JPS62249952A - Production of hydroxycyclobutenedione derivative - Google Patents
Production of hydroxycyclobutenedione derivativeInfo
- Publication number
- JPS62249952A JPS62249952A JP61091259A JP9125986A JPS62249952A JP S62249952 A JPS62249952 A JP S62249952A JP 61091259 A JP61091259 A JP 61091259A JP 9125986 A JP9125986 A JP 9125986A JP S62249952 A JPS62249952 A JP S62249952A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- reaction
- compound
- derivative
- chloride
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- KGPQKNJSZNXOPV-UHFFFAOYSA-N moniliformin Chemical class OC1=CC(=O)C1=O KGPQKNJSZNXOPV-UHFFFAOYSA-N 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000000565 sulfonamide group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- DNJNUCYAVRRVMW-UHFFFAOYSA-N 3-chlorocyclobut-3-ene-1,2-dione Chemical class ClC1=CC(=O)C1=O DNJNUCYAVRRVMW-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000005521 carbonamide group Chemical group 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 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 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 229940124530 sulfonamide Drugs 0.000 abstract 1
- 150000003456 sulfonamides Chemical class 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- 150000001448 anilines Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CWOMTHDOJCARBY-UHFFFAOYSA-N n,n,3-trimethylaniline Chemical compound CN(C)C1=CC=CC(C)=C1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-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
- 229940126657 Compound 17 Drugs 0.000 description 1
- 102100025027 E3 ubiquitin-protein ligase TRIM69 Human genes 0.000 description 1
- 101000830203 Homo sapiens E3 ubiquitin-protein ligase TRIM69 Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 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
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical group NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
-
- 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
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Photoreceptors In Electrophotography (AREA)
- Thermal Transfer Or Thermal Recording In General (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、電子写真用感光材料、光デイスク用記録材料
、太陽電池、赤外線カットフィルターの〔従来の技術〕
従来、下記反応式（１）および（ｉｆ）に示すように４
４−ジクロロ−３−シクロブテン−Ｒ２−ジオン（スク
エアリンク酸塩化物）はルイス酸触媒の存在下で芳香族
化合物と反応して、対応する
３−アリール−４−クロロ−３−シクロブテン−Ｌ２−
ジオント生成することが知られている。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to electrophotographic photosensitive materials, recording materials for optical disks, solar cells, and infrared cut filters [Prior Art] Conventionally, the following reaction formula (1) and 4 as shown in (if)
4-dichloro-3-cyclobutene-R2-dione (square link acid chloride) reacts with aromatic compounds in the presence of a Lewis acid catalyst to form the corresponding 3-aryl-4-chloro-3-cyclobutene-L2-
It is known to generate geonts.
〔Ｂ＋Ｒ，Ｇｒｅｅｎ ら、 ５ｙｎｔｈｅｓｉｓ
、 １９７４．４６ ）（Ｌ、Ａ−Ｗｅｎｄ’ｌｉｎｇ
ら、Ｊ、Ｏｒｇ、 Ｃｈｅｍ 、 、 ４２ （７）
、１１２６ （１９７７））これらの反応では、選択性
に問題があシ、特に（ｉｌｌの反応では目的化合物（収
率３４チ）のほかに次式
で示されるＲ２−付加体（収率３％）力＼゛生成る。[B+R, Green et al., 5ynthesis
, 1974.46) (L, A-Wend'ling
et al., J.Org.Chem., 42 (7)
, 1126 (1977)) These reactions have problems with selectivity, especially in the reaction (ill), in addition to the target compound (yield 34%), the R2-adduct represented by the following formula (yield 3%) ) to generate force.
スクエアリック酸塩化物とＮ、Ｎ−ジメチルアニリンな
どの第三級芳香族アミンとのフリーデルクラフッ反応に
ついては報告例がない。なお、一般のフリーデルクラフ
ッ反応において第三級芳香族アミンを用いた例として下
記反応式（ｌｌｉ）で示されるものがあるが、収率は３
８〜４２％と低い。There are no reports on the Friedel-Crauff reaction between square acid chlorides and tertiary aromatic amines such as N,N-dimethylaniline. In addition, as an example of using a tertiary aromatic amine in a general Friedel-Crauch reaction, there is one shown by the following reaction formula (lli), but the yield is 3
It is low at 8-42%.
