JP3000110B2 - Tetrahydroquinacridine derivative and method for producing the same - Google Patents
Tetrahydroquinacridine derivative and method for producing the sameInfo
- Publication number
- JP3000110B2 JP3000110B2 JP2275286A JP27528690A JP3000110B2 JP 3000110 B2 JP3000110 B2 JP 3000110B2 JP 2275286 A JP2275286 A JP 2275286A JP 27528690 A JP27528690 A JP 27528690A JP 3000110 B2 JP3000110 B2 JP 3000110B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- same
- tetrahydroquinacridine
- derivative
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 description 25
- 239000000049 pigment Substances 0.000 description 23
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- -1 lauryloxy group Chemical group 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- JXPDNDHCMMOJPC-UHFFFAOYSA-N 2-hydroxybutanedinitrile Chemical compound N#CC(O)CC#N JXPDNDHCMMOJPC-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SCZWJXTUYYSKGF-UHFFFAOYSA-N 5,12-dimethylquinolino[2,3-b]acridine-7,14-dione Chemical compound CN1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3N(C)C1=C2 SCZWJXTUYYSKGF-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- MIPHFLMKCGTJIH-UHFFFAOYSA-N quinolino[2,3-b]acridine Chemical compound C1=CC=CC2=NC3=CC4=CC5=CC=CC=C5N=C4C=C3C=C21 MIPHFLMKCGTJIH-UHFFFAOYSA-N 0.000 description 1
- ZJDQEEYSMBGACW-UHFFFAOYSA-N quinolino[2,3-b]acridine-7,14-dione Chemical compound O=C1C2=CC=CC=C2N=C2C1=CC1=NC3=CC=CC=C3C(=O)C1=C2 ZJDQEEYSMBGACW-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、自動車用塗料、印刷インキ、プラスチック
材料用の着色材として有用な新規テトラヒドロキナクリ
ジン誘導体およびその製造法を提供するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a novel tetrahydroquinacridine derivative useful as a coloring material for automotive coatings, printing inks, and plastic materials, and a method for producing the same.
一般に、塗料、印刷インキ、樹脂の着色などに用いら
れる色材は、顔料が主であり、無機系と有機系に大別さ
れる。有機顔料は、無機系と比較して彩度、透明度、着
色力に優れ、種類も豊富な為、広く多用されている。着
色材としての用途に要求される特性として、１）色調が
鮮明であること、２）耐光性、３）耐熱性、４）耐薬品
性、５）耐溶剤性、６）分散性および７）耐摩擦堅牢性
が優れていることなどが挙げられる。特に、耐光性の強
い顔料を得るために、これらの有機顔料の特性を改良す
る検討が行われ、例えば、アゾ顔料のもつ欠点、すなわ
ち、耐マイグレーション性、耐候性、耐熱性を改良し、
銅フタロシアニン顔料の性能に近づける試みが行われて
いるが、特に良好な結果は得られていない（特公昭55−
10630、特公昭55−49087、特開昭55−135165、特開昭61
−83257参照）。又、従来のキナクリドン顔料の性能を
改良する検討が行われ、例えば、新しいキナクリドン顔
料として、アザキナクリドン顔料（Bull.Chem.Soc.Jp
n.,48 591（1975），日化誌,398（1979）,Helv.Chim.A
cta.611146（1978）参照）等が報告されているが、それ
らは、これらの要求を必ずしも満足していない。Generally, coloring materials used for coloring paints, printing inks, resins, and the like are mainly pigments, and are roughly classified into inorganic and organic materials. Organic pigments are widely used because they are excellent in saturation, transparency and coloring power as compared with inorganic pigments, and are rich in types. Characteristics required for use as a coloring material are 1) sharp color tone, 2) light resistance, 3) heat resistance, 4) chemical resistance, 5) solvent resistance, 6) dispersibility and 7). Excellent fastness to rubbing. In particular, in order to obtain a pigment having strong light resistance, studies have been made to improve the properties of these organic pigments.For example, the disadvantages of azo pigments, namely, migration resistance, weather resistance, and heat resistance,
Attempts have been made to approach the performance of copper phthalocyanine pigments, but no particularly good results have been obtained (Japanese Patent Publication No.
