JPH01146851A - Novel squarylium compound and production thereof - Google Patents
Novel squarylium compound and production thereofInfo
- Publication number
- JPH01146851A JPH01146851A JP62305863A JP30586387A JPH01146851A JP H01146851 A JPH01146851 A JP H01146851A JP 62305863 A JP62305863 A JP 62305863A JP 30586387 A JP30586387 A JP 30586387A JP H01146851 A JPH01146851 A JP H01146851A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- represented
- derivative
- mathematical
- chemical
- 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 25
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000126 substance Substances 0.000 claims abstract description 17
- 150000001448 anilines Chemical class 0.000 claims abstract description 7
- MHGIJXSAUHOIDU-UHFFFAOYSA-N n-[3-(dimethylamino)phenyl]acetamide Chemical compound CN(C)C1=CC=CC(NC(C)=O)=C1 MHGIJXSAUHOIDU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- KGPQKNJSZNXOPV-UHFFFAOYSA-N moniliformin Chemical class OC1=CC(=O)C1=O KGPQKNJSZNXOPV-UHFFFAOYSA-N 0.000 claims description 10
- DNJNUCYAVRRVMW-UHFFFAOYSA-N 3-chlorocyclobut-3-ene-1,2-dione Chemical class ClC1=CC(=O)C1=O DNJNUCYAVRRVMW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- RGBVWCQARBEPPW-UHFFFAOYSA-N cyclobut-3-ene-1,2-dione Chemical class O=C1C=CC1=O RGBVWCQARBEPPW-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000002904 solvent Substances 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
- 229910015900 BF3 Inorganic materials 0.000 abstract description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 chloroform Chemical compound 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 108091008695 photoreceptors Proteins 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 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
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VABNKPWLESVOJG-UHFFFAOYSA-N ethylboron Chemical compound [B]CC VABNKPWLESVOJG-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 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
- 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
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-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
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- UFHHEWUNBJORRL-UHFFFAOYSA-J tetrachlorobismuth Chemical compound Cl[Bi](Cl)(Cl)Cl UFHHEWUNBJORRL-UHFFFAOYSA-J 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Optical Record Carriers And Manufacture Thereof (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。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８０−１４２９４６号公
報、同６０−１４２９４７号公報、同６１−１０５４０
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, pyrylium, etc. are known, and in recent years, certain squarylium compounds have shown excellent photoconductive properties and It has been reported that it can be used as a photographic light-sensitive material (for example, JP-A-60-136542, JP-A No. 80-142946, JP-A No. 60-142947, JP-A No. 61-10540).
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、下記す
（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。Means for Solving the Problems The novel squarylium compound of the present invention is as shown below (wherein, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group). ,
It is manufactured as follows.
第１の方法は、下記構造式（ｎ）
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、Ｘは前記と同じ意味を表わす〉で示されるアニ
リン誘導体とを反応させて、下記一般式（１ｖ）
（式中、Ｘ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合成し、次いでこのクロ
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）
（式中、Ｘは前記と同じ意味を表わす）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、更に、この
ヒロドキシシクロプテンジオン誘導体を下記構造式（Ｖ
ｌ）
ｌ
で示される３−アセチルアミノ−Ｎ、Ｎ−ジメチルアニ
リンと反応させることよりなる。The first method is 3,4-dichloro-3-cyclobutene-1, represented by the following structural formula (n).
2-dione and an aniline derivative represented by the following general formula (III) (wherein, X represents the same meaning as above) are reacted to form the following general formula (1v) (wherein, A chlorocyclobutenedione derivative represented by the formula (representing the same meaning) is synthesized, and then this chlorocyclobutenedione derivative is hydrolyzed to obtain the following general formula (V) (wherein, X represents the same meaning as above). The hydroxycyclobutenedione derivative shown is synthesized, and further, this hydroxycyclobutenedione derivative is represented by the following structural formula (V
l) It consists of reacting with 3-acetylamino-N,N-dimethylaniline represented by l.
又、第２の方法は、上記構造式（ｎ）で示される３、４
−ジクロロ−３−シクロブテン−１，２−ジオンと、上
記構造式（Ｖｌ）で示される３−アセチルアミノ−Ｎ、
Ｎ−ジメチルアニリンとを反応させて、下記構造式（■
）
にｌ
で示されるクロロシクロブテンジオン誘導体を合成し、
次いでこの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（■）
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、更に、このヒロドキシシクロプテンジオン誘導体を
上記一般式（ＩＩＩ）で示されるアニリン誘導体と反応
させることよりなる。In addition, the second method uses 3, 4 represented by the above structural formula (n).
