JPH01146843A - Production of squarylium compound - Google Patents
Production of squarylium compoundInfo
- Publication number
- JPH01146843A JPH01146843A JP62305857A JP30585787A JPH01146843A JP H01146843 A JPH01146843 A JP H01146843A JP 62305857 A JP62305857 A JP 62305857A JP 30585787 A JP30585787 A JP 30585787A JP H01146843 A JPH01146843 A JP H01146843A
- Authority
- JP
- Japan
- Prior art keywords
- optionally substituted
- group
- aliphatic alcohol
- salt
- squarylium compound
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- -1 (substituted) phenyl Chemical group 0.000 claims abstract description 13
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 125000005521 carbonamide group Chemical class 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 4
- 150000007524 organic acids Chemical class 0.000 claims abstract description 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000005843 halogen group Chemical group 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
- 125000000565 sulfonamide group Chemical class 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 150000003510 tertiary aliphatic amines Chemical class 0.000 claims description 2
- 125000005208 trialkylammonium group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 32
- 108091008695 photoreceptors Proteins 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001448 anilines Chemical class 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MESJRHHDBDCQTH-UHFFFAOYSA-N 3-(dimethylamino)phenol Chemical compound CN(C)C1=CC=CC(O)=C1 MESJRHHDBDCQTH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YKKPYMXANSSQCA-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-(3-pyrazol-1-ylazetidin-1-yl)methanone Chemical compound N1(N=CC=C1)C1CN(C1)C(=O)C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F YKKPYMXANSSQCA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- FOTDHUVOUZZTTB-UHFFFAOYSA-N cyclobuten-1-ol Chemical class OC1=CCC1 FOTDHUVOUZZTTB-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ISGXOWLMGOPVPB-UHFFFAOYSA-N n,n-dibenzylaniline Chemical compound C=1C=CC=CC=1CN(C=1C=CC=CC=1)CC1=CC=CC=C1 ISGXOWLMGOPVPB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- WSNKEJIFARPOSQ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(1-benzothiophen-2-ylmethyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC2=CC3=C(S2)C=CC=C3)C=CC=1 WSNKEJIFARPOSQ-UHFFFAOYSA-N 0.000 description 1
- VTNULXUEOJMRKZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(2H-tetrazol-5-ylmethyl)benzamide Chemical compound N=1NN=NC=1CNC(C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)=O VTNULXUEOJMRKZ-UHFFFAOYSA-N 0.000 description 1
- DNJNUCYAVRRVMW-UHFFFAOYSA-N 3-chlorocyclobut-3-ene-1,2-dione Chemical class ClC1=CC(=O)C1=O DNJNUCYAVRRVMW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical class CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 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
- 239000012442 inert solvent Substances 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PRCZDSXLFJMOAT-UHFFFAOYSA-N n-[(4-chlorophenyl)methyl]-n-methylaniline Chemical compound C=1C=CC=CC=1N(C)CC1=CC=C(Cl)C=C1 PRCZDSXLFJMOAT-UHFFFAOYSA-N 0.000 description 1
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical compound FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 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
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 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、スクアリリウム化合物の改良製造法に関す歳
。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for producing squarylium compounds.
従来の技術
電子写真感光体などの光導電材料、とじて、無機及び有
機の数多くの物質が報告されている。このうち、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すことが報告されている
。BACKGROUND OF THE INVENTION Numerous inorganic and organic materials have been reported for photoconductive materials such as electrophotographic photoreceptors. Among these, known organic photoconductive materials include bisazo pigments, trisazo pigments, phthalocyanine pigments, cyanines, and pyrylium compounds, and in recent years, certain squarylium compounds have shown excellent photoconductive properties. It has been reported that
スクアリリウム化合物としては、四員環の左右が同一な
対称スクアリリウム化合物及び左右が異なる非対称スク
アリリウム化合物が知られており、これ等は下記一般式
（Ｉ［Ｉ）で示される。As squarylium compounds, symmetric squarylium compounds in which the left and right sides of the four-membered ring are the same and asymmetric squarylium compounds in which the left and right sides are different are known, and these are represented by the following general formula (I[I).
（式中、Ｒ１、Ｒ２、Ｒ５及びＲ６は、互いに独立した
ものであって、各々置換されてもよいアルキル基、置換
されてもよいフェニル基、又は置換されでもよいベンジ
ル基を表わし、Ｒ３、Ｒ４、Ｒ及びＲ８はそれぞれ、水
素原子、置換されてもよいアルキル基、ハロゲン原子、
水酸基、カルボキシル基、置換されていてもよいアルキ
ル基又はフェニル基置換カルボンアミド基、又は置換さ
れていてもよいアルキル基又はフェニル基置換スルホン
アミド基を表わす）
一般に対称スクアリリウム化合物は、スクアリック酸と
相当するアニリン誘導体とをアルコール中で反応させる
ことによって合成される。(In the formula, R1, R2, R5 and R6 are each independent of each other and each represents an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, R3, R4, R and R8 are each a hydrogen atom, an optionally substituted alkyl group, a halogen atom,
hydroxyl group, carboxyl group, optionally substituted alkyl group or phenyl group-substituted carbonamide group, or optionally substituted alkyl group or phenyl group-substituted sulfonamide group) In general, symmetrical squarylium compounds are equivalent to squaric acid. It is synthesized by reacting aniline derivatives in alcohol.
一方非対称スクアリリウム化合物は、下記に示す反応に
よって合成される。即ち、スクアリック酸を塩化チオニ
ル等の塩素化剤により塩素化し、次にこれをアニリン誘
導体と反応させ、クロロシクロブテンジオン誘導体とし
、次いでこの誘導体を加水分解してヒドロキシシクロブ
テン誘導体とし、これに先に示したものと異なるアニリ
ン誘導体を反応させて非対称スクアリリウム化合物を合
成する。On the other hand, an asymmetric squarylium compound is synthesized by the reaction shown below. That is, squaric acid is chlorinated with a chlorinating agent such as thionyl chloride, this is then reacted with an aniline derivative to form a chlorocyclobutenedione derivative, this derivative is then hydrolyzed to form a hydroxycyclobutene derivative, and this is followed by Asymmetric squarylium compounds are synthesized by reacting aniline derivatives different from those shown in .
