FI76342B - FRAMEWORK FOR FRAME STATION 4-AZAFTALIDFOERENINGAR. - Google Patents
FRAMEWORK FOR FRAME STATION 4-AZAFTALIDFOERENINGAR. Download PDFInfo
- Publication number
- FI76342B FI76342B FI831866A FI831866A FI76342B FI 76342 B FI76342 B FI 76342B FI 831866 A FI831866 A FI 831866A FI 831866 A FI831866 A FI 831866A FI 76342 B FI76342 B FI 76342B
- Authority
- FI
- Finland
- Prior art keywords
- process according
- formula
- compound
- carbon atoms
- anhydride
- Prior art date
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- -1 pyrrolidino, piperidino Chemical group 0.000 claims description 50
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- YSJHADWSLVFGGT-UHFFFAOYSA-N 7h-furo[3,4-b]pyridin-5-one Chemical class C1=CC=C2C(=O)OCC2=N1 YSJHADWSLVFGGT-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- MCQOWYALZVKMAR-UHFFFAOYSA-N furo[3,4-b]pyridine-5,7-dione Chemical compound C1=CC=C2C(=O)OC(=O)C2=N1 MCQOWYALZVKMAR-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 6
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012430 organic reaction media Substances 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 229960000583 acetic acid Drugs 0.000 description 9
- 239000011592 zinc chloride Substances 0.000 description 9
- 235000005074 zinc chloride Nutrition 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- VIHJMAPRLIOYER-UHFFFAOYSA-N 5h-furo[3,4-b]pyridin-7-one Chemical class C1=CN=C2C(=O)OCC2=C1 VIHJMAPRLIOYER-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- MOVCYDNEZZZSLV-UHFFFAOYSA-N 2-methyl-1-octylindole Chemical compound C1=CC=C2N(CCCCCCCC)C(C)=CC2=C1 MOVCYDNEZZZSLV-UHFFFAOYSA-N 0.000 description 2
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- BETNPSBTDMBHCZ-UHFFFAOYSA-N 1-(chloromethyl)-2,4-dimethylbenzene Chemical compound CC1=CC=C(CCl)C(C)=C1 BETNPSBTDMBHCZ-UHFFFAOYSA-N 0.000 description 1
- OPAHUBUOHKIOOL-UHFFFAOYSA-N 1-butyl-2-methylindole Chemical compound C1=CC=C2N(CCCC)C(C)=CC2=C1 OPAHUBUOHKIOOL-UHFFFAOYSA-N 0.000 description 1
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 1
- XMOWAIVXKJWQBJ-UHFFFAOYSA-N 1-ethyl-2-methylindole Chemical compound C1=CC=C2N(CC)C(C)=CC2=C1 XMOWAIVXKJWQBJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000220479 Acacia Species 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012435 aralkylating agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229940075417 cadmium iodide Drugs 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940013688 formic acid Drugs 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- OGEFOJOVOASOPB-UHFFFAOYSA-N mercury strontium Chemical compound [Hg].[Sr] OGEFOJOVOASOPB-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005506 phthalide group Chemical group 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229940095574 propionic acid Drugs 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- 229940005605 valeric acid Drugs 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
-
- 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
-
- 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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Color Printing (AREA)
- Indole Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
7 6 3 4 27 6 3 4 2
Menetelmä 4-atsaftalidiyhdisteiden valmistamiseksi Förfarande för framställning av 4-azaftalidföreningarMethod for the preparation of 4-azaphthalide compounds For the preparation of 4-azaphthalide compounds
Keksinnön kohteena on uusi menetelmä atsaftalidiyhdisteiden valmistamiseksi, joita voidaan käyttää värinmuo-5 dostajina paine- tai lämpöherkissä merkintäaineissa.The invention relates to a new process for the preparation of azaphthalide compounds which can be used as colorants in pressure- or heat-sensitive markers.
Paineherkissä, hiilettömissä kopiointijärjestelmissä kromogeenisen värinmuodostajän, kuten esimerkiksi kristal-liviolettilaktonin, bentsoyylileukometyleenisinen, ftali-dien tai fluoraanien öljyinen liuos on eristetty tavanomai-10 sesti paineella rikottaviin mikrokapseleihin, jotka voivat esiintyä joko erillisellä siirtoarkilla kerroksena toisistaan riippuvaisen kopiointiarkkiparin muodostamiseksi, tai jotka voivat esiintyä itse kopionvastaanottoarkin herkistetyllä puolella itsereagoivan paperiarkin muodostamiseksi.In pressure-sensitive, carbon-free copying systems, an oily solution of a chromogenic color former, such as crystalline violet lactone, benzoyl leukomethylene, phthalides, or fluoranes, is conventionally isolated by self-sealing. on the sensitized side to form a self-reactive sheet of paper.
15 Tällaisissa paineherkissä kopiontijärjestelmissä käy tetään useimmiten kromogeenisena värinmuodostajana kristalli-violettilaktonia [3,3-bis-(4'-dimetyyliaminofenyyli)-6-dime-tyyliaminoftalidi).Kristalliviolettilaktonilla tuotettu painatus haalistuu tunnetusti hyvin nopeasti valon vaikutukses-20 ta, niin että on yritetty jatkuvasti löytää sille sopivaa korviketta.In such pressure-sensitive copying systems, crystal violet lactone [3,3-bis- (4'-dimethylaminophenyl) -6-dimethylaminophthalide) is most often used as the chromogenic color former. The printing produced with crystal violet lactone is known to fade so rapidly that constantly find a suitable substitute for it.
Hyviä korviketuotteita, jotka muodostavat tyydyttävän sinisen painatuksen, jolla on parantunut valonkestävyys,ovat atsaftalidit, jotka sisältävät 3 asemassa aminofenyyli- ja in-25 dolyylisubstituentin. Näiden värinmuodostajien valmistus tuottaa kuitenkin aina 4- ja 7-atsaftalidien isomeeriseoksia. Vaikka näillä isomeeriseoksilla voidaan saada aikaan valon-kestävyyden parannus ja samalla myös reaktiivisuuden vähenemisen pienentyminen (CB-väheneminen), esiintyy kuitenkin 30 yleensä paineherkkien merkintämateriaalien valmistuksessa kromogeenisen aineen sisältävien mikrokapseleiden ei- toivottua värin muuttumista, joka aiheutuu 7-atsaftalidi-isomee-rin läsnäolosta isomeeriseoksessa.Good substitute products that form a satisfactory blue print with improved lightfastness include azaphthalides containing an aminophenyl and indolyl substituent at the 3-position. However, the preparation of these color formers always produces isomeric mixtures of 4- and 7-azaphthalides. Although these isomer mixtures can provide an improvement in light fastness and at the same time a decrease in reactivity (CB reduction), in the manufacture of pressure sensitive marking materials, undesirable discoloration of chromogenic microcapsules due to the presence of the 7-azaphthalide isomer generally occurs. .