ｅ
（Ｏｒｇ−８７ｎ−＋ ４１ ＋ １ ）また触媒を使
用しないフリーデルクラフッ反応の例としては、アニソ
ール等の芳香族化合物とベンゾイルクロライド等の反応
が知られているが（反応式（１ｖ）参照）、比較的高い
温度が必要であ）、収率も低い。e (Org-87n-+ 41 + 1) Furthermore, as an example of the Friedel-Crach reaction that does not use a catalyst, the reaction between an aromatic compound such as anisole and benzoyl chloride is known (reaction formula (1v) (see ), relatively high temperatures are required) and yields are low.
（Ｄ、Ｅ、Ｐｅａｒｓｏｎら、 ５ｙｎｔｈｅｓｉｓ、
１９７２．５３３ ）〔発明が解決しようとする問題
点〕
本発明の目的は電子写真感光体等の光導電材料として有
用なスクェアリリウム化合物の中間体であるヒドロキシ
シクロブテンジオン誘導体を選択性よく、高純度で容易
に製造できる方法を提供することにある。(D.E. Pearson et al. 5ynthesis,
1972.533) [Problems to be Solved by the Invention] The object of the present invention is to develop hydroxycyclobutenedione derivatives with good selectivity and high The objective is to provide a method that allows easy production with high purity.
本発明は代印
ｌ
で示されるａ４−ジクロロ−３−シクロブテン−Ｒ２−
ジオンと一般式（ＩＩ）
〔式中、Ｘは水素原子、置換されていてもよいアルキル
基、ハロゲン原子、水酸基、置換されていてもよいフェ
ニル基、またはアルキル基が結合したカルボンアミド基
もしくはスルホンアミド基を表わし、Ｒ１およびＲ２は
互に独立したものであって、各々置換されていてもよい
アルキル基、置換されていてもよいフェニル基または置
換されていてもよいベンジル基を表わす。〕
で示されるアニリン誘導体とを反応させ、一般式リ
〔式中、すべての記号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、この誘
導体を加水分解することを特徴とする一般式（Ｉ）
〔式中、すべての記号は前記と同じ意味を表わす。〕で
示されるヒト９０キシシクロブテンジオン誘導体の製造
方法を提供したものである。The present invention is characterized by a4-dichloro-3-cyclobutene-R2-
Dione and general formula (II) [wherein, It represents an amide group, and R1 and R2 are each independently an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group. [In the formula, all symbols represent the same meanings as above. A chlorocyclobutenedione derivative represented by formula (I) is obtained, and this derivative is hydrolyzed. The present invention provides a method for producing a human 90-xycyclobutenedione derivative represented by the following.
本発明の方法では、まず式（損のスクエアリック酸塩化
物と代価のアニリン誘導体との反応によって式（ＩＶ）
のクロロシクロブテンジオン誘導体を合成する。In the method of the present invention, the formula (IV) is first obtained by reacting a squaric acid chloride of the formula (IV) with a substitute aniline derivative.
Synthesize a chlorocyclobutenedione derivative of
この合成反応においては、原料の式（２）で示されるア
ニリン誘導体は式（ＩＩ）のスクエアリック酸塩化物に
対して１轟音以上、好ましくは２〜５自量使用する。In this synthesis reaction, the aniline derivative represented by the formula (2) as a raw material is used in an amount of 1 or more, preferably 2 to 5 moles, based on the squaric acid chloride of the formula (II).
原料のアニリン誘導体が液体の場合には溶媒を兼ねるの
で必ずしも溶媒を用いなくてもよいが、塩化メチレン、
四塩化炭素、クロロホルムなどの八Ｅｌ ）ｙ’ン化炭
化水素、ニトロベンゼン、エチルエーテル、二硫化炭素
、アセトニトリルなど、好ましくは塩化メチレンを溶媒
として使用するのがよい。When the raw material aniline derivative is liquid, it also serves as a solvent, so it is not necessary to use a solvent, but methylene chloride,
Hydrocarbons such as carbon tetrachloride and chloroform, nitrobenzene, ethyl ether, carbon disulfide, acetonitrile, and preferably methylene chloride are preferably used as solvents.