又、スクアリリウム化合物の改良合成法とじては、スク
アリック酸と芳香族アニリン、フェノール類、フェノー
ルスクアリリウム類からなる群より選ばれた化合物を反
応させる方法（特開昭６０−１７６７５０号公報）、ス
クアリック酸の半エステルを酸触媒の存在下、アニリン
誘導体と反応させる方法（特開昭６０−２０２８４９号
公報）、脂肪族アミンの存在下、スクアリック鼠と芳香
族アニリンとを反応させる方法（特開昭８０−２０８３
６１号公報）、又、スクアリック酸と芳香族アニリン及
びフルオロアニリンを反応させる方法（特開昭６１−８
７６４７号公報）等が知られている。In addition, improved synthesis methods for squarylium compounds include a method of reacting squarylic acid with a compound selected from the group consisting of aromatic anilines, phenols, and phenolic squarylium compounds (Japanese Patent Laid-Open Publication No. 176750/1983); A method of reacting a half ester of with an aniline derivative in the presence of an acid catalyst (JP-A-60-202849), a method of reacting Squaric with an aromatic aniline in the presence of an aliphatic amine (JP-A-Sho 80) -2083
61), and a method of reacting squaric acid with aromatic aniline and fluoroaniline (Japanese Unexamined Patent Publication No. 61-8
No. 7647) and the like are known.
発明が解決しようとする問題点
ところで、これ等の改良合成法は、不純物を減らすよう
な反応条件を設定するか、或いは逆に、種々の不純物を
合成時に混在させて反応させるものであって、得られた
スクアリリウム化合物を電子写真感光体の光導電材料と
して用いた場合における電子写真特性の改善を目的とし
たものである。Problems to be Solved by the Invention By the way, these improved synthesis methods either set reaction conditions to reduce impurities, or conversely, mix various impurities during synthesis and react. The purpose of this invention is to improve electrophotographic properties when the obtained squarylium compound is used as a photoconductive material for an electrophotographic photoreceptor.
しかしながら、これ等の改良合成法にについては、生成
するスクアリリウム化合物の電子写真特性に影響を及ぼ
している要因が不明でおり、又、合成条件のわずかな変
化により、得られたスクアリリウム化合物を電子写真感
光体の光導電材料として用いた場合、その電子写真特性
が変化するという事情があり、良好な電子写真特性を示
す電子写真感光体を得るのに使用できるスクアリリウム
化合物を常に安定して製造することが困難であった。However, with regard to these improved synthesis methods, the factors that influence the electrophotographic properties of the resulting squarylium compounds are unknown, and slight changes in the synthesis conditions can improve the electrophotographic properties of the resulting squarylium compounds. When used as a photoconductive material for a photoreceptor, its electrophotographic properties change, so it is desirable to constantly and stably produce squarylium compounds that can be used to obtain electrophotographic photoreceptors exhibiting good electrophotographic properties. was difficult.
本発明は、上記のような問題点に鑑みて成されたもので
ある。The present invention has been made in view of the above problems.
本発明の目的は、高感度で、しかも帯電性がよく、暗減
衰が小さく、残留電位が小さく、繰返し使用に対する安
定性に優れた電子写真感光体を製造するのに適したスク
アリリウム化合物を提供することにある。An object of the present invention is to provide a squarylium compound suitable for producing an electrophotographic photoreceptor that has high sensitivity, good chargeability, low dark decay, low residual potential, and excellent stability against repeated use. There is a particular thing.
問題点を解決するための手段
本発明者等は、鋭意検討を重ねた結果、スクアリリウム
化合物の合成反応において、反応の中間段階で生成する
ヒドロキシシクロブテン誘導体が、スクアリリウム化合
物に不純物として混在し、これを用いて電子写真感光体
を製造した場合、この不純物が、その電子写真感光体の
帯電性、暗減衰、繰り返し安定性等に影響を与えること
が分かった。Means for Solving the Problems As a result of extensive studies, the present inventors discovered that in the synthesis reaction of squarylium compounds, hydroxycyclobutene derivatives, which are produced in the intermediate stages of the reaction, are mixed in squarylium compounds as impurities. It has been found that when an electrophotographic photoreceptor is manufactured using this impurity, this impurity affects the charging properties, dark decay, repeated stability, etc. of the electrophotographic photoreceptor.
特に、非対称スクアリリウム化合物、の合成においては
、出発物質がヒドロキシブテン誘導体となり、この誘導
体は、反応溶媒系べの溶解度が低く、そのため合成時に
生成物の結晶中に混入してくることが液体クロマトグラ
フィー分析により確認された。。In particular, in the synthesis of asymmetric squarylium compounds, the starting material is a hydroxybutene derivative, and this derivative has low solubility in the reaction solvent system. Confirmed by analysis. .
本発明のスクアリリウム化合物の改良合成法は、下記一
般式（Ｉ＞で示されるアリールヒドロキシシクロブテン
ジオン塩を溶媒に溶解してなる溶液を、下記一般式（ｎ
）で示されるアニリン誘導体及び酸性物質を含有する脂
肪族アルコールよりなるか又は脂肪族アルコール含有反
応溶媒中に滴下しつつ反応を行なうことを特徴とする。In the improved synthesis method of squarylium compounds of the present invention, a solution obtained by dissolving an arylhydroxycyclobutenedione salt represented by the following general formula (I>) in a solvent,
) and an aliphatic alcohol containing an acidic substance, or is characterized in that the reaction is carried out while being dropped into a reaction solvent containing an aliphatic alcohol.
（式中、Ｒ１、Ｒ２、Ｒ５及びＲ６は、互いに強めした
ものであって、゛各々置換されてもよいアルキル基、置
換されてもよいフェニル基、又は置換されてもよいベン
ジル基を表やし、Ｒ３、Ｒ４、Ｒ７及びＲ８は、互いに
独立したものであって、各々水素原子、置換されていて
もよいアルキル基、ハロゲン原子、水酸基、カルボキシ
ル基、置換されていてもよいアルキル基又はフェニル基
置換カルボンアミド基、又は置換されていてもよいアル
キル基又はフェニル基置換スルホンアミド基を表わし、
Ｍ＋はアルカリ金属イオン、テトラアルキルアンモニウ
ムイオン、トリアルキルアンモニウムイオン、置換され
ていてもよいピリジニウムイオン又は置換されていても
よいキノリニウムイオンを表わす。）
本発明において製造されるスクアリリウム化合物は、一
般式（ＩＩ）で示される。(In the formula, R1, R2, R5 and R6 are reinforced with each other, and each represents an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group. However, R3, R4, R7 and R8 are each independent of each other, and each represents a hydrogen atom, an optionally substituted alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, or phenyl. Represents a group-substituted carbonamide group, or an optionally substituted alkyl group or phenyl group-substituted sulfonamide group,
M+ represents an alkali metal ion, a tetraalkylammonium ion, a trialkylammonium ion, an optionally substituted pyridinium ion, or an optionally substituted quinolinium ion. ) The squarylium compound produced in the present invention is represented by general formula (II).
