JPS621386B2 - - Google Patents
Info
- Publication number
- JPS621386B2 JPS621386B2 JP9118579A JP9118579A JPS621386B2 JP S621386 B2 JPS621386 B2 JP S621386B2 JP 9118579 A JP9118579 A JP 9118579A JP 9118579 A JP9118579 A JP 9118579A JP S621386 B2 JPS621386 B2 JP S621386B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- dye
- formula
- groups
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000013626 chemical specie Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000975 dye Substances 0.000 description 42
- 230000015572 biosynthetic process Effects 0.000 description 35
- 238000003786 synthesis reaction Methods 0.000 description 30
- -1 silver halide Chemical class 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005804 alkylation reaction Methods 0.000 description 9
- 125000001624 naphthyl group Chemical group 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 229940124530 sulfonamide Drugs 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- HPNKKTVEGUKEEG-UHFFFAOYSA-N n-(4-hexadecoxy-2-hydroxyphenyl)acetamide Chemical compound CCCCCCCCCCCCCCCCOC1=CC=C(NC(C)=O)C(O)=C1 HPNKKTVEGUKEEG-UHFFFAOYSA-N 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004442 acylamino group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 125000002971 oxazolyl group Chemical group 0.000 description 4
- 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 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000002948 undecyl 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])[H] 0.000 description 4
- RZKJWYDRDBVDJJ-UHFFFAOYSA-N 2-methyl-1,3-benzoxazol-6-ol Chemical compound C1=C(O)C=C2OC(C)=NC2=C1 RZKJWYDRDBVDJJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 125000000565 sulfonamide group Chemical group 0.000 description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- SULYEHHGGXARJS-UHFFFAOYSA-N 2',4'-dihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1O SULYEHHGGXARJS-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- BOMDYWWCQBJGDU-UHFFFAOYSA-N n-(5-tert-butyl-4-hexadecoxy-2-hydroxyphenyl)acetamide Chemical compound CCCCCCCCCCCCCCCCOC1=CC(O)=C(NC(C)=O)C=C1C(C)(C)C BOMDYWWCQBJGDU-UHFFFAOYSA-N 0.000 description 2
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003461 sulfonyl halides Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- WLDWSGZHNBANIO-UHFFFAOYSA-N 2',5'-Dihydroxyacetophenone Chemical class CC(=O)C1=CC(O)=CC=C1O WLDWSGZHNBANIO-UHFFFAOYSA-N 0.000 description 1
- JYDIMKQXBFZQAL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-5-nitrobenzenesulfonic acid Chemical compound COCCOC1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O JYDIMKQXBFZQAL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MOCMBTHPKMYRRK-UHFFFAOYSA-N 2-amino-4-tert-butyl-5-hexadecoxyphenol;hydrochloride Chemical compound Cl.CCCCCCCCCCCCCCCCOC1=CC(O)=C(N)C=C1C(C)(C)C MOCMBTHPKMYRRK-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- BRSSKYAQQBLTHL-UHFFFAOYSA-N 2-cyclohexylbenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1C1CCCCC1 BRSSKYAQQBLTHL-UHFFFAOYSA-N 0.000 description 1
- DQSHFKPKFISSNM-UHFFFAOYSA-N 2-methylbenzoxazole Chemical compound C1=CC=C2OC(C)=NC2=C1 DQSHFKPKFISSNM-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- FQPRUMXSHZSJGM-UITAMQMPSA-N 4-[(Z)-N-hydroxy-C-methylcarbonimidoyl]benzene-1,3-diol Chemical class O/N=C(/C)C1=CC=C(O)C=C1O FQPRUMXSHZSJGM-UITAMQMPSA-N 0.000 description 1
- MCWZWCWOKFQFBZ-UHFFFAOYSA-N 6-hexadecoxy-2-methyl-1,3-benzoxazole Chemical compound CCCCCCCCCCCCCCCCOC1=CC=C2N=C(C)OC2=C1 MCWZWCWOKFQFBZ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 CâOH Inorganic materials 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910006080 SO2X Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000001013 indophenol dye Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- ATAFOXBIKQRELK-UHFFFAOYSA-N n-(3-cyclohexyl-2,6-dihydroxyphenyl)acetamide Chemical compound CC(=O)NC1=C(O)C=CC(C2CCCCC2)=C1O ATAFOXBIKQRELK-UHFFFAOYSA-N 0.000 description 1
- SQVVMIQDMRVDNY-UHFFFAOYSA-N n-[4-hexadecoxy-2-hydroxy-5-(3-methylheptan-3-yl)phenyl]acetamide Chemical compound CCCCCCCCCCCCCCCCOC1=CC(O)=C(NC(C)=O)C=C1C(C)(CC)CCCC SQVVMIQDMRVDNY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- KLAKIAVEMQMVBT-UHFFFAOYSA-N p-hydroxy-phenacyl alcohol Natural products OCC(=O)C1=CC=C(O)C=C1 KLAKIAVEMQMVBT-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- ZEGCHJISUHKIKS-UHFFFAOYSA-M sodium;2-(2-methoxyethoxy)-5-nitrobenzenesulfonate Chemical compound [Na+].COCCOC1=CC=C([N+]([O-])=O)C=C1S([O-])(=O)=O ZEGCHJISUHKIKS-UHFFFAOYSA-M 0.000 description 1
- OUERFXCJVYJQJO-UHFFFAOYSA-M sodium;2-chloro-5-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=C(Cl)C(S([O-])(=O)=O)=C1 OUERFXCJVYJQJO-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
æ¬çºæã¯ã«ã©ãŒæå
ææã«çšããåæäžéäœã«
é¢ãããã®ã§ãããããã«è©³ããã¯ãããã²ã³å
éã®çŸåã«åŒç¶ãã¬ããã¯ã¹åå¿ã«ãã€ãŠãæ¡æ£
æ§è²çŽ ãæŸåºããååç©ã®äžéäœã«é¢ãããã®ã§
ããã ç¹éæ48â33826å·ã«ã¯ãè²çŽ æŸåºã¬ããã¯ã¹
ååç©ãçšããã«ã©ãŒæ¡æ£è»¢åè²å圢ææ³ãè¿°ã¹
ãããŠãããããã«èšèŒãããŠããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ãšã¯ãè²çŽ éšãšéæ¡æ£æ§ããšããŒã«
éšïŒãŸãã¯ããããŒã«éšïŒãšãïœâäœã§ã¹ã«ãã³
ã¢ããåºãä»ããŠçµåããŠããïœâã¹ã«ãã³ã¢ã