10630, JP-B-55-49087, JP-A-55-135165, JP-A-61
-83257). Investigations have been made to improve the performance of conventional quinacridone pigments. For example, azaquinacridone pigments (Bull. Chem. Soc. Jp.
n., 48 591 (1975), Nikkei Magazine, 398 (1979), Helv. Chim. A
cta. 61 1146 (1978)), but they do not always satisfy these requirements.
本発明者らは、このような状況に鑑み、従来技術の問
題点を解決すべく使用適性の優れた着色材について鋭意
研究を重ねた結果、有用で新規なテトラヒドロキナクリ
ジン誘導体およびその製造法を見出し、本発明を完成す
るに到った。In view of such circumstances, the present inventors have conducted intensive studies on coloring materials having excellent usability in order to solve the problems of the prior art, and as a result, have found useful and novel tetrahydroquinacridine derivatives and a method for producing the same. Heading, the present invention has been completed.
即ち、本発明は、 １）一般式［１］ （式中、R1,R2およびR3は水素原子、ハロゲン原子、ア
ルキル基、アルコキシ基を表わし、R1,R2およびR3は同
一でも異なってもよい。R4,R5はそれぞれ水素原子、ア
ルキル基、アルケニル基、アラルキル基およびアリール
基を表わし、R4およびR5は同一でも異なってもよい。） で表わされるテトラヒドロキナクリジン誘導体およびそ
の製造法をその要旨とするものである。That is, the present invention provides: 1) General formula [1] (Wherein R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 1 , R 2 and R 3 may be the same or different. R 4 and R 5 are each A hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group and an aryl group, and R 4 and R 5 may be the same or different.) And a method for producing the same. .
本発明で得られる前記一般式［１］で示されるテトラ
ヒドロキナクリジン誘導体は、新規化合物であり、この
ものは、一般式［２］ （式中、R1,R2およびR3は水素原子、ハロゲン原子、ア
ルキル基、アルコキシ基を表わし、R1,R2およびR3は同
一でも異なってもよい。R4,R5はそれぞれ水素原子、ア
ルキル基、アルケニル基、アラルキル基およびアリール
基を表わし、R4およびR5は同一でも異なってもよい。） で表わされるキナクリドン誘導体をマロニトリルと反応
させることによって合成できる。The tetrahydroquinacridine derivative represented by the general formula [1] obtained by the present invention is a novel compound, and is a compound represented by the general formula [2] (Wherein R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 1 , R 2 and R 3 may be the same or different. R 4 and R 5 are each A hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, and an aryl group, and R 4 and R 5 may be the same or different.) The compound can be synthesized by reacting with a malonitrile.
本発明の態様を更に詳しく説明すると、テトラヒドロ
キナクリジン誘導体を得る基本の反応は（式１）によっ
て表わされる。Describing the embodiment of the present invention in more detail, the basic reaction for obtaining a tetrahydroquinacridine derivative is represented by (Formula 1).
（式中、R1,R2およびR3は水素原子、ハロゲン原子、ア
ルキル基、、アルコキシ基を表わし、R1,R2およびR3は
同一でも異なってもよい。R4,R5はそれぞれ水素原子、
アルキル基、アルケニル基、アラルキル基およびアリー
ル基を表わし、R4およびR5は同一でも異なってもよ
い。） すなわち、公知の方法で得られる一般式［２］で表わ
されるキナクリドン誘導体（U.S.S.R 455,102,工化誌，
70,2199（1967）参照）とマロノニトリルを有機溶媒
中、又は、無溶媒中で、脱水剤の存在下、所定の温度
で、所定の時間反応させ対応する一般式［１］で示され
るトテラヒドロキナクリジン誘導体を高品質で合成する
ことが出来る。 (Wherein R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and R 1 , R 2 and R 3 may be the same or different. R 4 , R 5 are A hydrogen atom,
Represents an alkyl group, an alkenyl group, an aralkyl group and an aryl group, and R 4 and R 5 may be the same or different. That is, a quinacridone derivative represented by the general formula [2] obtained by a known method (USSR 455,102, Koka,
70 , 2199 (1967)) and malononitrile in an organic solvent or in the absence of a solvent in the presence of a dehydrating agent at a predetermined temperature for a predetermined time to react with the corresponding terahydroxyl represented by the general formula [1]. Naclidine derivatives can be synthesized with high quality.