（式中、ＲないしＲ８は前記したと同一のものを意味す
る）
本発明、によれば、高純度のスクアリリウム化合物を製
造することができ、得られたスクアリリウム化合物は、
高感度で、しかも帯電性がよく、暗減衰が小さく、残留
電位が小ざく、繰り返し使用に対する安定性に優れた電
子写真感光体を製造するのに適したものである。(In the formula, R to R8 mean the same as described above.) According to the present invention, a highly purified squarylium compound can be produced, and the obtained squarylium compound is
It is suitable for producing electrophotographic photoreceptors that have high sensitivity, good charging properties, small dark decay, small residual potential, and excellent stability against repeated use.
以下、本発明について詳記する。本発明において出発原
料として用いる上記一般式（Ｉ＞で示されるアリールヒ
ドロキシシクロブテンジオン塩は、一般式（ＩＶ）で示
されるアリールヒドロキシシクロブテンジオンを塩基で
処理することによって得（式中、Ｒ１ないしＲ４は、上
記と同じ意味を表わす）
上記一般式（ＩＶ ＞で示されるアリールヒドロキシシ
クロブテンジオンの代表的なものを例示すると、例えば
次のものをあげることができる。The present invention will be described in detail below. The arylhydroxycyclobutenedione salt represented by the general formula (I>) used as a starting material in the present invention can be obtained by treating the arylhydroxycyclobutenedione represented by the general formula (IV) with a base (in the formula, R1 to R4 have the same meanings as above) Typical examples of the arylhydroxycyclobutenediones represented by the general formula (IV>) include the following.
使用できる塩基としては、アルカリ金属水酸化物、２級
脂肪族アミン、例えばトリエチルアミン、トリ（ｎ−ブ
チル）アミン等の３級脂肪族アミン、ピリジン、メチル
ピリジン等のピリジン類、キノリン、メチルキノリン等
のキノリン類をあげることができる。Usable bases include alkali metal hydroxides, secondary aliphatic amines, tertiary aliphatic amines such as triethylamine and tri(n-butyl)amine, pyridines such as pyridine and methylpyridine, quinoline, methylquinoline, etc. quinolines can be mentioned.
上記一般式（１）で示されるアリールヒドロキシシクロ
ブテンジオン塩は、溶媒に溶解して溶液を製造するが、
溶媒としては、１−ブタノール、１−ヘプタツール、１
−オクタツール、等の炭素数４〜８の脂肪族アルコール
、又は炭素数４〜８の脂肪族アルコールとベンゼン、ト
ルエン、等の芳香族炭化水素との混合溶媒が好ましく使
用される。上記溶媒は、続いて行われる反応に際して使
用する反応溶媒と同一のものであってもよく、文具なっ
ていてもよい。更に又、反応を阻害しないものであれば
、他の不活性溶媒を単、独で又は混合して使用してもよ
い。The arylhydroxycyclobutenedione salt represented by the above general formula (1) is dissolved in a solvent to produce a solution, but
As a solvent, 1-butanol, 1-heptatool, 1
- An aliphatic alcohol having 4 to 8 carbon atoms such as octatool, or a mixed solvent of an aliphatic alcohol having 4 to 8 carbon atoms and an aromatic hydrocarbon such as benzene or toluene is preferably used. The above solvent may be the same as the reaction solvent used in the subsequent reaction, or may be a stationery. Furthermore, other inert solvents may be used alone or in combination as long as they do not inhibit the reaction.
一方、アリールヒドロキシシクロブテンジオン塩と反応
させる上記一般式（Ｉ［＞で示されるア二リン誘導体と
しては、例えば次のものをめげるここれ等のアニリン誘
導体は酸性物質と共に、反応溶媒に溶解させる。酸性物
質としては、無機酸及び有機酸のいずれを用いることも
できる。例えば硫酸、トルエンスルホン酸、トリクロロ
酢酸、モノクロロ酢酸、燐酸、しゅう酸、酒石酸、安息
香酸、酢酸等のρＫａ＜５の無機酸又は有機版が好まし
く、特に硫酸が好ましく用いられる。又、比較的反応性
の高い系においてはしゅう酸が好ましく用いられる。こ
れ等酸性物質は、アリールヒドロキシシクロブテンジオ
ン塩に対して当量以上、好ましくは１．１〜３当量用い
る。On the other hand, the aniline derivatives represented by the above general formula (I [>) to be reacted with the arylhydroxycyclobutenedione salt include, for example, the following. As the acidic substance, both inorganic acids and organic acids can be used.For example, inorganic acids with ρKa<5 such as sulfuric acid, toluenesulfonic acid, trichloroacetic acid, monochloroacetic acid, phosphoric acid, oxalic acid, tartaric acid, benzoic acid, acetic acid, etc. Acid or organic versions are preferred, with sulfuric acid being particularly preferred. Oxalic acid is also preferred in systems with relatively high reactivity. Preferably 1.1 to 3 equivalents are used.
反応溶媒としては、１−ブタノール、１−ヘプタツール
、１−オクタツール、等の炭素数４〜８の脂肪族アルコ
ール、又は炭素数４〜８の脂肪族アルコールとベンゼン
、トルエン、等の芳香族炭化水素との混合溶媒が好まし
く使用される。As a reaction solvent, an aliphatic alcohol having 4 to 8 carbon atoms such as 1-butanol, 1-heptatool, 1-octatool, or an aliphatic alcohol having 4 to 8 carbon atoms and an aromatic alcohol such as benzene, toluene, etc. Mixed solvents with hydrocarbons are preferably used.