-dichloro-3-cyclobutene-1,2-dione and 3-acetylamino-N represented by the above structural formula (Vl),
By reacting with N-dimethylaniline, the following structural formula (■
) to synthesize a chlorocyclobutenedione derivative represented by l,
Next, this chlorocyclobutenedione derivative is hydrolyzed to synthesize a hydroxycyclobutenedione derivative represented by the following structural formula (■), and further, this hydroxycyclobutenedione derivative is synthesized by the above general formula (III). It consists of reacting with an aniline derivative represented by
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−ジオンを第１の方法においては一般式（ＩＩ）で
示されるアニリン誘導体と反応させ、又第２の方法にお
いては３−アセチルアミノ−Ｎ。That is, first, 3,4-dichloro-3-cyclobutene-1
, 2-dione in the first method with an aniline derivative of general formula (II) and in the second method with 3-acetylamino-N.
Ｎ−ジメチルアニリンと反応させるが、一般式（ＩＩ）
で示されるアニリン誘導体としては、Ｎ。Although reacted with N-dimethylaniline, general formula (II)
As the aniline derivative represented by 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。N-dimethylaniline, 3-methyl-N,N-dimethylaniline, 3-fluoro-N,N-dimethylaniline and 3-hydroxy N,N-dimethylaniline are used.
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
の通常のフリーゾルタラフッ反応溶媒に溶解し、所望な
らば触媒、例えば三フフ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（Ｉ［＞又は
（Ｉ［Ｉ）、塩化チタン（ＩＶ）、塩化錫（ＩＶ）、塩
化ビスマス（ＩＶ）、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 can be carried out by dissolving them in a suitable solvent such as methylene chloride, carbon tetrachloride, halogenated hydrocarbons such as chloroform, common free-sol fluorine reaction solvents such as nitrobenzene, ethyl ether, acetonitrile, etc. Catalysts such as boron trifluoride ethyl ether complex, aluminum chloride, antimony chloride, iron chloride (I[> or (I[I), titanium(IV) chloride, tin(IV) chloride, bismuth(IV) chloride, chloride This can be carried out by stirring at 0 to 40°C in the presence of zinc (■), 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、第１の方法においては３−アセチ
ルアミノ−Ｎ、Ｎ−ジメチルアニリンと反応させ、又第
２の方法に於いては、一般式（ＩＩ）で示されるアニリ
ン誘導体と反応させるが、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。Subsequently, the hydroxycyclobutenedione derivative obtained by hydrolysis is reacted with 3-acetylamino-N,N-dimethylaniline in the first method, and with the general formula ( The reaction is carried out using a suitable solvent such as an aliphatic alcohol having 4 to 8 carbon atoms such as n-butyl alcohol, n-heptyl alcohol, or the like. This can be carried out by heating in a mixed solvent of and an aromatic hydrocarbon such as benzene or 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
１５．１ｇ（、０，１モル）、Ｎ、Ｎ−ジメチルアニ
リン ８０ｄ （、０，５モル）及び三フッ化硼素エチ
ルエーテル錯体１３ｄ（０，１モル）を塩化メチレン
８０ｍに溶解し、室温で５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１９．０ｇ（収率８１％）を得た。Example 1 3.4-dichloro-3-cyclobutene-1,2-dione 15.1 g (0.1 mol), N,N-dimethylaniline 80d (0.5 mol) and ethyl boron trifluoride Ether complex 13d (0.1 mol) in methylene chloride
80ml and stirred at room temperature for 5 hours to carry out the reaction. After the reaction was completed, the reaction mixture was washed with dilute hydrochloric acid and then with water, and separated and purified using column chromatography to obtain 19.0 g (yield: 81%) of a chlorocyclobutenedione compound represented by the following structural formula.
Ｉ
得られたクロロシクロブテンジオン化合物１９．０ｇ（
０，８モル）に酢１７５ｄ及び水２５ｄを加え、１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１７．２９ （収率９８％）を得た。I 19.0 g of the obtained chlorocyclobutenedione compound (
0.8 mol) was added with 175 d of vinegar and 25 d of water, heated under reflux for 1 hour, allowed to cool, and filtered out the precipitate.
A hydroxycyclobutenedione compound 17.29 (yield 98%) represented by the following structural formula was obtained.