意外なことではあるが、触媒は使用しなくても反応は充
分に進行し、かえって触媒を用いる場合よシも高純度の
目的物を得ることができるので好ましい。しかし反応性
の低いアニリン誘導体（Ｘがハロゲン原子、アルキル基
が結合したカルボンアミド基およびスルホンアミＰ基を
表わす化合物）については通常のフリーデルクラフッ反
応触媒、例えば塩化アルミニウム、塩化アンチモン、塩
化鉄、塩化チタン、塩化スズ、塩化ビスマス、塩化亜鉛
、塩化水銀、三フッ化ホウ素などのルイス酸、好ましく
は三フッ化ホウ素を、スクエアリンク酸塩化物に対して
０．０１当量以上、好ましくは０．１〜１当量使用する
。Although it is surprising, the reaction proceeds satisfactorily even without the use of a catalyst, and on the contrary, it is preferable because the desired product can be obtained with higher purity than when a catalyst is used. However, for aniline derivatives with low reactivity (compounds in which X represents a halogen atom, a carbonamide group to which an alkyl group is bonded, and a sulfonamide P group), conventional Friedel-Craf reaction catalysts such as aluminum chloride, antimony chloride, iron chloride, A Lewis acid such as titanium chloride, tin chloride, bismuth chloride, zinc chloride, mercury chloride, or boron trifluoride, preferably boron trifluoride, is added in an amount of 0.01 equivalent or more, preferably 0.01 equivalent or more, based on the square link acid chloride. Use 1 to 1 equivalent.
反応温度は０〜８０℃、好ましくは０〜４０℃であり、
反応時間は３０分〜２０時間である。The reaction temperature is 0 to 80°C, preferably 0 to 40°C,
Reaction time is 30 minutes to 20 hours.
反応終了後は、常法によシ後処理し、カラムクロマトグ
ラフィーによシ分離精製して目的物を得ることができる
。After the reaction is completed, the desired product can be obtained by post-treatment by a conventional method and separation and purification by column chromatography.
このようにして得られた一般式ＧＶ）のクロロシクロブ
テンジオン誘導体を加水分解することによって、一般式
（Ｉ）のヒドロキシクロブテンジオン誘導体を容易に得
ることができる。By hydrolyzing the chlorocyclobutenedione derivative of the general formula GV) thus obtained, the hydroxyclobutenedione derivative of the general formula (I) can be easily obtained.
この加水分解反応は、水の存在下で触媒を用いることな
く、または酸あるいは塩基触媒の存在下室温乃至還流温
度で行われる。好ましくは、水−酢酸混合溶媒中還流加
熱して行われる。反応終了後は、生成した結晶をＦ別、
洗浄して高純度の目的物をほぼ定量的に得ることができ
る。This hydrolysis reaction is carried out in the presence of water without a catalyst or in the presence of an acid or base catalyst at room temperature to reflux temperature. Preferably, the reaction is carried out by heating under reflux in a mixed solvent of water and acetic acid. After the reaction is complete, separate the generated crystals by
After washing, the target product of high purity can be obtained almost quantitatively.
本発明はヒドロキシシクロブテンジオン誘導体を選択性
よく、高純度で容易に得ることのできる製造方法を提供
したものである。The present invention provides a manufacturing method that allows hydroxycyclobutenedione derivatives to be easily obtained with good selectivity and high purity.
本発明によシ得られるヒドロキシシクロブテンジオン誘
導体は新規な化合物であシ、この化合物を各種アニリン
誘導体等と反応させて、電子写真感光体の光導電材料と
して有用な、対称型あるいは非対称型のスフリニアＩＪ
ＩＪウム化合物を合成することができる。The hydroxycyclobutenedione derivative obtained according to the present invention is a new compound. By reacting this compound with various aniline derivatives, etc., a symmetrical or asymmetrical Sufrinia IJ
IJium compounds can be synthesized.
以下、実施例を単けて本発明を説明する。 Hereinafter, the present invention will be explained by referring to Examples.