ãããšããŒã«ïŒãŸãã¯ïœâã¹ã«ãã³ã¢ããããã
ãŒã«ïŒã§ãããããããšæå æ§ããã²ã³åéä¹³å€
ãšå ±åãããŠé²å ãã次ãã§çŸåãããšãçŸåã
ããããã²ã³åééã«å¿ããŠããããã®ïœâã¹ã«
ãã³ã¢ããããšããŒã«ãŸãã¯ããããŒã«ãé žåã
ããããã®é žåäœã¯ãã¢ã«ã«ãªåŠç液ã®æ»æã«ã
ã€ãŠãæ¡æ£æ§ã®ã¹ã«ãã³ã¢ããåºãæããè²çŽ éš
ãšãéæ¡æ£æ§ãã³ãŸããã³ãŸãã¯éæ¡æ£æ§ããã
ããã³ãšã«å解ããããã®ããã«ããŠçããæ¡æ£
æ§è²çŽ ãååå±€ã«è»¢åããããšãããŠããããã
ããªãããæ¬çºæè ãã®è¿œè©Šã«ããã°ãäžè¿°ã®ïœ
âã¹ã«ãã³ã¢ããããšããŒã«ã¯ååãªè»¢åæ¿åºŠã
äžãé£ãããšãå€ãã€ãããŸããäžè¿°ã®ïœâã¹ã«
ãã³ã¢ããããããŒã«ã¯ãè²çŽ æŸåºåŸè±éåŠçã
è¡ã€ããšããŠããæå å±€åŽã«ïœâãããããã³ã
æ®åããŠé»è²ã¹ãã€ã³ãçãããããæå å±€åŽã«
æ®åããè²åããã¬ãŸãã¯ããžç»åãšããŠå©çšã
ãããšã¯ã§ããªãã ç¹éæ51â113624ã«ã¯ãïŒäœã«ã¢ã«ã³ãã·ã«åº
ã眮æãããïœâã¹ã«ãã³ã¢ããããšããŒã«ãªã
è²çŽ æŸåºã¬ããã¯ã¹ååç©ãèšèŒãããŠãããã
ã®ååç©ã¯åŸæ¥ã®ãã®ãããããªãåããæ§èœã
æããããè²çŽ ã®æŸåºèœåã®ç¹ã§æŽã«ãã€ããã®
æ¹è¯ãæãŸããŠãããããã«ãç¹éæ53â149328
ã«ã¯ãïŒäœã«ã¢ã«ã³ãã·ã«åºãïŒäœã«ã¡ãã«åºã
ãã€ãïœâã¹ã«ãã³ã¢ããããšããŒã«ãªãè²çŽ æŸ
åºã¬ããã¯ã¹ååç©ãèšèŒãããŠãããããã¯
ããè²çŽ ã®æŸåºèœåã®ç¹ã§ãã€ããã®æ¹è¯ãæãŸ
ããŠããã æ¬çºæã®ç®çã¯ç¬¬äžã«æ°èŠãªè²çŽ æŸåºã¬ããã¯
ã¹ååç©ã®äžéäœããã³ãã®åææ³ãæäŸããã
ãšã§ããã 第äºã«æ¡æ£è»¢åã«çšããå Žåé«ã転åæ¿åºŠãäž
ããè²çŽ æŸåºã¬ããã¯ã¹ååç©ã®äžéäœããã³ã
ã®åææ³ãæäŸããããšã§ããã 第äžã«è²çŽ æŸåºåŸã®é»è²ã®æ®è²ã®å°ãªããããª
æ®åè²çŽ åãäžããè²çŽ æŸåºã¬ããã¯ã¹ååç©ã®
äžéäœããã³ãã®åææ³ãæäŸããããšã«ããã 第åã«ãè²çŽ ã®æŸåºå¹çã®ããè²çŽ æŸåºã¬ãã
ã¯ã¹ååç©ã®äžéäœããã³ãã®åææ³ãæäŸãã
ããšã§ããã æ¬çºæè ãã¯ãäžèšäžè¬åŒïŒïŒã§è¡šãããã
ååç©ãäžèšã®ç®çãããæºè¶³ããããšãèŠåºã
ãã ãã ã R1ããã³R2ã¯ãåãã§ãç°ãªã€ãŠããŠãããã
ããããã¢ã«ãã«åºãŸãã¯è³éŠæåºãè¡šããïŒ
R1ãšR2ãšãçµåããŠç°ã圢æããŠãããïŒ R3ã¯ãæ°ŽçŽ ååãã¢ã«ãã«åºãŸãã¯è³éŠæåºã
è¡šããïŒ R4ã¯ãã¢ã«ãã«åºãŸãã¯è³éŠæåºãè¡šããïŒR5
ã¯æ°ŽçŽ ååãåã¯ã¢ã«ãã«åºãè¡šããïŒ ïœã¯ïŒïŒïŒãŸãã¯ïŒã§ããïŒ ãã€R1ïŒR2ïŒR3ïŒR4ããã³ïŒ²ïŒ ïœã®åèšççŽ æ°ã¯çŽ
ïŒä»¥äžã§ããïŒ R6ã¯ãã¡ãã«åºãè¡šããã R1ïŒããã³R2ïŒã§è¡šããããã¢ã«ãã«åºã®ççŽ
æ°ã¯ïŒã40奜ãŸããã¯ïŒã24ã§ãããçŽéã§ãå
æããŠãããããŸãç°ç¶ã§ããããããã«ããã
ã«çœ®æåºïŒäŸãã°ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Ž
é žåºãããã²ã³ååãããšããã·åºã眮æããšã
ãã·åºãã¢ã·ã«ã¢ããåºãªã©ïŒã眮æããŠããŠã
ãããR1ïŒããã³R2ïŒã®å¥œãŸããäŸãšããŠã¯ãã¡
ãã«åºããšãã«åºããããã«åºãããã«åºããã³
ãã«åºãããã·ã«åºããããã«åºããŠã³ãã·ã«
åºããã³ã¿ãã·ã«åºãããã¿ãã·ã«åºãªã©ã®çŽé
ã¢ã«ãã«åºïŒã€ãœãããã«åºãã€ãœããã«åºãïœ
âããã«åºãïœâã¢ãã«åºãããªãã³ãã«åºãªã©
ã®åæã¢ã«ãã«åºïŒãããããããR1ïŒããã³
R2ïŒã§è¡šããããè³éŠæåºã®äŸãšããŠã¯ãããšã
ã«åºã眮æããšãã«åºããããã«åºã眮æããã
ã«åºããããããããããã®çœ®æããšãã«åºãŸã
ã¯ãããã«åºã®çœ®æåºã®äŸãšããŠã¯ãã¢ã«ã³ãã·
åºãã·ã¢ãåºãæ°Žé žåºããããåºãã¢ã«ãã«åºãª
ã©ãããããããR1ãšR2ãçµåããŠç°ã圢æã
ãŠããå Žåã¯ãïŒã40å¡ç°å¥œãŸããã¯ïŒã12å¡ç°
ã圢æããŠããããšãæãŸããã R3ã§è¡šããããã¢ã«ãã«åºã®ççŽ æ°ã¯ïŒã40
奜ãŸããã¯ïŒã24ã§ãããçŽéã§ãåæããŠãã
ãããŸãç°ç¶ã§ããããããã«ããã«çœ®æåºïŒäŸ
ãã°ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºãããã²
ã³ååãããšããã·åºã眮æããšããã·åºãã¢ã·
ã«ã¢ããåºãªã©ïŒã眮æããŠããŠããããR3ã®
奜ãŸããäŸãšããŠã¯ãã¡ãã«åºããšãã«åºããã
ãã«åºãããã«åºããã³ãã«åºãããã·ã«åºãã
ããã«åºããŠã³ãã·ã«åºããã³ã¿ãã·ã«åºããã
ã¿ãã·ã«åºãªã©ã®çŽéã¢ã«ãã«åºïŒã€ãœãããã«
åºãã€ãœããã«åºãïœâããã«åºãïœâã¢ãã«
åºãããªãã³ãã«åºãªã©ã®åæã¢ã«ãã«åºïŒãã
ãããããR3ã§è¡šããããè³éŠæåºã®äŸãšããŠ
ã¯ãããšãã«åºã眮æããšãã«åºããããã«åºã
眮æãããã«åºããããããããããã®çœ®æããš
ãã«åºãŸãã¯ãããã«åºã®çœ®æåºã®äŸãšããŠã¯ã
ã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºããããåºãã¢
ã«ãã«åºãªã©ããããããã R4ã§è¡šããããã¢ã«ãã«åºã®ççŽ æ°ã¯ïŒã40
奜ãŸããã¯ïŒã24ã§ãããçŽéã§ãåæããŠãã
ãããŸãç°ç¶ã§ããããããã«ãããã«çœ®æåº
ïŒäŸãã°ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºãã
ãã²ã³ååãããšããã·åºã眮æããšããã·åºã
ã¢ã·ã«ã¢ããåºãªã©ïŒã眮æããŠããŠãããã
R4ã®å¥œãŸããäŸãšããŠã¯ãã¡ãã«åºããšãã«
åºããããã«åºãããã«åºããã³ãã«åºãããã·
ã«åºããããã«åºããŠã³ãã·ã«åºããã³ã¿ãã·ã«
åºãããã¿ãã·ã«åºãªã©ã®çŽéã¢ã«ãã«åºïŒã€ãœ
ãããã«åºãã€ãœããã«åºãïœâããã«åºãïœâ
ã¢ãã«åºãããªãã³ãã«åºãªã©ã®åæã¢ã«ãã«
åºïŒãããããããR4ã§è¡šããããè³éŠæåºã®
äŸãšããŠã¯ãããšãã«åºã眮æããšãã«åºããã
ãã«åºã眮æãããã«åºããããããããããã®
眮æããšãã«åºãŸãã¯ãããã«åºã®çœ®æåºã®äŸãš
ããŠã¯ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºããã
ãåºãã¢ã«ãã«åºãªã©ããããããã R5ã§è¡šããããã¢ã«ãã«åºã®ççŽ æ°ã¯ïŒã40
奜ãŸããã¯ïŒã24ã§ããã奜ãŸããäŸãšããŠã¯ã
ã¡ãã«åºããšãã«åºããããã«åºãããã«åºãã
ã³ãã«åºãããã·ã«åºããããã«åºããŠã³ãã·ã«
åºããã³ã¿ãã·ã«åºãããã¿ãã·ã«åºãªã©ã®çŽé
ã¢ã«ãã«åºïŒã€ãœãããã«åºãã€ãœããã«åºãïœ
âããã«åºãïœâã¢ãã«åºãããªãã³ãã«åºãªã©
ã®åæã¢ã«ãã«åºïŒãªã©ããããããã R5ã§è¡šããããã¢ãªãŒã«ããªåºã¯ã奜ãŸãã
ã¯ããšãã«ããªåºãŸãã¯çœ®æããšãã«ããªåºããŸ
ãã¯è€çŽ ç°ããªåºïŒäŸãã°ããã©ãŸãŒã«ç°ïŒã§ã
ãã R5ã§è¡šããããã¢ã·ã«ã¢ããåºã®äŸã¯ãã¢ã«
ãã«âCONHâåºãïŒçœ®æãŸãã¯ç¡çœ®æïŒããšã
ã«âCONHâåºã代衚çãªãã®ã§ããã äžèšã®çœ®æããšãã«åºã®çœ®æåºãšããŠãã¢ã«ã³
ãã·åºãã·ã¢ãåºãæ°Žé žåºããããåºãã¢ã«ãã«
åºãªã©ãæããããã R4ãšR5ïŒR1ãšR4ïŒR1ãšR5ïŒãçž®åç°ã圢æã
ãŠããŠããããããã®äŸã¯äŸç€ºååç©ã«ãã€ãŠæ
ãããšãªããããªãè³éŠæçåæ°ŽçŽ çž®åç°ã圢æ
ããã®ã¯ãæ®åéšåã«ã«ã©ãŒã¹ãã€ã³ãçããã®
ã§å¥œãŸãããªãã 奜ãŸããæ æ§ã«ãããŠã¯æ¬çºæã®ååç©ã¯ã次
ã®äžè¬åŒïŒïŒã§è¡šããããã ïŒãã ã5aã¯æ°ŽçŽ åååã¯R5ãšå矩ã®çœ®æåº
ãè¡šãããR1ïŒR2ïŒR3ïŒR4ããã³R6ã¯åŒïŒïŒ
ãšåçŸ©ïŒ æŽã«å¥œãŸããã¯äžè¬åŒïŒïŒã«ãããŠ
é¢ãããã®ã§ãããããã«è©³ããã¯ãããã²ã³å
éã®çŸåã«åŒç¶ãã¬ããã¯ã¹åå¿ã«ãã€ãŠãæ¡æ£
æ§è²çŽ ãæŸåºããååç©ã®äžéäœã«é¢ãããã®ã§
ããã ç¹éæ48â33826å·ã«ã¯ãè²çŽ æŸåºã¬ããã¯ã¹
ååç©ãçšããã«ã©ãŒæ¡æ£è»¢åè²å圢ææ³ãè¿°ã¹
ãããŠãããããã«èšèŒãããŠããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ãšã¯ãè²çŽ éšãšéæ¡æ£æ§ããšããŒã«
éšïŒãŸãã¯ããããŒã«éšïŒãšãïœâäœã§ã¹ã«ãã³
ã¢ããåºãä»ããŠçµåããŠããïœâã¹ã«ãã³ã¢ã
ãããšããŒã«ïŒãŸãã¯ïœâã¹ã«ãã³ã¢ããããã
ãŒã«ïŒã§ãããããããšæå æ§ããã²ã³åéä¹³å€
ãšå ±åãããŠé²å ãã次ãã§çŸåãããšãçŸåã
