JPH0322380B2 - - Google Patents
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- Publication number
- JPH0322380B2 JPH0322380B2 JP57149499A JP14949982A JPH0322380B2 JP H0322380 B2 JPH0322380 B2 JP H0322380B2 JP 57149499 A JP57149499 A JP 57149499A JP 14949982 A JP14949982 A JP 14949982A JP H0322380 B2 JPH0322380 B2 JP H0322380B2
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- JP
- Japan
- Prior art keywords
- group
- reaction
- compound
- substituted
- unsubstituted
- 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 - Lifetime
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- -1 silver halide Chemical class 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005917 acylation reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000001308 synthesis method Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000010933 acylation Effects 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical group ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical class NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JFCHSQDLLFJHOA-UHFFFAOYSA-N n,n-dimethylsulfamoyl chloride Chemical compound CN(C)S(Cl)(=O)=O JFCHSQDLLFJHOA-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GFFGYTMCNVMFAJ-UHFFFAOYSA-N 1-isocyanato-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(N=C=O)=C1 GFFGYTMCNVMFAJ-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- DOPJTDJKZNWLRB-UHFFFAOYSA-N 2-Amino-5-nitrophenol Chemical compound NC1=CC=C([N+]([O-])=O)C=C1O DOPJTDJKZNWLRB-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
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 description 1
- 125000004471 alkyl aminosulfonyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 150000008331 benzenesulfonamides Chemical group 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000001035 drying Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 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
- 238000000605 extraction 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
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 238000005694 sulfonylation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
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ããã補é æ¹æ³ã«é¢ãããDETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing phenolic cyan couplers.
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ãšã«ãã€ãŠã«ã©ãŒç»åãåŸãããšãã§ããã Generally, in silver halide color photographic light-sensitive materials, the color light-sensitive material after exposure is reduced with an aromatic primary amine color developing agent, and the oxidation product of the color developing agent produced at this time,
A color image can be obtained by reacting couplers capable of developing yellow, magenta, and cyan colors through oxidative coupling to form a dye image consisting of the three colors described above.
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ããããšãããã The couplers that develop yellow, magenta, and cyan colors are usually contained in the constituent layers of the color photosensitive material, but they may also be used together with the color developing agent and the like in a color developer. .
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ã«ãããã®ãäžè¬çã«ç¥ãããŠããã Among the above-mentioned couplers that develop three colors, the couplers used to form cyan dyes are phenolic couplers or naphthol couplers. As a method for producing a 5-acylamino type phenolic coupler, which is particularly useful among the above-mentioned phenolic couplers, the following reaction method is generally known.
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ãŠè±é¢å¯èœãªåºãè¡šããã In the above reaction formula, R 1 X represents an acylating agent or sulfonylating agent such as acyl chloride or sulfonyl chloride, and R 2 represents a palast group. Further, Y represents a hydrogen atom or a group capable of being eliminated during a coupling reaction with an oxidized product of a color developing agent.
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èŠãšãããã Attempts to variously change the type of residue of the acylating agent represented by R 1 without changing the palast group represented by R 2 in the above compound () resulted in the following:
This is a synthetic method that is always used in coupler manufacturing technology. However, according to traditional manufacturing methods,
If you try to change only R 1 without changing R 2 above, as shown in the reaction process above, at least () ~
It requires the four steps in parentheses and cannot be called an efficient manufacturing method. In addition, since the starting material compound () contains a nitro group, which is an electron-withdrawing group, the use of weak acylating agents or sulfonylating agents such as dimethylcarbamoyl chloride or dimethylsulfamoyl chloride may Compound () is difficult to obtain. Furthermore, since the above reaction step includes a reduction reaction, for example, benzoyl chloride having an aromatic ring is used as the acylating agent, and this aromatic ring has a reducing effect such as a nitro group or a benzyl group. However, if the compound is substituted, the nitro group or benzyl group, which should not be reduced, will also be subjected to the reduction action, so the desired compound () will not be obtained. become. Also, since compound () is easily oxidized,
Isolation is difficult, and therefore the ballast group introduction reaction must be carried out in the atmosphere of the reduction reaction solution, or cumbersome operations such as introducing nitrogen gas are required.
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ååšããã There are several drawbacks to the well-known method for producing the above-mentioned phenolic cyan couplers.
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ãšã«ããã Therefore, an object of the present invention is to eliminate the drawbacks of the conventional methods, namely, to eliminate the troublesome operation, and to be efficient.