前記、一般式［１］，一般式［２］および（式１）で
示されるR1,R2,R3,R4,R5のうち、アルキル基としては、
例えばメチル基、エチル基、プロピル基、ブチル基、ペ
ンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニ
ル基、デシル基、ラウリル基、ヘキサデシル基、ステア
リル基などが挙げられ、アルコキシ基としては、例え
ば、メトキシ基、エトキシ基、プロポキシ基、イソプロ
ポシ基、ブトキシ基、イソブトキシ基、tert−ブトキシ
基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオ
キシ基、オクチルオキシ基、ノニルオキシ基、デシルオ
キシ基、ラウリルオキシ基、ヘキサデシルオキシ基、ス
テアリルオキシ基などが挙げられる。アルケニル基とし
ては、例えば、アリル基、ブテニル基、ペンテニル基、
ヘキセニル基などが挙げられ、アラルキル基としては、
例えば、ベンジル基、ベンゼン環にクロル、メトキシ基
または、ニトロ基が置換されたベンジル基、フェネチル
基などが挙げられ、アリール基としては、フェニル基ま
たは置換されたフェニル基などが挙げられる。ハロゲン
原子としては、例えば、フッ素、塩素、臭素などが挙げ
られる。Among the R 1 , R 2 , R 3 , R 4 and R 5 represented by the general formulas [1], [2] and (Formula 1), the alkyl group includes
For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, hexadecyl group, stearyl group, and the like. , Methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, lauryloxy group, Examples include a hexadecyloxy group and a stearyloxy group. Examples of the alkenyl group include, for example, an allyl group, a butenyl group, a pentenyl group,
Hexenyl group and the like, and as the aralkyl group,
For example, a benzyl group, a benzyl group in which a chloro, methoxy group, or nitro group is substituted on a benzene ring, a phenethyl group, and the like, and an aryl group include a phenyl group or a substituted phenyl group. Examples of the halogen atom include fluorine, chlorine, and bromine.
本発明で用いられる脱水剤は、Ｎ−メチルピロリジ
ン、Ｎ−メチルモルホリン、トリエチルアミン、ピペリ
ジンなどの塩基や、無水酢酸などの酸無水物、又は、塩
化亜鉛、塩化アルミニウム、四塩化チタン、塩化第二ス
ズ、五酸化リン、五フッ化アンチモン、三フッ化ホウ素
などのルイス酸、Ｐ−トルエンスルホン酸、ポリリン
酸、硫酸、塩化水素、リン酸などの酸が挙げられるが、
特に無水酢酸のような有機酸無水物が好ましい。The dehydrating agent used in the present invention may be a base such as N-methylpyrrolidine, N-methylmorpholine, triethylamine, or piperidine, or an acid anhydride such as acetic anhydride, or zinc chloride, aluminum chloride, titanium tetrachloride, or secondary chloride. Tin, phosphorus pentoxide, antimony pentafluoride, Lewis acids such as boron trifluoride, P-toluenesulfonic acid, polyphosphoric acid, sulfuric acid, hydrogen chloride, acids such as phosphoric acid,
Particularly, an organic acid anhydride such as acetic anhydride is preferable.
本発明で用いられる溶媒は、原料であるマロノニトリ
ルおよびキナクリドン誘導体を溶解し、反応させること
ができるものであれば良く、例えば、ニトロベンゼン、
ジクロロベンゼン、キノリン、N,N−ジメチルホルムア
ミド、ジメチルスルホキシド、Ｎ−メチルピロリドン、
1,3−ジメチル−２−イミダゾリジノンの如き非プロト
ン性極性溶媒などが好ましい。The solvent used in the present invention may be any solvent capable of dissolving and reacting the raw materials malononitrile and quinacridone derivative, for example, nitrobenzene,
Dichlorobenzene, quinoline, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone,
An aprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone is preferred.
本発明において適用される反応温度は、テトラヒドロ
キナクリジン誘導体の生成率が最も良好になるように適
宜選択が可能であり、40〜200℃、特に70〜150℃が好ま
しい。The reaction temperature applied in the present invention can be appropriately selected so that the production rate of the tetrahydroquinacridine derivative becomes the best, and is preferably from 40 to 200 ° C, particularly preferably from 70 to 150 ° C.