2 763422,76342
Nyt on havaittu, että voidaan saada isomeereistä vapaa 4-atsaftalidiyhdiste, kun välituotteena tarvittavan isomeereistä vapaan ketohapon valmistamiseksi saatetaan kinoliinihappoanhydridi reagoimaan indoliyhdisteen kanssa erityisessä orgaanisessa reaktioväliaineessa ja moniarvoisen metallin läsnäollessa.It has now been found that a isomer-free 4-azaphthalide compound can be obtained by reacting a quinoline anhydride with an indole compound in a specific organic reaction medium and in the presence of a polyvalent metal to prepare the isomer-free keto acid required as an intermediate.
Esillä olevan keksinnön kohteena on siten menetelmä kaavan Ϊ jsf'\ /\ / λ i A n_f: fi i v \/\\ λ/y (1)*The present invention therefore relates to a method of the formula Ϊ jsf '\ / \ / λ i A n_f: fi i v \ / \\ λ / y (1) *
i 11 5Li 11 5L
\ /--00 mukaisten 4-atsaftalidiyhdisteiden valmistamiseksi, missä kaavassa Y merkitsee vetyä, 1-12 hiiliatomia sisältävää alkyyliä, 1-4 hiiliatomia sisältävää alempialkyylikarbonyy-liä tai bentsyyliä, Z merkitsee vetyä, alempialkyyliä tai fenyyliä, xRlTo prepare 4-azaphthalide compounds according to the formula, wherein Y represents hydrogen, alkyl having 1 to 12 carbon atoms, lower alkylcarbonyl having 1 to 4 carbon atoms or benzyl, Z represents hydrogen, lower alkyl or phenyl, xR1
X on -NX is -N
^r2^ r 2
Rl ja R2 merkitsevät toisistaan riippumatta kulloinkin 1-12 hiiliatomia sisältävää alkyyliä, sykloheksyyliä tai bentsyyliä tai Ri ja R2 merkitsevät yhdessä niitä yhdistävän typpiatomin kanssa pyrrolidinoa, piperidinoa tai morfoli-noa, V merkitsee vetyä, alempialkyyliä tai alempialkoksia ja missä rengas A on substituoimaton tai halogeenilla subs-tituoitu.R1 and R2 independently of one another denote alkyl, cyclohexyl or benzyl having 1 to 12 carbon atoms or R1 and R2 together with the nitrogen atom connecting them denote pyrrolidino, piperidino or morpholino, V denotes hydrogen, lower alkyl or lower alkoxy and where ring A is substituted by halogen or halogen subs--substituted.
Menetelmä on tunnettu siitä, että korkeintaan 65θ£.η lämpötilassa saatetaan kinoliinihappoanhydridi reagoimaan kaavan 3 7 6 3 4 2 ___The process is characterized in that the quinolinic anhydride is reacted at a temperature of up to 65h £ .η with the formula 3 7 6 3 4 2 ___
i A fi Mi A fi M
VV (2),VV (2),
YY
mukaisen indoliyhdisteen kanssa, missä substituentei11a A, Y ja Z on yllä esitetty merkitys, moniarvoisen metallin epäorgaanisen tai orgaanisen metallisuolan läsnäollessa orgaanisessa reaktioväliaineessa, joka koostuu alempiali-faattisesta monokarboksyylihaposta tai tämän hapon nitrii-listä, kondensoidaan edelleen saatu reaktiotuote kaavan • · · (3),A, Y and Z are as defined above, in the presence of an inorganic or organic metal salt of a polyvalent metal in an organic reaction medium consisting of a lower aliphatic monocarboxylic acid or a nitrile of this acid, the reaction product obtained is further condensed. ,
VV
mukaisen yhdisteen kanssa, jossa substituenteilla X ja V on esitetty merkitys, ja säädetään saadun reaktioseoksen pH vähintään arvoon 6.with the substituents X and V as indicated and adjusting the pH of the resulting reaction mixture to at least 6.
Alempialkyyli ja alempialkoksi merkitsevät 4-atsafta-lidien tähteiden määrityksessä yleensä sellaisia ryhmiä tai ryhmän osia, jotka sisältävät 1-5, etenkin 1-3 hiiliatomia, kuten esim. metyyliä, etyyliä, n-propyyliä, isopropyyliä, n-butyyliä, sek.-butyyliä, tai amyyliä tai vast, metoksia, etoksia tai isopropoksia.Lower alkyl and lower alkoxy in the determination of 4-azaphthalide residues generally mean groups or parts of a group containing 1 to 5, in particular 1 to 3, carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. butyl, or amyl or vast, methoxy, ethoxy or isopropoxy.
Jos substituentit R^, R2 ja Y merkitsevät alkyyliryh-miä, niin ne voivat olla suoraketjuisia tai haarautuneita alkyylitähteitä. Esimerkkinä tällaisista alkyylitähteistä ovat metyyli, etyyli, n-propyyli, isopropyyli, n-butyyli, sek.-butyyli, amyyli, n-heksyyli, 2-etyyli-heksyyli, n-hep-tyyli, n-oktyyli, iso-oktyyli, n-nonyyli, isonomyyli tai n-dodekyyli.If the substituents R 1, R 2 and Y denote alkyl groups, they can be straight-chain or branched alkyl radicals. Examples of such alkyl residues are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl, isooctyl, n -nonyl, isonomyl or n-dodecyl.
V on mieluimmin meta-asemassa substituentin X suhteen.V is preferably in the meta position with respect to the substituent X.