実施例 １
しｌ
スクエアリック酸塩化物１５．１９ （０，１ＮＯりお
よび三フッ化ホウ素エチルエーテル錯体１３ ｍｌ （
０，１７７ＬＯ６）を塩化メチレン６０ＷＬｌに溶解し
、Ｎ、Ｎ〜ジメチルアニリン６３ ｄ （０，５ＮＯり
と混合、室温で５時間攪拌して反応を行なった。反応終
了後、混合物を希塩酸、ついで水で洗浄し、カラムクロ
マトグラフィーを用いて分離生成を行ない、標題の化合
物ｘ９．ａｌｌ）（収率８１％）を得た。Example 1 15.19 ml of square acid chloride (0,1 NO and 13 ml of boron trifluoride ethyl ether complex)
0,177LO6) was dissolved in 60WLl of methylene chloride, mixed with N,N-dimethylaniline 63d (0,5NO), and stirred at room temperature for 5 hours to carry out the reaction. After the reaction was completed, the mixture was diluted with dilute hydrochloric acid and then water. The product was washed with water and separated using column chromatography to obtain the title compound x9.all) (yield: 81%).
ｍｐ ： １９４〜１９５℃（分解）；工Ｒ（ＫＢｒ）
： １８０２，１７７２．１７５４ｃｍ 。mp: 194-195℃ (decomposition); engineering R (KBr)
: 1802,1772.1754cm.
Ｕｖ（ＣＨ２Ｃ１２）：４０９ｒＬｒｒＬ：元素分析：
Ｃ１゜Ｈ１ｏＣＩＮＯ□として計算値（％） 実測値
（ｃＡ
Ｃ６１，１６６１，３２
Ｈ４，２８４，１７
Ｎ ５．９４ ５・８４実施例 ２
スクエアリンク酸塩化物１５．１９ （０，１ＮＯりを
塩化メチレン６０ゴに溶解し、Ｎ、Ｎ−ジメチルアニリ
ン６３ｍＪ（０，５７Ｆ１０りと混合、 室温で１０時
間攪拌し反応を行なった。反応終了後、混合物を希塩酸
、ついで水で洗浄し、カラムクロマトグラフィーを用い
て分離精製を行ない、実施例１と同じ化合物ｘｙ、７ｆ
（収率７５チ）を得た。Uv(CH2C12): 409rLrrL: Elemental analysis:
Calculated value (%) as C1゜H1oCINO□ Actual value (cA C61,1661,32 H4,284,17 N 5.94 5.84 Example 2 Square Link Acid Chloride 15.19 (0,1NO) methylene chloride After the reaction was completed, the mixture was washed with dilute hydrochloric acid and then with water, and subjected to column chromatography. The same compounds xy and 7f as in Example 1 were separated and purified using
(yield: 75 cm).
実施例 ３
スクエアリンク酸塩化物３．００ ｆ （０，０２ｍｏ
ｂ）を塩化メチレン３０−に溶かし塩化アルミニウム２
６７’ｊ （０，０２ｍｏｂ）を懸濁させ、水冷、攪拌
下Ｎ、Ｎ−ジメチルアニリン２．４３９ （０，０２ｍ
０Ｌ＞を滴下した。Example 3 Squarelink acid chloride 3.00 f (0,02 mo
Dissolve b) in 30-methylene chloride and add 2-2 aluminum chloride.
67'j (0,02mob) was suspended in N,N-dimethylaniline 2.439 (0,02m
0 L> was added dropwise.
さらに２．５時間水冷下で攪拌した後混合物を希塩酸、
ついで水で洗浄、カラムクロマトグラフィーを用いて分
離生成を行ない、実施例１と同じ化合物１．１７９（収
率２ト０を得た。 この際副生成物としてＬ２−付加体
がＣ１３９（収率２％）得られた。After further stirring for 2.5 hours under water cooling, the mixture was diluted with dilute hydrochloric acid,
Then, the compound 1.179 (yield: 2 to 0), which is the same as in Example 1, was obtained by washing with water and separating the product using column chromatography. 2%) was obtained.
実施例 ４
スクエアリック酸塩化物１５．１１１）（０，１ｍ０７
）および三フッ化ホウ素エチルエーテル錯体１３ｍＪ（
０，１ｒｒＬＯ６）を塩化メチレン６０−に溶解し、Ｎ
、Ｎ−ジメチル−ｍ−トルイジン７２ｔｔｔｌ（０，５
ｍＯりと混合、室温で１時間攪拌し反応を行ない、以下
実施例１と同様に処理して標題の化合物１６．８９（収
率６７％）を得た。Example 4 Squaric acid chloride 15.111) (0,1m07
) and boron trifluoride ethyl ether complex 13 mJ (
0,1rrLO6) was dissolved in methylene chloride 60- and N
, N-dimethyl-m-toluidine 72tttl (0,5
The reaction mixture was stirred at room temperature for 1 hour, and the reaction was carried out in the same manner as in Example 1 to obtain the title compound 16.89 (yield: 67%).