従来のキナクリドン顔料として、例えば、無置換キナ
クリドン（比較化合物［１］）又は、N,N−ジメチルキ
ナクリドン（比較化合物［２］）が、赤色の色調を示す
のに対し、本発明に係わる前記一般式［１］で示される
新規なテトラヒドロキナクリジン誘導体は、青色の色調
を有するのが特徴であり、 従来のキナクリドン顔料とは全く異なった色調を持つこ
とから、更に、広域の色調要求に応えることができる。
又、顔料としての基礎物性を検討した結果、前記一般式
［１］で示される新規なトテラヒドロキナクリジン誘導
体は、従来のキナクリドン顔料（例えば、比較化合物
［１］および［２］）と比較して、特に耐光性および耐
熱性に優れているのが特徴であり、又、他の顔料諸物性
として、例えば、耐薬品性、耐溶剤性、分散性、耐摩擦
堅牢性も良好であることから、広範囲の用途が期待でき
る。As a conventional quinacridone pigment, for example, unsubstituted quinacridone (Comparative Compound [1]) or N, N-dimethylquinacridone (Comparative Compound [2]) shows a red color tone, whereas the general quinacridone pigment according to the present invention is used. The novel tetrahydroquinacridine derivative represented by the formula [1] is characterized by having a blue color tone. Since it has a color tone completely different from that of the conventional quinacridone pigment, it can further meet a wide range of color tone requirements.
Further, as a result of examining the basic physical properties as a pigment, the novel toterahydroquinacridine derivative represented by the general formula [1] was compared with conventional quinacridone pigments (for example, comparative compounds [1] and [2]). Therefore, it is characterized by being particularly excellent in light resistance and heat resistance, and because other pigment physical properties, for example, chemical resistance, solvent resistance, dispersibility, and rub fastness are also good. Wide range of applications can be expected.
本発明に係わる前記一般式［１］で示される新規なテ
トラヒドロキナクリジン誘導体は、従来のキナクリドン
顔料が、赤色の色調を示すのに対し、吸収極大が、116
〜130nm深色シフトするため、青色の色調を有するのが
特徴であり、従来のキナクリドン顔料とは全く異なる色
調を持つことから、更に、広域の色調要求に応えること
ができる。又、顔料としての基礎物性を検討した結果、
前記一般式［１］で示される新規なテトラヒドロキナク
リジン誘導体は、従来のキナクリドン顔料（例えば、比
較化合物［１］および［２］）と比較して、特に耐光性
および耐熱性に優れていることが特徴であり、広範囲の
用途が期待できる。In the novel tetrahydroquinacridine derivative represented by the general formula [1] according to the present invention, the conventional quinacridone pigment shows a red color tone, while the absorption maximum is 116.
It is characterized by having a blue color tone due to a deep color shift of up to 130 nm, and has a color tone completely different from that of the conventional quinacridone pigment, so that it can further meet a wide range of color tone requirements. Also, as a result of examining the basic physical properties as a pigment,
The novel tetrahydroquinacridine derivative represented by the general formula [1] is particularly excellent in light resistance and heat resistance as compared with conventional quinacridone pigments (for example, comparative compounds [1] and [2]). The feature is that it can be used for a wide range of applications.
以下、本発明を実施例により詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
〔合成例１〕 5,7,12,14−テトラヒドロ−7,14−ジシアノメチレン−
キノ［2,3−ｂ］アクリジン（化合物No.1）の合成 5,12−ジヒドロ−キノ［2,3−ｂ］アクリジン−7,14
−ジオン0.5g,マロノニトリル1.94gをプロピオン酸無水
物200mlに添加し、160〜165℃で８時間攪拌した。反応
終了後、室温まで冷却し、析出した結晶をメタノールで
洗浄し、青色結晶性粉末として融点300℃以上の化合物
0.29g（収率45％）を得た。[Synthesis Example 1] 5,7,12,14-tetrahydro-7,14-dicyanomethylene-
Synthesis of Quino [2,3-b] acridine (Compound No. 1) 5,12-dihydro-quino [2,3-b] acridine-7,14
0.5 g of dione and 1.94 g of malononitrile were added to 200 ml of propionic anhydride, and the mixture was stirred at 160 to 165 ° C for 8 hours. After completion of the reaction, the mixture is cooled to room temperature, and the precipitated crystals are washed with methanol to obtain a compound having a melting point of 300 ° C. or more as blue crystalline powder.