ããããã²ã³åééã«å¿ããŠããããã®ïœâã¹ã«
ãã³ã¢ããããšããŒã«ãŸãã¯ããããŒã«ãé žåã
ããããã®é žåäœã¯ãã¢ã«ã«ãªåŠç液ã®æ»æã«ã
ã€ãŠãæ¡æ£æ§ã®ã¹ã«ãã³ã¢ããåºãæããè²çŽ éš
ãšãéæ¡æ£æ§ãã³ãŸããã³ãŸãã¯éæ¡æ£æ§ããã
ããã³ãšã«å解ããããã®ããã«ããŠçããæ¡æ£
æ§è²çŽ ãååå±€ã«è»¢åããããšãããŠããããã
ããªãããæ¬çºæè ãã®è¿œè©Šã«ããã°ãäžè¿°ã®ïœ
âã¹ã«ãã³ã¢ããããšããŒã«ã¯ååãªè»¢åæ¿åºŠã
äžãé£ãããšãå€ãã€ãããŸããäžè¿°ã®ïœâã¹ã«
ãã³ã¢ããããããŒã«ã¯ãè²çŽ æŸåºåŸè±éåŠçã
è¡ã€ããšããŠããæå å±€åŽã«ïœâãããããã³ã
æ®åããŠé»è²ã¹ãã€ã³ãçãããããæå å±€åŽã«
æ®åããè²åããã¬ãŸãã¯ããžç»åãšããŠå©çšã
ãããšã¯ã§ããªãã ç¹éæ51â113624ã«ã¯ãïŒäœã«ã¢ã«ã³ãã·ã«åº
ã眮æãããïœâã¹ã«ãã³ã¢ããããšããŒã«ãªã
è²çŽ æŸåºã¬ããã¯ã¹ååç©ãèšèŒãããŠãããã
ã®ååç©ã¯åŸæ¥ã®ãã®ãããããªãåããæ§èœã
æããããè²çŽ ã®æŸåºèœåã®ç¹ã§æŽã«ãã€ããã®
æ¹è¯ãæãŸããŠãããããã«ãç¹éæ53â149328
ã«ã¯ãïŒäœã«ã¢ã«ã³ãã·ã«åºãïŒäœã«ã¡ãã«åºã
ãã€ãïœâã¹ã«ãã³ã¢ããããšããŒã«ãªãè²çŽ æŸ
åºã¬ããã¯ã¹ååç©ãèšèŒãããŠãããããã¯
ããè²çŽ ã®æŸåºèœåã®ç¹ã§ãã€ããã®æ¹è¯ãæãŸ
ããŠããã æ¬çºæã®ç®çã¯ç¬¬äžã«æ°èŠãªè²çŽ æŸåºã¬ããã¯
ã¹ååç©ã®äžéäœããã³ãã®åææ³ãæäŸããã
ãšã§ããã 第äºã«æ¡æ£è»¢åã«çšããå Žåé«ã転åæ¿åºŠãäž
ããè²çŽ æŸåºã¬ããã¯ã¹ååç©ã®äžéäœããã³ã
ã®åææ³ãæäŸããããšã§ããã 第äžã«è²çŽ æŸåºåŸã®é»è²ã®æ®è²ã®å°ãªããããª
æ®åè²çŽ åãäžããè²çŽ æŸåºã¬ããã¯ã¹ååç©ã®
äžéäœããã³ãã®åææ³ãæäŸããããšã«ããã 第åã«ãè²çŽ ã®æŸåºå¹çã®ããè²çŽ æŸåºã¬ãã
ã¯ã¹ååç©ã®äžéäœããã³ãã®åææ³ãæäŸãã
ããšã§ããã æ¬çºæè ãã¯ãäžèšäžè¬åŒïŒïŒã§è¡šãããã
ååç©ãäžèšã®ç®çãããæºè¶³ããããšãèŠåºã
ãã ãã ã R1ããã³R2ã¯ãåãã§ãç°ãªã€ãŠããŠãããã
ããããã¢ã«ãã«åºãŸãã¯è³éŠæåºãè¡šããïŒ
R1ãšR2ãšãçµåããŠç°ã圢æããŠãããïŒ R3ã¯ãæ°ŽçŽ ååãã¢ã«ãã«åºãŸãã¯è³éŠæåºã
è¡šããïŒ R4ã¯ãã¢ã«ãã«åºãŸãã¯è³éŠæåºãè¡šããïŒR5
ã¯æ°ŽçŽ ååãåã¯ã¢ã«ãã«åºãè¡šããïŒ ïœã¯ïŒïŒïŒãŸãã¯ïŒã§ããïŒ ãã€R1ïŒR2ïŒR3ïŒR4ããã³ïŒ²ïŒ ïœã®åèšççŽ æ°ã¯çŽ
ïŒä»¥äžã§ããïŒ R6ã¯ãã¡ãã«åºãè¡šããã R1ïŒããã³R2ïŒã§è¡šããããã¢ã«ãã«åºã®ççŽ
æ°ã¯ïŒã40奜ãŸããã¯ïŒã24ã§ãããçŽéã§ãå
æããŠãããããŸãç°ç¶ã§ããããããã«ããã
ã«çœ®æåºïŒäŸãã°ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Ž
é žåºãããã²ã³ååãããšããã·åºã眮æããšã
ãã·åºãã¢ã·ã«ã¢ããåºãªã©ïŒã眮æããŠããŠã
ãããR1ïŒããã³R2ïŒã®å¥œãŸããäŸãšããŠã¯ãã¡
ãã«åºããšãã«åºããããã«åºãããã«åºããã³
ãã«åºãããã·ã«åºããããã«åºããŠã³ãã·ã«
åºããã³ã¿ãã·ã«åºãããã¿ãã·ã«åºãªã©ã®çŽé
ã¢ã«ãã«åºïŒã€ãœãããã«åºãã€ãœããã«åºãïœ
âããã«åºãïœâã¢ãã«åºãããªãã³ãã«åºãªã©
ã®åæã¢ã«ãã«åºïŒãããããããR1ïŒããã³
R2ïŒã§è¡šããããè³éŠæåºã®äŸãšããŠã¯ãããšã
ã«åºã眮æããšãã«åºããããã«åºã眮æããã
ã«åºããããããããããã®çœ®æããšãã«åºãŸã
ã¯ãããã«åºã®çœ®æåºã®äŸãšããŠã¯ãã¢ã«ã³ãã·
åºãã·ã¢ãåºãæ°Žé žåºããããåºãã¢ã«ãã«åºãª
ã©ãããããããR1ãšR2ãçµåããŠç°ã圢æã
ãŠããå Žåã¯ãïŒã40å¡ç°å¥œãŸããã¯ïŒã12å¡ç°
ã圢æããŠããããšãæãŸããã R3ã§è¡šããããã¢ã«ãã«åºã®ççŽ æ°ã¯ïŒã40
奜ãŸããã¯ïŒã24ã§ãããçŽéã§ãåæããŠãã
ãããŸãç°ç¶ã§ããããããã«ããã«çœ®æåºïŒäŸ
ãã°ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºãããã²
ã³ååãããšããã·åºã眮æããšããã·åºãã¢ã·
ã«ã¢ããåºãªã©ïŒã眮æããŠããŠããããR3ã®
奜ãŸããäŸãšããŠã¯ãã¡ãã«åºããšãã«åºããã
ãã«åºãããã«åºããã³ãã«åºãããã·ã«åºãã
ããã«åºããŠã³ãã·ã«åºããã³ã¿ãã·ã«åºããã
ã¿ãã·ã«åºãªã©ã®çŽéã¢ã«ãã«åºïŒã€ãœãããã«
åºãã€ãœããã«åºãïœâããã«åºãïœâã¢ãã«
åºãããªãã³ãã«åºãªã©ã®åæã¢ã«ãã«åºïŒãã
ãããããR3ã§è¡šããããè³éŠæåºã®äŸãšããŠ
ã¯ãããšãã«åºã眮æããšãã«åºããããã«åºã
眮æãããã«åºããããããããããã®çœ®æããš
ãã«åºãŸãã¯ãããã«åºã®çœ®æåºã®äŸãšããŠã¯ã
ã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºããããåºãã¢
ã«ãã«åºãªã©ããããããã R4ã§è¡šããããã¢ã«ãã«åºã®ççŽ æ°ã¯ïŒã40
奜ãŸããã¯ïŒã24ã§ãããçŽéã§ãåæããŠãã
ãããŸãç°ç¶ã§ããããããã«ãããã«çœ®æåº
ïŒäŸãã°ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºãã
ãã²ã³ååãããšããã·åºã眮æããšããã·åºã
ã¢ã·ã«ã¢ããåºãªã©ïŒã眮æããŠããŠãããã
R4ã®å¥œãŸããäŸãšããŠã¯ãã¡ãã«åºããšãã«
åºããããã«åºãããã«åºããã³ãã«åºãããã·
ã«åºããããã«åºããŠã³ãã·ã«åºããã³ã¿ãã·ã«
åºãããã¿ãã·ã«åºãªã©ã®çŽéã¢ã«ãã«åºïŒã€ãœ
ãããã«åºãã€ãœããã«åºãïœâããã«åºãïœâ
ã¢ãã«åºãããªãã³ãã«åºãªã©ã®åæã¢ã«ãã«
åºïŒãããããããR4ã§è¡šããããè³éŠæåºã®
äŸãšããŠã¯ãããšãã«åºã眮æããšãã«åºããã
ãã«åºã眮æãããã«åºããããããããããã®
眮æããšãã«åºãŸãã¯ãããã«åºã®çœ®æåºã®äŸãš
ããŠã¯ãã¢ã«ã³ãã·åºãã·ã¢ãåºãæ°Žé žåºããã
ãåºãã¢ã«ãã«åºãªã©ããããããã R5ã§è¡šããããã¢ã«ãã«åºã®ççŽ æ°ã¯ïŒã40
奜ãŸããã¯ïŒã24ã§ããã奜ãŸããäŸãšããŠã¯ã
ã¡ãã«åºããšãã«åºããããã«åºãããã«åºãã
ã³ãã«åºãããã·ã«åºããããã«åºããŠã³ãã·ã«
åºããã³ã¿ãã·ã«åºãããã¿ãã·ã«åºãªã©ã®çŽé
ã¢ã«ãã«åºïŒã€ãœãããã«åºãã€ãœããã«åºãïœ
âããã«åºãïœâã¢ãã«åºãããªãã³ãã«åºãªã©
ã®åæã¢ã«ãã«åºïŒãªã©ããããããã R5ã§è¡šããããã¢ãªãŒã«ããªåºã¯ã奜ãŸãã
ã¯ããšãã«ããªåºãŸãã¯çœ®æããšãã«ããªåºããŸ
ãã¯è€çŽ ç°ããªåºïŒäŸãã°ããã©ãŸãŒã«ç°ïŒã§ã
ãã R5ã§è¡šããããã¢ã·ã«ã¢ããåºã®äŸã¯ãã¢ã«
ãã«âCONHâåºãïŒçœ®æãŸãã¯ç¡çœ®æïŒããšã
ã«âCONHâåºã代衚çãªãã®ã§ããã äžèšã®çœ®æããšãã«åºã®çœ®æåºãšããŠãã¢ã«ã³
ãã·åºãã·ã¢ãåºãæ°Žé žåºããããåºãã¢ã«ãã«
åºãªã©ãæããããã R4ãšR5ïŒR1ãšR4ïŒR1ãšR5ïŒãçž®åç°ã圢æã
ãŠããŠããããããã®äŸã¯äŸç€ºååç©ã«ãã€ãŠæ
ãããšãªããããªãè³éŠæçåæ°ŽçŽ çž®åç°ã圢æ
ããã®ã¯ãæ®åéšåã«ã«ã©ãŒã¹ãã€ã³ãçããã®
ã§å¥œãŸãããªãã 奜ãŸããæ æ§ã«ãããŠã¯æ¬çºæã®ååç©ã¯ã次
ã®äžè¬åŒïŒïŒã§è¡šããããã ïŒãã ã5aã¯æ°ŽçŽ åååã¯R5ãšå矩ã®çœ®æåº
ãè¡šãããR1ïŒR2ïŒR3ïŒR4ããã³R6ã¯åŒïŒïŒ
ãšåçŸ©ïŒ æŽã«å¥œãŸããã¯äžè¬åŒïŒïŒã«ãããŠ
ãåŒããã€ãœãããã«åºãïœâããã«åºã
ïœâã¢ãã«åºãã·ã¯ãããã·ã«åºãïŒâãšãã«â
ïŒâã¡ãã«ãã³ãã«åºãïœâãªã¯ãã«åºãŸãã¯
ïŒâã¡ãã«ãã³ãã«åºãïœâãªã¯ãã«åºãŸãã¯
ãåŒãã®å Žåã§ãããåäžè¬åŒ
ïŒïŒã«ãããŠR4ãç¡çœ®æã¢ã«ãã«åºãŸãã¯ã¢ãª
ãŒã«ãªãã·ã¢ã«ãã«åºïŒãããã®åºã®åã ã®å šç
çŽ æ°ãïŒã24ã®ãã®ããªãã§ã奜ãŸããïŒã®å Žå
ã§ãããåäžè¬åŒïŒïŒã«ãããŠïŒ²5aãæ°ŽçŽ å
åãã¢ã«ãã«åºãŸãã¯ã¢ã«ã³ãã·åºïŒãããã®åº
åã ã®å šççŽ æ°ãïŒã24ã®ãã®ããªãã§ã奜ãŸã
ãïŒãè¡šããå Žåã§ããã æ¬çºæã®ååç©ã®å ·äœäŸã以äžã«ç€ºãã åŒïŒïŒã§ç€ºãããååç©ã®åææ³ã®ä»£è¡šçãª
ãã®ãšããŠæ¬¡ã®å³åŒã®çµè·¯ããããããã çµè·¯ã«ã€ããŠèª¬æãããïŒïŒã®ããšãã¬ãŸ
ã«ã·ããŒã«èªå°äœãããããœåãéå 次ãã§ã¢ã»
ãã«åããããšã«ãã€ãŠååç©ïŒïŒãåŸããã
ããã®å段éã«ã€ããŠã¯ãW.M.McLamoreïŒJ.