Substituentit Ri ja R2 voivat olla erilaisia tai ne ovat mieluimmin identtisiä. Ri ja R2 merkitsevät mieluimmin bentsyyliä tai alempialkyyliä ja etenkin metyyliä tai etyyliä.The substituents R 1 and R 2 may be different or are preferably identical. R 1 and R 2 preferably denote benzyl or lower alkyl and especially methyl or ethyl.
4 76342 V on edullisesti vety, metyyli, metoksi tai ennen kaikkea etoksi.4,76342 V is preferably hydrogen, methyl, methoxy or, above all, ethoxy.
N-subtituentti Y on mieluimmin bentsyyli, asetyyli, propionyyli tai etenkin 1-8 hiiliatomia sisältävä alkyyli, kuten esim. n-oktyyli, n-butyyli, metyyli tai etyyli. Erittäin edullinen N-substituentti Y on etyyli tai n-oktyyli.The N-substituent Y is preferably benzyl, acetyl, propionyl or especially alkyl having 1 to 8 carbon atoms, such as, for example, n-octyl, n-butyl, methyl or ethyl. A highly preferred N substituent Y is ethyl or n-octyl.
Z on mieluimmin fenyyli tai ennen kaikkea metyyli.Z is preferably phenyl or above all methyl.
Bentseenirengas A on mieluimmin edelleen substituoi-maton.Preferably, the benzene ring A is further unsubstituted.
Halogeeni merkitsee esimerkiksi fluoria, bromia tai mieluimmin klooria.Halogen means, for example, fluorine, bromine or, preferably, chlorine.
Suoritettaessa keksinnön mukaista menetelmää käytetään reaktioon osallistuvia aineita mieluimmin kulloinkin molaarisin määrin.In carrying out the process according to the invention, the reactants are preferably used in each case in molar amounts.
Kaavan (1) mukaisten atsaftalidiyhdisteiden valmistus suoritetaan niin kutsutun yksiastiamenetelmän (Eintopfver-fahren) kahdessa vaiheessa ja jatkuvasti.The preparation of azaphthalide compounds of the formula (1) is carried out in two steps in a so-called one-pot process (Eintopfver-fahren) and continuously.
Ensimmäinen vaihe, jossa kinoiliinihappoanhydridi saatetaan reagoimaan kaavan (2) mukaisen indoliyhdisteen kanssa määritelmän mukaisissa orgaanisissa liuottimissa ja orgaanisen tai epäorgaanisen metallisuolan läsnäollessa, tapahtuu tarkoituksenmukaisesti 0-50°C:n lämpötilassa, mieluimmin huoneenlämpötilassa (17-30°C).The first step of reacting the quinoline anhydride with an indole compound of formula (2) in organic solvents as defined and in the presence of an organic or inorganic metal salt is conveniently carried out at a temperature of 0 to 50 ° C, preferably at room temperature (17 to 30 ° C).
Reaktion kesto riippuu lämpötilasta ja katalysaattorina käytetystä metallisuolasta ja liuottimesta ja on yleensä 1/2-10, mieluimmin 2-6 tuntia.The reaction time depends on the temperature and the metal salt and solvent used as a catalyst, and is usually 1 / 2-10, preferably 2-6 hours.
Keksinnön mukaisessa menetelmässä reaktioväliaineena käytetty alempialifaattinen monokarboksyylihappo on tarkoituksenmukaisesti reaktio-olosuhteissa nestemäinen kar- 76342 boksyylihappo, joka voi sisältää 1 - 5 hiiliatomia.The lower aliphatic monocarboxylic acid used as the reaction medium in the process of the invention is suitably a liquid carboxylic acid which may contain 1 to 5 carbon atoms under the reaction conditions.
Sopivia alifaattisia monokarboksyylihappoja, jotka muodostavat reaktioväliaineen, ovat muurahaishappo, etikkahappo, dikloorietikkahappo, propionihappo, voi-5 happo, isovoihappo, valeriaanahappo tai näiden happo jen seokset.Suitable aliphatic monocarboxylic acids which form the reaction medium include formic acid, acetic acid, dichloroacetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid or mixtures of these acids.
Vastaavina nitriileinä, joita voidaan käyttää samoin reaktioväliaineena keksinnön mukaisessa menetelmässä, tulevat kysymykseen esim. asetonitriili, pro-10 pionitriili tai butyronitriili.Suitable nitriles which can likewise be used as reaction medium in the process according to the invention are, for example, acetonitrile, propionitrile or butyronitrile.
Parhaimpana pidettyjä liuottimia ovat kuitenkin alifaattiset monokarboksyylihapot, jotka sisältävät 2-4 hiiliatomia, kuten esim. voihappo, isovoihappo, propionihappo tai etenkin etikkahappo tai myös näiden 15 karboksyylihappojen seokset. Keksinnön mukaisesti käy tetyt metallisuojat ovat peräisin edullisesti moniarvoisista metalleista, joiden atomipaino on 24 - 210, mieluummin 26 - 140 ja etenkin 26 - 120. Esimerkkeinä tällaisista metalleista ovat alumiini, barium, lyijy, 20 kadmium, kalsium, kromi, rauta, gallium, koboltti, kupari, magnesium, mangaani, molybdeeni, nikkeli, elohopea strontium, tantaali, titaani, vanadiini, wolframi, sinkki, tina ja sirkonium. Tällöin pidetään parhaimpina alumiinia, kalsiumia, kadmiumia, rautaa,kromia, 25 kobolttia, kuparia, nikkeliä, mangaania, strontiumia, tinaa ja sinkkiä. Näiden metallisuolojen anioninen osa johtuu tarkoituksenmukaisesti mineraalihapoista tai myös orgaanisista hapoista, ja se on esim. sulfaatti, halogenidi, nitraatti, formiaatti, asetaatti, propio-30 naatti, sitraatti tai stearaatti.However, the most preferred solvents are aliphatic monocarboxylic acids containing 2 to 4 carbon atoms, such as, for example, butyric acid, isobutyric acid, propionic acid or especially acetic acid or also mixtures of these carboxylic acids. The metal protectors used according to the invention are preferably derived from polyvalent metals having an atomic weight of 24 to 210, more preferably 26 to 140 and especially 26 to 120. Examples of such metals are aluminum, barium, lead, cadmium, calcium, chromium, iron, gallium, cobalt. , copper, magnesium, manganese, molybdenum, nickel, mercury strontium, tantalum, titanium, vanadium, tungsten, zinc, tin and zirconium. In this case, aluminum, calcium, cadmium, iron, chromium, 25 cobalt, copper, nickel, manganese, strontium, tin and zinc are considered the best. The anionic part of these metal salts is suitably derived from mineral acids or also from organic acids and is, for example, sulphate, halide, nitrate, formate, acetate, propionate, citrate or stearate.