本発明においては、上記アリールヒドロキシシクロブテ
ンジオン塩の溶液を、アニリン誘導体及び酸性物質を含
む反応溶媒中に滴下することによって反応を行うことが
必要である。In the present invention, it is necessary to carry out the reaction by dropping a solution of the arylhydroxycyclobutenedione salt into a reaction solvent containing an aniline derivative and an acidic substance.
反応は、反応混合物を溶剤中で加熱するのみで充分進行
するが、必要ならばディーンスタークトラップや脱水剤
の使用、或いは減圧下で加熱し、生成してくる水を除去
しながら行うのが好ましい。The reaction proceeds sufficiently by simply heating the reaction mixture in a solvent, but if necessary, it is preferable to use a Dean-Stark trap, a dehydrating agent, or heat under reduced pressure to remove the water produced. .
反応温度は、約り０℃〜約１４０℃が好ましく、反応時
間は、１〜５０時間程度である。The reaction temperature is preferably about 0°C to about 140°C, and the reaction time is about 1 to 50 hours.
アリールヒドロキシシクロブテンジオン塩の溶液の滴下
速度は、実用的な範囲において遅いほうが好ましく、実
際には十分に攪拌された反応溶媒中に１０分〜１０時間
、より好ましくは１〜５時間をかけて滴下する。アリー
ルヒドロキシシクロブテンジオン塩の滴下速度としては
、０．０１ミリモル／分〜１０ミリモル／分、より好ま
しくは、１ミリモル／分以下である。The dropwise addition rate of the arylhydroxycyclobutenedione salt solution is preferably slow within a practical range; in reality, it is added over a period of 10 minutes to 10 hours, more preferably 1 to 5 hours, into a sufficiently stirred reaction solvent. Drip. The dropping rate of the arylhydroxycyclobutenedione salt is 0.01 mmol/min to 10 mmol/min, more preferably 1 mmol/min or less.
反応系の酸強度は、一定に保持することが好ましいが、
その為には、上記酸性物質と共に、相当する塩又は塩基
を含有させて緩衝溶液の形態にすればよい。使用できる
塩としては、例えば、しゆう酸／シゆう酸リチウム、し
ゆう醸／トリエチルアミン、リン鍍／トリブチルアミン
、酢酸／酢酸ナトリウム、酢酸／トリエタノールアミン
等の系が用いられる。It is preferable to keep the acid strength of the reaction system constant, but
For this purpose, a buffer solution may be prepared by containing a corresponding salt or base together with the above-mentioned acidic substance. Examples of usable salts include systems such as oxalic acid/lithium oxalate, oxalic acid/triethylamine, phosphorus/tributylamine, acetic acid/sodium acetate, and acetic acid/triethanolamine.
本発明によって製造される上記一般式（Ｉ［［）で示さ
れるスクアリリウム化合物の具体例として、以下のもの
をあげることができる。Specific examples of the squarylium compound represented by the above general formula (I[[) produced by the present invention include the following.
〇−
Ｆ Ｏ
ＦＯ
本発明によれば、高純度のスクアリリウム化合物を製造
することができ、得られたスクアリリウム化合物は、電
子写真感光体における光導電材料として適したものであ
る。電子写真感光体の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の場合には、このスクアリ
リウム化合物は、電荷発生剤として電荷発生層に含ませ
ることができる。それにより、高感度で、しがも帯電性
がよく、暗減衰が小さく、残留電位が小さく、繰返使用
に対する安定性に優れた電子写真感光体が形成される。〇-FO FO According to the present invention, a highly purified squarylium compound can be produced, and the obtained squarylium compound is suitable as a photoconductive material in an electrophotographic photoreceptor. When the photosensitive layer of the electrophotographic photoreceptor has a laminated structure in which a charge generation layer and a charge transport layer are functionally separated, the squarylium compound can be included in the charge generation layer as a charge generation agent. As a result, an electrophotographic photoreceptor is formed which has high sensitivity, good chargeability, low dark decay, low residual potential, and excellent stability against repeated use.
実施例 以下、本発明を実施例によって説明する。Example Hereinafter, the present invention will be explained by examples.
実施例１
３−ヒドロキシ−４−（４’ −ジメチルアミノフェニ
ル）−１−シクロブテン−１，２−ジオン（例示化合物
ＩＶ−１＞ ２．２９ （１０ミリモル）をメタノー
ル ５０ＩＩＪ１に分散し、トリエチルアミン２ｄ（１
４ミリモル）を加え、完全に溶解させた後、溶媒を減圧
除去し、得られた固体をヘキサンで洗浄、乾燥し、下記
構造式（Ｉ−１＞で示されるトリエチルアンモニウム・
４−（４’ −ジメチルアミノフェニル）−１−シクロ
ブテン−１，２−ジオン−３−オレート３．２９ （収
率：９８％）を橙色粉末として得た。融点８３〜８５℃
リ
元素分析：
Ｃ（χ） Ｈ（％） Ｎ（＄）
計算値 ６７．９０ Ｂ、２３ ８．８０実測値
６７．７２ ８．１１ ８．８４次に、Ｎ、Ｎ−
ジメチル−ｍ−アミノフェノール（例示化合物ｎ−３＞
１．３７９（１０ミリモル）及びしゆう酸０．９ｇ（
１０ミリモル）を１−ブタノール５０ｍｆｌ中に溶解し
、還流下に攪拌しながら、前記トリエチルアンモニウム
・４−（４’ −ジメチルアミノフェニル）−１−シク
ロブテン−１，２−ジオン−３−オレート ２．５５９
（８ミリモル）を１−ブタノール ２（７に溶解させ
た溶液を、約２時間で滴下した。滴下終了後、混合物を
更に２時間還流した。析出した濃青色の結晶を濾別し、
洗浄、乾燥して前記例示化合物■−３２゜４０９ （収
率：８９％）を得た。融点：２９２℃（分解）実施例１
によって合成された例示化合物ｌｌｌ−３１重量部にポ
リビニルブチラール樹脂［積水化学ＴＩＡ：ｌ３ＸＬ（
登録商標）］ １１重量部シクロへキサノン ４０重量
部を加え、ボールミルで４時間粉砕、混合した。得られ
た分散液をバーコータを用いてアルミニウムを蒸着した
ポリエステルフィルム［東し製：メタルミー（登録商標
）］上に塗布し、乾燥して、厚さ０．２ｍの電荷発生層
を形成した。Example 1 3-Hydroxy-4-(4'-dimethylaminophenyl)-1-cyclobutene-1,2-dione (Illustrative Compound IV-1> 2.29 (10 mmol) was dispersed in methanol 50IIJ1, and triethylamine 2d (1
After complete dissolution, the solvent was removed under reduced pressure, and the resulting solid was washed with hexane and dried to obtain triethylammonium chloride represented by the following structural formula (I-1>).