Furthermore, it is an object of the present invention to provide an improved method for producing phenolic couplers, which yields highly pure synthetic products.
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ã€ãã As a result of various studies, the present inventors have found that the above object can be achieved by reacting a 5-acylamino-2-aminophenol compound with an acylating agent or a sulfonylating agent. .
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ããã«è¡šç€ºãããã That is, when the method for producing a phenolic cyan coupler according to the present invention is expressed as a chemical reaction, it is expressed as follows.
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ãã In the above reaction formula, R 11 (R 12 )N-X 0 represents an acylating agent or a sulfonylating agent, and specifically, R 11 and R 12 are each a hydrogen atom, a lower alkyl group, a substituted or unsubstituted represents a substituted phenyl group,
They may be the same or different,
X 0 is âCO, âCOX 1 , âCOOR 13 , âCS, â
Represents a group arbitrarily selected from SO2X1 , X1 represents a halogen atom, R13 represents a substituted or unsubstituted phenyl group, and Link represents -CO- or -SO2- .
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ãããåºãè¡šããã R 2 represents a ballast group, preferably a straight or branched alkyl group having 4 to 30 carbon atoms (for example, t
-butyl group, n-octyl group, t-octyl group,
n-dodecyl group, etc.), alkenyl group, aralkyl group, aralkenyl group, alkoxyalkyl group,
It represents a substituted or unsubstituted cycloalkyl group, a 5- or 6-membered heterocyclic group, or a group represented by the following general formula ().
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ã¯ïŒã®æŽæ°ãããããè¡šããã General formula () In the formula, J is an oxygen atom or a sulfur atom, R6 is a linear or branched alkyl group having 1 to 20 carbon atoms,
R 7 is a hydrogen atom, a halogen atom (preferably chloro, bromo), an alkyl group {preferably a linear or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl, tert-butyl, tert-pentyl, tert-octyl, dodecyl, pentadecyl)}, aryl groups (e.g. phenyl), heterocyclic groups (preferably nitrogen-containing heterocyclic groups), aralkyl groups (e.g. benzyl,
phenethyl), alkoxy groups {preferably linear or branched alkyloxy groups having 1 to 20 carbon atoms (e.g., methoxy, ethoxy, tert-butyloxy, octyloxy, decyloxy, dodecyloxy)}, aryloxy groups (e.g., phenoxy), hydroxy group, acyloxy group {preferably substituted or unsubstituted alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy, benzoyloxy)}, carboxy group, alkoxycarbonyl group (preferably substituted or unsubstituted carbon straight-chain or branched alkyloxycarbonyl having 1 to 20 carbon atoms), aryloxycarbonyl group (preferably substituted or unsubstituted phenoxycarbonyl), mercapto group, alkylthio group (preferably straight-chain or branched alkyloxycarbonyl having 1 to 20 carbon atoms) (branched substituted or unsubstituted benzenesulfonyl), acyl group (preferably linear or branched allylcarbonyl having 1 to 20 carbon atoms), acylamino group (preferably linear or branched alkylcarbonyl having 1 to 20 carbon atoms) , substituted or unsubstituted benzenecarboxamide), sulfonamide group (preferably a linear or branched substituted or unsubstituted alkylsulfonamide group having 1 to 20 carbon atoms, substituted or unsubstituted benzenesulfonamide group), carbamoyl group (preferably linear or branched alkylaminocarbonyl having 1 to 20 carbon atoms, substituted or unsubstituted phenylaminocarbonyl), sulfamoyl group (preferably linear or branched alkylaminosulfonyl having 1 to 20 carbon atoms), (substituted or unsubstituted phenylaminosulfonyl), m represents an integer of 1 to 4, and l represents an integer of 0 or 1, respectively.
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ã®ïœãè¡šããã In addition, Y is a hydrogen atom or a group that can be eliminated during the coupling reaction with the oxidized product of the color developing agent (for example, a halogen atom (e.g., chlorine, bromine, fluorine, etc.), an oxygen atom or a nitrogen atom at a direct coupling position). Examples include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, and more specific examples include,
U.S. Pat.
No. 117422, No. 50-130441, No. 51-108841, No. 117422, No. 50-130441, No. 51-108841, No.
No. 50-120334, No. 52-18315, No. 53-52423,
53-105226 and other publications}.