0.29 g (yield 45%) was obtained.
〔合成例２〕 5,7,12,14−テトラヒドロ−5,12−ジメチル−7,14−ジ
シアノメチレン−キノ［2,3−ｂ］アクリジン（化合物N
o.2）の合成 5,12−ジヒドロ−5,12−ジメチル−キノ［2,3−ｂ］
アクリジン−7,14−ジオン1.6g,マロノニトリル6.2gを
無水酢酸500mlに添加し、135〜140℃で８時間攪拌し
た。反応終了後、室温まで冷却し、析出した結晶をメタ
ノールで洗浄した後、ニトロベンゼンから再結晶し、青
色結晶性粉末として融点300℃以上の化合物1.74g（収率
85％）を得た。Synthesis Example 2 5,7,12,14-Tetrahydro-5,12-dimethyl-7,14-dicyanomethylene-quino [2,3-b] acridine (compound N
Synthesis of o.2) 5,12-dihydro-5,12-dimethyl-quino [2,3-b]
1.6 g of acridine-7,14-dione and 6.2 g of malononitrile were added to 500 ml of acetic anhydride and stirred at 135 to 140 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and the precipitated crystals were washed with methanol and then recrystallized from nitrobenzene to give 1.74 g of a compound having a melting point of 300 ° C. or more as a blue crystalline powder (yield).
85%).
〔合成例３〕 5,7,12,14−テトラヒドロ−5,12−ジブチル−7,14−ジ
シアノメチレン−キノ［2,3−ｂ］アクリジン（化合物N
o.4）の合成 5,12,−ジヒドロ−5,12−ジブチル−キノ［2,3−ｂ］
アクリジン−7,14−ジオン1.2g,マロノニトリル3.7g,無
水酢酸30mlをＮ−メチルピロリドン250mlに添加し、135
〜140℃で20時間攪拌した。反応終了後、室温まで冷却
し、析出した結晶をメタノールで洗浄した後、ピリジン
から再結晶し、青色結晶性粉末として融点300℃以上の
化合物1.15g（収率78％）を得た。Synthesis Example 3 5,7,12,14-Tetrahydro-5,12-dibutyl-7,14-dicyanomethylene-quino [2,3-b] acridine (compound N
Synthesis of o.4) 5,12, -dihydro-5,12-dibutyl-quino [2,3-b]
Acridine-7,14-dione (1.2 g), malononitrile (3.7 g), and acetic anhydride (30 ml) were added to N-methylpyrrolidone (250 ml).
Stirred at ~ 140 ° C for 20 hours. After completion of the reaction, the mixture was cooled to room temperature, and the precipitated crystals were washed with methanol and recrystallized from pyridine to obtain 1.15 g (yield: 78%) of a compound having a melting point of 300 ° C. or higher as blue crystalline powder.
〔合成例４〕 5,7,12,14−テトラヒドロ−5,12−ジブチル−3,10−ジ
クロロ−7,14−ジシアノメチレン−キノ［2,3−ｂ］ア
クリジン（化合物No.6）の合成 5,12−ジヒドロ−5,12−ジブチル−3,10−ジクロロ−
キノ［2,3−ｂ］アクリジン−7,14−ジオン1.0g,マロノ
ニトリル2.7gをプロピオン酸無水物30mlに添加し、160
〜165℃で３時間攪拌した。反応終了後、室温まで冷却
し、析出した結晶をメタノールで洗浄した後、ニトロベ
ンゼンから再結晶し、青色結晶性粉末として融点264〜2
65℃の化合物0.90g（収率75％）を得た。Synthesis Example 4 Synthesis of 5,7,12,14-tetrahydro-5,12-dibutyl-3,10-dichloro-7,14-dicyanomethylene-quino [2,3-b] acridine (Compound No. 6) Synthesis 5,12-dihydro-5,12-dibutyl-3,10-dichloro-
Quino [2,3-b] acridine-7,14-dione (1.0 g) and malononitrile (2.7 g) were added to propionic anhydride (30 ml).
Stirred at 165165 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were washed with methanol, and then recrystallized from nitrobenzene to obtain a blue crystalline powder having a melting point of 264-2.