Amer.Chem.Soc.ïŒ73ïŒ2225ã2230ïŒ1951ïŒã«ïŒ
âã·ã¯ãããã·ã«ã¬ãŸã«ã·ããŒã«ãããïŒâã¢ã»
ãã¢ããâïŒâã·ã¯ãããã·ã«ã¬ãŸã«ã·ããŒã«ã
åŸãå Žåã«èšèŒããŠããæäœãå¿çšããããšãã§
ããããªããµãŸãŒã«ç°ã®åœ¢æã¯ãååç©ïŒïŒã
ïœâãã«ãšã³ã¹ã«ãã³é žã®ããšãé žè§Šåªã®ããšã«
è¡ãããšãã§ããããªããµãŸãŒã«ç°ã®åœ¢æã«ã€ã
ãŠã¯ãç¹éæ52â153923ã®èšèŒãåèã«ãªãããª
ããµãŸãŒã«èªå°äœïŒïŒã®ïœâã¢ã«ãã«åã§ã¯ã
éåžžR4âïŒïŒžã¯ããã²ã³ååïŒãçšãè±ãã
ã²ã³åæ°ŽçŽ åå€ãšããŠããããªãŠã ã¢ã«ã³ãã·
ããçé žã«ãªãŠã ãªã©ã®å¡©åºæ§ç©è³ªã䜿çšããã
ãã®ã¢ã«ãã«åã®æ®µéã«ã€ããŠã¯ãç¹éæ52â
153923ã®èšèŒãåèã«ãªããååç©ïŒïŒã®ãªã
ãµãŸãŒã«ã®éç°ã«ãã€ãŠãã¢ã»ãã¢ããäœïŒïŒ
ãåŸãããšãã§ããã çµè·¯ã«ãããŠã¯ãã¬ãŸã«ã·ããŒã«èªå°äœãã
æ žã¢ã»ãã«åïŒããšãã°BF3âé ¢é žã®æ¡ä»¶ã§ïŒã
ãã®ã¡ãããããã·ã«ã¢ãã³ãšåå¿ãããŠãªãã·
ã ïŒXIIïŒãšãããååç©ïŒXIIïŒããé ¢é žäžå¡©åæ°Ž
çŽ ã¬ã¹ãå¹èŸŒãæ¡ä»¶ïŒãªãã·å¡©åãªã³åã¯äºå¡©å
ãªã³ãªã©ã§åŠçããããšã«ãã€ãŠãããã¯ãã³è»¢
äœâãªããµãŸãŒã«åœ¢æãåæã«è¡ããããããšã
ã§ããããã®ããã«ããŠåŸãååç©ïŒïŒã¯ãäž
èšã®çµè·¯ã«ãŠè¿°ã¹ãæ¹æ³ã§ãååç©ïŒïŒãžå°
ãããšãã§ããã çµè·¯ã«ãããŠã¯ãïŒïŒïŒâãžããããã·ã¢ã»
ãããšãã³èªå°äœïŒãã¡ãããã¢ã»ãã«åºãä»ã®
ã±ãã³æ®åºã§çœ®æããååç©ãåºçºç©è³ªãšããŠæ
çšã§ããããåæã®ããããããã¯ã¢ã»ãã«åºã
奜ãŸããïŒãã«ããããã·ã«ã¢ãã³ãåå¿ãã
ãŠããªãã·ã ïŒXIïŒãšããäžèšçµè·¯ã®ååç©
ïŒXIIïŒã®å Žåãšåæ§ã«ãããã¯ãã³è»¢äœâãªããµ
ãŸãŒã«åœ¢æãåæã«è¡ãããããçãããªããµãŸ
ãŒã«ïŒïŒãïœâã¢ã«ãã«åããŠååç©ïŒXI
ïŒãåŸãã«ã¯ãR6âïŒïŒžã¯ããã²ã³ååïŒ
ãçšããè±ããã²ã³åæ°ŽçŽ åå€ãšããŠããããªãŠ
ã ã¢ã«ã³ãã·ããããã¯çé žã«ãªãŠã ãªã©ã®å¡©åº
æ§ç©è³ªãçšããããã®ïœâã¢ã«ãã«åã®æ®µéã«ã€
ããŠã¯ãç¹éæ52â153923ã®èšèŒãåèã«ãªãã 次ãã§ãåžå¡©é žãªã©ã§åŠçããŠããªããµãŸãŒã«
ç°ãéç°ããããååç©ïŒïŒãåŸããååç©
ïŒïŒã«ã次åŒïŒïŒã§è¡šããããååŠçš®ãäœçš ãããããšã«ãã€ãŠæ žã¢ã«ãã«åããåŒïŒïŒã®
ååç©ãåæããããšãã§ããããã ãR1ïŒR2
ããã³R3ã¯åŒïŒïŒãšå矩ã§ãããçµè·¯ïŒ
ããã³ã®ãã¡ãç¹ã«åææäœã®ç°¡äŸ¿ããç·åç
ãªã©ã®ç¹ã§çµè·¯ã奜ãŸããã åŒïŒïŒã§è¡šããããååŠçš®ãçæããããã«
ã¯ããªã¬ãã€ã³ïŒãŸãã¯ã¢ã«ã³ãŒã«ãŸãã¯ã¢ã«ã
ã«ãã©ã€ãïŒããé žè§Šåªãšåå¿ããããããšã«ã
ãããã®ç®çã«äœ¿çšãããªã¬ãã€ã³ãšããŠã¯ã
R1R3CïŒïŒ²2aïŒãã ãR1ïŒR3ã¯åŒïŒïŒãšå矩ã
2aã¯ãããã³åã«ãã€ãŠR2ãäžãããããªåºã
è¡šããïŒãçšãããããšãã°ãã€ãœããã³ããªã¬
ãã€ã³ãšããŠçšããã°ãïœâããã«åºãå°å ¥ãã
ããšãã§ãããååŠçš®ïŒïŒãçæãããããã
ã®ã¢ã«ã³ãŒã«ãšããŠã¯ãR1R2R3CâOHïŒãã
ããR1ïŒR2ïŒR3ã¯åŒïŒïŒãšå矩ïŒãçšããã
ãšãã§ãããååŠçš®ïŒïŒãçæããããããã®
ã¢ã«ãã«ãã©ã€ãã¯ãR1R2R3CâïŒãã ãã
R1ïŒR2ïŒR3ã¯åŒïŒïŒãšå矩ãã¯ããã²ã³å
åïŒã®äžè¬åŒã§è¡šãããããæ žã¢ã«ãã«åã«äœ¿çš
ã§ãã觊åªãšããŠã¯ãç¡«é žããªã³é žãªã©ã®ãã¬ã³
ã¹ãããé žïŒå¡©åã¢ã«ãããŠã ãäžããåããŠ
çŽ ãå¡©åäºéãå¡©åéãå¡©åãã¿ã³ãäºå¡©åã¢ã³
ãã¢ã³ãªã©ã®ã«ã€ã¹é žïŒé žæ§çœåããã³ããã€
ããã«ãªãªã³ãªã©ã®ç²åé±ç©ãããã¯ã·ãªã«ã¢ã«
ãã系觊åªãªãåºäœé žïŒã±ã€è»åãç³è±ç ã«ç¡«
é žããªã³é žãªã©ãä»çãããŠè£œé ããåºååãªã
åºäœé žïŒã¢ã³ããŒã©ã€ãIRâ120ïŒïŒšïŒã¢ã³ããŒ
ã©ã€ãIRâ112ïŒïŒšïŒãã¢ã³ããŒãªã¹ã15ïŒäžèš
ã®äžã€ã¯ç±³åœããŒã ã»ã¢ã³ãã»ããŒã¹ç€Ÿç»é²å
æšïŒãªã©ã®ã€ãªã³äº€ææš¹èãªãåºäœé žçãæãã
ããããããã®è§Šåªã®è©³çŽ°ããã³ä»ã®äŸã«ã€ããŠ
ã¯ãç°éšæµ©äžã竹äžåžžäžèãé žå¡©åºè§Šåªã23ã
224ããŒãžãç£æ¥å³æžãæ±äº¬ïŒ1966ïŒã®èšèŒãå
èã«ãªããæ žã¢ã«ãã«åã®åå¿æ¡ä»¶ã«ã€ããŠã¯ã
G.A.Olahç·šâFriedelâCrafts and Related
ReactionsâVol Alkylation and Related
ReactionïŒInterscience PublishersïŒNew York
ïŒ1964ïŒïŒR.M.Robertsè Chem.and Eng.
NewsïŒ112Jan.25ïŒ1965ïŒãªã©ã®èšèŒãåèã«ãª
ãã®ã§ãããŠããã 次ã«æ¬çºæã«é¢ããååç©ã®äžããããã€ãã®
å ·äœçãªå®æœäŸã以äžã«èšãã åæäŸïŒïŒïŒâããããã·âïŒâã¡ãã«ãã³ãºãª
ããµãŸãŒã«ã®åæïŒããã¯ãã³è»¢äœã«ãããªã
ãµãŸãŒã«ç°ã®åœ¢æïŒã ïŒïŒïŒâãžããããã·ã¢ã»ãããšãã³306ïœã
ããããã·ã«ã¢ãã³å¡©é ž164ïœãé ¢é žãããªãŠã
328ïœããšã¿ããŒã«1000mlãããã³æ°Ž500mlãæ··å
ããïŒæéå ç±éæµãããåå¿æ¶²ãæ°Ž10ã«ã
ããæåºããçµæ¶ãåããŠããªãã·ã 314ïœã
åŸãã ãã®ïŒïŒïŒâãžããããã·ã¢ã»ãããšãã³ãªã
ã·ã 100ïœãé ¢é ž700mlã«æº¶è§£ãã120ã140âã«ãŠ
å ç±æ¹æããªããã2.5æéå¡©åæ°ŽçŽ ã¬ã¹ãå¹èŸŒ
ãã ãå·åŽåŸæåºããçµæ¶ãåãã次ãã§æ°Žã§
æŽæµããŠãïŒâããããã·âïŒâã¡ãã«ãã³ãºãª
ããµãŸãŒã«ïŒèç¹194ã196âïŒ62ïœãåŸãã åæäŸïŒïŒïŒâãããµãã·ã«ãªãã·âïŒâã¡ãã«
ãã³ãºãªããµãŸãŒã«ã®åæïŒïœâã¢ã«ãã«
åïŒã åæäŸïŒã§åæããïŒâããããã·âïŒâã¡ã
ã«ãã³ãºãªããµãŸãŒã«18.0ïœãïŒâããã¢ãããµ
ãã«ã³36.6ïœãçé žã«ãªãŠã 24.0ïœãïŒïŒ®âãž
ã¡ãã«ãã«ã ã¢ãã120mlã90âã§4.5æéæ¹æã
ããåå¿æ¶²ãããåºäœãå»ãã液ãã¡ã¿ããŒ
ã«500mlã«ããããæåºããçµæ¶ãåããŠãïŒ
âãããµãã·ã«ãªãã·âïŒâã¡ãã«ãã³ãºãªããµ
ãŸãŒã«ïŒèç¹53ã54âïŒ45.0ïœãåŸãã åæäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâãããµãã·
ã«ãªãã·ããšããŒã«ã®åæïŒãªããµãŸãŒã«ç°ã®
éç°ïŒã åæäŸïŒã§åŸãïŒâãããµãã·ã«ãªãã·âïŒâ
ã¡ãã«ãã³ãºãªããµãŸãŒã«111ïœããšã¿ããŒã«
1300mlã35ïŒ å¡©é ž110mlãæ°Ž550mlãæ··åãã55ã
60âã§ïŒæéæ¹æãããå·åŽåŸæåºããçµæ¶ã
åãïŒâã¢ã»ãã«ã¢ããâïŒâãããµãã·ã«ãªã
ã·ããšããŒã«ïŒèç¹123ã125âïŒ113ïœãåŸãã å®æœäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâïœâããã«
âïŒâãããµãã·ã«ãªãã·ããšããŒã«ïŒååç©
ïŒïŒã®åæïŒæ žã¢ã«ãã«åïŒã åæäŸïŒã§åŸãïŒâã¢ã»ãã«ã¢ããâïŒâãã
ãµãã·ã«ãªãã·ããšããŒã«30.0ïœãã¢ã³ããŒãªã¹
ã15ïŒç±³åœã»ããŒã ã»ã¢ã³ãã»ããŒã¹ç€Ÿç»é²å
æšïŒ20.0ïœããã«ãšã³300mlãæ··åãã80ã90â
ã§å ç±æ¹æããªãããã€ãœããã³ãïŒæéæµéã
ããåºäœãå»ããã®ã¡ã液ãæ¿çž®ããæ®æž£ã«
ïœâãããµã³350mlãå ãããšçµæ¶ãæåºããã
åããŠãïŒâã¢ã»ãã«ã¢ããâïŒâïœâããã«
âïŒâãããµãã·ã«ãªãã·ããšããŒã«ïŒèç¹65ã
68âïŒ23.5ïœãåŸãã å®æœäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâïŒïŒïŒïŒâ
ãžã¡ãã«ãã³ãžã«ïŒâïŒâãããµãã·ã«ãªãã·
ããšããŒã«ïŒååç©ïŒïŒã®åæã åæäŸïŒã§åŸãïŒâã¢ã»ãã«ã¢ããâïŒâãã