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ããšãã§ããã The 5-acylamino-2-aminophenol used in the production of the compound (), which is the target phenolic cyan coupler in the present invention, has the production shown in the compound () above, and this compound is a 5-nitrocyanic coupler. It can be synthesized by the following steps using -2-aminophenol as a starting material.
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åãè¡šããã In the above reaction formula, R 2 and Y are as described above, and Z represents a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, etc.), an alkoxy group (e.g., methoxy group, ethoxy group, etc.), or a halogen atom. .
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ãã®ã§ããã That is, the method for producing a phenolic cyan coupler of the present invention is characterized in that an acylating reagent is applied to 2-aminophenol into which a ballast group has been introduced at the 5-position to acylate the amino group at the 2-position. The process is naturally different from the conventional production method in which an acyl group is first introduced into the amino group at the 2-position, and then a ballast group is substituted into the amino group at the 5-position. It is meant to be.
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ãããã€åŸãããååç©ã®çŽåºŠãé«ãã And in the step of producing the compound (),
There are no various disadvantages in the synthesis technology that are found in the conventional manufacturing process described above, the operation is simple, the yield is high, and the purity of the obtained compound is also high.
次ã«äžèšè£œé å·¥çšã«ã€ãé 次説æããã Next, the above manufacturing steps will be sequentially explained.
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ã§åŸãããã(1) Synthesis method of compound (V-2) from compound (-1) An acylation reaction is performed on the above-mentioned compound (-1) using a commonly used acylating agent. A preferred acylating reagent is benzyl chloroformate, which is used in a range of about 0.9 equivalents to 2.0 equivalents, preferably 1.0 equivalents to 1.5 equivalents, and the reaction temperature is 10°C to
A temperature of 100°C and a reaction time of 1 to 5 hours are appropriate.
Examples of the base used in the reaction catalyst include organic bases such as pyridine, triethylamine, and quinoline, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium acetate. The amount is 1.0
The range is from equivalent to 4.0 equivalent. These bases do not necessarily have to be used. As the reaction solvent, solvents used in normal acylation reactions, such as DMF,
Acetone, ethyl acetate, acetonitrile, benzene, acetic acid, etc. are suitable. The most preferred reaction conditions are to add 1.2 mol of benzyl chloroformate to compound (-1), and boil and reflux the mixture using acetonitrile as a solvent without using a base. In this way, compound (-2) can be obtained in good yield.
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ããã(2) Synthesis method of compound (V-3) from compound (-2) Although this reaction is a reduction, chemical reduction using hydrazine or iron is particularly preferred. The reduction reaction using hydrazine can be carried out, for example, according to the method described in Journal of the Chemical Society of Japan, 1975, No. 7, p. 1223. Regarding the reduction reaction with iron, reduced iron equivalent to 3 to 30 equivalents of compound (-2) is used, preferably 3 to 10 equivalents.
Equivalent range. The reaction temperature is 60° to 110°C, and the solvent used is preferably hydrofuran or dioxane.
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ãã(3) Synthesis method of compound (-4) from compound (-3) This reaction step is an acylation reaction, but the reaction conditions are the same as in (1) above by simply changing the acylating agent.
It is preferable to carry out the reaction under the same conditions as in the case of .
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ãŠãããšèããããã(4) Synthesis method of compound () from compound (-4) The reaction in this step can be carried out under normal hydrogenolysis reaction conditions. Preferred conditions for this reaction include using methanol, ethanol, or tetrahydrofuran as a solvent, and using palladium-carbon as a catalyst in a range of 5 to 50% relative to compound (-4), and allowing the reaction to occur at room temperature and pressure. . Although carbamic acid is thought to be produced as a reaction intermediate in this reaction step, the final product can be obtained in the next step without the need for any treatment that causes decarboxylation (e.g., by addition of acid). Therefore, it is considered that the decarboxylation reaction occurs under the reaction conditions of the above-mentioned hydrogenolysis or the post-treatment conditions of the reaction.
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ãã The manufacturing process for compound (), which is a raw material for the synthesis of compound (), which is the phenolic cyan coupler of the present invention, is as described in detail above.
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ã€ããŠè¿°ã¹ãã Next, a synthetic method for producing the compound (2), which is a phenolic cyan coupler according to the present invention, from the compound (2), which is a feature of the present invention, will be described.
