JPH01146864A - Novel squarylium compound and production thereof - Google Patents
Novel squarylium compound and production thereofInfo
- Publication number
- JPH01146864A JPH01146864A JP30586187A JP30586187A JPH01146864A JP H01146864 A JPH01146864 A JP H01146864A JP 30586187 A JP30586187 A JP 30586187A JP 30586187 A JP30586187 A JP 30586187A JP H01146864 A JPH01146864 A JP H01146864A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- charge
- derivative
- following general
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- DNJNUCYAVRRVMW-UHFFFAOYSA-N 3-chlorocyclobut-3-ene-1,2-dione Chemical class ClC1=CC(=O)C1=O DNJNUCYAVRRVMW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- KGPQKNJSZNXOPV-UHFFFAOYSA-N moniliformin Chemical class OC1=CC(=O)C1=O KGPQKNJSZNXOPV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- RGBVWCQARBEPPW-UHFFFAOYSA-N cyclobut-3-ene-1,2-dione Chemical class O=C1C=CC1=O RGBVWCQARBEPPW-UHFFFAOYSA-N 0.000 claims 1
- 150000002440 hydroxy compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract 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 abstract description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 108091008695 photoreceptors Proteins 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 chloro-9form Chemical compound 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001448 anilines Chemical class 0.000 description 3
- 150000001716 carbazoles Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- MESJRHHDBDCQTH-UHFFFAOYSA-N 3-(dimethylamino)phenol Chemical compound CN(C)C1=CC=CC(O)=C1 MESJRHHDBDCQTH-UHFFFAOYSA-N 0.000 description 1
- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 description 1
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 150000002894 organic compounds Chemical class 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
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Indole Compounds (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
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。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application 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６０−１４２９４７号公報、同６１−１０５４
０号公報、同６２−４５０号公報等参照）。2. Description of the Related Art Various types of photosensitive materials have been known for use in electrophotographic photoreceptors, but in recent years electrophotographic photoreceptors using organic photosensitive materials have attracted attention and various studies have been conducted. As organic photoconductive materials, bisazo pigments, trisazo pigments, phthalocyanine pigments, cyanines, pyryliums, etc. are known, and in recent years, certain squarylium compounds have shown excellent photoconductive properties. It has been reported that it can be used as an electrophotographic light-sensitive material (for example, JP-A No. 60-136542, JP-A No. 60-142946, JP-A No. 60-142947, JP-A No. 61-1054).
(See Publication No. 0, Publication No. 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 Although various organic compounds that have been proposed in the past can be used as charge generating agents in electrophotographic photoreceptors, it is desired to provide other excellent charge generating agents. .
本発明者等は、−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 studying squarylium compounds in the - group, the present inventors discovered that the novel squarylium compounds shown below are useful as charge generating agents, leading to the completion of 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 electrophotographic photoreceptors 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−最大（
Ｉ＞で示される。Means for Solving the Problems The novel squarylium compounds of the present invention have the following - maximum (
It is indicated by I>.
（式中、Ｘは水素原子、メチル基、フッ素原子又は水酸
基を表わし、Ｒはメチル基又はエチル基を表わす）
上記−最大（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, and R represents a methyl group or an ethyl group) The squarylium compound represented by -maximum (I>) is
It is manufactured as follows.
即ち、下記構造式（ＩＩ＞
し１
で示される３、４−ジクロロ−３−°シクロブテンー１
．２−ジオンと、下記−最大（Ｉ［Ｉ）＾
（式中、Ｒは前記と同じ意味を表わす）で示されるカル
バゾール誘導体とを反応させて、下記−最大（ＩＶ）
（式中、び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製造し、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−最
大（Ｖ）
（式中、び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を製造し、該ヒロド
キシシクロブテンジオン・誘導体を下記−最大（Ｖｌ）
（式中、Ｘは前記と同じ意味を表わす）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。That is, 3,4-dichloro-3-°cyclobutene-1 represented by the following structural formula (II>
．． 2-dione is reacted with a carbazole derivative represented by the following maximum (I [I) ^ (wherein R represents the same meaning as above) to form the following maximum (IV) (in the formula, and R represents the same meaning as above), and then hydrolyzes the chlorocyclobutenedione derivative to produce the following - maximum (V) (wherein and R have the same meaning as above). ), and the hydroxycyclobutenedione derivative is then combined with an aniline derivative represented by the following maximum (Vl) (wherein X represents the same meaning as above). It can be produced by reaction.
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 reactions in each step can be carried out according to known similar reactions.
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−最大（ＩＩＩ）で示されるカルバ
ゾール誘導体と反応させるが、カルバゾール誘導体とし
ては、Ｎ−メチルカルバゾール又はＮ−エチルカルバゾ
ールが使用される。That is, first, 3,4-dichloro-3-cyclobutene-1
, 2-dione is reacted with the carbazole derivative represented by maximum (III) above, and N-methylcarbazole or N-ethylcarbazole is used as the carbazole derivative.
