JPH0571583B2 - - Google Patents
Info
- Publication number
- JPH0571583B2 JPH0571583B2 JP61091257A JP9125786A JPH0571583B2 JP H0571583 B2 JPH0571583 B2 JP H0571583B2 JP 61091257 A JP61091257 A JP 61091257A JP 9125786 A JP9125786 A JP 9125786A JP H0571583 B2 JPH0571583 B2 JP H0571583B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- general formula
- represented
- derivative
- 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 - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- KGPQKNJSZNXOPV-UHFFFAOYSA-N moniliformin Chemical class OC1=CC(=O)C1=O KGPQKNJSZNXOPV-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052731 fluorine Chemical group 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- DNJNUCYAVRRVMW-UHFFFAOYSA-N 3-chlorocyclobut-3-ene-1,2-dione Chemical class ClC1=CC(=O)C1=O DNJNUCYAVRRVMW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- SXOQOOQUBDERIZ-UHFFFAOYSA-N 3,4-dichlorocyclobut-3-ene-1,2-dione Chemical compound ClC1=C(Cl)C(=O)C1=O SXOQOOQUBDERIZ-UHFFFAOYSA-N 0.000 claims 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 108091008695 photoreceptors Proteins 0.000 description 5
- 239000000049 pigment Substances 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000001448 anilines Chemical class 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- CWOMTHDOJCARBY-UHFFFAOYSA-N n,n,3-trimethylaniline Chemical compound CN(C)C1=CC=CC(C)=C1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
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)
- Photoreceptors In Electrophotography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
〔産業上の利用分野〕
本発明は、光導電性材料として有用な非対称型
スクエアリリウム化合物の製造方法に関する。
〔従来の技術〕
電子写真感光体等の光導電性材料としては無機
および有機の数多くの物質が知られている。この
うち有機系の光導電性材料としては、従来ビスア
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、ピリリウム類などが知られて
おり、また近年下記式
[Industrial Application Field] The present invention relates to a method for producing an asymmetric squarerylium compound useful as a photoconductive material. [Prior Art] Many inorganic and organic substances are known as photoconductive materials for electrophotographic photoreceptors and the like. Among these, conventionally known organic photoconductive materials include bisazo pigments, trisazo pigments, phthalocyanine pigments, cyanines, and pyrylium pigments.
本発明の目的は、新規な非対称型のスクエアリ
リウム化合物の製造方法を提供することにある。
〔問題点を解決するための手段〕
本発明者等は、鋭意研究を重ねた結果、３，４
−ジクロロ−３−シクロブテン−１，２−ジオン
（スクエアリツク酸塩化物）とアニリン誘導体と
を反応させてクロロシクロブテンジオン誘導体を
得、この誘導体を加水分解してヒドロキシシクロ
ブテンジオン誘導体とした後、これに他のアニリ
ン誘導体を反応させることによつて非対称型のス
クエアリリウム化合物を高純度で収率よく得るこ
とができることを見出し、本発明を完成した。
すなわち、本発明は一般式（）
An object of the present invention is to provide a method for producing a novel asymmetric squarerylium compound. [Means for solving the problem] As a result of intensive research, the present inventors have found 3.4
- Dichloro-3-cyclobutene-1,2-dione (squaric acid chloride) is reacted with an aniline derivative to obtain a chlorocyclobutenedione derivative, and this derivative is hydrolyzed to obtain a hydroxycyclobutenedione derivative; The inventors have discovered that an asymmetric squarerium compound can be obtained with high purity and good yield by reacting this with other aniline derivatives, and have completed the present invention. That is, the present invention is based on the general formula ()
【化】
〔式中、Ｒは水素原子またはメチル基を表わ
し、R′は水素原子またはフツ素原子を表わす。
ただし、ＲとR′は同時に水素原子を表わさない
ものとする。〕で示されるスクエアリリウム化合
物の製造方法を提供したものである。
下記に本発明の製造方法により得られる前記一
般式（）で示される非対称型スクエアリリウム
化合物の具体例を構造式で示す。[In the formula, R represents a hydrogen atom or a methyl group, and R' represents a hydrogen atom or a fluorine atom.