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ãããã The above reaction is as shown in the chemical reaction formula above,
This is carried out by reacting the compound () with an acylating reagent R 11 (R 12 )N-X 0 . So above R 11
(R 12 ) When an acylating reagent having a halogen atom -CO- group or a halogen atom -SO 2 - group as N-X 0 is used, 1.0 for the compound ()
Equivalents to 2.0 equivalents of acylating reagent are used,
Preferably it is in the range of 1.0 equivalent to 1.5 equivalent. The appropriate reaction temperature is 10° to 100°C, and the reaction time is 1 to 24 hours. In addition, as a base for the reaction catalyst,
Organic bases such as pyridine, triethylamine, quinoline, and sodium hydroxide, potassium hydroxide,
Inorganic bases such as sodium carbonate and sodium acetate are used, and the amount used is preferably 1 to 10 equivalents based on the compound (). However, the purpose of the present invention can be achieved even without the need for these bases. In addition, as a solvent, a solvent normally used in an acylation or sulfonylation reaction is used, but in the present invention, a pyridine solvent or a
Schotten-Bauman reaction conditions may also be used.
In addition, as the acylation reagent R 11 (R 12 )N-X 0 -
When using an acylation reagent having an NCS group or a -NCO group, the acylation reaction can be carried out using reaction conditions used for isocyanate reactions and isothiocyanate reactions. . Further above
When R 11 (R 12 )N-X 0 is used as an acylating reagent having a -CO 2 R 5 group, the acylating reagent is used in an equivalent amount or slightly in excess of the compound (),
Imidazole is present as a reaction catalyst in an amount of 0.1 to 1.0 equivalents relative to the compound (), and benzene, toluene, or xylene is used as a solvent.
The acylation reaction is carried out at a reaction temperature of 80° to 150°C.
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ã¢ã·ã«ååå¿ãè¡ãªãããšãã§ããã Alternatively, without using the above solvent,
Also preferred is a method in which the phenol derivative produced is distilled off under reduced pressure. Also acylation reagent
When R 1
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ã¯ãããã«ãã€ãŠéå®ããããã®ã§ã¯ãªãã Specific examples of the phenolic cyan coupler according to the present invention obtained by the production process and reaction conditions described in detail above are described below, but the present invention is not limited thereto.
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·äœçã«åæäŸãšããŠèšèŒããã(Exemplary compound) Next, the method for synthesizing the compound (), which is a raw material for synthesizing the phenolic cyan coupler according to the present invention, will be described in more detail as a synthesis example.
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åºäœ250ïœãåŸããSynthesis Example 1 Synthesis of 2-amino-5-[α-(2,4-di-t-pentylphenoxy)butanamide]phenol 154 g of 2-amino-5-nitrophenol and 570 g of benzyl chloroformate (30% toluene solution) were boiled and refluxed in 1500 ml of acetonitrile for 5 hours.
After refluxing, acetonitrile was distilled off under reduced pressure, water was added to the residue, and solids were collected. The obtained solid was recrystallized from methanol to obtain 250 g of a colorless solid having a melting point of 194° to 196°C.
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142ãã143âã®èãè¶è²ã®åºäœ203ïœãåŸãã Dissolve 288 g of the compound obtained in step a above in 3000 ml of tetrahydrofuran, and add 335 g of reduced iron to this solution.
After refluxing, the reaction mixture was filtered on filter paper lined with activated carbon. The solid obtained by drying the filtrate under reduced pressure was collected, washed with toluene, and the melting point
203 g of a light brown solid with a temperature of 142 DEG -143 DEG C. was obtained.
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ã€ãã Dissolve 561 g of the compound obtained in step b above in 5000 ml of ethanol, and add palladium-carbon to the solution.
112 g was added and hydrogenolysis was carried out at room temperature and pressure.
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ãšããŒã«ãåæ§ã«åŸãããšãã§ããã After absorbing the theoretical amount of hydrogen gas, the catalyst was filtered off. The filtrate was concentrated under reduced pressure, and the residue was crystallized from cyclohexane and collected by suction filtration.
380 g of a colorless solid with a melting point of 109 DEG -110 DEG C. was obtained. Other 2-amino-5-acylaminophenols could be similarly obtained using this method.
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æããã Hereinafter, the present invention will be explained in more detail with reference to Examples.