ｒｌＬＰ ： １７０．５〜１７１．５℃（分解）；Ｉ
Ｒ（ＫＢｒ） ： １７９０．１７７０ｃｍ 。rlLP: 170.5-171.5°C (decomposition); I
R (KBr): 1790.1770cm.
Ｕｖ（ＣＨ２Ｃ／２）＝４２１ｒＬｒＩＬ；４２１ｒＬ
ｒｒＬＨ１□ＣＡ’ＮＯ２として計算値（％） 実
測値（チ）
Ｃ６２，５３６２，４８
Ｈ４，８４４，７９
Ｎ ５．６１ ５．６０実施例
５
スクエアリンク酸塩化物’Ｚ５ ’ｊ Ｃ０，０５ｍｏ
ｌ）を塩化メチレン３０ｄに溶解し、Ｎ、Ｎ−ジメチル
−ｍ−トルイジン２２ｍＪ（０，１５ｍｏりと混合、室
温で５時間攪拌し反応を行ない、以下実施例１と同様に
処理し、実施例４と同じ化合物７９ｇ（収率６３チ）を
得た。Uv(CH2C/2)=421rLrIL; 421rL
Calculated value (%) as rrLH1□CA'NO2 Actual value (chi) C62,5362,48 H4,844,79 N 5.61 5.60 Example
5 Square link acid chloride 'Z5 'j C0,05mo
1) was dissolved in 30 d of methylene chloride, mixed with 22 mJ (0.15 mol) of N,N-dimethyl-m-toluidine, and stirred at room temperature for 5 hours to react. 79 g (yield: 63 g) of the same compound as 4 was obtained.
実施例 ６
スクエアリツク酸塩化物７．５ ｇ＜０．０５ｍｏＬ）
および三フッ化ホウ素エチルエーテル錯体６．５ｍ（０
，０５ｍ０りを塩化メチレン３０１に溶解し、 Ｎ、Ｎ
−ジメチル−ｍ−フルオロアニリン３５１１）（０，２
５ｒＩＬＯｔ）と混合、室温で１６時間攪拌し反応を行
ない。以下実施例１と同様に処理し、標題の化合物９．
１ｇ（収率７２チ）を得た。Example 6 Squaric acid chloride 7.5 g < 0.05 mol)
and boron trifluoride ethyl ether complex 6.5 m (0
,05m0 was dissolved in methylene chloride 301, N,N
-dimethyl-m-fluoroaniline 3511) (0,2
5rILOt) and stirred at room temperature for 16 hours to carry out the reaction. The following treatment was carried out in the same manner as in Example 1, and the title compound 9.
1 g (yield: 72 g) was obtained.
ｍｐ ： ２２４℃（分解）；
工Ｒ（Ｋ＆） ： １８１６．１７８４．１７６０ ｃ
ｍ−” ；ＵＶ （ＣＨ２Ｃ／２） ： ４０２ ｎｍ
；元素分析： Ｃ，Ｈ９Ｃ４ＰＮＯ□として計算値（
チ） 実測値部）
０ ５６．８２ ５６゜８５）Ｉ
３．５８ ３．３９Ｎ
５．５２ ５．３９実施例 ７
スクエアリック酸塩化物７５ ｆｊ （０，０５ｍ０り
を、塩化メチレン３０＋ｌに溶解し、Ｎ、Ｎ−ジメチル
−ｍ−アミノフェノ−Ｎ１３．７９ （０，１ｍ０Ｌ）
を塩化メチレン１００罰に溶解した溶液を５〜１０℃で
徐々に加え、３０分間攪拌した。反応終了後、生じた沈
澱を炉別し、カラムクロマトグラフィーを用いて分離生
成を行ない、標題の化合物ａ３９（収率５０％）を得た
。mp: 224℃ (decomposition); Engineering R (K&): 1816.1784.1760c
m-”; UV (CH2C/2): 402 nm
; Elemental analysis: Calculated value as C, H9C4PNO□ (
H) Actual measurement part) 0 56.82 56°85) I
3.58 3.39N
5.52 5.39 Example 7 Squaric acid chloride 75 fj (0.05 ml) was dissolved in 30+l of methylene chloride, N,N-dimethyl-m-aminopheno-N13.79 (0.1 ml)
A solution prepared by dissolving 100% of methylene chloride was gradually added at 5 to 10°C, and the mixture was stirred for 30 minutes. After the reaction was completed, the resulting precipitate was filtered and separated using column chromatography to obtain the title compound a39 (yield 50%).
