JPH01146847A - Novel squarylium compound and production thereof - Google Patents
Novel squarylium compound and production thereofInfo
- Publication number
- JPH01146847A JPH01146847A JP62305862A JP30586287A JPH01146847A JP H01146847 A JPH01146847 A JP H01146847A JP 62305862 A JP62305862 A JP 62305862A JP 30586287 A JP30586287 A JP 30586287A JP H01146847 A JPH01146847 A JP H01146847A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- expressed
- derivative
- squarylium compound
- mathematical
- 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 23
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000126 substance Substances 0.000 claims abstract description 8
- DNJNUCYAVRRVMW-UHFFFAOYSA-N 3-chlorocyclobut-3-ene-1,2-dione Chemical class ClC1=CC(=O)C1=O DNJNUCYAVRRVMW-UHFFFAOYSA-N 0.000 claims description 8
- KGPQKNJSZNXOPV-UHFFFAOYSA-N moniliformin Chemical class OC1=CC(=O)C1=O KGPQKNJSZNXOPV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- RGBVWCQARBEPPW-UHFFFAOYSA-N cyclobut-3-ene-1,2-dione Chemical class O=C1C=CC1=O RGBVWCQARBEPPW-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 4
- 150000001448 anilines Chemical class 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 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
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- LSFWPIDPPNCVHV-UHFFFAOYSA-N 3,5-difluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC(F)=CC(F)=C1 LSFWPIDPPNCVHV-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 108091008695 photoreceptors Proteins 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 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
- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035945 sensitivity Effects 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
- MOYHVSKDHLMMPS-UHFFFAOYSA-N 3-methoxy-n,n-dimethylaniline Chemical compound COC1=CC=CC(N(C)C)=C1 MOYHVSKDHLMMPS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001914 filtration 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
- 239000012046 mixed solvent 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
- -1 nitrobempine Chemical compound 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
- 239000002244 precipitate Substances 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 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
- 238000005406 washing Methods 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
- G03G5/0609—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)
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。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.
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６０−１４２９４
６号公報、同６０−１４２９４７号公報、同６１−１０
５４０号公報、同６２−４５０号公報等参照）。As organic photoconductive materials, bisazo pigments, trisazo pigments, phthalocyanine pigments, cyanines, pyrylium, 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-60-136542, JP-A-60-14294).
Publication No. 6, Publication No. 60-142947, Publication No. 61-10
(See Publication No. 540, 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, 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 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、下記一般式（
Ｉ＞で示される。Means for Solving the Problems The novel squarylium compound of the present invention has the following general formula (
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（■）
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（１ｖ）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, 3,4-dichloro-3-cyclobutene-1, represented by the following structural formula (■),
2-dione and 3,5 represented by the following structural formula (III)
-difluoro-N,N-dimethylaniline to synthesize a chlorocyclobutenedione derivative represented by the following structural formula (1v), and then hydrolyze the chlorocyclobutenedione derivative to synthesize a chlorocyclobutenedione derivative represented by the following structural formula (1v). V) Synthesize a hydroxycyclobutenedione derivative represented by the following general formula (VI) (where X represents a hydrogen atom, a methyl group, a fluorine atom, or a hydroxyl group) ) It can be produced by reacting with the aniline derivative shown below.
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−ジオンを前記構造式（Ｉ［ｌ）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、ニトロベンピン、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（ｎ）又
は（■）、塩化チタン（ＩＶ＞、塩化錫（ＩＶＹ、塩化
ビスマス（ＩＶ＞、塩化亜鉛（ｎ）、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。That is, first, 3,4-dichloro-3-cyclobutene-1
,2-dione represented by the above structural formula (I[l)
-difluoro-N,N-dimethylaniline, which is carried out in a suitable solvent such as a halogenated hydrocarbon such as methylene chloride, carbon tetrachloride, chloroform, nitrobempine, ethyl ether, acetonitrile, etc. Catalysts, such as boron trifluoride ethyl ether complex, aluminum chloride, antimony chloride, iron chloride (n) or (■), titanium chloride (IV>), tin chloride, are dissolved in the usual Friedel-Craf reaction solvents, if desired. (IVY, bismuth chloride (IV>), zinc chloride (n), mercury chloride, etc.) by 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、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, which is carried out by heating in water containing a suitable acid, 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一般式（Ｖｌ）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 (Vl), but as the aniline derivative,
N,N-dimethylaniline, 3-methyl-N,N-dimethylaniline, 3-fluoro-N,N-dimethylaniline and 3-hydroxy-N,N-dimethylaniline are 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 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
３．６４９ （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
．２ｑ （４８，０ミリモル）を塩化メチレン１５ｍ１
に溶解し、室温で２４時間攪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２．３１９ （収率３５％）を得た。（融点＝１
８９〜１９０℃）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１０ｍ及び水
５ｄ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１．６１ｙ （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゜５０
ｇ（５，９２ミリモル）と３−ヒドロキシ−Ｎ。Example 1 3.4-dichloro-3-cyclobutene-1,2-dione 3.649 (24.1 mmol), 3.5-difluoro-N,N-dimethylaniline 7.54 g (,48
,0 mmol) and boron trifluoride ethyl ether complex 7
．． 2q (48.0 mmol) in 15 ml of methylene chloride
The reaction mixture was stirred at room temperature for 24 hours to carry out the reaction. After the reaction, the reaction mixture was washed with dilute hydrochloric acid and then with water, and separated and purified using column chromatography to obtain the chlorocyclobutenedione derivative 2.319 (yield: 35%) represented by the structural formula (IV). Obtained. (Melting point = 1
89-190°C) 10 m of acetic acid and 5 d of water were added to 2.01 g (7.4 mmol) of the obtained chlorocyclobutenedione derivative, heated under reflux for 2 hours, allowed to cool, and separated by filtration. The hydroxycyclobutenedione derivative represented by the structural formula (V) 1.61y (yield: 85
%) was obtained. (Melting point: 223°C (decomposition)) Obtained hydroxycyclobutenedione derivative 1°50
g (5,92 mmol) and 3-hydroxy-N.