Halogenidina voi tulla kysymykseen fluoridi, jodidi, bromidi tai mieluummin kloridi, sekä myös pseudohalogenidi, kuten rodanidi.Suitable halides are fluoride, iodide, bromide or, preferably, chloride, as well as a pseudohalide such as rhodanide.
Metallisuoloja voidaan käyttää yksinään tai seoksina.Metal salts can be used alone or in mixtures.
6 763426,76342
Parhaimpina pidettyjä metallisuoloja ovat ryhmään alumiini, kalsium, rauta, kadmium, koboltti, kupari, mangaani, nikkeli, tina ja sinkki kuuluvien metallien sulfaatit ja ennen kaikkea halogenidit, kuten esim. alu-5 miinikloridi, kalsiumkloridi, nikkelikloridi, koboltti- kloridi, rautakloridi, kuparikloridi, sinkkikloridi, tinakloridi, tinabromidi, mangaanikloridi, nikkelibro-midi, kalsiumfluoridi, kadmiumjodidi tai näiden seokset. Yleensä parhaimmat tulokset saadaan alumiinin, kalsiumin, 10 koboltin, raudan, kuparin tai sinkin kloridien läsnäollessa. Erityisen mielenkiintoisia ovat sinkkikloridi ja alumiinikloridi. Samoin on edullinen kalsiumkloridin ja sinkkikloridin seos, jolloin sekoitussuhde on mieluummin 1:9 - 2:1.Preferred metal salts include sulfates of metals belonging to the group of aluminum, calcium, iron, cadmium, cobalt, copper, manganese, nickel, tin and zinc, and above all halides, such as, for example, aluminum chloride, calcium chloride, nickel chloride, cobalt chloride, rhodium chloride, copper chloride, zinc chloride, tin chloride, tin bromide, manganese chloride, nickel bromide, calcium fluoride, cadmium iodide or mixtures thereof. In general, the best results are obtained in the presence of chlorides of aluminum, calcium, cobalt, iron, copper or zinc. Of particular interest are zinc chloride and aluminum chloride. Also preferred is a mixture of calcium chloride and zinc chloride, with a mixing ratio of preferably 1: 9 to 2: 1.
15 Metallisuolan osuus ensimmäisessä reaktiovai- heessa on edullisesti 10 - 100 mooli-%, mieluummin 12-50 mooli-% suhteessa käytettyyn kinoliinihappoan-hydridiin.The proportion of the metal salt in the first reaction step is preferably 10 to 100 mol%, more preferably 12 to 50 mol%, relative to the quinolinic anhydride used.
Ensimmäisen reaktiovaiheen päätyttyä reaktiotuote 20 (eristämätön ketohappo) kondensoidaan suoraan kaavan (3) mukaisen yhdisteen kanssa. Tämä toinen reaktiovaihe suoritetaan mieluummin niin,että reaktiokomponentit saatetaan reagoimaan happamen vedenpoistoaineen läsnäollessa 20 - 80°C:n lämpötilassa. Esimerkkeinä tällaisista konden-25 sointiaineista mainittakoon rikkihappo, fosforihappo, fos-forioksikloridi ja ennenkaikkea etikkahappoanhydridi. Käytettässä etikkahappoanhydridiä käytetään mieluummin 20 - 60°C:n lämpötiloja. Toisen vaiheen reaktionkesto on yleensä 1-4 tuntia, mieluummin li — 3 tuntia.At the end of the first reaction step, the reaction product 20 (uninsulated keto acid) is condensed directly with the compound of formula (3). This second reaction step is preferably carried out by reacting the reaction components in the presence of an acidic dehydrating agent at a temperature of 20 to 80 ° C. Examples of such condensing agents are sulfuric acid, phosphoric acid, phosphorus oxychloride and, above all, acetic anhydride. When using acetic anhydride, temperatures of 20 to 60 ° C are preferably used. The reaction time of the second step is generally 1 to 4 hours, preferably 1 to 3 hours.
30 Reaktioseos säädetään lopuksi pH-arvoon, joka on vähintään 6. Tähän tarkoitukseen sopivat tarkoituksenmukaisesti alkalit, kuten alkalimetallihyroksidit, esim. natrium- tai kaliumhydroksidi, ammoniakki tai alkalime-tal1ikarbonaatit tai -bikarbonaatit sekä näiden yhdistei-35 den seokset. Mieluummin pH saatetaan arvoon 7-11.The reaction mixture is finally adjusted to a pH of at least 6. Suitable for this purpose are alkalis, such as alkali metal hydroxides, e.g. sodium or potassium hydroxide, ammonia or alkali metal carbonates or bicarbonates, and mixtures of these compounds. Preferably, the pH is adjusted to 7-11.
7 763427 76342
Kaavan (1) mukaisen lopputuotteen eristys tapahtuu yleisesti tunnetulla tavalla erottamalla muodostunut sakka, pesemällä ja kuivaamalla tai käsittelemällä orgaanisilla liuottimilla, kuten esim. metanolilla tai iso-5 propanililla ja mahdollisesti kiteyttämällä tuote uudelleen .Isolation of the final product of formula (1) is carried out in a generally known manner by separating the precipitate formed, washing and drying or treating with organic solvents such as, for example, methanol or iso-5-propanil and, if appropriate, recrystallizing the product.
Jos 0R-| ja/tai V merkitsevät kaavan (1) mukaisessa reaktiotuotteessa kulloinkin hydroksyyliä, niin hydrok-syyliryhmä voidaan alkyloida tai aralkyloida jälkikäteen 10 substituenttien ja V määritelmän mukaisesti.If 0R- | and / or V in each case in the reaction product of the formula (1) denotes hydroxyl, so that the hydroxyl group can be alkylated or aralkylated afterwards according to the substituents and the definition of V.