3.29 (yield: 98%) of 4-(4'-dimethylaminophenyl)-1-cyclobutene-1,2-dione-3-oleate was obtained as an orange powder. Melting point 83-85℃ Elemental analysis: C (χ) H (%) N ($) Calculated value 67.90 B, 23 8.80 Actual value 67.72 8.11 8.84 Next, N, N-
Dimethyl-m-aminophenol (exemplary compound n-3>
1.379 (10 mmol) and 0.9 g of oxalic acid (
10 mmol) in 50 mfl of 1-butanol, and while stirring under reflux, add the triethylammonium 4-(4'-dimethylaminophenyl)-1-cyclobutene-1,2-dione-3-oleate 2. 559
A solution of (8 mmol) dissolved in 1-butanol 2 (7) was added dropwise over about 2 hours. After the addition, the mixture was further refluxed for 2 hours. The dark blue crystals that had precipitated were filtered off.
After washing and drying, the above-mentioned exemplary compound (1)-32°409 (yield: 89%) was obtained. Melting point: 292°C (decomposition) Example 1
Polyvinyl butyral resin [Sekisui Chemical TIA: l3XL (
(registered trademark)] 11 parts by weight of cyclohexanone and 40 parts by weight were added, and the mixture was ground and mixed in a ball mill for 4 hours. The resulting dispersion was coated using a bar coater on a polyester film on which aluminum had been vapor-deposited [Metal Me (registered trademark) manufactured by Toshi Co., Ltd.] and dried to form a charge generation layer with a thickness of 0.2 m.
この電荷発生層上に、Ｎ、Ｎ’ −ジフェニル−Ｎ、Ｎ
’−ビス（３−メチルフェニル）−［１゜１′−ビフェ
ニル］−４．４’−ジアミン１重量部、ポリカーボネー
ト樹脂「帝人製：パンライト（登録商標）］ １１重量
部びテトラヒドロフラン１０重量部からなる均一溶液を
、バーコータを用いて塗布し、乾燥して、厚ざ１５ＩＩ
ｍの電荷輸送層を形成し、電子写真感光体を作成した。On this charge generation layer, N,N'-diphenyl-N,N
1 part by weight of '-bis(3-methylphenyl)-[1°1'-biphenyl]-4.4'-diamine, 11 parts by weight of polycarbonate resin "Teijin Panlite (registered trademark)" and 10 parts by weight of tetrahydrofuran. A uniform solution consisting of
A charge transport layer of m was formed to prepare an electrophotographic photoreceptor.
次に、得られた電子写真感光体について、静電複写紙試
験装置（用日電機製：エレクロロスタティク・ペーパー
アナライザー、５Ｐ−４２８）を用いて、−６ＫＶのコ
ロナ放電を施して負帯電させた後、２秒間暗所に放置し
、続いてタングステンランプを用い、表面の照度が５ル
ツクスになるように感光層に光照射を施した。Next, the obtained electrophotographic photoreceptor was subjected to -6KV corona discharge using an electrostatic copying paper tester (manufactured by Yonichi Denki: Electrostatic Paper Analyzer, 5P-428) to become negatively charged. After that, the photosensitive layer was left in a dark place for 2 seconds, and then the photosensitive layer was irradiated with light using a tungsten lamp so that the surface illuminance was 5 lux.
帯電直後の電位をｖＯ１２秒間暗所放置゛後の電位をＶ
［）ＯＰ、表面電位がＶ ［）ＤＰの１７２になる露光
量をＥ１／２．５ルツクスの光を１０秒間照射した後の
表面電位をＶＲＰとし、同様の測定を２０回繰り返して
行った。 ′
その結果を第１表に示す。The potential immediately after charging is V.The potential after being left in the dark for 12 seconds is V.
[)OP, the surface potential is VRP] The surface potential after irradiation with light of E1/2.5 lux for 10 seconds at an exposure amount of 172 of [)DP was taken as VRP, and similar measurements were repeated 20 times. ' The results are shown in Table 1.
比較例１
Ｎ、Ｎ−ジメチル−ｍ−アミノフェノール１．２３ｇ（
９ミリモル）と３−ヒドロキシ−４−（４′−ジメチル
アミノフェニル）−１−シクロブテン−１，２−ジオン
（例示化合物ＩＶ−１＞１．７３９（８ミリモル）とを
１−ブタノール ５０ｄ中に加え、攪拌下に４時間還流
した。放冷後、析出した結晶を濾別し、洗浄、乾燥して
例示化合物［−３２，５０９゛（収率：９３％）を得た
。Comparative Example 1 1.23 g of N,N-dimethyl-m-aminophenol (
9 mmol) and 3-hydroxy-4-(4'-dimethylaminophenyl)-1-cyclobutene-1,2-dione (Illustrative Compound IV-1 > 1.739 (8 mmol)) in 1-butanol 50d. The mixture was stirred and refluxed for 4 hours. After cooling, the precipitated crystals were filtered off, washed, and dried to obtain the exemplified compound [-32,509゛ (yield: 93%).
以上のようにして得られた例示化合物ｌｌ−３を用い、
実施例１におけると同様にして電子写真感光体を作成し
、同様に評価した。その結果を第２表に示す。Using exemplified compound ll-3 obtained as above,
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 2.