0.90 g (yield 75%) of the compound at 65 ° C. was obtained.
〔合成例５〕 5,7,12,14−テトラヒドロキノ−5,12−ジブチル−2,9−
ジメチル−7,14−ジシアノメチレン−キノ［2,3−ｂ］
アクリジン（化合物No.7）の合成 5,12−ジヒドロ−5,12−ジブチル−2,9−ジメチル−
キノ［2,3−ｂ］アクリジン−7,14−ジオン0.8g,マロノ
ニトリル2.3gを無水酢酸40mlに添加し、135〜140℃で９
時間攪拌した。反応終了後、室温まで冷却し、析出した
結晶をメタノールで洗浄した後、ニトロベンゼンから再
結晶し、青色結晶性粉末として融点300℃以上の化合物
0.89g（収率92％）を得た。Synthesis Example 5 5,7,12,14-tetrahydroquino-5,12-dibutyl-2,9-
Dimethyl-7,14-dicyanomethylene-quino [2,3-b]
Synthesis of acridine (Compound No. 7) 5,12-dihydro-5,12-dibutyl-2,9-dimethyl-
0.8 g of quino [2,3-b] acridine-7,14-dione and 2.3 g of malononitrile were added to 40 ml of acetic anhydride, and the solution was added at 135-140 ° C for 9 hours.
Stirred for hours. After completion of the reaction, the mixture was cooled to room temperature, and the precipitated crystals were washed with methanol, and then recrystallized from nitrobenzene to obtain a compound having a melting point of 300 ° C or higher as a blue crystalline powder.
0.89 g (92% yield) was obtained.
本発明の方法によって合成したテトラヒドロキナクリ
ジン誘導体を表１に示す。Table 1 shows tetrahydroquinacridine derivatives synthesized by the method of the present invention.
実施例1.耐光性および耐熱性試験 得られたテトラヒドロキナクリジン誘導体について、
耐光性および耐熱性を調べ、他の高級赤色顔料であるキ
ナクリドン（大日本インキ化学工業（株）製）比較化合
物［１］と比較した。 Example 1.Light resistance and heat resistance test Regarding the obtained tetrahydroquinacridine derivative,
The light resistance and heat resistance were examined, and compared with another high-grade red pigment, quinacridone (manufactured by Dainippon Ink and Chemicals, Inc.) comparative compound [1].
１）5,7,12,14−テトラヒドロ−5,12−ジメチル−7,14
−ジシアノメチレン−キノ［2,3−ｂ］アクリジン（化
合物No.2）をメラミンアルキド樹脂で塗料化し、アルミ
板上に展色して試料とし、アトラスウエザオメーターCI
35により。耐光性試験を行った。450時間という過酷な
条件下で試験し、グレースケールで判定した結果、化合
物No.2の耐光性はキナクリドン顔料とほぼ同等以上であ
ることが明らかになった（表２）。1) 5,7,12,14-tetrahydro-5,12-dimethyl-7,14
-Dicyanomethylene-quino [2,3-b] acridine (compound No. 2) is coated with a melamine alkyd resin and painted on an aluminum plate to obtain a sample.
By 35. A light fastness test was performed. The test was carried out under the harsh condition of 450 hours, and as judged by the gray scale, it was found that the light fastness of Compound No. 2 was almost equal to or higher than that of the quinacridone pigment (Table 2).
２）5,7,12,14−テトラヒドロ−5,12−ジメチル−7,14
−ジシアノメチレン−キノ［2,3−ｂ］アクリジン（化
合物No.2）の耐熱挙動をキナクリドン顔料と比較するた
め、示差熱重量分析（DTA,TGA）を行なった。測定は、
顔料の実用上から空気中で行い、測定機器はマック・サ
イエンスTG−DTA2000型を使用した。試料は、白金皿上
に10〜15mg秤量し、開放状態で室温から700℃まで15℃/
minで昇温して熱分解曲線図１および図２を得た。その
結果、化合物No.2は、キナクリドン顔料と比較し、約34
5℃から熱変化をうけることが明らかになった。顔料の
実用耐熱性を問題にする場合、その温度はせいぜい300
℃までと考えられており、化合物No.2が320℃までまっ
たく重量変化を受けていないことから、耐熱性に優れて
いることが明らかになった。2) 5,7,12,14-tetrahydro-5,12-dimethyl-7,14
Differential thermogravimetric analysis (DTA, TGA) was performed to compare the heat resistance behavior of -dicyanomethylene-quino [2,3-b] acridine (Compound No. 2) with quinacridone pigment. The measurement is
Practical use of the pigment was carried out in the air, and the measuring instrument used was Mac Science TG-DTA2000. The sample is weighed 10-15 mg on a platinum dish, and 15 ° C /
The temperature was raised in min to obtain thermal decomposition curves 1 and 2. As a result, Compound No. 2 was compared with the quinacridone pigment by about 34%.