Ｎ−ジメチルアニリン ０，８２ｉ１１ ｇ（６，１ミ
リモル）をブタノール ６（７中で５時間加熱攪拌した
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）。After heating and stirring 0.82i11 g (6.1 mmol) of N-dimethylaniline in butanol 6 (7) for 5 hours, the precipitate was filtered to obtain blue-green crystals. After washing this with methanol and diethyl ether, After drying, 1.98 g (yield 90%) of a squarylium compound represented by the following structural formula was obtained. Melting point: m, p, = 302°C (decomposed).
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 ＞ ： ６１４ｎｍであった。又、元素分
析値は、Ｃ２０Ｈ１８Ｆ２ Ｎ２ 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>: 614 nm. Further, the elemental analysis value of C20H18F2 N2 o3 was as follows.
計算値（％） 実測値（％）
ＣＢ４，５１ ６４．５４
Ｈ４，８７４，９７
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 (%) Actual value (%) CB4,51 64.54 H4,874,97 N 7.52 7.50 Examples 2 to 4 Shown by the above structural formula (V) in the same manner as in Example 1 Hydroxycyclobutenedione derivatives are prepared and converted into N,N-dimethylaniline, 3-methoxy-N,N
-dimethylaniline or 3-fluoro-N,N-dimethylaniline were reacted in the same manner to produce the squarylium compounds shown in Table 1. Their ultraviolet absorption spectra (maximum) are also shown in Table 1.
第１表
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。Table 1 Effects of the Invention The squarylium compound of the present invention is a novel compound, 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. An electrophotographic photoreceptor can be obtained. 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)
基を表わす） で示されるスクアリリウム化合物。(1) A squarylium compound represented by the following general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, X represents a hydrogen atom, methyl group, fluorine atom, or hydroxyl group).
２−ジオンと、下記構造式（III） ▲数式、化学式、表等があります▼（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）▲数式、化学式
、表等があります▼（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） ▲数式、化学式、表等があります▼（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） ▲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)
The following structural formula (IV )▲Mathematical formulas, chemical formulas, tables, etc.▼(IV) Synthesize the chlorocyclobutenedione derivative shown by
Next, the chlorocyclobutenedione derivative is hydrolyzed to synthesize a hydroxycyclobutenedione derivative represented by the following structural formula (V) ▲Mathematical formula, chemical formula, table, etc.▼(V) A cyclobutenedione derivative is reacted with an aniline derivative represented by the following general formula (VI) ▲Mathematical formula, chemical formula, table, etc.▼(VI) (wherein, X represents a hydrogen atom, methyl group, fluorine atom, or hydroxyl group) A method for producing a squarylium compound represented by the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (wherein, X represents the same meaning as above).
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 true JPH01146847A (en) | 1989-06-08 |
| JPH07107031B2 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) |
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 |
| US5488601A (en) * | 1992-10-26 | 1996-01-30 | Dai Nippon Printing Co., Ltd. | Photoelectric sensor, information recording system, and information recording method |
| US6171759B1 (en) | 1992-05-14 | 2001-01-09 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
-
1987
- 1987-12-04 JP JP62305862A patent/JPH07107031B2/en not_active Expired - Fee Related
Cited By (5)
| 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 |
| US5488601A (en) * | 1992-10-26 | 1996-01-30 | Dai Nippon Printing Co., Ltd. | Photoelectric sensor, information recording system, and information recording method |
| US5629920A (en) * | 1992-10-26 | 1997-05-13 | Dai Nippon Printing Co., Ltd. | Photoelectric sensor, information recording system, and information recording method |
| US5470683A (en) * | 1993-07-28 | 1995-11-28 | Brother Kogyo Kabushiki Kaisha | Photosensitive microcapsule toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07107031B2 (en) | 1995-11-15 |
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