得られたヒドロキシシクロブテンジオン化合物１．００
ｇ（４，６０ミリモル）と３−アセチルアミノ−Ｎ、Ｎ
−ジメチルアニリン １．６４ｇ（９，２０ミリモル）
をブタノール１００ａｆ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１．６０ｇ（収率９２％）を得た。Obtained hydroxycyclobutenedione compound 1.00
g (4,60 mmol) and 3-acetylamino-N,N
-dimethylaniline 1.64 g (9.20 mmol)
After heating and stirring in butanol 100af for 5 hours, the precipitated crystals were filtered off and washed with methanol and diethyl ether to obtain 1.60 g (yield: 92%) of a squarylium compound represented by the following structural formula.
融点 ｍ、 ｌ）、 ＝２６６℃（分解）。Melting point m, l), = 266°C (decomposed).
す
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
ＣＩ２） ：６４Ｂ止であった。又、元素分析値は、Ｃ
２２Ｈ２３Ｎ３ 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): It stopped at 64B. In addition, the elemental analysis value is C
22H23N3 o3 was as follows.
計算値（％） 実測値（％）
Ｃ７０，０１Ｂ９．８９
Ｈ６，１４６，１３
Ｎ １１．１３ １１．１０実施例２
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 ４．５２９（２５，
４ミリモル）を塩化メチレン ２０ｍに溶解し、室温で
２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、前記構造式（■）で示
されるクロロシクロブテンジオン化合物２．１６１ （
収率５８％）を得た。Calculated value (%) Actual value (%) C70,01B9.89 H6,146,13 N 11.13 11.10 Example 2 3.4-dichloro-3-cyclobutene-1,2-dione 1.93 g (12 , 8 mmol) and 3-acetylamino-N,N-dimethylaniline 4.529 (25,
4 mmol) was dissolved in 20 m of methylene chloride and stirred at room temperature for 2 hours to carry out a reaction. After completion of 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 compound 2.161 (
A yield of 58% was obtained.
（融点：２１８℃（分解））
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１０ｒｎｌ及び水１ｄ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、前記構造式（■）で示されるヒドロキシシク
ロブテンジオン化合物０．８６ｇ（収率９２％）を得た
。（融点：２８０℃（分解））
得られたヒドロキシシクロブテンジオン化合物０．５５
ｇ（２，０ミリモル）と３−ヒドロキシ−Ｎ。(Melting point: 218°C (decomposition)) 1.00 g of the obtained chlorocyclobutenedione compound (
3.42 mmol) was added with 10 rnl of acetic acid and 1 d of water, heated under reflux for 10 minutes, allowed to cool, and the deposited precipitate was filtered to obtain a hydroxycyclobutenedione compound represented by the above structural formula (■). .86 g (yield 92%) was obtained. (Melting point: 280°C (decomposition)) Obtained hydroxycyclobutenedione compound 0.55
g (2,0 mmol) and 3-hydroxy-N.
Ｎ−ジメチルアニリン ０．３０ｇ（２，２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
０．７５９ （収率９５％）を得た。融点 ｍ、 ｐ、
＝３０３℃（分解）。N-dimethylaniline 0.30g (2.2 mmol)
After heating and stirring in butanol 2 (7) for 5 hours, the precipitated crystals were filtered and washed with methanol and diethyl ether to obtain squarylium compound 0.759 (yield 95%) represented by the following structural formula. Melting point m, p,
=303°C (decomposition).
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 （ＣＨ
２Ｃｌ ２ ） ： ６５３ｎｍであった。又、元素
分析値は、Ｃ２２Ｈ２３Ｎ２ ｏ４として、次の通りで
あった。The infrared absorption spectrum of this compound is as shown in Figure 2, and the ultraviolet absorption spectrum ((maximum) is UV (CH
2Cl 2 ): 653 nm. In addition, the elemental analysis value of C22H23N2 o4 was as follows.
計算値（％） 実測値（％）
ＣＢ７．１６ ６７．１４
１−１ ５．８９ ５．９２
Ｎ １０．６８ １０．７３実施例３及び４
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誘導体
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 (%) CB7.16 67.14 1-1 5.89 5.92 N 10.68 10.73 Examples 3 and 4 Raw material corresponding to the target compound was selected, and the Example Hydroxycyclobutenedione derivatives were 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、電荷亜発生層
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 sub-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、第２図は実施例２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, and FIG. 2 is an infrared absorption spectrum diagram of the squarylium compound in Example 2.