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Synthesis method of -(2,4-di-t-pentylphenoxy)butanamide]phenol (Exemplified Compound 2) 2-Amino-5- obtained in Synthesis Example 1
[α-(2,4-di-t-pentylphenoxy)butanamide] 42.7 g of phenol was dissolved in 500 ml of pyridine, 11.8 g of N,N-dimethylcarbamoyl chloride was added at room temperature, and the mixture was incubated at the same temperature for 24 hours. Stirred. After stirring, the reaction solution was poured into ice water containing dilute hydrochloric acid, and the separated oil was extracted with ethyl acetate.
After washing this extraction solution with water, only the ethyl acetate layer was separated, dried over magnesium sulfate, and concentrated to obtain an extract. This extracted reaction crude product was isolated and purified using silica gel column chromatography.
36.4 g of a slightly brown solid with a melting point of 127 DEG -128 DEG C. was obtained.
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ããã In this way, exemplified compound (2), which was difficult to obtain using conventional synthesis methods, could be obtained in good yield. In addition, N,N-dimethylsulfamoyl chloride may be used to react in the same manner,
Exemplary compound (1) (mp 130-131°C) could be obtained.
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Synthesis method of (2,4-di-t-pentylphenoxy)butanamide]phenol (Exemplary Compound 6) 2-Amino-5- obtained in Synthesis Example 1
[α-(2,4-di-t-pentylphenoxy)butanamide] 42.7 g of phenol and 16.4 g of m-nitrophenyl isocyanate were dissolved in 600 ml of toluene and allowed to stand at room temperature for 24 hours. After standing, toluene was distilled off under reduced pressure, and the reaction crude product was isolated and purified using silica gel column chromatography. Fractions containing the target product were collected and dried under reduced pressure, and the residue was crystallized by adding hexane-toluene. This is collected by suction filtration and is a pale yellow solid with a melting point of 146° to 148°C.
45.2g was obtained.
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ãåŸããExample 3 Synthesis method of 2-(4-ethylsulfonylphenyl)ureido-5-[α-(2,4-di-t-pentylphenyxy)butanamide]phenol (exemplified compound (10) According to Synthesis Example 1 above) The obtained 2-amino-5-
[α-(2,4-di-t-pentylphenoxy)butanamide] 42.7 g of phenol and phenyl-p-
30.5 g of ethylsulfonylphenyl carpamate and 1.4 g of imidazole were dissolved in 600 ml of toluene and boiled under reflux for 2 hours. After refluxing, the reaction solution was concentrated under reduced pressure, and the crude product was isolated and purified using silica gel column chromatography. 553g light brown caramel
I got it.
Claims (1)
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åºãè¡šããã[Claims] 1. A method for producing a phenolic cyan coupler, which comprises reacting a 5-acylamino-2-aminophenol compound with an acylating agent or sulfonylating agent represented by the following general formula [A]. . General formula [A] R 11 (R 12 )N-X 0 In the formula, R 11 and R 12 each represent a hydrogen atom, a lower alkyl group, or a substituted or unsubstituted phenyl group, and may be the same or different. X 0 is âCO, âCOX 1 , âCOOR 13 , âCS, â
Represents a group arbitrarily selected from SO 2 X 1 , where X 1 represents a halogen atom and R 13 represents a substituted or unsubstituted phenyl group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14949982A JPS5939859A (en) | 1982-08-27 | 1982-08-27 | Preparation of phenolic cyan coupler |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14949982A JPS5939859A (en) | 1982-08-27 | 1982-08-27 | Preparation of phenolic cyan coupler |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5939859A JPS5939859A (en) | 1984-03-05 |
JPH0322380B2 true JPH0322380B2 (en) | 1991-03-26 |
Family
ID=15476484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14949982A Granted JPS5939859A (en) | 1982-08-27 | 1982-08-27 | Preparation of phenolic cyan coupler |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5939859A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2788770B1 (en) | 1999-01-21 | 2001-02-16 | Oreal | NOVEL CATIONIC 2-SULFONYLAMINOPHENOLS, THEIR USE AS A COUPLER FOR OXIDATION DYE, COMPOSITIONS COMPRISING THE SAME AND DYEING METHODS |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55163537A (en) * | 1979-05-07 | 1980-12-19 | Konishiroku Photo Ind Co Ltd | Forming method of cyan dye image |
-
1982
- 1982-08-27 JP JP14949982A patent/JPS5939859A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55163537A (en) * | 1979-05-07 | 1980-12-19 | Konishiroku Photo Ind Co Ltd | Forming method of cyan dye image |
Also Published As
Publication number | Publication date |
---|---|
JPS5939859A (en) | 1984-03-05 |
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