However, it is assumed that R and R' do not represent hydrogen atoms at the same time. The present invention provides a method for producing a squarerium compound shown in the following. Specific examples of the asymmetric squarerium compounds represented by the general formula () obtained by the production method of the present invention are shown below in terms of structural formulas.
【化】[ka]
【化】[ka]
【化】
本発明のスクエアリリウム化合物の製造方法
は、下記反応工程式Ａおよび反応工程式Ｂで示さ
れる。[Chemical Formula] The method for producing the squarylium compound of the present invention is shown by the following reaction scheme A and reaction scheme B.
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
本発明は新規な非対称型スクエアリリウム化合
物の製造方法を提供したものである。本発明によ
れば、高純度で容易に非対称型スクエアリリウム
化合物を得ることができる。本発明のスクエアリ
リウム化合物は電子写真感光体等の有機光導電体
として有効に用いることができる。電子写真感光
体としては種々の形態のものが考えられるが、特
に本発明のスクエアリリウム化合物は機能分離型
感光体、すなわち電荷発生層と電荷輸送層から構
成される感光体において、特に電荷発生層として
用いられる光導電性物質として有用である。
〔実施例〕
以下、実施例を挙げて本発明を説明する。
実施例 １
３，４−ジクロル−３−シクロブテン−１，２
−ジオン6.00ｇと塩化アルミニウム5.30ｇとを塩
化メチレン60ml中で５℃以下に保ち、塩化アルミ
ニウムが溶解するまで攪拌した。
これに、３−フルオロ−Ｎ，Ｎ−ジメチルアニ
リン5.53ｇを40分間で滴下し、その後2.5時間５
℃以下に保つて反応させた。反応終了後、1M−
HCl、水で洗浄し、次にカラムクロマトグラフイ
ーで分離し、下記式
The present invention provides a method for producing a novel asymmetric squarerium compound. According to the present invention, an asymmetric squarerium compound can be easily obtained with high purity. The squarylium compound of the present invention can be effectively used as an organic photoconductor such as an electrophotographic photoreceptor. Various types of electrophotographic photoreceptors can be considered, but in particular, the squarerium compound of the present invention can be used in a functionally separated photoreceptor, that is, a photoreceptor composed of a charge generation layer and a charge transport layer. It is useful as a photoconductive material used as a photoconductive material. [Example] The present invention will be described below with reference to Examples. Example 1 3,4-dichloro-3-cyclobutene-1,2
- 6.00 g of dione and 5.30 g of aluminum chloride were stirred in 60 ml of methylene chloride while keeping the temperature below 5°C until the aluminum chloride was dissolved. To this, 5.53 g of 3-fluoro-N,N-dimethylaniline was added dropwise over 40 minutes, and then 5.53 g was added for 2.5 hours.
The reaction was carried out by keeping the temperature below ℃. After the reaction, 1M−
Washed with HCl and water, then separated by column chromatography, and the following formula was used:
【化】
で示される生成物（式でR′＝Ｆの化合物）3.53
ｇ（収率35％）を得た。
次にこの生成物1.90ｇを氷酢酸30ml、水８mlの
混合溶媒中で２時間還流し、室温まで冷却した後
別し、下記式The product represented by [chemical formula] (a compound where R′=F in the formula) 3.53