ãµãã·ã«ãªãã·ããšããŒã«20ïœããã«ãšã³150ml
äžã«æº¶è§£ããã¢ã³ããŒãªã¹ã15ïŒç±³åœããŒã ã»ã¢
ã³ãã»ããŒã¹ç€Ÿç»é²åæšïŒïŒïœãšå ±ã«80ã90âã«
å ç±ãããããã«Î±âã¡ãã«ã¹ãã¬ã³30mlã滎äž
ãçŽïŒæéãã®ãŸãŸå ç±ãããåå¿çµäºåŸãã¢ã³
ããŒãªã¹ã15ãå»ã液ãæ¿çž®ããã¡ã¿ããŒã«
å ããŠæ°·å·ãããšç®çç©ãæåºããããããå
ãã¡ã¿ããŒã«ã§ããæŽæµãããåé6.6ïœãåå
ç©ïŒã®èç¹84ã86âã å®æœäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâïŒïŒâãšã
ã«âïŒâã¡ãã«ãã³ãã«ïŒâïŒâãããµãã·ã«
ãªãã·ããšããŒã«ååç©ïŒã®åæã ïŒâã¢ã»ãã«ã¢ããâïŒâãããµãã·ã«ãªãã·
ããšããŒã«25ïœãïŒâãšãã«âïŒâããã»ã³250
mlãã¢ã³ããŒãªã¹ãâ15 100ïœãããã³ãã«ãšã³
750mlãããªãæ··åç©ã80âã§ïŒæéå ç±æ¹æã
ãã次ãã§ã¢ã³ããŒãªã¹ãâ15ãå¥ãã液ã
ããã«ãšã³ãçå»ãããæ®æž£ã«ãããµã³150mlã
å ããïŒæéæ°·å·ãããçããçµæ¶ãåããã
ããµã³ã§æŽæµããåŸé¢šä¹Ÿãããåé6.0ïœãåå
ç©ïŒã®èç¹65ã67â æ¬çºæã®ååç©ãäžéäœãšããŠçšããŠãã«ã©ãŒ
æ¡æ£è»¢åæ³ã«æçšãªè²çŽ æŸåºã¬ããã¯ã¹ååç©ã
åæããããšãã§ããããã®ãããªã¬ããã¯ã¹å
åç©ã®ä»£è¡šäŸãšããŠäžèšäžè¬åŒïŒïŒã§è¡šãã
ããååç©ãæããããã ãã ãR1ïŒR2ïŒR3ïŒR4ïŒR5ã¯åŒïŒïŒãšå矩
ã§ãããã¯æ°Žé žåºããŸãã¯å æ°Žå解ã«ããæ°Žé ž
åºãäžããåºãè¡šããïŒColã¯è²çŽ ãŸãã¯è²çŽ å
é§äœãè¡šããã ã®å ·äœäŸãšããŠã¯æ°Žé žåºã®ã»ãã«ãççŽ æ°ïŒ
ã40奜ãŸããã¯ïŒãïŒãã奜ãŸããã¯ïŒãïŒã®ã¢
ã«ãã«âCOOâã§è¡šããããåºïŒäŸãã°ã¢ã»ã
ãã·ã«åºãããããªãã«ãªãã·åºãªã©ïŒãççŽ æ°
ïŒã40奜ãŸããã¯ïŒã15ãã奜ãŸããã¯ïŒãïŒã®
è³éŠæã«ã«ããã«ãªãã·åºïŒããšãã°ããã³ãŸã€
ã«åºã眮æãã³ãŸã€ã«åºãªã©ïŒããããããã Colã®äŸãšããŠã¯ã¢ãŸè²çŽ ãã¢ãŸã¡ãã³è²çŽ ã
ã€ã³ãã¢ããªã³è²çŽ ãã€ã³ãããšããŒã«è²çŽ ãã
ãªããšãã«ã¡ã¿ã³ç³»è²çŽ ãã¢ã³ã¹ã©ããã³è²çŽ ã
ã€ã³ãžãŽè²çŽ ãŸãã¯ãããã®éå±é¯å¡©çã ã®åºã
æããããã»ããå æ°Žå解ã«ããããããã®è²çŽ
ãäžãããã®ãšããŠã¯äŸãã°ç¹éæ48â125818
å·ãç±³åœç¹èš±3222196å·ããã³å3307947å·çã«èš
ãããããã«è²çŽ ã®å©è²å£ãã¢ã·ã«åãããããª
ãã®ãæããããšãã§ãããåŸè ã¯ãšãã«ããã
ãã®è²å圢æå€ãæå ä¹³å€ãšæ··åããŠå¡åžããå Ž
åã«èµ·ããå åžåã«åºã¥ãæžæãé²ãç®çã§è²çŽ
ã®åžåãé²å ã®éäžæçã«çæ³¢åãããŠãããã
ã«æçšã§ããããªãããã®ç®çã®ããã«ã¯ãåªæ
å€äžã«è»¢åããå Žåãšãä¹³å€å±€äžã«ååšããå Žå
ãšã§ãè²çžãç°ãªããããªè²çŽ ãå©çšããããšã
ã§ããããªããColéšã¯äŸãã°ã«ã«ããã·ã«åºã
ã¹ã«ãã³ã¢ããåºã®ãããªæ°Žæº¶æ§ãäžãããããª
åºãæããããšãã§ããã æ¬çºæã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ã¯æå ææã®çŸåæã«äœ¿çšãããã¢
ã«ã«ãªã«ãã€ãŠãã®ãŸãŸã®åœ¢ã§æ¡æ£ãŸãã¯æµåºã
ãŠããŸãããšãé¿ããããã«ãå®è³ªçã«æ¡æ£ãã
ãã¯æµåºããªããããããªãã©ã¹ãåºãå¿ èŠãšã
ãããã©ã¹ãåºã«èŠæ±ãããåºã®ãµã€ãºãããã
ã¯ççŽ æ°ã¯äœ¿çšããæ¡ä»¶ãããšãã°åŠçæéãã¢
ã«ã«ãªæ¿åºŠããColéšã«æãã氎溶æ§åºã®æ°ãšçš®
é¡ã«ããç°ãããå°ããšãR1.R2ïŒR3ïŒR4ããã³
R5ã®åèšã§ïŒä»¥äžã¯å¿ èŠã§ãããççŽ æ°ãå¿ èŠ
以äžã«å€§ãããªããšã溶解床ããåžå ä¿æ°ã®ç¹ã§
äžå©ãšãªã€ãŠããããåççã«ççŽ æ°ã®äžéãšã
ããã®ã¯ãªããäžè¬ã«R1ïŒR5ã®åèšãïŒã80ã
奜ãŸããã¯13ã40ãæãŸããç¯å²ã§ããã ãªãµãŒããã€ã¹ããŒã·ã€ïŒResareh
DisclnsureïŒèª13024å·ïŒâ75ïŒã«ã¯ïŒâã¹ã«ã
ãªã³ã¢ããããšããŒã«é¡ãèšèŒãããŠãããã®äž
ã§ïŒäœã«ã¢ã«ãã«åºãæããïŒâã¹ã«ããªã³ã¢ã
ãããšããŒã«ãçŸå掻æ§ããã»ãšãã©ãªããåŸã€
ãŠè²çŽ ãé¢è±ããªãããšã瀺ãããŠãããæ¬çºæ
ã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ããã¯ã¹å
åç©ã«ãããŠã¯ãããšããŒã«ã®ïŒäœã«R4Oâåºã
çµåãããããïŒäœã«ç¬¬äºçŽãŸãã¯ç¬¬äžçŽã®ã¢ã«
ãã«åºïŒããªãã¡R1R2R3CâåºïŒãçµåããŠãã
ããšãé倧ãªåçæ§èœäžã®å·®ç°ããããããŠãã
ããšã¯æããã§ãããç¹éæ51â113624ããã³ç¹
éæ53â149328èšèŒã®è²çŽ æŸåºã¬ããã¯ã¹ååç©
ã«æ¯èŒãããšæ¬çºæã®ååç©ãçšããŠåŸãããè²
çŽ æŸåºã¬ããã¯ã¹ååç©ã«ãããŠã¯ã第äºçŽãŸã
ã¯ç¬¬äžçŽã¢ã«ãã«ïŒR1R2R3CâåºïŒã®ç«äœé害ã«
ãã€ãŠé žåäœã®å æ°Žå解ã®å¯åå¿ããããããã
è²çŽ ã®æŸåºå¹çãåäžãããšããç¹ã§åªããŠã
ãããã®ããšã«ãã€ãŠãé žåãããååç©ã¯ãäº
å®äžç¡å¹åããããšãªããå¹çããæ¡æ£è²çŽ ãæŸ
åºããã æ¬çºæã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ã¯çŸåæã®ã¬ããã¯ã¹åå¿ã«ãã€ãŠ
ïœâããã³ã€ãããçæãããããå æ°Žå解ãã
ããŠãã¹ã«ããªã³ã¢ããéšãé¢è±ããã®ã§ãã
ããããã«ããçããïœâãã³ãŸããã³äœãæ¢è¿°
ã®ãããããã³é¡ã«æ¯ãæµ è²çãªåžåãããããª
ãããšãè²çŽ æŸåºåŸã®æ®è²ãå°ãããŠãããšèã
ãããã æ¬çºæã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ã¯ç¹éæ51â113624ãªã©ã®æ现æžã«
é瀺ãããŠããè²çŽ æŸåºã¬ããã¯ã¹ååç©ãšåæ§
ã«ã«ã©ãŒæ¡æ£è»¢åæ³æå ææã«çšããããã ç¹ã«å¥œãŸããã¯ãæ¬çºæãçšããŠåŸãããè²çŽ
æŸåºã¬ããã¯ã¹ååç©ã¯æ¬¡ã®äžè¬åŒã§è¡šããã
ãã ïŒãã ããR1ïŒR2ïŒR3ïŒR4ããã³Colã¯åŒïŒ
ïŒãšå矩ãè¡šããã5aã¯åŒïŒïŒãšå矩ïŒåŒ
ïŒïŒã§è¡šããããæ¬çºæã®è²çŽ æŸåºã¬ããã¯
ã¹ååç©ã®å ·äœäŸã次ã«ç€ºãã æ¬çºæã«æŒããäžè¬åŒïŒïŒã§è¡šããããå
åç©ã¯äžè¬ã«ã¢ãŸè²çŽ ã®ã¹ã«ããã«ãã©ã€ãïŒ
ïŒãšçš®ã ã®ææ©ãã©ã¹ãåºãæããïœâã¢ãã
ããšããŒã«èªå°äœïŒïŒãšçž®ååå¿ãããããš
ã«ãã€ãŠåæããããšãã§ããã ColâSO2X ïŒïŒ ïŒãã ãã¯ããã²ã³ååãä»ã®ç¬Šå·ã¯åŒ
ïŒïŒãšåçŸ©ïŒ è²çŽ éšããã³ãããã®ã¹ã«ããã«ãã©ã€ãïŒ
ïŒã®åææ³ã¯ãç¹éæ48â12581å·ãå48â
33826å·ãå49â114424å·ãå49â126332å·ãªã©
ã«èšèŒãããŠããã åŒïŒïŒã§è¡šããããååç©ã¯ãæ¬çºæã®å
åç©ïŒïŒãå æ°Žå解ããããšã«ãã€ãŠåŸãã
ããå æ°Žå解ã®æ¹æ³ãšããŠã¯ãåžéããå¡©é žãªã©
ã®é žã§åŠçããæ¹æ³ã簡䟿ã§ãããå ·äœäŸãšããŠ
次ã®åèåæäŸããããŠããã åèåæäŸïŒïŒïŒâã¢ããâïŒâïœâããã«âïŒ
âãããµãã·ã«ãªãã·ããšããŒã«å¡©é žå¡©ã®åæ
ïŒè±ã¢ã»ãã«åïŒ å®æœäŸïŒã§åŸãïŒâã¢ã»ãã«ã¢ããâïŒâïœâ
ããã«âïŒâãããµãã·ã«ãªãã·ããšããŒã«23.0
ïœããšã¿ããŒã«120mlã35ïŒ å¡©é ž96mlãæ··åãã
ïŒæéæ¹æéæµãããåå¿æ¶²ãå·åŽããã®ã¡ãæ
åºããçµæ¶ãåããŠãïŒâã¢ããâïŒâïœâã
ãã«âïŒâãããµãã·ã«ãªãã·ããšããŒã«å¡©é žå¡©
23.2ïœãåŸãã åèåæäŸïŒïŒïŒâã¢ããâïŒâïŒÎ±ïŒÎ±âãžã¡
ãã«ãã³ãžã«ïŒâïŒâãããµãã·ã«ãªãã·ããš
ããŒã«å¡©é žå¡©ã®åæ å®æœäŸïŒã§åŸãååç©6.4ïœããšã¿ããŒã«45ml
ããã³æ¿å¡©é ž30mlãšãšãã«ïŒæééæµãããåå¿
çµäºåŸãæŸå·ãããšçµæ¶ãæåºããã®ã§åã