Reaktiotuotteiden alkylointi tai aralkylointi, joissa V ja/tai 0R.| merkitsevät hydroksia, suoritetaan yleensä tunnettujen menetelmien mukaisesti. Esimerkiksi reaktio suoritetaan happoa sitovan aineen, kuten esim. alkalikar-15 bonaatin tai tertiäärisen typpiemäksen, kuten trietyyli-amiinin läsnäollessa ja mahdollisesti inertin, orgaanisen liuottimen, kuten esim. asetonin, isopropyylialkoholin, klocribentseenin ja nitrobentseenin läsnäollessa.Alkylation or aralkylation of reaction products in which V and / or 0R represent hydroxy, are generally carried out according to known methods. For example, the reaction is carried out in the presence of an acid scavenger such as alkali carbonate or a tertiary nitrogen base such as triethylamine and optionally in the presence of an inert organic solvent such as acetone, isopropyl alcohol, clocribenzene and nitrobenzene.
Sopivia alkylointiaineita ovat alkyylihalogenidit, 20 kuten esim. metyyli- tai etyylijodidi tai -kloridi, tai dialkyylisulfaatit, kuten esim. dimetyyli- tai dietyyli-sulfaatti. Aralkylointiaineiksi soveltuvat etenkin bent-syylikloridi ja vastaavat substituointituotteet, kuten esim. p-klooribentsyylikloridi tai 2,4-dimetyylibentsyy-25 likloridi, joita käytetään mieluummin ei-polaarisessa, orgaanisessa liuottimessa, kuten esim. bentseenissä, tolueenissatai ksyleenissä.Suitable alkylating agents are alkyl halides, such as, for example, methyl or ethyl iodide or chloride, or dialkyl sulfates, such as, for example, dimethyl or diethyl sulfate. Suitable aralkylating agents are, in particular, benzyl chloride and the corresponding substitution products, such as, for example, p-chlorobenzyl chloride or 2,4-dimethylbenzyl chloride, which are preferably used in a non-polar organic solvent such as, for example, benzene, toluene or xylene.
Uuden menetelmän eräs erittäin tarkoituksenmukainen sovellutusmuoto on sellainen, että kinoliinihappoanhydri-30 di liuotetaan tai suspendoidaan tyydytetyssä alifaatti- sessa C2-C4-monokarboksyylihapossa, etenkin etikkahapossa tai myös asetonitriilissä, siihen lisätään kaavan (2) mukainen indoliyhdiste ja seosta sekoitetaan moniarvoisen, atomipainoltaan 26 - 66 olevan metallin epäorgaanisen me- 8 76342 tallisuolan, etenkin metallihalogenidin, kuten esim. sinkkikloridin, kalsiumkloridin, alumiinikloridin, rau-takloridin, kobolttikloridin tai kuparidikloridin läsnäollessa huoneenlämpötilassa, mieluummin 2-6 tuntia.A very suitable embodiment of the new process is that the quinoline anhydride is dissolved or suspended in a saturated aliphatic C2-C4 monocarboxylic acid, especially acetic acid or also acetonitrile, a compound of formula (2) is added, in the presence of an inorganic metal salt of a metal, especially a metal halide such as, for example, zinc chloride, calcium chloride, aluminum chloride, ferric chloride, cobalt chloride or copper chloride at room temperature, preferably for 2-6 hours.
5 Tämän jälkeen lisätään kaavan (3) mukainen yhdiste ja reaktioseosta kuumennetaan etikkahappoanhydridin lisäyksen jälkeen 30 - 60°C:n lämpötilaan tarkoituksenmukaisesti 1-3 tuntia. Tämän jälkeen saatetaan esim. alkali-metallihydroksidilla tai vesipitoisella ammoniakilla 10 pH arvoon 7,5 - 9. Kaavan (1) mukainen saostunut 4-atsa-ftalidiyhdiste erotetaan ja kiteytetään haluttaessa uudelleen. Parhaimpina pidettyjä kaavan (1) mukaisia 4-atsa-ftalidiyhdisteitä, jotka valmistetaan keskeytymättömästi keksinnön mukaisen yksiastiamenetelmän mukaisesti, ovat 15 sellaiset, joissa V merkitsee vetyä, metyyliä, hydroksyyliä, metoksia tai ennen kaikkea etoksia ja X on kaavan -NR-|R2 mukainen ryhmä, jossa R-j ja R2 merkitsevät metyyliä Y on mieluummin 1 - 8 hiiliatomia sisältävä alkyyli, Z on ennen kaikkea metyyli ja rengas A on mieluummin substituoi-20 maton. Useimmin kaavan (1) mukaiset parhaimpina pidetyt atsaftalidiyhdisteet ovat sellaisissa, joissa ryhmäThe compound of formula (3) is then added and, after the addition of acetic anhydride, the reaction mixture is heated to a temperature of 30 to 60 ° C, suitably for 1 to 3 hours. The pH is then adjusted to 7.5-9 with, for example, alkali metal hydroxide or aqueous ammonia. The precipitated 4-aza-phthalide compound of formula (1) is separated off and recrystallized if desired. Preferred 4-aza-phthalide compounds of formula (1) which are prepared continuously according to the one-pot process of the invention are those in which V represents hydrogen, methyl, hydroxyl, methoxy or, above all, ethoxy and X is a group of formula -NR-R 2. wherein R 1 and R 2 represent methyl Y is preferably alkyl of 1 to 8 carbon atoms, Z is primarily methyl and ring A is preferably unsubstituted. Most often, the preferred azaphthalide compounds of formula (1) are those in which the group
, /-X T, / -X T
VV
merkitsee 2-etoksi-4-dimetyyliaminofenyyliä tai 2-etoksi- 4-dietyyliaminofenyyliä, Y merkitsee etyyliä tai oktyyliä ja Z merkitsee metyyliä ja rengas A on substituoimaton.represents 2-ethoxy-4-dimethylaminophenyl or 2-ethoxy-4-diethylaminophenyl, Y represents ethyl or octyl and Z represents methyl and ring A is unsubstituted.