第２表
実施例２
Ｎ、Ｎ−ジベンジルアニリン（例示化合物■−４）２．
７３９ （１０ミリモル）を１−ブタノール／トルエン
（２／１）混合溶媒１ｏｏｉに溶解し、濃硫１０．５ｄ
を、加え、ディーンスタークトラップを付けた反応容器
中で、撹拌のもとに還流させながら、実施例１における
と同様にして得られたトリエチルアンモニウム・４−（
４’ −ジメチルアミノフェニル）−１−シクロブテン
−１，２−ジオン−３−オレート ２．５５９ （８ミ
リモル〉を１−ブタノール２０ｄに溶解して得られた溶
液を、約２時間で滴下した。滴下終了後、ざらに２０時
間還流を続けた後、空温まで放冷し、析出した結晶を濾
別し、洗浄、乾燥して例示化合物１１１−４ １．２５
ｇ（収率：３３％）を得た。融点＝２５０℃（分解）
以上のようにして得られた例示化合物１１ｉ４を用い、
実施例１におけると同様にして電子写真感光体を作成し
、同様に評価した。その結果を第３表に示す。Table 2 Example 2 N,N-dibenzylaniline (Exemplary Compound ■-4) 2.
739 (10 mmol) was dissolved in 100 ml of 1-butanol/toluene (2/1) mixed solvent, and 10.5 d of concentrated sulfur
was added to the triethylammonium 4-(obtained in the same manner as in Example 1) while stirring and refluxing in a reaction vessel equipped with a Dean-Stark trap.
A solution obtained by dissolving 2.559 (8 mmol) of 4'-dimethylaminophenyl)-1-cyclobutene-1,2-dione-3-oleate in 20 d of 1-butanol was added dropwise over about 2 hours. After the completion of the dropwise addition, the mixture was kept under reflux for 20 hours, then allowed to cool to air temperature, and the precipitated crystals were filtered out, washed, and dried to obtain Exemplified Compound 111-4 1.25
g (yield: 33%) was obtained. Melting point = 250°C (decomposition) Using exemplary compound 11i4 obtained as above,
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 3.
第３表
比較例２
Ｎ、Ｎ−ジメチル−ｍ−アミンフェノール１．２３９（
９ミリモル）と３−ヒドロキシ−４−（４′−ジメチル
アミノフェニル）−１−シクロブテン−１，２−ジオン
１．７３ｇ（８ミリモル〉及びＮ、Ｎ−ジベンジルア
ニリン ２．７３９ （１０７りを、１−ブタノール／
トルエン（２／１）混合溶媒１００ ｄ中に加え、ディ
ーンスタークトラップで溜出する水を除去しながら、３
０時間、還流下撹拌した。放冷後、析出した結晶を濾別
し、洗浄、乾燥して例示化合物１［１−４０，９８９（
収率：２６％）を得た。Table 3 Comparative Example 2 N,N-dimethyl-m-aminephenol 1.239 (
9 mmol), 1.73 g (8 mmol) of 3-hydroxy-4-(4'-dimethylaminophenyl)-1-cyclobutene-1,2-dione and 2.739 g (107 mmol) of N,N-dibenzylaniline. , 1-butanol/
Added to 100 d of toluene (2/1) mixed solvent, and while removing distilled water with a Dean-Stark trap,
The mixture was stirred under reflux for 0 hours. After cooling, the precipitated crystals were filtered, washed, and dried to obtain Exemplified Compound 1 [1-40,989(
Yield: 26%) was obtained.
以上のようにして得られた例示化合物ｍ−４を用い、実
施例１におけると同様にして電子写真感光体を作成し、
同様に評価した。その結果を第４表に示す。Using the exemplary compound m-4 obtained as above, an electrophotographic photoreceptor was prepared in the same manner as in Example 1,
They were evaluated in the same way. The results are shown in Table 4.
実施例３
３−ヒドロキシ−４−（４’ −ジメチルアミノ−２′
−フルオロフェニル）−１−シクロブテン＝１．２−
ジオン（例示化合物ＩＶ−３＞ １．８８ｇ（８ミリモ
ル）に１−ブタール ２０ｄ及トリエチルアミン１．２
ｄ （９ミリモル）を加え、溶解させて溶液を得た。次
に、Ｎ、Ｎ−ジメチル−ｍ−アミノフェノール（例示化
合物ｌｌ−３） １．３７９ （１０ミリモル）及びし
ゆう１ｍ ２．２Ｓ？ （２４ミリモル）及びトリエチ
ルアミン１．１１ｒ１１（８ｄ）を１−ブタノール５０
威中に溶解した溶液を、還流下に攪拌しながら、前記の
溶液を、約２時間で滴下した。滴下終了後、混合物を更
に５時間還流した。析出した青緑色の結晶を濾別し、洗
浄、乾燥して前記例示化合物■−１０１，６９９（収率
：６０％）を得た。融点：２９０℃（分解）
以上のようにして得られた例示化合物［）−１０を用い
、実施例１にあけると同様にして電子写真感光体を作成
し、同様に評価した。その結果を第５表に示す。Example 3 3-hydroxy-4-(4'-dimethylamino-2'
-fluorophenyl)-1-cyclobutene = 1.2-
Dione (Exemplary Compound IV-3> 1.88 g (8 mmol), 1-butal 20d and triethylamine 1.2
d (9 mmol) was added and dissolved to obtain a solution. Next, 1.379 (10 mmol) of N,N-dimethyl-m-aminophenol (exemplified compound 11-3) and 1 m of 2.2 S? (24 mmol) and triethylamine 1.11r11 (8d) in 1-butanol 50
The above solution was added dropwise to the solution in about 2 hours while the solution was stirred under reflux. After the addition was complete, the mixture was refluxed for an additional 5 hours. The precipitated blue-green crystals were filtered, washed and dried to obtain the above-mentioned exemplified compound 1-101,699 (yield: 60%). Melting point: 290°C (decomposition) Using the exemplary compound [)-10 obtained as described above, an electrophotographic photoreceptor was prepared in the same manner as in Example 1, and evaluated in the same manner. The results are shown in Table 5.
第５表
比較例３
比較例１におけると同様な方法で例示化合物■−１０を
合成した。収量：１．６１ｇ （収率：５７％）以上
のようにして得られた例示化合物ｌｌ−１０を用い、実
施例１におけると同様にして電子写真感光体を作成し、
同様に評価した。その結果を第６表に示す。Table 5 Comparative Example 3 Exemplary compound 1-10 was synthesized in the same manner as in Comparative Example 1. Yield: 1.61 g (yield: 57%) Using the exemplified compound 11-10 obtained above, an electrophotographic photoreceptor was prepared in the same manner as in Example 1,
They were evaluated in the same way. The results are shown in Table 6.