Claims (1)
基を表わす） で示されるスクアリリウム化合物 〈２〉下記構造式（II） ▲数式、化学式、表等があります▼（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） ▲数式、化学式、表等があります▼（III） （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を反応させて、下記一般式
（IV） ▲数式、化学式、表等があります▼（IV） （式中、Ｘ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、下記一般式（Ｖ） ▲数式、化学式、表等があります▼（Ｖ） （式中、Ｘは前記と同じ意味を表わす） 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構造
式（VI） ▲数式、化学式、表等があります▼（VI） で示される３−アセチルアミノ−Ｎ、Ｎ−ジメチルアニ
リン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。 〈３〉下記構造式（II） ▲数式、化学式、表等があります▼（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（VI）▲数式、化学式、表等
があります▼（VI） で示される３−アセチルアミノーＮ、Ｎ−ジメチルアニ
リンとを反応させて、下記構造式（VII）▲数式、化学
式、表等があります▼（VII） 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（VIII） ▲数式、化学式、表等があります▼（VIII） 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（III） ▲数式、化学式、表等があります▼（III） （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。[Claims] <1> Represented by the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom, or a hydroxyl group) Squarylium compound <2> 3,4-dichloro-3-cyclobutene-1, shown by the following structural formula (II) ▲Mathematical formula, chemical formula, table, etc.▼(II)
2-dione and the aniline derivative represented by the following general formula (III) ▲Mathematical formula, chemical formula, table, etc.▼(III) (wherein, X represents a hydrogen atom, methyl group, fluorine atom, or hydroxyl group) By reacting, synthesize a chlorocyclobutenedione derivative represented by the following general formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼(IV) (wherein, X represents the same meaning as above),
Next, the chlorocyclobutenedione derivative is hydrolyzed to obtain a hydrode represented by the following general formula (V) ▲ Numerical formula, chemical formula, table, etc. ▼ (V) (wherein, X represents the same meaning as above) A hydroxycyclobutenedione derivative was synthesized, and the hydroxycyclobutenedione derivative was converted into 3-acetylamino-N,N-dimethyl represented by the following structural formula (VI). 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), which is characterized by reacting with aniline. <3> 3,4-dichloro-3-cyclobutene-1, shown by the following structural formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II)
The following structural formula (VII) is obtained by reacting 2-dione with 3-acetylamino-N,N-dimethylaniline represented by the following structural formula (VI) ▲ Numerical formula, chemical formula, table, etc. ▼ (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) Synthesize the chlorocyclobutenedione derivative shown by
Next, the chlorocyclobutenedione derivative is hydrolyzed to synthesize a hydroxycyclobutenedione derivative represented by the following structural formula (VIII) ▲Mathematical formula, chemical formula, table, etc.▼(VIII) A cyclobutenedione derivative is reacted with an aniline derivative represented by the following general formula (III) ▲Mathematical formula, chemical formula, table, etc.▼(III) (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 |
|---|---|---|---|
| JP62305863A JP2522334B2 (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 |
|---|---|---|---|
| JP62305863A JP2522334B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01146851A true JPH01146851A (en) | 1989-06-08 |
| JP2522334B2 JP2522334B2 (en) | 1996-08-07 |
Family
ID=17950266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62305863A Expired - Fee Related JP2522334B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2522334B2 (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 |
| JP2015171790A (en) * | 2014-03-12 | 2015-10-01 | 富士フイルム株式会社 | Thermosensitive color developing composition and infrared-sensitive color developing composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60169453A (en) * | 1984-02-13 | 1985-09-02 | Mitsubishi Chem Ind Ltd | 2,4-bis(2'-monosubstituted amino-4'-disubstituted aminophenyl)cyclobutenediylium-1,3-diolate |
| JPS62138459A (en) * | 1985-12-11 | 1987-06-22 | Mitsubishi Chem Ind Ltd | Squarylium compound and optical recording material containing said compound |
-
1987
- 1987-12-04 JP JP62305863A patent/JP2522334B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60169453A (en) * | 1984-02-13 | 1985-09-02 | Mitsubishi Chem Ind Ltd | 2,4-bis(2'-monosubstituted amino-4'-disubstituted aminophenyl)cyclobutenediylium-1,3-diolate |
| JPS62138459A (en) * | 1985-12-11 | 1987-06-22 | Mitsubishi Chem Ind Ltd | Squarylium compound and optical recording material containing said compound |
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 |
| JP2015171790A (en) * | 2014-03-12 | 2015-10-01 | 富士フイルム株式会社 | Thermosensitive color developing composition and infrared-sensitive color developing composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2522334B2 (en) | 1996-08-07 |
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