25 Keksinnön mukaisen menetelmän suuri etu on se, että se voidaan toteuttaa teknisesti helposti ja se tuottaa eristämättä välillisesti muodostuneita ketohappoja puhtaita lopputuotteita erittäin hyvillä saannoilla. Etenkin saadaan 4-atsaftalodiyhdisteitä,jotka ovat täysin vapaita 30 kaavan 9 76342A great advantage of the process according to the invention is that it can be carried out technically easily and it produces pure end products without indirect isolation of pure keto acids in very good yields. In particular, 4-azaphthalodi compounds are obtained which are completely free of formula 9 76342
YY
t \ /\ /Z /% /*Xt \ / \ / Z /% / * X
T · · · ·T · · · ·
I A I! Il II II A I! Il II I
V’ ' ”\/\< (A) .· A ^ f S|·' $ 7 mukaisista vastaavista 7-atsaftalidi-isomeereistä.V '' ”\ / \ <(A). · A ^ f S | · 'of the corresponding 7-azaphthalide isomers according to $ 7.
Keksinnön mukaisen menetelmän mukaisesti valmistetut kaavan (1) mukaiset 4-atsaftalidiyhdisteet ovat normaalisti värittömiä tai korkeintaan hieman värillisiä.The 4-azaphthalide compounds of formula (1) prepared according to the process of the invention are normally colorless or at most slightly colored.
5 Ne soveltuvat ennen kaikkea nopeasti kehittyvine värin- muodostajina käytettäviksi lämpöherkissä tai etenkin paineherkissä merkintämateriaaleissa, joka voi olla sekä kopiointi- että rekisteröimismateriaalia. Kun nämä värinmuodostajat saatetaan kosketuksiin mieluummin 10 happamen kehittimen, s.o. elektroniakseptorin kanssa, niin ne muodostavat intensiivisiä, vihreänsinisiä, sinisiä tai violetinsinisiä värisävyjä, jotka ovat sekä savien, kuten myös etenkin fenolisten alustojen päällä sublimoinnin- ja valonkestäviä.5 They are particularly suitable for use as fast-developing color formers in heat-sensitive or, in particular, pressure-sensitive marking materials, which can be both copying and registration materials. When these color formers are contacted, preferably 10 acid generators, i. with an electron acceptor, so they form intense, green-blue, blue, or purple-blue hues that are both sublimation- and light-resistant on both clays and especially phenolic substrates.
15 Tähän asti DE-hakemusjulkaisusta 2 842 263 tai DE-hakemusjulkaisusta 3 116 815 tunnettuihin 4 - ja 7-atsaftalidien isomeeriseoksiin verrattuna, jolloin DE-hakemus julkaisun 3 116 815 mukaisesti häiritsevä 7-atsaf-talidiyhdiste on vähennetty 2%:seen osuuteen, on keksin-20 nön mukaisesti valmistetuille isomeereistä vapaille 4-atsaftalidiyhdisteille tunnusomaista se etu, että ne eivät saa aikaan valmistuksen yhteydessä eivätkä merkin-tämateriaalien varastoinnin aikana mitään ei-toivottua ennenaikaista värinmuutosta.15 Compared with the isomeric mixtures of 4- and 7-azaphthalides known to date from DE-A-2 842 263 or DE-A-3 116 815, in which the 7-azaphthalide compound which interferes with DE-A-3 116 815 has been reduced to 2%, The isomer-free 4-azaphthalide compounds prepared according to the invention are characterized by the advantage that they do not cause any undesired premature discoloration during manufacture or during storage of the labeling materials.
25 Seuraavissa esimerkeissä esitetyt prosenttimäärät koskevat painoa, mikäli toisin ei ole esitetty.25 The percentages given in the following examples are by weight, unless otherwise indicated.
10 7 6 3 4 210 7 6 3 4 2
Esimerkki 1: 20,0 g kinoliinihappoanhydridiä, 80 ml etikkahappoa, 20,3 g N-etyyli-2-metyyli-indolia ja 2,74 g sinkkikloridia sekoitetaan 5 tuntia 20°C:ssa.Example 1: 20.0 g of quinolinic anhydride, 80 ml of acetic acid, 20.3 g of N-ethyl-2-methylindole and 2.74 g of zinc chloride are stirred for 5 hours at 20 ° C.
Sitten lisätään 23,6 g 3-(Ν,Ν-dietyyliamino)-fenetolia 5 ja 30 ml etikkahappoanhydridiä, minkä jälkeen reaktio-seos lämmitetään 50-60°C:n lämpötilaan ja sekoitetaan 2 tuntia tässä lämpötilassa. Lisätään 170 ml 30 %:sta vesipitoista ammoniakkia ja 100 ml vettä, minkä jälkeen tuote saostuu taikinana ja se erotetaan. Taikinaan lisä-10 tään 160 ml isopropanolia ja keitetään tunnin ajan palautus jäähdyttäen . Jäähtymisen jälkeen erotetaan uudel-leenkiteytetty tuote, pestään isopropanolilla ja kuivataan. Saadaan 46,9 g isomeereistä vapaata, kaavan c2„523.6 g of 3- (Ν, Ν-diethylamino) phenethol 5 and 30 ml of acetic anhydride are then added, after which the reaction mixture is heated to 50-60 ° C and stirred for 2 hours at this temperature. 170 ml of 30% aqueous ammonia and 100 ml of water are added, after which the product precipitates as a dough and is separated. Add 160 ml of isopropanol to the dough and boil for one hour at reflux. After cooling, the recrystallized product is separated off, washed with isopropanol and dried. 46.9 g of isomer-free, of formula c2-5 are obtained
,0C H N.0C H N
2 52 l IJ CH3"fl il I2 52 l IJ CH3 "fl il I
v\ ^—\/ uu λ a; > '* ϊ % /— mukaista 4 atsaftalidiyhdistettä, jonka sulamispiste 15 on 156-158°C.v \ ^ - \ / uu λ a; > '* ϊ% / - 4 azaphthalide compounds with a melting point of 15-15-158 ° C.