ããåé6.1ïœ åèåæäŸïŒïŒïŒâã¢ããâïŒâïŒïŒâãšãã«â
ïŒâã¡ãã«ãã³ãã«ïŒâïŒâãããµãã·ã«ãªã
ã·ããšããŒã«å¡©é žå¡©ã®åæ å®æœäŸïŒã§åŸãïŒâã¢ã»ãã¢ããâïŒâïŒïŒâ
ãšãã«âïŒâã¡ãã«ãã³ãã«ïŒâïŒâãããµãã·
ã«ãªãã·ããšããŒã«ïŒïœã«ãšã¿ããŒã«30mlããã³
æ¿å¡©é ž25mlãå ããèžæ°æµŽäžã§ïŒæéå ç±ããã
次ãã§åå¿æ¶²ãæ°·å·ãããšããäºå±€ã«åãããã®
ã§æ²¹å±€ãåãåºããŠæžå§äžã«ä¹Ÿç¥ããã åé3.5ïœ ååç©ïŒïŒãšååç©ïŒïŒãšã®çž®ååå¿
ã¯ãéåžžå¡©åºæ§ç©è³ªã®ååšäžã«è¡ãªãããšãæãŸ
ããããããå¡©åºæ§ç©è³ªã®äŸãšããŠã¯ãã¢ã«ã«ãª
éå±ãããã¯ã¢ã«ã«ãªåéå±ã®æ°Žé žåç©ïŒããšã
ã°æ°Žé žåãããªãŠã ãæ°Žé žåã«ãªãŠã ãæ°Žé žåã
ãªãŠã ãæ°Žé žåã«ã«ã·ãŠã ãªã©ïŒãèèªæã¢ãã³
ïŒããšãã°ããªãšãã«ã¢ãã³ãªã©ïŒãè³éŠæã¢ãã³
ïŒããšãã°ïŒ®ïŒïŒ®âãžãšãã«ã¢ããªã³ãªã©ïŒããã
ãè³éŠæã¢ãã³ããšãã°ïŒããªãžã³ããããªã³ã
αâãβâããŸãã¯Î³âãã³ãªã³ãã«ããžã³ãã³
ãªãžã³ãïŒâïŒïŒ®ïŒïŒ®âãžã¡ãã«ã¢ããïŒããªãž
ã³ãªã©ïŒãããã³ãããç°å¡©åºïŒïŒïŒïŒâãžã¢ã¶
ãã·ã¯ããïŒïŒïŒïŒïŒãããã³âïŒïŒïŒïŒïŒâãž
ã¢ã¶ãã·ã¯ããïŒïŒïŒïŒïŒããŠã³ãã»ã³âïŒãª
ã©ïŒããããããããå¡©çŽ ã®å Žåãããªãã¡åŒ
ãïŒãã¹ã«ããã«ã¯ãã©ã€ãã§ããå Žåã«
ã¯ãç¹ã«äžèšã®ãã¡ãããè³éŠæã¢ãã³ïŒå¥œãŸã
ãã¯ããªãžã³ïŒãåªããŠããã次ã«æ¬çºæã®äžé
äœã䜿çšããããšã«ãã€ãŠãè²çŽ æŸåºã¬ããã¯ã¹
ååç©ãåæããäŸã瀺ãã åèåæäŸïŒïŒååç©DRRâïŒã®åæ (a) ïŒâïŒïŒâã¡ããã·ãšããã·ïŒâïŒâããã
ãã³ãŒã³ã¹ã«ãã³é žãããªãŠã ã®åæ 300mlã¡ãã«ã»ããœã«ãäžã«7.3ïœæ°ŽçŽ åãããª
ãŠã ïŒ50ïŒ æµåãã©ãã€ã³æžæ¿ç©ã®åœ¢ã§14.6ïœïŒ
ãå ããŠèª¿è£œãããããªãŠã âïŒâã¡ããã·âãš
ãã©ãŒã液ã«æ¹æãã€ã€ïŒâã¯ããâïŒâããã
ãã³ãŒã³ã¹ã«ãã³é žãããªãŠã ã55ïœå ãããå
å¿æ··åç©ãã湯济ã§30åé80ã85âã§å ç±æ¹æã
ããç±ãéãè¡ã€ãŠåŸãæ¯æ¶²ã«ã€ãœãããã«ã¢ã«
ã³ãŒã«1.5ãå ããŠæ¶æããããæåºçµæ¶ãã
éåŸãã€ãœãããã«ã¢ã«ã³ãŒã«100mlã«ãŠæŽæµã
ãã åé59ïœ m.p.238ã239â (b) ïŒâã¢ããâïŒâïŒïŒâã¡ããã·ãšããã·ïŒ
ãã³ãŒã³ã¹ã«ãã³é žã®åæ ïŒâïŒïŒâã¡ããã·ãšããã·ïŒâïŒâãããã
ã³ãŒã³ã¹ã«ãã³é ž30ïœãéå é30ïœãå¡©åã¢ã³ã¢
ããŠã 0.6ïœããã³æ°Ž60mlã®æ··å溶液ã80ã85â
ã«ä¿ã€ãŠïŒæéå ç±æ¹æãããåå¿çµäºåŸãäžæº¶
ç©ããå¥ãã液ã«ã€ãœãããã«ã¢ã«ã³ãŒã«200
mlå ããŠæ°·å·ãããææ¶ããçµæ¶ãåããã€ãœ
ãããã«ã¢ã«ã³ãŒã«50mlã«ãŠæŽæµãã颚也ããã åé23ïœ m.p.250âä»¥äž (c) ïŒâã·ã¢ãâïŒâïŒïŒâã¡ããã·ãšããã·â
ïŒâã¹ã«ãããšãã«ã¢ãŸïŒâïŒâããšãã«âïŒ
âãã©ãŸãã³ã®åæ æ°Žé žåãããªãŠã 8.0ïœãæ°Ž200mlãããªã溶液
ã«ãïŒâã¢ããâïŒâïŒïŒâã¡ããã·ãšããã·ïŒ
ãã³ãŒã³ã¹ã«ãã³é ž49.4ïœãå ããããã«äºç¡é ž
ãœãŒã13.8ïœã®æ°Žæº¶æ¶²ïŒ50mlïŒãå ãããå¥ã«æ¿
å¡©é ž60mlãæ°Ž400mlã§åžéããå¡©é žã調補ããïŒ
â以äžã§äžèšå¡©é žã滎äžããããã®åŸäžèšã®æ··å
液ãïŒâ以äžã§30åéæ¹æãåå¿ãå®çµããã
ïŒãã®æº¶æ¶²ããžã¢ãŸæ¶²ãšç§°ããïŒã å¥ã«æ°Žé žåãããªãŠã 16.0ïœãæ°Ž200mlãé ¢é ž
ãããªãŠã 33.0ïœããã³ã¡ã¿ããŒã«200mlãããª
ãæ··å溶液ã«ãïŒâã·ã¢ãâïŒâããšãã«âïŒâ
ãã©ãŸãã³37.0ïœãå ãã10â以äžã§äžèšèª¿è£œæž
ã®ãžã¢ãŸæ¶²ã滎äžããã滎äžçµäºåŸ10â以äžã§30
åéæ¹æããã€ãã§å®€æž©ã§ïŒæéæ¹æããåŸãæ
åºããçµæ¶ãåããã¢ã»ãã³200mlã§æŽæµãã
颚也ããã åé52.0ïœ m.p.263ã265â (d) ïŒâã·ã¢ãâïŒâïŒïŒâã¡ããã·ãšããã·â
ïŒâã¯ããã¹ã«ããã«ããšãã«ã¢ãŸïŒâïŒâã
ãšãã«âïŒâãã©ãŸãã³ã®åæ äžèš(1)ã§åŸãïŒâã·ã¢ãâïŒâïŒïŒâã¡ããã·
ãšããã·âïŒâã¹ã«ãããšãã«ã¢ãŸïŒâïŒâããš
ãã«âïŒâãã©ãŸãã³51.0ïœãã¢ã»ãã³250mlã
ãã³ãªãã·å¡©åãªã³50mlãããªãæ··å溶液ã«ïŒ®ïŒ
âãžã¡ãã«ã¢ã»ãã¢ãã50mlã50â以äžã§æ»Žäž
ããã滎äžåŸçŽïŒæéæ¹æããæ°·æ°Ž1.0ã®äžã«
åŸã ã«æ³šãã ãæåºããçµæ¶ãå¥åŸãã¢ã»ãã
ããªã«100mlã§æŽæµã颚也ããã åé46.7ïœ m.p. 181ã183â (e) ååç©DRRâïŒã®åæ ïŒïŒ®âãžã¡ãã«ã¢ã»ãã¢ãã20mlã«ãåèå
æäŸïŒã§åŸã4.4ïœã®ïŒâã¢ããâïŒâïœâãã
ã«âïŒâãããµãã·ã«ãªãã·âïŒâã¡ãã«âããš
ããŒã«å¡©é žå¡©ãšäžèš(d)ã§åŸãïŒâã·ã¢ãâïŒâ
ïŒïŒâã¡ããã·ãšããã·âïŒâã¯ããã¹ã«ããã«
ããšãã«ã¢ãŸïŒâïŒâããšãã«âïŒâãã©ãŸãã³
4.6ïœãšãå ãããäžèšã®æ··å溶液ãæ¹æãã€ã€
ããã«ããªãžã³4.7mlã滎äžãã滎äžåŸããã«å®€
æž©ã§ïŒæéæ¹æãããæ¹æããåŸãã¡ã¿ããŒã«30
mlãæ°Ž10mlãåå¿æ¶²ã«å ãããæåºããæ²¹ç¶ç©ã«
ãšã¿ããŒã«çŽ20mlãå ãããšçµæ¶ãæåºããã®ã§
åãããåé4.8ïœã
ãŒã«ãªãã·ã¢ã«ãã«åºïŒãããã®åºã®åã ã®å šç
çŽ æ°ãïŒã24ã®ãã®ããªãã§ã奜ãŸããïŒã®å Žå
ã§ãããåäžè¬åŒïŒïŒã«ãããŠïŒ²5aãæ°ŽçŽ å
åãã¢ã«ãã«åºãŸãã¯ã¢ã«ã³ãã·åºïŒãããã®åº
åã ã®å šççŽ æ°ãïŒã24ã®ãã®ããªãã§ã奜ãŸã
ãïŒãè¡šããå Žåã§ããã æ¬çºæã®ååç©ã®å ·äœäŸã以äžã«ç€ºãã åŒïŒïŒã§ç€ºãããååç©ã®åææ³ã®ä»£è¡šçãª
ãã®ãšããŠæ¬¡ã®å³åŒã®çµè·¯ããããããã çµè·¯ã«ã€ããŠèª¬æãããïŒïŒã®ããšãã¬ãŸ
ã«ã·ããŒã«èªå°äœãããããœåãéå 次ãã§ã¢ã»
ãã«åããããšã«ãã€ãŠååç©ïŒïŒãåŸããã
ããã®å段éã«ã€ããŠã¯ãW.M.McLamoreïŒJ.
Amer.Chem.Soc.ïŒ73ïŒ2225ã2230ïŒ1951ïŒã«ïŒ
âã·ã¯ãããã·ã«ã¬ãŸã«ã·ããŒã«ãããïŒâã¢ã»
ãã¢ããâïŒâã·ã¯ãããã·ã«ã¬ãŸã«ã·ããŒã«ã
åŸãå Žåã«èšèŒããŠããæäœãå¿çšããããšãã§
ããããªããµãŸãŒã«ç°ã®åœ¢æã¯ãååç©ïŒïŒã
ïœâãã«ãšã³ã¹ã«ãã³é žã®ããšãé žè§Šåªã®ããšã«
è¡ãããšãã§ããããªããµãŸãŒã«ç°ã®åœ¢æã«ã€ã
ãŠã¯ãç¹éæ52â153923ã®èšèŒãåèã«ãªãããª
ããµãŸãŒã«èªå°äœïŒïŒã®ïœâã¢ã«ãã«åã§ã¯ã
éåžžR4âïŒïŒžã¯ããã²ã³ååïŒãçšãè±ãã
ã²ã³åæ°ŽçŽ åå€ãšããŠããããªãŠã ã¢ã«ã³ãã·
ããçé žã«ãªãŠã ãªã©ã®å¡©åºæ§ç©è³ªã䜿çšããã
ãã®ã¢ã«ãã«åã®æ®µéã«ã€ããŠã¯ãç¹éæ52â
153923ã®èšèŒãåèã«ãªããååç©ïŒïŒã®ãªã
ãµãŸãŒã«ã®éç°ã«ãã€ãŠãã¢ã»ãã¢ããäœïŒïŒ
ãåŸãããšãã§ããã çµè·¯ã«ãããŠã¯ãã¬ãŸã«ã·ããŒã«èªå°äœãã
æ žã¢ã»ãã«åïŒããšãã°BF3âé ¢é žã®æ¡ä»¶ã§ïŒã
ãã®ã¡ãããããã·ã«ã¢ãã³ãšåå¿ãããŠãªãã·
ã ïŒXIIïŒãšãããååç©ïŒXIIïŒããé ¢é žäžå¡©åæ°Ž
çŽ ã¬ã¹ãå¹èŸŒãæ¡ä»¶ïŒãªãã·å¡©åãªã³åã¯äºå¡©å
ãªã³ãªã©ã§åŠçããããšã«ãã€ãŠãããã¯ãã³è»¢
äœâãªããµãŸãŒã«åœ¢æãåæã«è¡ããããããšã
ã§ããããã®ããã«ããŠåŸãååç©ïŒïŒã¯ãäž
èšã®çµè·¯ã«ãŠè¿°ã¹ãæ¹æ³ã§ãååç©ïŒïŒãžå°
ãããšãã§ããã çµè·¯ã«ãããŠã¯ãïŒïŒïŒâãžããããã·ã¢ã»
ãããšãã³èªå°äœïŒãã¡ãããã¢ã»ãã«åºãä»ã®
ã±ãã³æ®åºã§çœ®æããååç©ãåºçºç©è³ªãšããŠæ