第６表
実施例４
３−ヒドロキシ−４−（４’−ジメチルアミノ−２′
−フルオロフェニル）−１−シクロブテン−１，２−ジ
オン（例示化合物ＩＶ−３） １．８８９ （８ミリモ
ル）に１−ブタール ２（７及トリエチルアミン１．２
ｄ （９ミリモル）を加え、溶解させて溶液を得た。Table 6 Example 4 3-hydroxy-4-(4'-dimethylamino-2'
-fluorophenyl)-1-cyclobutene-1,2-dione (exemplified compound IV-3) 1.889 (8 mmol) to 1-butal 2 (7 and triethylamine 1.2
d (9 mmol) was added and dissolved to obtain a solution.
次に、Ｎ−メチル−Ｎ−（ｐ−クロロベンジル）−アニ
リン（例示化合物ｎ−５＞ ２．３２９ （１０ミリモ
ル）を１−ブタノール／トルエン（２／１）混合溶媒１
００ ｍｌｌに溶解し、濃硫酸０．５ｄを加え、ディー
ンスタークトラップを付けた反応容器中で還流下撹拌し
ながら、前記の溶液を、約２時間で滴下した。Next, N-methyl-N-(p-chlorobenzyl)-aniline (exemplary compound n-5> 2.329 (10 mmol)) was dissolved in 1-butanol/toluene (2/1) mixed solvent 1
0.00 ml, and 0.5 d of concentrated sulfuric acid was added thereto, and the above solution was added dropwise over about 2 hours while stirring under reflux in a reaction vessel equipped with a Dean-Stark trap.
滴下終了後、混合物を更に１７時間還流した。析出した
結晶を濾別し、洗浄、乾燥して前記例示化合物ｌｌｌ−
１２１，６０９（収率：４５％）を得た。融点＝２５０
″Ｃ（分解）
以上のようにして得られた例示化合物■−１２を用い、
実施例１におけると同様にして電子写真感光体を作成し
、同様に評価した。その結果を第７表に示す。After the addition was complete, the mixture was refluxed for an additional 17 hours. The precipitated crystals were filtered, washed and dried to obtain the above-mentioned exemplified compound lll-
121,609 (yield: 45%) was obtained. Melting point = 250
``C (Decomposition) Using the exemplary compound ■-12 obtained as above,
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 7.
比較例４
比較例２におけると同様な方法で例示化合物■−１２を
合成した。収量： ２．６４ｇ（収率ニア３％）以上の
ようにして得られた例示化合物■−１２を用い、実施例
１におけると同様にして電子写真感光体を作成し、同様
に評価した。その結果を第８表に示す。Comparative Example 4 Exemplary compound 1-12 was synthesized in the same manner as in Comparative Example 2. Yield: 2.64 g (yield near 3%) An electrophotographic photoreceptor was prepared in the same manner as in Example 1 using Exemplified Compound 1-12 obtained above and evaluated in the same manner. The results are shown in Table 8.
実施例５
３−ヒドロキシ−４−（４’ −ジメチルアミノ−２′
−フルオロフェニル）−１−シクロブテン−１，２−
ジオン（例示化合物ＩＶ−３） １．８８９ （８ミリ
モル）に１−プタール／トルエン（２／１） ２５威
及トリ（ｍ−ブチル）アミン２．４７ （１０ミリモル
）を加え、溶解させて溶液を得た。Example 5 3-hydroxy-4-(4'-dimethylamino-2'
-fluorophenyl)-1-cyclobutene-1,2-
To 1.889 (8 mmol) of dione (exemplified compound IV-3) was added 2.47 (10 mmol) of 1-butal/toluene (2/1) and dissolved to form a solution. I got it.
次に、Ｎ−メチル−Ｎ−（ｐ−クロロベンジル）−ｍ−
アミンフェノール（例示化合物ｌｌ−６＞２．４８９（
１０ミリモル）、シゅう酸２．２９ （２４ミリモル）
及トリ（ｍ−ブチル）アミン１．９ｒｄ （８ミリモル
）を１〜ブタノール／トルエン（２／１）混合溶媒１０
０ｄに溶解した溶液を、ディーンストークトラップを付
けた反応溶液中で、還流下撹拌しながら、前記の溶液を
、約２時間で滴下した。滴下終了後、混合物を更に４時
間速流した。析出した結晶を濾別し、洗浄、乾燥して前
記例示化合物■−１３２，９６９（収率：８０％）を得
た。融点：２６８℃（分解）
以上のようにして得られた例示化合物■−１３を用い、
実施例１におけると同様にして電子写真感光体を作成し
、同様に評価した。その結果を第９表に示す。Next, N-methyl-N-(p-chlorobenzyl)-m-
Amine phenol (Exemplary compound ll-6>2.489(
10 mmol), oxalic acid 2.29 (24 mmol)
and 1.9rd (8 mmol) of tri(m-butyl)amine in 1 to 10 butanol/toluene (2/1) mixed solvent.
The above solution was added dropwise over about 2 hours to a reaction solution equipped with a Dean-Stoke trap while stirring under reflux. After the addition was complete, the mixture was allowed to flow rapidly for an additional 4 hours. The precipitated crystals were separated by filtration, washed and dried to obtain the exemplified compound 1-132,969 (yield: 80%). Melting point: 268°C (decomposition) Using exemplified compound ■-13 obtained as above,
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 9.
第９表
比較例５
比較例２におけると同様な方法で例示化合物■−１３を
合成した。収量：２．５３Ｑ （収率：６８％）以上
のようにして得られた例示化合物１［１−１３を用い、
実施例１におけると同様にして電子写真感光体を作成し
、同様に評価した。その結果を第１０表に示す。Table 9 Comparative Example 5 Exemplary compound 1-13 was synthesized in the same manner as in Comparative Example 2. Yield: 2.53Q (Yield: 68%) Using Exemplary Compound 1[1-13 obtained as above,
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 10.
第１０表
発明の効果
本発明は、上記の構成を有するから、製造されたスクア
リリウム化合物は、電子写真感光体にあける光導電材料
として用いるのに優れたものとなる。即ち、このスクア
リリウム化合物を用いて形成された電子写真感光体は、
高感度で、しかも帯電性がよく、暗減衰が小さく、残留
電位が・小さく、繰返使用に対する安定性に優れたもの
となる。Table 10 Effects of the Invention Since the present invention has the above configuration, the produced squarylium compound is excellent for use as a photoconductive material for electrophotographic photoreceptors. That is, an electrophotographic photoreceptor formed using this squarylium compound is
It has high sensitivity, good chargeability, low dark decay, low residual potential, and excellent stability for repeated use.