Esimerkki 2: 6,0 g kinoliinihappoanhydridiä, 9,5 g N-oktyyli-2-metyyli-indolia ja 0,56 g sinkkikloridia sekoitetaan 30 ml:an kanssa etikkahappoa 5 tuntia 20°C:ssa. Sitten lisätään 6,6 g 3-dietyyliaminofenetolia ja 8 ml 20 etikkahappoanhydridiä, minkä jälkeen seosta sekoitetaan 2\ tuntia 50°C:ssa. Lisätään 30%:sta vesipitoista ammoniakkia, minkä jälkeen tuote saostuu. Tämä erotetaan ja kiteytetään uudelleen isopropanolista. Saadaan 16,5 g isomeereistä vapaata kaavan 11 76342 n-C H K 17 OC H. CH 'Example 2: 6.0 g of quinolinic anhydride, 9.5 g of N-octyl-2-methylindole and 0.56 g of zinc chloride are mixed with 30 ml of acetic acid for 5 hours at 20 ° C. 6.6 g of 3-diethylaminophenol and 8 ml of acetic anhydride are then added, after which the mixture is stirred for 2 hours at 50 ° C. 30% aqueous ammonia is added, after which the product precipitates. This is separated and recrystallized from isopropanol. 16.5 g of isomer-free n-C H K 17 OC H. CH 'of formula 11 76342 are obtained.
(C H 1 r ^ ' 7 2 5 3 N(C H 1 r ^ '7 2 5 3 N
<C2H5)2N“T ; V V \ ^ J — '\ } (12) ,K.<^ i il y \/—io mukaista 4-atsaftalidiyhdistettä, jonka sulamispiste on 113-118°C.<C2H5) 2N 'T; A 4-azaphthalide compound according to (V), having a melting point of 113-118 ° C.
Jos käytetään sinkkikloridin 0,56 g:n sijasta 0,30 g kupari(II)-dikloridia tai 0,53 g alumiinitriklo-5 ridia ja menetellään muutoin esimerkissä esitetyllä ta valla, niin saadaan 15,9 g tai vast. 16,8 g kaavan (12) mukaista 4-atsaftalidiyhdistettä, jonka sulamispiste on 113-116°C tai vast. 115-119°C.If 0.30 g of copper (II) dichloride or 0.53 g of aluminum trichloride is used instead of 0.56 g of zinc chloride and the procedure is otherwise as described in the example, 15.9 g or the like are obtained. 16.8 g of a 4-azaphthalide compound of the formula (12) having a melting point of 113-116 ° C or the like. 115-119 ° C.
Esimerkki 3: 1,5 g kinoliinihappoanhydridiä, 2,3 g 10 N-oktyyli-2-metyyli-indolia, 10 ml jääetikkaaa ja seosta, jossa on 0,11 g kalsiumkloridia ja 0,14 g sinkkikloridia, sekoitetaan 5 tuntia 20°C:ssa. Sitten lisätään 1,6 g 3-die-tyyliaminofenetolia ja 2 ml etikkahappoanhydridiä, minkä jälkeen reaktioseosta sekoitetaan 2J tuntia 50°C:ssa. Li-15 sätään 30%:sta vesipitoista ammoniakkia, minkä jälkeen tuote saostuu. Tämä erotetaan vesipitoisesta faasista ja kiteytetään uudelleen isopropanolista. Saadaan 3,8 g kaavan (12) mukaista isomeereistä vapaata 4-atsaftalidiyh-distettä, sp. 114-117°C.Example 3: 1.5 g of quinolinic anhydride, 2.3 g of 10 N-octyl-2-methylindole, 10 ml of glacial acetic acid and a mixture of 0.11 g of calcium chloride and 0.14 g of zinc chloride are stirred for 5 hours at 20 ° C. :in. 1.6 g of 3-diethylaminophenol and 2 ml of acetic anhydride are then added, after which the reaction mixture is stirred for 2 hours at 50 ° C. Li-15 is adjusted to 30% aqueous ammonia, after which the product precipitates. This is separated from the aqueous phase and recrystallized from isopropanol. 3.8 g of an isomer-free 4-azaphthalide compound of the formula (12) are obtained, m.p. 114-117 ° C.
20 Jos käytetään esitetyn metallisuolaseoksen sijasta 0,19 g rautatrikloridia tai 0,14 g kobolttidikloridia ja menetellään muutoin esimerkissä esitetyllä tavalla, niin saadaan 3,3 g tai vast. 3,8 g kaavan (12) mukaista 4-atsa-ftalidiyhdistettä, sp. 113-117°C tai vast. 113-116°C.If 0.19 g of ferric trichloride or 0.14 g of cobalt dichloride are used instead of the metal salt mixture shown and otherwise treated as described in the example, 3.3 g or the like are obtained. 3.8 g of a 4-aza-phthalide compound of formula (12), m.p. 113-117 ° C or resp. 113-116 ° C.
25 Esimerkki 4: 8 g kinoliinihappoanhydridiä, 1,1 g sinkkikloridia, 40 ml etikkahappoa ja 9,95 g N-butyyli-2-metyyli-indolia sekoitetaan 5 tuntia 20-23°C:ssa. Tämän 12 76342 jälkeen lisätään 9,3 g 3-(N,N-dietyyliamino)-fenetolia ja 7,5 ml etikkahappoanhydridiä. Sitten reaktioseosta sekoitetaan 2 tuntia 50-60°C:ssa. Reaktion loputtua neutraloidaan etikkahapan liuos 30%:sella vesipitoi-5 della ammoniakilla, jolloin reaktiotuote eroaa. Vesipitoisen faasin poistamisen jälkeen raakatuote liuote taan jääetikassa ja se saostetaan jälleen 30%:sella vesipitoisella ammoniakilla. Kiteytetään uudelleen etanolista, jolloin saadaan 16,8 g isomeereistä vapaa- 10 ta,kaavan n-C,H 14 9Example 4: 8 g of quinolinic anhydride, 1.1 g of zinc chloride, 40 ml of acetic acid and 9.95 g of N-butyl-2-methylindole are stirred for 5 hours at 20-23 ° C. After this 12,76342, 9.3 g of 3- (N, N-diethylamino) phenethol and 7.5 ml of acetic anhydride are added. The reaction mixture is then stirred for 2 hours at 50-60 ° C. After completion of the reaction, the acetic acid solution is neutralized with 30% aqueous ammonia, whereupon the reaction product separates. After removal of the aqueous phase, the crude product is dissolved in glacial acetic acid and reprecipitated with 30% aqueous ammonia. Recrystallization from ethanol gives 16.8 g of isomer-free, n-C, H149
A A AA A A
(13) I .....JJ CH3 '3 i N(C2H5)2 v aV y i'Y> Λ mukaista 4-atsaftalidiyhdistettä, sp. 152-154°C.(13) A 4-azaphthalide compound according to I ..... JJ CH3 '3 i N (C2H5) 2 v aV y i'Y>,, m.p. 152-154 ° C.