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９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ッ反応溶媒に溶解し、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
（Ｉ［Ｉ）、塩化チタン（ＩＶ＞、塩化錫（ＩＶ）、塩
化ビスマス（工■）、塩化亜鉛（■）、塩化水銀等の存
在下、０〜４０℃において攪拌することによって行なう
ことができる。This reaction involves dissolving them in a suitable solvent, such as methylene chloride, carbon tetrachloride, halogenated hydrocarbons such as chloro-9form, common Friedel-Crach reaction solvents such as nitrobenzene, ethyl ether, acetonitrile, etc. If desired, catalysts such as boron trifluoride ethyl ether complex, aluminum chloride, antimony chloride, iron chloride (II> or (I)), titanium chloride (IV>), tin (IV) chloride, bismuth chloride (T) This can be carried out by stirring at 0 to 40° C. in the presence of zinc chloride (■), mercury chloride, or the like.
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、適当な狼、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, which is carried out by heating in water containing a suitable solution, such as 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−最大（ＶＤ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用い
られる。Subsequently, the hydroxycyclobutenedione derivative obtained by hydrolysis is reacted with the aniline derivative represented by -max (VD), but as the aniline derivative, N
, N-dimethylaniline, 3-methyl-N,N-dimethylaniline, 3-fluoro-N,N-dimethylaniline and 3-hydroxy-N,N-dimethylaniline.
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 dissolving these compounds in a suitable solvent, e.g.
- C4-C8 aliphatic alcohol such as butyl alcohol, n-heptyl alcohol, or it and benzene,
This can be carried out 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 electrophotographic photoreceptors. For example, when the photosensitive layer has a laminated structure in which a charge generation layer and a charge transport layer are functionally separated, the charge generation layer can be formed by using the squarylium compound together with a film-forming resin.
実施例 以下、本発明の実施例を示す。Example 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
１．１６９ （７，７ミリモル）、Ｎ−エチルカルバ
ゾール ３．００！？ （１５，４ミリモル〉及び三フ
ッ化硼素エチルエニテル錯体１．２ｇ（８，０ミリモル
）を塩化メチレン ２０ｄに溶解し、室温で２４時間攪
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０．８２ｇ（収率３４％）を得
た。Example 1 3.4-dichloro-3-cyclobutene-1,2-dione 1.169 (7.7 mmol), N-ethylcarbazole 3.00! ? (15.4 mmol) and 1.2 g (8.0 mmol) of boron trifluoride ethyleniter complex were dissolved in 20 d of methylene chloride and stirred at room temperature for 24 hours to carry out the reaction. After the reaction was completed, the reaction mixture was dissolved in dilute hydrochloric acid Then, the mixture was washed with water, and separated and purified using column chromatography to obtain 0.82 g (yield: 34%) of a chlorocyclobutenedione compound represented by the following structural formula.
得られたクロロシクロブテンジオン化合物０．５１０ｇ
（１，６５ミリモル）に酢１５ｍｌ及び水１ｄ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、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０．４５０！？ （収率９４％）を得た。融
点： ｍｐ＝２４０℃（徐々に分解）。0.510 g of the obtained chlorocyclobutenedione compound
(1.65 mmol), add 15 ml of vinegar and 1 d of water,
After heating under reflux for 2 hours, the precipitate was allowed to cool and the precipitate was filtered off to obtain a hydroxycyclobutenedione compound represented by the following structural formula: 0.450! ? (yield 94%). Melting point: mp=240°C (gradual decomposition).
得られたヒドロキシシクロブテンジオン化合物０．４０
０９ （１，３７ミリモル）と３−ヒドロキシ−Ｎ。Obtained hydroxycyclobutenedione compound 0.40
09 (1,37 mmol) and 3-hydroxy-N.
Ｎ−ジメチルアニリン０．１８８ｇ（１，３７ミリモル
）をブタノール ２（７中で５時間加熱攪拌した後、析
出した結晶を濾別し、メタノール及びジエチルエーテル
で洗浄して、下記構造式で示されるスクアリリウム化合
物０．５１７ｇ（収率９２％）を得た。After heating and stirring 0.188 g (1,37 mmol) of N-dimethylaniline in butanol 2 (7) for 5 hours, the precipitated crystals were filtered and washed with methanol and diethyl ether to obtain a product represented by the following structural formula. 0.517 g (yield 92%) of squarylium compound was obtained.