特許出願人 富士ゼロックス株式会社代理人
弁理士 渡部 剛Patent applicant Fuji Xerox Co., Ltd. Agent
Patent attorney Tsuyoshi Watanabe
Claims (8)
シシクロブテンジオン塩 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１及びＲ＿２は、互いに独立したものであ
つて、各々置換されてもよいアルキル基、置換されても
よいフェニル基、又は置換されてもよいベンジル基を表
わし、Ｒ＿３及びＲ＿４は、互いに独立したものであつ
て、各々水素原子、置換されてもよいアルキル基、ハロ
ゲン原子、水酸基、カルボキシル基、置換されていても
よいアルキル基又はフェニル基置換カルボンアミド基、
又は置換されていてもよいアルキル基又はフェニル基置
換スルホンアミド基を表わし、Ｍ＾＋はアルカリ金属イ
オン、テトラアルキルアンモニウムイオン、トリアルキ
ルアンモニウムイオン、置換されていてもよいピリジニ
ウムイオン又は置換されていてもよいキノリニウムイオ
ンを表わす。） を溶媒に溶解してなる溶液を、下記一般式（II）で示さ
れるアニリン誘導体 ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿５及びＲ＿６は互いに独立したものであつ
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、又は置換されていてもよいベン
ジル基を表わし、Ｒ＿７及びＲ＿８は、それぞれ水素原
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、カルボキシル基、置換されていてもよいアルキ
ル基又はフェニル基置換カルボンアミド基、又は置換さ
れていてもよいアルキル基又はフェニル基置換スルホン
アミド基を表わす。） 及び酸性物質を含有する脂肪族アルコールよりなるか又
は脂肪族アルコール含有反応溶媒中に滴下しつつ反応を
行なうことを特徴とする下記一般式（III）で示される
スクアリリウム化合物の製造方法。 ▲数式、化学式、表等があります▼（III） （式中、Ｒ＿１ないしＲ＿８は前記したと同一のものを
意味する）(1) Arylhydroxycyclobutenedione salt represented by the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R_1 and R_2 are independent of each other, and each is substituted. represents an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, and R_3 and R_4 are each independently a hydrogen atom and an optionally substituted alkyl group. , halogen atom, hydroxyl group, carboxyl group, optionally substituted alkyl group or phenyl group-substituted carbonamide group,
or an optionally substituted alkyl group or phenyl group-substituted sulfonamide group, and M^+ represents an alkali metal ion, a tetraalkylammonium ion, a trialkylammonium ion, an optionally substituted pyridinium ion, or an optionally substituted pyridinium ion. It represents a good quinolinium ion. ) is dissolved in a solvent to form an aniline derivative represented by the following general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_5 and R_6 are independent of each other. , each represents an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, R_7 and R_8 are a hydrogen atom, an optionally substituted alkyl group, halogen atom,
It represents a hydroxyl group, a carboxyl group, an optionally substituted alkyl group or a phenyl group-substituted carbonamide group, or an optionally substituted alkyl group or phenyl group-substituted sulfonamide group. ) and an aliphatic alcohol containing an acidic substance, or a method for producing a squarylium compound represented by the following general formula (III), characterized in that the reaction is carried out while dropping the aliphatic alcohol into a reaction solvent containing an aliphatic alcohol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_1 to R_8 mean the same thing as above)
りなるか、又は炭素数４〜８の脂肪族アルコールを含有
する混合溶媒である特許請求の範囲第１項に記載のスク
アリリウム化合物の製造方法。(2) The squarylium compound according to claim 1, wherein the reaction solvent is an aliphatic alcohol having 4 to 8 carbon atoms or a mixed solvent containing an aliphatic alcohol having 4 to 8 carbon atoms. Production method.
させる溶媒が、炭素数４〜８の脂肪族アルコールよりな
るか、又は炭素数４〜８の脂肪族アルコールを含有する
混合溶媒である特許請求の範囲第１項に記載のスクアリ
リウム化合物の製造方法。(3) The solvent in which the arylhydroxycyclobutenedione salt is dissolved is composed of an aliphatic alcohol having 4 to 8 carbon atoms, or is a mixed solvent containing an aliphatic alcohol having 4 to 8 carbon atoms. A method for producing a squarylium compound according to item 1.
リアルキルアンモニウム塩である特許請求の範囲第１項
に記載のスクアリリウム化合物の製造方法。(4) The method for producing a squarylium compound according to claim 1, wherein the arylhydroxycyclobutenedione salt is a trialkylammonium salt.
囲第１項に記載にスクアリリウム化合物の製造方法。(5) The method for producing a squarylium compound according to claim 1, wherein the acidic substance is an inorganic acid or an organic acid.
れる特許請求の範囲第１項に記載のスクアリリウム化合
物の製造方法。(6) The method for producing a squarylium compound according to claim 1, wherein the reaction solvent contains a salt or a base together with an acidic substance.
含有される特許請求の範囲第１項に記載のスクアリリウ
ム化合物の製造方法。(7) The method for producing a squarylium compound according to claim 1, wherein the reaction solvent contains a tertiary aliphatic amine together with an acidic substance.
の範囲第１項に記載のスクアリリウム化合物の製造方法
。(8) The method for producing a squarylium compound according to claim 1, wherein the acidic substance is sulfuric acid or oxalic acid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305857A JPH01146843A (en) | 1987-12-04 | 1987-12-04 | Production of squarylium compound |
| US07/278,397 US5041665A (en) | 1987-12-04 | 1988-12-01 | Process for preparing squarylium compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305857A JPH01146843A (en) | 1987-12-04 | 1987-12-04 | Production of squarylium compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01146843A true JPH01146843A (en) | 1989-06-08 |
Family
ID=17950194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62305857A Pending JPH01146843A (en) | 1987-12-04 | 1987-12-04 | Production of squarylium compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01146843A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5488601A (en) * | 1992-10-26 | 1996-01-30 | Dai Nippon Printing Co., Ltd. | Photoelectric sensor, information recording system, and information recording method |
-
1987
- 1987-12-04 JP JP62305857A patent/JPH01146843A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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