g (yield 35%) was obtained. Next, 1.90 g of this product was refluxed for 2 hours in a mixed solvent of 30 ml of glacial acetic acid and 8 ml of water, cooled to room temperature, separated, and the following formula
【化】
で示される生成物（式においてR′＝Ｆの化合
物）1.58ｇ（収率90％）を得た。
次にこの化合物1.20ｇ、Ｎ，Ｎ−ジメチルアニ
リン1.85ｇをブタノール100ml中で20時間還流し
た後別して青緑色結晶を得た。これをメタノー
ル、ジエチルエーテルで洗浄後、乾燥して前記構
造式(3)で示される生成物を得た。収量1.20ｇ（収
率70％）。
分解点：276℃；
元素分析：C20H19FN2O2として
Ｃ Ｈ Ｎ
計算値（％） 70.99 5.66 8.28
実測値（％） 71.05 5.74 8.29
IRスペクトル：第１図。
実施例 ２
実施例１と全く同様にして式でR′＝Ｆのヒ
ドロキシシクロブテンジオン誘導体を得た。
次に、この誘導体1.20ｇ、３−メチル−Ｎ，Ｎ
−ジメチルアニリン2.07ｇをブタノール100ml中
で20時間還流した後、別して青緑色結晶を得
た。これをメタノール、ジエチルエーテルで洗浄
後、乾燥して前記構造式(2)で示されるスクエアリ
リウム化合物を得た。収量1.25ｇ（収率70％）。
分解点：259〜260℃；
元素分析：C21H21FN2O2として
Ｃ Ｈ Ｎ
計算値（％） 71.57 6.01 7.95
実測値（％） 71.60 6.07 7.89
IRスペクトル：第２図
実施例 ３
３，４−ジクロロ−３−シクロブテン−１，２
−ジオン6.00ｇと塩化アルミニウム5.80ｇとを塩
化メチレン50ml中で５℃以下に保ちながら塩化ア
ルミニウムが溶解するまで攪拌した。
これに３−メチル−Ｎ，Ｎ−ジメチルアニリン
5.40ｇを塩化メチレン30mlに溶解したものを約１
時間かけて滴下し、さらに５℃以下に保つて30分
間攪拌した。
反応終了後1M−HCl、水で洗浄しカラムクロ
マトグラフイーで分離することにより次式1.58 g (yield: 90%) of the product represented by the following formula (a compound where R'=F in the formula) was obtained. Next, 1.20 g of this compound and 1.85 g of N,N-dimethylaniline were refluxed in 100 ml of butanol for 20 hours and separated to obtain blue-green crystals. This was washed with methanol and diethyl ether and then dried to obtain a product represented by the structural formula (3). Yield: 1.20g (yield 70%). Decomposition point: 276°C; Elemental analysis: C 20 H 19 FN 2 O 2 as C H N Calculated value (%) 70.99 5.66 8.28 Actual value (%) 71.05 5.74 8.29 IR spectrum: FIG. Example 2 A hydroxycyclobutenedione derivative having the formula R'=F was obtained in exactly the same manner as in Example 1. Next, 1.20 g of this derivative, 3-methyl-N,N
- After refluxing 2.07 g of dimethylaniline in 100 ml of butanol for 20 hours, a blue-green crystal was obtained separately. This was washed with methanol and diethyl ether and then dried to obtain a squarerium compound represented by the structural formula (2). Yield: 1.25g (yield 70%). Decomposition point: 259-260°C; Elemental analysis: C 21 H 21 FN 2 O 2 Calculated value (%) 71.57 6.01 7.95 Actual value (%) 71.60 6.07 7.89 IR spectrum: Figure 2 Example 3 3, 4-dichloro-3-cyclobutene-1,2
- 6.00 g of dione and 5.80 g of aluminum chloride were stirred in 50 ml of methylene chloride while keeping the temperature below 5°C until the aluminum chloride was dissolved. To this, 3-methyl-N,N-dimethylaniline
Approximately 1
The mixture was added dropwise over a period of time, and the mixture was further stirred for 30 minutes while keeping the temperature below 5°C. After the reaction is completed, the following formula is obtained by washing with 1M HCl and water and separating by column chromatography.