融点： ｍｐ＝３００℃（分解）。Melting point: mp=300°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 （ＣＨ２
ＣＩ ２ ） ： ６０４ｎｍであった。又、元素分析
値は、Ｃ２６Ｈ２２Ｎ２ ｏ３として、次の通りであっ
た。The infrared absorption spectrum of this compound is as shown in Figure 1, and the ultraviolet absorption spectrum (maximum) is UV (CH2
CI2): 604 nm. Further, the elemental analysis value of C26H22N2 o3 was as follows.
計算値（％） 実測値（％）
０ ７６．０８ ７Ｂ、１５
）１ ５．４０ ５．３４
Ｎ ６．８３ ６．９２
実施例２〜８
目的化合物に対応する原料物質を選択し、実施例１にお
けると同様にしてヒドロキシシクロブテンジオン化合物
を製造し、同様にして、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）を第１
表に示す。Calculated value (%) Actual value (%) 0 76.08 7B, 15 ) 1 5.40 5.34 N 6.83 6.92 Examples 2 to 8 A raw material corresponding to the target compound was selected, and the Example A hydroxycyclobutenedione compound was produced in the same manner as in Table 1, and the compounds shown in Table 1 were produced in the same manner. The ultraviolet absorption spectra (maximum) of these compounds are
Shown in the table.
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 and is a substance useful as a charge generating agent in electrophotographic photoreceptors, and has sensitivity over a wide range from the visible region to the near-infrared region. You can get a body. In particular, in an electrophotographic photoreceptor having a laminated structure in which a charge generation layer and a charge transport layer are functionally separated, when it is included in the charge generation layer, good 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。
特許出願人 富士ゼロックス株式会社代理人
弁理士 製部 剛FIG. 1 is an infrared absorption spectrum diagram of the squarylium compound in Example 1. Patent applicant Fuji Xerox Co., Ltd. Agent
Patent attorney Tsuyoshi Seibe
Claims (2)
基を表わし、Ｒはメチル基又はエチル基を表わす） で示されるスクアリリウム化合物。(1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a hydrogen atom, methyl group, fluorine atom, or hydroxyl group, and R represents a methyl group or ethyl group. ) A squarylium compound represented by
２−ジオンと、下記一般式（III） ▲数式、化学式、表等があります▼（III） （式中、Ｒはメチル基又はエチル基を表わす）で示され
るカルバゾール誘導体とを反応させて、下記一般式（I
V） ▲数式、化学式、表等があります▼（IV） （式中、び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製造し、
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、下記一般式（Ｖ） ▲数式、化学式、表等があります▼（Ｖ） （式中、び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を製造
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） ▲数式、化学式、表等があります▼（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 ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｘ及びＲ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) 3,4-dichloro-3-cyclobutene-1, shown by the following structural formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II)
By reacting 2-dione with a carbazole derivative represented by the following general formula (III) ▲Mathematical formula, chemical formula, table, etc.▼(III) (in the formula, R represents a methyl group or ethyl group), the following General formula (I
V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, and R represent the same meanings as above) Produce a chlorocyclobutenedione derivative represented by
Next, the chlorocyclobutenedione derivative is hydrolyzed to form a hydroxy compound represented by the following general formula (V) ▲Mathematical formula, chemical formula, table, etc.▼(V) (wherein, and R represent the same meanings as above) A cyclobutenedione derivative is produced, and the hydroxycyclobutenedione derivative is expressed by the following general formula (VI) ▲ Numerical formula, chemical formula, table, etc. ▼ (VI) (wherein, The following general formula (I) is characterized by reacting with an aniline derivative represented by A method for producing a squarylium compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30586187A JP2507941B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30586187A JP2507941B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01146864A true JPH01146864A (en) | 1989-06-08 |
| JP2507941B2 JP2507941B2 (en) | 1996-06-19 |
Family
ID=17950244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30586187A Expired - Fee Related JP2507941B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2507941B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275917A (en) * | 1991-07-09 | 1994-01-04 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
| US5470683A (en) * | 1993-07-28 | 1995-11-28 | Brother Kogyo Kabushiki Kaisha | Photosensitive microcapsule toner |
| US6171759B1 (en) | 1992-05-14 | 2001-01-09 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
| JP2008275726A (en) * | 2007-04-26 | 2008-11-13 | Konica Minolta Holdings Inc | Composition for optical filter, optical filter, front filter for display and squarylium compound |
-
1987
- 1987-12-04 JP JP30586187A patent/JP2507941B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275917A (en) * | 1991-07-09 | 1994-01-04 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
| US6171759B1 (en) | 1992-05-14 | 2001-01-09 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
| US5470683A (en) * | 1993-07-28 | 1995-11-28 | Brother Kogyo Kabushiki Kaisha | Photosensitive microcapsule toner |
| JP2008275726A (en) * | 2007-04-26 | 2008-11-13 | Konica Minolta Holdings Inc | Composition for optical filter, optical filter, front filter for display and squarylium compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2507941B2 (en) | 1996-06-19 |
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