çšã§ããããåæã®ããããããã¯ã¢ã»ãã«åºã
奜ãŸããïŒãã«ããããã·ã«ã¢ãã³ãåå¿ãã
ãŠããªãã·ã ïŒXIïŒãšããäžèšçµè·¯ã®ååç©
ïŒXIIïŒã®å Žåãšåæ§ã«ãããã¯ãã³è»¢äœâãªããµ
ãŸãŒã«åœ¢æãåæã«è¡ãããããçãããªããµãŸ
ãŒã«ïŒïŒãïœâã¢ã«ãã«åããŠååç©ïŒXI
ïŒãåŸãã«ã¯ãR6âïŒïŒžã¯ããã²ã³ååïŒ
ãçšããè±ããã²ã³åæ°ŽçŽ åå€ãšããŠããããªãŠ
ã ã¢ã«ã³ãã·ããããã¯çé žã«ãªãŠã ãªã©ã®å¡©åº
æ§ç©è³ªãçšããããã®ïœâã¢ã«ãã«åã®æ®µéã«ã€
ããŠã¯ãç¹éæ52â153923ã®èšèŒãåèã«ãªãã 次ãã§ãåžå¡©é žãªã©ã§åŠçããŠããªããµãŸãŒã«
ç°ãéç°ããããååç©ïŒïŒãåŸããååç©
ïŒïŒã«ã次åŒïŒïŒã§è¡šããããååŠçš®ãäœçš ãããããšã«ãã€ãŠæ žã¢ã«ãã«åããåŒïŒïŒã®
ååç©ãåæããããšãã§ããããã ãR1ïŒR2
ããã³R3ã¯åŒïŒïŒãšå矩ã§ãããçµè·¯ïŒ
ããã³ã®ãã¡ãç¹ã«åææäœã®ç°¡äŸ¿ããç·åç
ãªã©ã®ç¹ã§çµè·¯ã奜ãŸããã åŒïŒïŒã§è¡šããããååŠçš®ãçæããããã«
ã¯ããªã¬ãã€ã³ïŒãŸãã¯ã¢ã«ã³ãŒã«ãŸãã¯ã¢ã«ã
ã«ãã©ã€ãïŒããé žè§Šåªãšåå¿ããããããšã«ã
ãããã®ç®çã«äœ¿çšãããªã¬ãã€ã³ãšããŠã¯ã
R1R3CïŒïŒ²2aïŒãã ãR1ïŒR3ã¯åŒïŒïŒãšå矩ã
2aã¯ãããã³åã«ãã€ãŠR2ãäžãããããªåºã
è¡šããïŒãçšãããããšãã°ãã€ãœããã³ããªã¬
ãã€ã³ãšããŠçšããã°ãïœâããã«åºãå°å ¥ãã
ããšãã§ãããååŠçš®ïŒïŒãçæãããããã
ã®ã¢ã«ã³ãŒã«ãšããŠã¯ãR1R2R3CâOHïŒãã
ããR1ïŒR2ïŒR3ã¯åŒïŒïŒãšå矩ïŒãçšããã
ãšãã§ãããååŠçš®ïŒïŒãçæããããããã®
ã¢ã«ãã«ãã©ã€ãã¯ãR1R2R3CâïŒãã ãã
R1ïŒR2ïŒR3ã¯åŒïŒïŒãšå矩ãã¯ããã²ã³å
åïŒã®äžè¬åŒã§è¡šãããããæ žã¢ã«ãã«åã«äœ¿çš
ã§ãã觊åªãšããŠã¯ãç¡«é žããªã³é žãªã©ã®ãã¬ã³
ã¹ãããé žïŒå¡©åã¢ã«ãããŠã ãäžããåããŠ
çŽ ãå¡©åäºéãå¡©åéãå¡©åãã¿ã³ãäºå¡©åã¢ã³
ãã¢ã³ãªã©ã®ã«ã€ã¹é žïŒé žæ§çœåããã³ããã€
ããã«ãªãªã³ãªã©ã®ç²åé±ç©ãããã¯ã·ãªã«ã¢ã«
ãã系觊åªãªãåºäœé žïŒã±ã€è»åãç³è±ç ã«ç¡«
é žããªã³é žãªã©ãä»çãããŠè£œé ããåºååãªã
åºäœé žïŒã¢ã³ããŒã©ã€ãIRâ120ïŒïŒšïŒã¢ã³ããŒ
ã©ã€ãIRâ112ïŒïŒšïŒãã¢ã³ããŒãªã¹ã15ïŒäžèš
ã®äžã€ã¯ç±³åœããŒã ã»ã¢ã³ãã»ããŒã¹ç€Ÿç»é²å
æšïŒãªã©ã®ã€ãªã³äº€ææš¹èãªãåºäœé žçãæãã
ããããããã®è§Šåªã®è©³çŽ°ããã³ä»ã®äŸã«ã€ããŠ
ã¯ãç°éšæµ©äžã竹äžåžžäžèãé žå¡©åºè§Šåªã23ã
224ããŒãžãç£æ¥å³æžãæ±äº¬ïŒ1966ïŒã®èšèŒãå
èã«ãªããæ žã¢ã«ãã«åã®åå¿æ¡ä»¶ã«ã€ããŠã¯ã
G.A.Olahç·šâFriedelâCrafts and Related
ReactionsâVol Alkylation and Related
ReactionïŒInterscience PublishersïŒNew York
ïŒ1964ïŒïŒR.M.Robertsè Chem.and Eng.
NewsïŒ112Jan.25ïŒ1965ïŒãªã©ã®èšèŒãåèã«ãª
ãã®ã§ãããŠããã 次ã«æ¬çºæã«é¢ããååç©ã®äžããããã€ãã®
å ·äœçãªå®æœäŸã以äžã«èšãã åæäŸïŒïŒïŒâããããã·âïŒâã¡ãã«ãã³ãºãª
ããµãŸãŒã«ã®åæïŒããã¯ãã³è»¢äœã«ãããªã
ãµãŸãŒã«ç°ã®åœ¢æïŒã ïŒïŒïŒâãžããããã·ã¢ã»ãããšãã³306ïœã
ããããã·ã«ã¢ãã³å¡©é ž164ïœãé ¢é žãããªãŠã
328ïœããšã¿ããŒã«1000mlãããã³æ°Ž500mlãæ··å
ããïŒæéå ç±éæµãããåå¿æ¶²ãæ°Ž10ã«ã
ããæåºããçµæ¶ãåããŠããªãã·ã 314ïœã
åŸãã ãã®ïŒïŒïŒâãžããããã·ã¢ã»ãããšãã³ãªã
ã·ã 100ïœãé ¢é ž700mlã«æº¶è§£ãã120ã140âã«ãŠ
å ç±æ¹æããªããã2.5æéå¡©åæ°ŽçŽ ã¬ã¹ãå¹èŸŒ
ãã ãå·åŽåŸæåºããçµæ¶ãåãã次ãã§æ°Žã§
æŽæµããŠãïŒâããããã·âïŒâã¡ãã«ãã³ãºãª
ããµãŸãŒã«ïŒèç¹194ã196âïŒ62ïœãåŸãã åæäŸïŒïŒïŒâãããµãã·ã«ãªãã·âïŒâã¡ãã«
ãã³ãºãªããµãŸãŒã«ã®åæïŒïœâã¢ã«ãã«
åïŒã åæäŸïŒã§åæããïŒâããããã·âïŒâã¡ã
ã«ãã³ãºãªããµãŸãŒã«18.0ïœãïŒâããã¢ãããµ
ãã«ã³36.6ïœãçé žã«ãªãŠã 24.0ïœãïŒïŒ®âãž
ã¡ãã«ãã«ã ã¢ãã120mlã90âã§4.5æéæ¹æã
ããåå¿æ¶²ãããåºäœãå»ãã液ãã¡ã¿ããŒ
ã«500mlã«ããããæåºããçµæ¶ãåããŠãïŒ
âãããµãã·ã«ãªãã·âïŒâã¡ãã«ãã³ãºãªããµ
ãŸãŒã«ïŒèç¹53ã54âïŒ45.0ïœãåŸãã åæäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâãããµãã·
ã«ãªãã·ããšããŒã«ã®åæïŒãªããµãŸãŒã«ç°ã®
éç°ïŒã åæäŸïŒã§åŸãïŒâãããµãã·ã«ãªãã·âïŒâ
ã¡ãã«ãã³ãºãªããµãŸãŒã«111ïœããšã¿ããŒã«
1300mlã35ïŒ å¡©é ž110mlãæ°Ž550mlãæ··åãã55ã
60âã§ïŒæéæ¹æãããå·åŽåŸæåºããçµæ¶ã
åãïŒâã¢ã»ãã«ã¢ããâïŒâãããµãã·ã«ãªã
ã·ããšããŒã«ïŒèç¹123ã125âïŒ113ïœãåŸãã å®æœäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâïœâããã«
âïŒâãããµãã·ã«ãªãã·ããšããŒã«ïŒååç©
ïŒïŒã®åæïŒæ žã¢ã«ãã«åïŒã åæäŸïŒã§åŸãïŒâã¢ã»ãã«ã¢ããâïŒâãã
ãµãã·ã«ãªãã·ããšããŒã«30.0ïœãã¢ã³ããŒãªã¹
ã15ïŒç±³åœã»ããŒã ã»ã¢ã³ãã»ããŒã¹ç€Ÿç»é²å
æšïŒ20.0ïœããã«ãšã³300mlãæ··åãã80ã90â
ã§å ç±æ¹æããªãããã€ãœããã³ãïŒæéæµéã
ããåºäœãå»ããã®ã¡ã液ãæ¿çž®ããæ®æž£ã«
ïœâãããµã³350mlãå ãããšçµæ¶ãæåºããã
åããŠãïŒâã¢ã»ãã«ã¢ããâïŒâïœâããã«
âïŒâãããµãã·ã«ãªãã·ããšããŒã«ïŒèç¹65ã
68âïŒ23.5ïœãåŸãã å®æœäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâïŒïŒïŒïŒâ
ãžã¡ãã«ãã³ãžã«ïŒâïŒâãããµãã·ã«ãªãã·
ããšããŒã«ïŒååç©ïŒïŒã®åæã åæäŸïŒã§åŸãïŒâã¢ã»ãã«ã¢ããâïŒâãã
ãµãã·ã«ãªãã·ããšããŒã«20ïœããã«ãšã³150ml
äžã«æº¶è§£ããã¢ã³ããŒãªã¹ã15ïŒç±³åœããŒã ã»ã¢
ã³ãã»ããŒã¹ç€Ÿç»é²åæšïŒïŒïœãšå ±ã«80ã90âã«
å ç±ãããããã«Î±âã¡ãã«ã¹ãã¬ã³30mlã滎äž
ãçŽïŒæéãã®ãŸãŸå ç±ãããåå¿çµäºåŸãã¢ã³
ããŒãªã¹ã15ãå»ã液ãæ¿çž®ããã¡ã¿ããŒã«
å ããŠæ°·å·ãããšç®çç©ãæåºããããããå
ãã¡ã¿ããŒã«ã§ããæŽæµãããåé6.6ïœãåå
ç©ïŒã®èç¹84ã86âã å®æœäŸïŒïŒïŒâã¢ã»ãã«ã¢ããâïŒâïŒïŒâãšã
ã«âïŒâã¡ãã«ãã³ãã«ïŒâïŒâãããµãã·ã«
ãªãã·ããšããŒã«ååç©ïŒã®åæã ïŒâã¢ã»ãã«ã¢ããâïŒâãããµãã·ã«ãªãã·
ããšããŒã«25ïœãïŒâãšãã«âïŒâããã»ã³250
mlãã¢ã³ããŒãªã¹ãâ15 100ïœãããã³ãã«ãšã³
750mlãããªãæ··åç©ã80âã§ïŒæéå ç±æ¹æã
ãã次ãã§ã¢ã³ããŒãªã¹ãâ15ãå¥ãã液ã
ããã«ãšã³ãçå»ãããæ®æž£ã«ãããµã³150mlã
å ããïŒæéæ°·å·ãããçããçµæ¶ãåããã
ããµã³ã§æŽæµããåŸé¢šä¹Ÿãããåé6.0ïœãåå
ç©ïŒã®èç¹65ã67â æ¬çºæã®ååç©ãäžéäœãšããŠçšããŠãã«ã©ãŒ
æ¡æ£è»¢åæ³ã«æçšãªè²çŽ æŸåºã¬ããã¯ã¹ååç©ã
åæããããšãã§ããããã®ãããªã¬ããã¯ã¹å
åç©ã®ä»£è¡šäŸãšããŠäžèšäžè¬åŒïŒïŒã§è¡šãã
ããååç©ãæããããã ãã ãR1ïŒR2ïŒR3ïŒR4ïŒR5ã¯åŒïŒïŒãšå矩
ã§ãããã¯æ°Žé žåºããŸãã¯å æ°Žå解ã«ããæ°Žé ž
åºãäžããåºãè¡šããïŒColã¯è²çŽ ãŸãã¯è²çŽ å
é§äœãè¡šããã ã®å ·äœäŸãšããŠã¯æ°Žé žåºã®ã»ãã«ãççŽ æ°ïŒ