ｍＰ＝２０７〜２０９℃（分解）；
ＩＲ（ＫＢｒ） ： １８１６．１７６６、１７３０ｍ
。mP=207-209℃ (decomposition); IR (KBr): 1816.1766, 1730m
.
ＵＮ’ （ＣＨ２Ｃ７２） ＝ ４２１ ｎｍ 、ｅ元
素分析：Ｃｌ２Ｈ１ｏＣｌＮ０３として計算値（チ）
実測値（％）
Ｃ５７，２７５７，４１
Ｈ４，００４，０６
Ｎ ５．５７ ５．３９実施例 ８
スクエアリック酸塩化物７．５９ Ｃ０，０５ｍ０す、
Ｎ−メチル−Ｎ−（Ｐ−１０ロインジル）アニリン３５
９（０，１５ｍ０りおよび三フッ化ホウ素エチルエーテ
ル錯体６．５ ｔｒｔｌ （０，０５ｍｏｌ ）を塩化
メチレン１００１に溶解し、室温で２４時間攪拌した。UN' (CH2C72) = 421 nm, e elemental analysis: Calculated value as Cl2H1oClN03 (ch)
Actual value (%) C57,2757,41 H4,004,06 N 5.57 5.39 Example 8 Square acid chloride 7.59 C0,05m0S,
N-methyl-N-(P-10 loindyl)aniline 35
9 (0.15 mol) and 6.5 trtl (0.05 mol) of boron trifluoride ethyl ether complex were dissolved in 100 ml of methylene chloride and stirred at room temperature for 24 hours.
以下実施例１と同様に処理し、標題の化合物ｘｏ、２ｇ
（収率５９チ）を得た。The following treatment was carried out in the same manner as in Example 1, and 2 g of the title compound xo was obtained.
(yield: 59 cm).
ｍｐ ： １７５〜１７６℃（分解）；ＩＲ（ＫＢｒ）
： １８００，１７５８ｃＷＬ。mp: 175-176°C (decomposition); IR (KBr)
: 1800, 1758cWL.
Ｕｖ（ＣＨ２０１２）：４０５ｒＬｎＬ；元素分析：
Ｃ，８Ｈ１３（Ｊ２Ｎｏ□として計算値（係） 実
測値価）
Ｃ６２，４５６２，６７
Ｈ３，７８３，６６
Ｎ ４．０５ ４．０２実施例
９
スクエアリック酸塩化物７．５ｇ（０，０５ｍ６りとＮ
、Ｎ−ジベンジルアニリン２７．３９ （０，１ｍＯり
を塩化メチレン５０罰に溶解し、１０時間、加熱還流し
た。Uv (CH2012): 405rLnL; Elemental analysis:
C, 8H13 (Calculated value as J2No□ (related) Actual value) C62, 4562, 67 H3, 783, 66 N 4.05 4.02 Example
9 Square acid chloride 7.5g (0.05m6ritoN
, N-dibenzylaniline (27.39 mO) was dissolved in 50 methylene chloride and heated under reflux for 10 hours.
放冷後、混合物を希塩酸、ついで水で洗浄、カラムクロ
マトグラフィーによシ分離生成を行ない、標題の化合物
１４．３ ｇ（収率７４チ）を得た。After cooling, the mixture was washed with dilute hydrochloric acid and then with water, and separated by column chromatography to obtain 14.3 g (yield: 74 g) of the title compound.
ｍｐ ： １７１〜１７３℃； 工Ｒ（ＫＢｒ） ： １７５６ｃｍ 。mp: 171-173℃; Engineering R (KBr): 1756cm.
