated value (%) Measured value (%) C 61.31 61.29 H 5.15 5.10 N 10.21 10.09 Examples 3 to 8 Starting materials corresponding to the target compounds were selected, and 3,4-dichloro-3 was prepared in the same manner as in Example 1. -Cyclobutene-
The compounds shown in Table 1 were prepared by reacting with 1,2-dione. The UV absorption spectra (maximum) of these compounds are also shown in Table 1.
実施例９〜14 実施例３〜５によって得られた化合物を、実施例２にお
けると同様に処理して第２表に示す化合物を製造した。
これ等の化合物の紫外吸収スペクトル（最大）も又第２
表に示す。 Examples 9 to 14 The compounds obtained in Examples 3 to 5 were treated in the same manner as in Example 2 to produce the compounds shown in Table 2.
The UV absorption spectra (maximum) of these compounds are also second
Shown in the table.
発明の効果 本発明のジクロブテンジオン誘導体は、新規な化合物で
あって、電子写真感光材料、光ディスク用記録材料、太
陽電池、赤外線カットフィルターの分野で有用なスクエ
アリリウム化合物の合成原料として使用することができ
る。本発明のジクロブテンジオン誘導体を用い、例えば
N,N−ジアルキルアニリン誘導体と反応させることによ
って合成されたスクアリリウム化合物を含有する電子写
真感光体は、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ものとなる。 EFFECTS OF THE INVENTION The diclobutenedione derivative of the present invention is a novel compound, and can be used as a raw material for synthesizing a squarylium compound useful in the fields of electrophotographic photosensitive materials, recording materials for optical disks, solar cells, and infrared cut filters. You can Using the diclobutenedione derivative of the present invention, for example
The electrophotographic photoreceptor containing the squarylium compound synthesized by reacting with the N, N-dialkylaniline derivative has sensitivity over a wide range from the visible region to the near infrared region.
第１図は実施例１のシクロブテンジオン化合物の赤外吸
収スペクトル図であり、第２図は実施例２のシクロブテ
ンジオン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 cyclobutenedione compound of Example 1, and FIG. 2 is an infrared absorption spectrum diagram of the cyclobutenedione compound of Example 2.
Claims (5)
基、プロピル基又はブチル基を表わし、Ｘは塩素原子又
は水酸基を表わす） で示されるシクロブテンジオン誘導体。1. The following general formula (I): (In the formula, R 1 , R 2 and R 3 each represent a methyl group, an ethyl group, a propyl group or a butyl group, and X represents a chlorine atom or a hydroxyl group).
わす） で示される特許請求の範囲第１項に記載のシクロブテン
ジオン誘導体。2. The following structural formula (Ia) (Wherein R 1 , R 2 and R 3 have the same meanings as described above), and the cyclobutenedione derivative according to claim 1.
わす） で示される特許請求の範囲第１項に記載のシクロブテン
ジオン誘導体。3. The following structural formula (Ib) (Wherein R 1 , R 2 and R 3 have the same meanings as described above), and the cyclobutenedione derivative according to claim 1.
す） で示される特許請求の範囲第１項に記載のシクロブテン
ジオン誘導体。4. The following structural formula (Ic) (In the formula, R 1 and R 2 have the same meanings as described above.) The cyclobutenedione derivative according to claim 1.
す） で示される特許請求の範囲第１項に記載のシクロブテン
ジオン誘導体。5. The following structural formula (Id) (In the formula, R 1 and R 2 have the same meanings as described above.) The cyclobutenedione derivative according to claim 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30586687A JPH0768195B2 (en) | 1987-12-04 | 1987-12-04 | Novel cyclobutenedione derivative |
| 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 |
|---|---|---|---|
| JP30586687A JPH0768195B2 (en) | 1987-12-04 | 1987-12-04 | Novel cyclobutenedione derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01146852A JPH01146852A (en) | 1989-06-08 |
| JPH0768195B2 true JPH0768195B2 (en) | 1995-07-26 |
Family
ID=17950297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30586687A Expired - Fee Related JPH0768195B2 (en) | 1987-12-04 | 1987-12-04 | Novel cyclobutenedione derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768195B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005122320A1 (en) * | 2004-06-09 | 2005-12-22 | Kyowa Hakko Chemical Co., Ltd. | Photoelectric conversion material, photoelectric converter and photoelectrochemical cell |
-
1987
- 1987-12-04 JP JP30586687A patent/JPH0768195B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01146852A (en) | 1989-06-08 |
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