Esimerkki 5: Liuos, jossa on 3 g kaavan (11) mukaista 4-atsaftalidiyhdistettä 80 g:ssa di-isopropyylinafta-liinia ja 17 g kerosiiniä, mikrokapseloidaan sinänsä tun-15 netulla tavalla gelatiinilla ja arabikumilla koaservaation avulla, minkä jälkeen ei esiinny mitään muodostavien mik-rokapseleiden värinmuutosta. Saadut mikrokapselit sekoitetaan tärkkelysliuoksen kanssa ja levitetään paperiarkille. Toinen paperiarkki päällystetään etusivulta feno-20 lihartsilla, joka toimii värinkehittimenä. Ensimmäinen, mikrokapseleita sisältävä paperiarkki ja toinen värinke-hittimellä päällystetty paperi asetetaan päällekkäin päällysteet vierekkäin. Saadaan paineherkkä kopiointipaperi, joka ei muuta väriään myöskään varastoinnin yhteydessä.Example 5: A solution of 3 g of a 4-azaphthalide compound of formula (11) in 80 g of diisopropylnaphthalene and 17 g of kerosene is microencapsulated in a manner known per se with gelatin and acacia by coacervation, without any constituents. discoloration of microcapsules. The resulting microcapsules are mixed with the starch solution and applied to a sheet of paper. The second sheet of paper is coated on the front with feno-20 meat resin, which acts as a color developer. A first sheet of paper containing microcapsules and a second paper coated with a dye hit are superimposed on the coatings side by side. A pressure-sensitive copy paper is obtained which does not change color even during storage.
25 Kirjoittamalla käsin tai kirjoituskoneella kohdistetaan ensimmäiseen arkkiin painetta, ja heti kehittyy kehitti-mellä päällystetylle arkille intensiivinen sininen kopio, 13 76342 joka on erittäin valonkestävä.25 By typing by hand or typewriter, pressure is applied to the first sheet, and an intense blue copy, 13 76342, which is highly lightfast, immediately develops on the developer-coated sheet.
Vastaavia ei-väriään muuttavia paineherkkiä ko-piointipapereita ja kirjoittamalla intensiivisiä ja va-lonkestäviä sinisiä kopioita saadaan myös käytettäessä 5 jotakin toista valmistusesimerkeissä 2, 3 tai 4 saatua värinmuodostajaa.Corresponding non-color-changing pressure-sensitive copying papers and writing intense and light-resistant blue copies are also obtained using 5 other color formers obtained in Production Examples 2, 3 or 4.
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Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3509173A (en) * | 1967-01-30 | 1970-04-28 | Ncr Co | 3,3-bis-(indol-3-yl) phthalides |
JPS4916726B1 (en) * | 1970-12-28 | 1974-04-24 | ||
US4096176A (en) * | 1972-12-12 | 1978-06-20 | Sterling Drug Inc. | Benzoylbenzoic acids |
JPS49118514A (en) * | 1973-03-15 | 1974-11-13 | ||
JPS503426A (en) * | 1973-05-16 | 1975-01-14 | ||
JPS5031917A (en) * | 1973-07-24 | 1975-03-28 | ||
CH594511A5 (en) * | 1976-01-16 | 1978-01-13 | Ciba Geigy Ag | |
CA1110244A (en) * | 1977-09-29 | 1981-10-06 | Troy E. Hoover | Synthesis of chromogenic indolylphenyldihydrofuropyridin-one compounds |
IE49314B1 (en) * | 1978-12-11 | 1985-09-18 | Sterling Drug Inc | Substituted furopyridinones and furopyrazinones as color formers in pressure-sensitive and thermal imaging systems |
US4275905A (en) * | 1978-12-29 | 1981-06-30 | Appleton Papers Inc. | Pressure-sensitive record material |
DK536979A (en) * | 1978-12-29 | 1980-06-30 | Appleton Paper Inc | CHROMOGENT MATERIALS AND PROCEDURES FOR PRODUCING THEREOF |
JPS56151597A (en) * | 1980-04-28 | 1981-11-24 | Yamamoto Kagaku Gosei Kk | Recording material |
JPS57212092A (en) * | 1981-06-23 | 1982-12-27 | Yamada Kagaku Kogyo Kk | Color-forming recording material |
-
1983
- 1983-04-07 CH CH1868/83A patent/CH652733A5/en not_active IP Right Cessation
- 1983-05-25 FI FI831866A patent/FI76342C/en not_active IP Right Cessation
- 1983-06-01 DE DE3319978A patent/DE3319978C2/en not_active Expired - Fee Related
- 1983-06-07 FR FR8309446A patent/FR2543955B1/en not_active Expired
- 1983-06-08 ES ES523098A patent/ES8407492A1/en not_active Expired
- 1983-06-08 GB GB08315666A patent/GB2138836B/en not_active Expired
- 1983-06-09 BE BE0/210964A patent/BE897007A/en not_active IP Right Cessation
- 1983-06-10 IT IT48477/83A patent/IT1171836B/en active
- 1983-06-14 JP JP58106605A patent/JPS59190993A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
GB2138836A (en) | 1984-10-31 |
IT1171836B (en) | 1987-06-10 |
IT8348477A0 (en) | 1983-06-10 |
FR2543955B1 (en) | 1986-04-11 |
GB2138836B (en) | 1986-07-23 |
FI831866A0 (en) | 1983-05-25 |
BE897007A (en) | 1983-12-09 |
ES523098A0 (en) | 1984-10-01 |
FI831866L (en) | 1984-10-08 |
CH652733A5 (en) | 1985-11-29 |
FR2543955A1 (en) | 1984-10-12 |
FI76342C (en) | 1988-10-10 |
DE3319978A1 (en) | 1984-10-11 |
DE3319978C2 (en) | 1995-03-09 |
ES8407492A1 (en) | 1984-10-01 |
JPH0316954B2 (en) | 1991-03-06 |
GB8315666D0 (en) | 1983-07-13 |
JPS59190993A (en) | 1984-10-29 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM | Patent lapsed |
Owner name: CIBA-GEIGY AG |