ｕＶ（ＣＨ２０１２） ： ４０６ ｎｍ ；元素分析
： Ｃ２，Ｈ１８Ｃ７ＮＯ□として計算値（％）
実測値（如
Ｃ７４，３２７４，２１
Ｈ４，５８４，７５
Ｎ ３．６１ ３．６９実施例
１０
スクエアリック酸塩化物７．５９ （０，０５ｍＪＺ）
とトリフ ｘ ＝ ／Ｉ／アミン１４．７９ Ｃｏ、ｏ
６ｍｏｌ）を塩化メチレン５０１に溶解し、２４時間、
加熱還流した。放冷後、混合物を水で洗浄、カラムクロ
マトグラフィーによシ分離生成を行ない、標題化合物７
ｏｆ（収率３９％）を得た。uV (CH2012): 406 nm; Elemental analysis: Calculated value as C2, H18C7NO□ (%)
Actual measurement value (like C74, 3274, 21 H4, 584, 75 N 3.61 3.69 Example
10 Square acid chloride 7.59 (0.05mJZ)
and trif x = /I/amine 14.79 Co, o
6 mol) was dissolved in methylene chloride 501 and dissolved for 24 hours.
The mixture was heated to reflux. After cooling, the mixture was washed with water and separated by column chromatography to obtain the title compound 7.
of (yield 39%) was obtained.
ｍｐ ： ２１８〜２１９．５℃（分解）；ＩＲ（ＫＢ
ｒ）： １８０２．１７８２ｃｍ ｐＵＶ （ＣＨ２
ＣＧ） ” ４２３ ｒＬ−ｐ元素分析：Ｃ２□Ｈ１４
（ＪＮＯ２として計算値（矧 実測値（チ）
Ｃ７３，４４７３，４８
Ｈ３，９２３，７７
Ｎ ３．８９ ３．６９実施例
１１
スクエアリンク酸塩化物７．５ ｇ（０，０５ｍＯす、
トリフェニルアミン１４．７ ｇ（０，０６ｍｏ乙）、
および三フッ化ホウ素ニー゛チル錯体６．５罰（Ｑ、
Ｑ５ｍＯＬ）を塩化メチレン５０罰に溶解し、１５時間
加熱攪拌した。放冷後、混合物を水で洗浄、カラムクロ
マトグラフィーにより分離精製を行ない、実施例１０と
同じ化合物８．Ｆｌ（収率４７％）を得た。mp: 218-219.5℃ (decomposition); IR (KB
r): 1802.1782cm pUV (CH2
CG) ” 423 rL-p elemental analysis: C2□H14
(Calculated value as JNO2 (Actual measured value (chi) C73,4473,48 H3,923,77 N 3.89 3.69 Example
11 Square link acid chloride 7.5 g (0.05 mO,
Triphenylamine 14.7 g (0.06 mo Otsu),
and boron trifluoride nityl complex 6.5 punishment (Q,
Q5mOL) was dissolved in 50% methylene chloride, and the mixture was heated and stirred for 15 hours. After cooling, the mixture was washed with water, separated and purified by column chromatography, and the same compound 8. as in Example 10 was obtained. Fl (yield 47%) was obtained.
実施例 １２〜１４
実施例１と同様の方法により、対応する原料を用いて表
１に示す化合物を得た。各化合物の物性値等をも表１に
示す。Examples 12 to 14 In the same manner as in Example 1, the compounds shown in Table 1 were obtained using the corresponding raw materials. Table 1 also shows the physical property values of each compound.
実施例 １５
実施例１で得た化合物１９．０ｇ（０，０８ｍａＺ）に
、酢酸７５ｄおよび水２５１を加え、１時間加熱還流、
放冷後、沈澱物をＰ別、水で洗浄し、標題化合物１７．
２ｇ（収率９８ｑｂ）を得た。Example 15 To 19.0 g (0.08 maZ) of the compound obtained in Example 1, 75 d of acetic acid and 251 ml of water were added, and the mixture was heated under reflux for 1 hour.
After cooling, the precipitate was separated from P and washed with water to obtain the title compound 17.
2g (yield 98qb) was obtained.