It became clear that it was subject to thermal change from 5 ℃. If the practical heat resistance of the pigment is an issue, the temperature should be at most 300.
° C, and Compound No. 2 did not undergo any weight change up to 320 ° C, indicating that it was excellent in heat resistance.
更にメラミンアルキド樹脂での耐熱性試験（200℃,30
分）を行い、変退色度をグレースケールで判定した（表
２）。その結果、200℃における化合物No.2の耐熱性
は、キナクリドン顔料とほぼ同等以上であることが明ら
かになった。In addition, heat resistance test with melamine alkyd resin (200 ℃, 30
Min), and the degree of discoloration was evaluated in a gray scale (Table 2). As a result, it was revealed that the heat resistance of Compound No. 2 at 200 ° C. was almost equal to or higher than that of the quinacridone pigment.
図１は本発明による化合物No.2の耐熱挙動を示すグラ
フ、図２は市販のキナクリドン顔料の耐熱挙動を示すグ
ラフである。FIG. 1 is a graph showing the heat resistance behavior of Compound No. 2 according to the present invention, and FIG. 2 is a graph showing the heat resistance behavior of a commercially available quinacridone pigment.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07D 471/04 C09B 48/00 ＣＡＰＬＵＳ ＲＥＧＩＳＴＲＹ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C07D 471/04 C09B 48/00 CAPLUS REGISTRY
Claims (2)
ルキル基、アルコキシ基を表わし、R1,R2およびR3は同
一でも異なってもよい。R4,R5はそれぞれ水素原子、ア
ルキル基、アルケニル基、アラルキル基およびアリール
基を表わし、R4およびR5は同一でも異なってもよい。） で表わされるテトラヒドロキナクリジン誘導体。1. The general formula [1] (Wherein R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 1 , R 2 and R 3 may be the same or different. R 4 and R 5 are each A hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and R 4 and R 5 may be the same or different.)
ルキル基、アルコキシ基を表わし、R1,R2およびR3は同
一でも異なってもよい。R4,R5はそれぞれ水素原子、ア
ルキル基、アルケニル基、アラルキル基およびアリール
基を表わし、R4およびR5は同一でも異なってもよい。） で表わされるキナクリドン誘導体をマロニトリルと反応
させることを特徴とする 一般式［１］ （式中、R1,R2,R3,R4およびR5は前記の意味を持つ。） で表わされるテトラヒドロキナクリジン誘導体の製造
法。2. The general formula [2] (Wherein R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R 1 , R 2 and R 3 may be the same or different. R 4 and R 5 are each A hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group and an aryl group, and R 4 and R 5 may be the same or different.) A quinacridone derivative represented by the following general formula [1]: ] (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 have the above-mentioned meanings.) A method for producing a tetrahydroquinacridine derivative represented by the following formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2275286A JP3000110B2 (en) | 1990-10-16 | 1990-10-16 | Tetrahydroquinacridine derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2275286A JP3000110B2 (en) | 1990-10-16 | 1990-10-16 | Tetrahydroquinacridine derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04154780A JPH04154780A (en) | 1992-05-27 |
| JP3000110B2 true JP3000110B2 (en) | 2000-01-17 |
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ID=17553311
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2275286A Expired - Fee Related JP3000110B2 (en) | 1990-10-16 | 1990-10-16 | Tetrahydroquinacridine derivative and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3000110B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060854A (en) * | 2010-11-25 | 2011-05-18 | 吉林大学 | Nitrile substituted quinacridone compounds and application thereof in organic solar cell |
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1990
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH04154780A (en) | 1992-05-27 |
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