【化】
で示される化合物（式においてＲ＝CH3の化合
物）2.30ｇ（収率23％）を得た。
次にこの化合物2.30ｇを酢酸20ml、水２mlの混
合溶媒中で10分間還流し、冷却後別することに
より次式2.30 g (yield: 23%) of a compound represented by the formula (R=CH 3 in the formula) was obtained. Next, 2.30 g of this compound was refluxed for 10 minutes in a mixed solvent of 20 ml of acetic acid and 2 ml of water, and after cooling, the following formula was obtained:
【化】
で示される化合物（式でＲ＝CH3の化合物）
1.96ｇ（収率92％）を得た。次いでこの生成物
1.00ｇ、Ｎ，Ｎ−ジメチルアニリン1.50ｇをブタ
ノール80ml中で20時間還流した後別して青緑色
結晶を得た。これをメタノール、ジエチルエーテ
ルで洗浄後乾燥して前記構造式(1)で示される生成
物を得た。収量0.92ｇ（収率64％）。
分解点：246℃；
元素分析：C21H22N2O2として
Ｃ Ｈ Ｎ
計算値（％） 75.42 6.63 8.38
実測値（％） 75.10 6.49 8.30
IRスペクトル：第３図。
実施例 ４
３，４−ジクロロ−３−シクロブテン−１，２
−ジオン3.00ｇと塩化アルミニウム2.65ｇとを塩
化メチレン30ml中で５℃以下に保ち、塩化アルミ
ニウムが溶解するまで攪拌した。
これに、Ｎ，Ｎ−ジメチルアニリン2.43ｇを30
分間で滴下し、その後2.5時間５℃以下に保つて
反応させた。反応終了後、1M−HCl、水で洗浄
し、次にカラムクロマトグラフイーで分離し、下
記式Compounds represented by [chemical formula] (compounds where R=CH 3 in the formula)
1.96g (yield 92%) was obtained. Then this product
1.00 g of N,N-dimethylaniline and 1.50 g of N,N-dimethylaniline were refluxed in 80 ml of butanol for 20 hours and separated to obtain blue-green crystals. This was washed with methanol and diethyl ether and dried to obtain the product represented by the structural formula (1). Yield: 0.92g (yield 64%). Decomposition point: 246°C; Elemental analysis: C 21 H 22 N 2 O 2 Calculated value (%) 75.42 6.63 8.38 Actual value (%) 75.10 6.49 8.30 IR spectrum: Figure 3. Example 4 3,4-dichloro-3-cyclobutene-1,2
- 3.00 g of dione and 2.65 g of aluminum chloride were stirred in 30 ml of methylene chloride while keeping the temperature below 5°C until the aluminum chloride was dissolved. To this, add 2.43 g of N,N-dimethylaniline to 30
The mixture was added dropwise over a period of minutes, and then the temperature was kept below 5° C. for 2.5 hours to react. After the reaction was completed, it was washed with 1M HCl and water, and then separated by column chromatography, and the following formula was obtained.
【化】
で示される生成物（式でＲ＝Ｈの化合物）1.64
ｇ（収率35％）を得た。
次にこの化合物1.56ｇを氷酢酸30ml、水６mlの
混合溶媒中で２時間還流し、室温まで冷却した
後、別し下記式Product represented by [chemical formula] (compound with R=H in the formula) 1.64
g (yield 35%) was obtained. Next, 1.56 g of this compound was refluxed for 2 hours in a mixed solvent of 30 ml of glacial acetic acid and 6 ml of water, cooled to room temperature, separated, and the following formula
【化】
で示される生成物（式でＲ＝Ｈの化合物）1.38
ｇ（収率96％）を得た。
次いで、この生成物1.00ｇ、３−フルオロ−
Ｎ，Ｎ−ジメチルアニリン1.92ｇをブタノール90
ml中で20時間還流した後別して青緑色結晶を得
た。これをメタノール、ジエチルエーテルで洗浄
後、乾燥して、前記構造式(3)で示される生成物
1.01ｇ（収率65％）を得た。
分解点：276℃；
元素分析：C20H19FN2O2として
Ｃ Ｈ Ｎ
計算値（％） 70.99 5.66 8.28
実測値（％） 71.01 5.80 8.30
IRスペクトル：実施例１で得た化合物に一致