ｍｐ ： ＞２４０℃（徐々に分解）；ＩＲ（ＫＢｒ）
： １７７２．１７５６．１７１０ｃＩｎｙＵＶ （
Ｈ２ｏ） ： ３８９ ｎ” ｓ元素分析” Ｃｌ２Ｈ
１１ＮＯ３として計算値（矧 実測値（チ）
Ｃ６６，３５６６，３４
Ｈ５，１０５，Ｏｆ
Ｎ ６．４５ ６．３５実施例 １
６〜２４
実施例１５と同様の方法によって、対応するクロロシク
ロノテンジオン誘導体を加水分解して表２に示すヒト５
０キシシクロブテンジオン誘導体を得た。物性値等の分
析結果をも表２に示す。mp: >240°C (gradual decomposition); IR (KBr)
: 1772.1756.1710cInyUV (
H2o): 389 n"s elemental analysis" Cl2H
Calculated value as 11NO3 (Actual measured value (chi) C66, 3566, 34 H5, 105, Of N 6.45 6.35 Example 1
6-24 By the same method as in Example 15, the corresponding chlorocyclonotenedione derivative was hydrolyzed to produce human 5 shown in Table 2.
A 0-oxycyclobutenedione derivative was obtained. Analysis results such as physical property values are also shown in Table 2.
Claims (1)
２−ジオンと一般式（III） 〔式中、Ｘは水素原子、置換されていてもよいアルキル
基、ハロゲン原子、水酸基、置換されていてもよいフェ
ニル基、またはアルキル基が結合したカルボンアミド基
もしくはスルホンアミド基を表わし、Ｒ＿１およびＲ＿
２は互に独立したものであって、各々置換されていても
よいアルキル基、置換されていてもよいフェニル基また
は置換されていてもよいベンジル基を表わす。〕 で示されるアニリン誘導体とを反応させ、一般式（IV） ▲数式、化学式、表等があります▼（IV） 〔式中、すべての記号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、この誘
導体を加水分解することを特徴とする一般式（ I ） ▲数式、化学式、表等があります▼（ I ） 〔式中、すべての記号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の製造方
法。 ２）式（II）と式（III）の化合物の反応にルイス酸触
媒を使用する特許請求の範囲第１項に記載の製造方法。 ３）ルイス酸触媒が三フッ化ホウ素である特許請求の範
囲第２項に記載の製造方法。 ４）溶媒を使用する特許請求の範囲第１項、第２項また
は第３項に記載の製造方法。[Claims] 1) 3,4-dichloro-3-cyclobutene-1, represented by formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II)
2-dione and general formula (III) [wherein, or represents a sulfonamide group, R_1 and R_
2 are independent of each other and each represents an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group. [In the formula, all symbols have the same meanings as above. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(I) [In the formula, all symbols are as above. expresses the same meaning as ] A method for producing a hydroxycyclobutenedione derivative. 2) The manufacturing method according to claim 1, wherein a Lewis acid catalyst is used for the reaction of the compounds of formula (II) and formula (III). 3) The manufacturing method according to claim 2, wherein the Lewis acid catalyst is boron trifluoride. 4) The manufacturing method according to claim 1, 2 or 3, which uses a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61091259A JPS62249952A (en) | 1986-04-22 | 1986-04-22 | Production of hydroxycyclobutenedione derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61091259A JPS62249952A (en) | 1986-04-22 | 1986-04-22 | Production of hydroxycyclobutenedione derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62249952A true JPS62249952A (en) | 1987-10-30 |
| JPH0557260B2 JPH0557260B2 (en) | 1993-08-23 |
Family
ID=14021420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61091259A Granted JPS62249952A (en) | 1986-04-22 | 1986-04-22 | Production of hydroxycyclobutenedione derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62249952A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4986935A (en) * | 1988-02-10 | 1991-01-22 | Fuji Xerox Co., Ltd. | Wavelength converting device |
| US5004661A (en) * | 1989-05-30 | 1991-04-02 | Xerox Corporation | Photoconductive member having symmetrical and unsymmetrical squaraine compositions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624251A (en) * | 1985-06-28 | 1987-01-10 | ゼロツクス コ−ポレ−シヨン | Asymmetric squaline compound and photoconductive image forming member |
-
1986
- 1986-04-22 JP JP61091259A patent/JPS62249952A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624251A (en) * | 1985-06-28 | 1987-01-10 | ゼロツクス コ−ポレ−シヨン | Asymmetric squaline compound and photoconductive image forming member |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4986935A (en) * | 1988-02-10 | 1991-01-22 | Fuji Xerox Co., Ltd. | Wavelength converting device |
| US5004661A (en) * | 1989-05-30 | 1991-04-02 | Xerox Corporation | Photoconductive member having symmetrical and unsymmetrical squaraine compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0557260B2 (en) | 1993-08-23 |
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