した。
実施例 ５
実施例４と全く同様にして、式でＲ＝Ｈのヒ
ドロキシシクロブテンジオン誘導体を得た。次に
この化合物1.00ｇ、３−メチル−Ｎ，N′−ジメチ
ルアニリン1.87ｇをブタノール90ml中で20時間還
流した後別して青緑色結晶を得た。これをメタ
ノール、ジエチルエーテルで洗浄後乾燥して、前
記構造式(1)で示される生成物を得た。収量0.99ｇ
（収率64％）。
分解点：246℃；
元素分析：C21H2202N2として
Ｃ Ｈ Ｎ
計算値（％） 75.42 6.63 8.38
実測値（％） 75.53 6.67 8.34
IRスペクトル：実施例３で得た化合物に一致
した。
実施例 ６
実施例３と全く同様にして式でＲ＝CH3のヒ
ドロキシシクロブテンジオン誘導体を得た。
次いで、この化合物0.50ｇ、３−フルオロ−
Ｎ，N′−ジメチルアニリン0.90ｇを１−ブタノー
ル40ml中で24時間還流し別して緑色結晶を得
た。これをメタノール、ジエチルエーテルで洗
浄、乾燥して前記構造式(2)で示される化合物0.53
ｇ（収率70％）を得た。
分解点：259〜260℃
元素分析：C21H21FN2O2として
Ｃ Ｈ Ｎ
計算値（％） 71.57 6.01 7.95
実測値（％） 71.67 5.96 8.09
IRスペクトル：実施例２で得た化合物に一致
した。The product represented by [chemical formula] (compound with R=H in the formula) 1.38
g (yield 96%) was obtained. Then 1.00 g of this product, 3-fluoro-
1.92 g of N,N-dimethylaniline and 90 g of butanol
After refluxing in ml for 20 hours, blue-green crystals were obtained. After washing this with methanol and diethyl ether and drying, the product represented by the above structural formula (3) is obtained.
1.01 g (yield 65%) was obtained. Decomposition point: 276°C; Elemental analysis: C H N as C 20 H 19 FN 2 O 2 Calculated value (%) 70.99 5.66 8.28 Actual value (%) 71.01 5.80 8.30 IR spectrum: Consistent with the compound obtained in Example 1 . Example 5 In exactly the same manner as in Example 4, a hydroxycyclobutenedione derivative with the formula R=H was obtained. Next, 1.00 g of this compound and 1.87 g of 3-methyl-N,N'-dimethylaniline were refluxed in 90 ml of butanol for 20 hours and separated to obtain blue-green crystals. This was washed with methanol and diethyl ether and dried to obtain a product represented by the structural formula (1). Yield 0.99g
(yield 64%). Decomposition point: 246°C; Elemental analysis: C 21 H 22 0 2 N 2 Calculated value (%) 75.42 6.63 8.38 Actual value (%) 75.53 6.67 8.34 IR spectrum: Consistent with the compound obtained in Example 3 . Example 6 In exactly the same manner as in Example 3, a hydroxycyclobutenedione derivative with the formula R=CH 3 was obtained. Then, 0.50 g of this compound, 3-fluoro-
0.90 g of N,N'-dimethylaniline was refluxed in 40 ml of 1-butanol for 24 hours and separated to obtain green crystals. This was washed with methanol and diethyl ether and dried to form a compound represented by the above structural formula (2).
g (yield 70%) was obtained. Decomposition point: 259-260°C Elemental analysis: C H N as C 21 H 21 FN 2 O 2 Calculated value (%) 71.57 6.01 7.95 Actual value (%) 71.67 5.96 8.09 IR spectrum: Consistent with the compound obtained in Example 2 did.
第１図乃至第３図は本発明のスクエアリリウム
化合物IRスペクトル図である。
FIGS. 1 to 3 are IR spectra of the squarylium compound of the present invention.
Claims (1)
−１，２−ジオンと一般式（） 【式】 （式中、Ｒは水素原子またはメチル基を表わ
す。） で示されるアニリン誘導体とを反応させ、一般式
（） 【式】 （式中、Ｒは前記と同じ意味を表わす。） で示されるクロロシクロブテンジオン誘導体を
得、次いでこの誘導体を加水分解して、一般式
（） 【式】 （式中、Ｒは前記と同じ意味を表わす。） で示されるヒドロキシシクロブテンジオン誘導体
とし、この一般式（）の化合物を、一般式
（） 【式】 （式中、R′は水素原子またはフツ素原子を表
わす。） で示されるアニリン誘導体と反応させることを特
徴とする一般式（） 【化】 （式中、ＲおよびR′は前記と同じ意味を表わ
す。ただし、ＲとR′は同時に水素原子を表わさ
ないものとする。） で示されるスクエアリリウム化合物の製造方法。 ２ 式（） 【式】 で示される３，４−ジクロロ−３−シクロブテン
−１，２−ジオンと式（） 【式】 （式中、R′は水素原子またはフツ素原子を表
わす。） で示されるアニリン誘導体と反応させ、一般式
（） 【化】 （式中、R′は前記と同じ意味を表わす。） で示されるクロロシクロブテンジオン誘導体を
得、次いでこの誘導体を加水分解して、一般式
（） 【化】 で示されるヒドロキシシクロブテンジオン誘導体
とし、この一般式（）の化合物を一般式（） 【式】 （式中、Ｒは水素原子またはメチル基を表わ
す。） で示されるアニリン誘導体と反応させることを特
徴とする一般式（） 【化】 （式中、ＲおよびR′は前記と同じ意味を表わ
す。ただし、ＲとR′は同時に水素原子を表わさ
ないものとする。） で示されるスクエアリリウム化合物の製造方法。[Scope of Claims] 1 3,4-dichloro-3-cyclobutene-1,2-dione represented by the formula () [Formula] and the general formula () [Formula] (wherein R is a hydrogen atom or a methyl group) ) to obtain a chlorocyclobutenedione derivative represented by the general formula () [Formula] (wherein R represents the same meaning as above), and then this derivative was Hydrolyzed to form a hydroxycyclobutenedione derivative represented by the general formula () [Formula] (wherein R represents the same meaning as above), and this compound of the general formula () is converted into a hydroxycyclobutenedione derivative represented by the general formula () [Formula] (wherein R represents the same meaning as above). [Formula, R' represents a hydrogen atom or a fluorine atom] General formula () [Chemical formula] (wherein, R' represents a hydrogen atom or a fluorine atom) have the same meaning.However, R and R' do not represent hydrogen atoms at the same time.) A method for producing a squarerylium compound represented by 2 3,4-dichloro-3-cyclobutene-1,2-dione represented by the formula () [formula] and the formula () [formula] (wherein, R' represents a hydrogen atom or a fluorine atom). A chlorocyclobutenedione derivative represented by the general formula () (wherein R′ represents the same meaning as above) is obtained by reacting with the aniline derivative shown, and then this derivative is hydrolyzed, A hydroxycyclobutenedione derivative represented by the general formula () [formula], and a compound of the general formula () represented by the general formula () [formula] (wherein, R represents a hydrogen atom or a methyl group) The general formula () is characterized in that it is reacted with an aniline derivative. (In the formula, R and R' have the same meanings as above. However, R and R' do not represent a hydrogen atom at the same time. ) A method for producing a squarerium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9125786A JPS62249950A (en) | 1986-04-22 | 1986-04-22 | Squarylium compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9125786A JPS62249950A (en) | 1986-04-22 | 1986-04-22 | Squarylium compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62249950A JPS62249950A (en) | 1987-10-30 |
| JPH0571583B2 true JPH0571583B2 (en) | 1993-10-07 |
Family
ID=14021370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9125786A Granted JPS62249950A (en) | 1986-04-22 | 1986-04-22 | Squarylium compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62249950A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4521621A (en) * | 1983-12-05 | 1985-06-04 | Xerox Corporation | Novel squarine systems |
| US4523035A (en) * | 1983-12-05 | 1985-06-11 | Xerox Corporation | Process for synthesizing squaraine compositions |
-
1986
- 1986-04-22 JP JP9125786A patent/JPS62249950A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4521621A (en) * | 1983-12-05 | 1985-06-04 | Xerox Corporation | Novel squarine systems |
| US4523035A (en) * | 1983-12-05 | 1985-06-11 | Xerox Corporation | Process for synthesizing squaraine compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62249950A (en) | 1987-10-30 |
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