ã40奜ãŸããã¯ïŒãïŒãã奜ãŸããã¯ïŒãïŒã®ã¢
ã«ãã«âCOOâã§è¡šããããåºïŒäŸãã°ã¢ã»ã
ãã·ã«åºãããããªãã«ãªãã·åºãªã©ïŒãççŽ æ°
ïŒã40奜ãŸããã¯ïŒã15ãã奜ãŸããã¯ïŒãïŒã®
è³éŠæã«ã«ããã«ãªãã·åºïŒããšãã°ããã³ãŸã€
ã«åºã眮æãã³ãŸã€ã«åºãªã©ïŒããããããã Colã®äŸãšããŠã¯ã¢ãŸè²çŽ ãã¢ãŸã¡ãã³è²çŽ ã
ã€ã³ãã¢ããªã³è²çŽ ãã€ã³ãããšããŒã«è²çŽ ãã
ãªããšãã«ã¡ã¿ã³ç³»è²çŽ ãã¢ã³ã¹ã©ããã³è²çŽ ã
ã€ã³ãžãŽè²çŽ ãŸãã¯ãããã®éå±é¯å¡©çã ã®åºã
æããããã»ããå æ°Žå解ã«ããããããã®è²çŽ
ãäžãããã®ãšããŠã¯äŸãã°ç¹éæ48â125818
å·ãç±³åœç¹èš±3222196å·ããã³å3307947å·çã«èš
ãããããã«è²çŽ ã®å©è²å£ãã¢ã·ã«åãããããª
ãã®ãæããããšãã§ãããåŸè ã¯ãšãã«ããã
ãã®è²å圢æå€ãæå ä¹³å€ãšæ··åããŠå¡åžããå Ž
åã«èµ·ããå åžåã«åºã¥ãæžæãé²ãç®çã§è²çŽ
ã®åžåãé²å ã®éäžæçã«çæ³¢åãããŠãããã
ã«æçšã§ããããªãããã®ç®çã®ããã«ã¯ãåªæ
å€äžã«è»¢åããå Žåãšãä¹³å€å±€äžã«ååšããå Žå
ãšã§ãè²çžãç°ãªããããªè²çŽ ãå©çšããããšã
ã§ããããªããColéšã¯äŸãã°ã«ã«ããã·ã«åºã
ã¹ã«ãã³ã¢ããåºã®ãããªæ°Žæº¶æ§ãäžãããããª
åºãæããããšãã§ããã æ¬çºæã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ã¯æå ææã®çŸåæã«äœ¿çšãããã¢
ã«ã«ãªã«ãã€ãŠãã®ãŸãŸã®åœ¢ã§æ¡æ£ãŸãã¯æµåºã
ãŠããŸãããšãé¿ããããã«ãå®è³ªçã«æ¡æ£ãã
ãã¯æµåºããªããããããªãã©ã¹ãåºãå¿ èŠãšã
ãããã©ã¹ãåºã«èŠæ±ãããåºã®ãµã€ãºãããã
ã¯ççŽ æ°ã¯äœ¿çšããæ¡ä»¶ãããšãã°åŠçæéãã¢
ã«ã«ãªæ¿åºŠããColéšã«æãã氎溶æ§åºã®æ°ãšçš®
é¡ã«ããç°ãããå°ããšãR1.R2ïŒR3ïŒR4ããã³
R5ã®åèšã§ïŒä»¥äžã¯å¿ èŠã§ãããççŽ æ°ãå¿ èŠ
以äžã«å€§ãããªããšã溶解床ããåžå ä¿æ°ã®ç¹ã§
äžå©ãšãªã€ãŠããããåççã«ççŽ æ°ã®äžéãšã
ããã®ã¯ãªããäžè¬ã«R1ïŒR5ã®åèšãïŒã80ã
奜ãŸããã¯13ã40ãæãŸããç¯å²ã§ããã ãªãµãŒããã€ã¹ããŒã·ã€ïŒResareh
DisclnsureïŒèª13024å·ïŒâ75ïŒã«ã¯ïŒâã¹ã«ã
ãªã³ã¢ããããšããŒã«é¡ãèšèŒãããŠãããã®äž
ã§ïŒäœã«ã¢ã«ãã«åºãæããïŒâã¹ã«ããªã³ã¢ã
ãããšããŒã«ãçŸå掻æ§ããã»ãšãã©ãªããåŸã€
ãŠè²çŽ ãé¢è±ããªãããšã瀺ãããŠãããæ¬çºæ
ã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ããã¯ã¹å
åç©ã«ãããŠã¯ãããšããŒã«ã®ïŒäœã«R4Oâåºã
çµåãããããïŒäœã«ç¬¬äºçŽãŸãã¯ç¬¬äžçŽã®ã¢ã«
ãã«åºïŒããªãã¡R1R2R3CâåºïŒãçµåããŠãã
ããšãé倧ãªåçæ§èœäžã®å·®ç°ããããããŠãã
ããšã¯æããã§ãããç¹éæ51â113624ããã³ç¹
éæ53â149328èšèŒã®è²çŽ æŸåºã¬ããã¯ã¹ååç©
ã«æ¯èŒãããšæ¬çºæã®ååç©ãçšããŠåŸãããè²
çŽ æŸåºã¬ããã¯ã¹ååç©ã«ãããŠã¯ã第äºçŽãŸã
ã¯ç¬¬äžçŽã¢ã«ãã«ïŒR1R2R3CâåºïŒã®ç«äœé害ã«
ãã€ãŠé žåäœã®å æ°Žå解ã®å¯åå¿ããããããã
è²çŽ ã®æŸåºå¹çãåäžãããšããç¹ã§åªããŠã
ãããã®ããšã«ãã€ãŠãé žåãããååç©ã¯ãäº
å®äžç¡å¹åããããšãªããå¹çããæ¡æ£è²çŽ ãæŸ
åºããã æ¬çºæã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ã¯çŸåæã®ã¬ããã¯ã¹åå¿ã«ãã€ãŠ
ïœâããã³ã€ãããçæãããããå æ°Žå解ãã
ããŠãã¹ã«ããªã³ã¢ããéšãé¢è±ããã®ã§ãã
ããããã«ããçããïœâãã³ãŸããã³äœãæ¢è¿°
ã®ãããããã³é¡ã«æ¯ãæµ è²çãªåžåãããããª
ãããšãè²çŽ æŸåºåŸã®æ®è²ãå°ãããŠãããšèã
ãããã æ¬çºæã®ååç©ãçšããŠåŸãããè²çŽ æŸåºã¬ã
ãã¯ã¹ååç©ã¯ç¹éæ51â113624ãªã©ã®æ现æžã«
é瀺ãããŠããè²çŽ æŸåºã¬ããã¯ã¹ååç©ãšåæ§
ã«ã«ã©ãŒæ¡æ£è»¢åæ³æå ææã«çšããããã ç¹ã«å¥œãŸããã¯ãæ¬çºæãçšããŠåŸãããè²çŽ
æŸåºã¬ããã¯ã¹ååç©ã¯æ¬¡ã®äžè¬åŒã§è¡šããã
ãã ïŒãã ããR1ïŒR2ïŒR3ïŒR4ããã³Colã¯åŒïŒ
ïŒãšå矩ãè¡šããã5aã¯åŒïŒïŒãšå矩ïŒåŒ
ïŒïŒã§è¡šããããæ¬çºæã®è²çŽ æŸåºã¬ããã¯
ã¹ååç©ã®å ·äœäŸã次ã«ç€ºãã æ¬çºæã«æŒããäžè¬åŒïŒïŒã§è¡šããããå
åç©ã¯äžè¬ã«ã¢ãŸè²çŽ ã®ã¹ã«ããã«ãã©ã€ãïŒ
ïŒãšçš®ã ã®ææ©ãã©ã¹ãåºãæããïœâã¢ãã
ããšããŒã«èªå°äœïŒïŒãšçž®ååå¿ãããããš
ã«ãã€ãŠåæããããšãã§ããã ColâSO2X ïŒïŒ ïŒãã ãã¯ããã²ã³ååãä»ã®ç¬Šå·ã¯åŒ
ïŒïŒãšåçŸ©ïŒ è²çŽ éšããã³ãããã®ã¹ã«ããã«ãã©ã€ãïŒ
ïŒã®åææ³ã¯ãç¹éæ48â12581å·ãå48â
33826å·ãå49â114424å·ãå49â126332å·ãªã©
ã«èšèŒãããŠããã åŒïŒïŒã§è¡šããããååç©ã¯ãæ¬çºæã®å
åç©ïŒïŒãå æ°Žå解ããããšã«ãã€ãŠåŸãã
ããå æ°Žå解ã®æ¹æ³ãšããŠã¯ãåžéããå¡©é žãªã©
ã®é žã§åŠçããæ¹æ³ã簡䟿ã§ãããå ·äœäŸãšããŠ
次ã®åèåæäŸããããŠããã åèåæäŸïŒïŒïŒâã¢ããâïŒâïœâããã«âïŒ
âãããµãã·ã«ãªãã·ããšããŒã«å¡©é žå¡©ã®åæ
ïŒè±ã¢ã»ãã«åïŒ å®æœäŸïŒã§åŸãïŒâã¢ã»ãã«ã¢ããâïŒâïœâ
ããã«âïŒâãããµãã·ã«ãªãã·ããšããŒã«23.0
ïœããšã¿ããŒã«120mlã35ïŒ å¡©é ž96mlãæ··åãã
ïŒæéæ¹æéæµãããåå¿æ¶²ãå·åŽããã®ã¡ãæ
åºããçµæ¶ãåããŠãïŒâã¢ããâïŒâïœâã
ãã«âïŒâãããµãã·ã«ãªãã·ããšããŒã«å¡©é žå¡©
23.2ïœãåŸãã åèåæäŸïŒïŒïŒâã¢ããâïŒâïŒÎ±ïŒÎ±âãžã¡
ãã«ãã³ãžã«ïŒâïŒâãããµãã·ã«ãªãã·ããš
ããŒã«å¡©é žå¡©ã®åæ å®æœäŸïŒã§åŸãååç©6.4ïœããšã¿ããŒã«45ml
ããã³æ¿å¡©é ž30mlãšãšãã«ïŒæééæµãããåå¿
çµäºåŸãæŸå·ãããšçµæ¶ãæåºããã®ã§åã
ããåé6.1ïœ åèåæäŸïŒïŒïŒâã¢ããâïŒâïŒïŒâãšãã«â
ïŒâã¡ãã«ãã³ãã«ïŒâïŒâãããµãã·ã«ãªã
ã·ããšããŒã«å¡©é žå¡©ã®åæ å®æœäŸïŒã§åŸãïŒâã¢ã»ãã¢ããâïŒâïŒïŒâ
ãšãã«âïŒâã¡ãã«ãã³ãã«ïŒâïŒâãããµãã·
ã«ãªãã·ããšããŒã«ïŒïœã«ãšã¿ããŒã«30mlããã³
æ¿å¡©é ž25mlãå ããèžæ°æµŽäžã§ïŒæéå ç±ããã
次ãã§åå¿æ¶²ãæ°·å·ãããšããäºå±€ã«åãããã®
ã§æ²¹å±€ãåãåºããŠæžå§äžã«ä¹Ÿç¥ããã åé3.5ïœ ååç©ïŒïŒãšååç©ïŒïŒãšã®çž®ååå¿
ã¯ãéåžžå¡©åºæ§ç©è³ªã®ååšäžã«è¡ãªãããšãæãŸ
ããããããå¡©åºæ§ç©è³ªã®äŸãšããŠã¯ãã¢ã«ã«ãª
éå±ãããã¯ã¢ã«ã«ãªåéå±ã®æ°Žé žåç©ïŒããšã
ã°æ°Žé žåãããªãŠã ãæ°Žé žåã«ãªãŠã ãæ°Žé žåã
ãªãŠã ãæ°Žé žåã«ã«ã·ãŠã ãªã©ïŒãèèªæã¢ãã³
ïŒããšãã°ããªãšãã«ã¢ãã³ãªã©ïŒãè³éŠæã¢ãã³
ïŒããšãã°ïŒ®ïŒïŒ®âãžãšãã«ã¢ããªã³ãªã©ïŒããã
ãè³éŠæã¢ãã³ããšãã°ïŒããªãžã³ããããªã³ã
αâãβâããŸãã¯Î³âãã³ãªã³ãã«ããžã³ãã³
ãªãžã³ãïŒâïŒïŒ®ïŒïŒ®âãžã¡ãã«ã¢ããïŒããªãž
ã³ãªã©ïŒãããã³ãããç°å¡©åºïŒïŒïŒïŒâãžã¢ã¶
ãã·ã¯ããïŒïŒïŒïŒïŒãããã³âïŒïŒïŒïŒïŒâãž
ã¢ã¶ãã·ã¯ããïŒïŒïŒïŒïŒããŠã³ãã»ã³âïŒãª
ã©ïŒããããããããå¡©çŽ ã®å Žåãããªãã¡åŒ
ãïŒãã¹ã«ããã«ã¯ãã©ã€ãã§ããå Žåã«
ã¯ãç¹ã«äžèšã®ãã¡ãããè³éŠæã¢ãã³ïŒå¥œãŸã
ãã¯ããªãžã³ïŒãåªããŠããã次ã«æ¬çºæã®äžé
äœã䜿çšããããšã«ãã€ãŠãè²çŽ æŸåºã¬ããã¯ã¹
ååç©ãåæããäŸã瀺ãã åèåæäŸïŒïŒååç©DRRâïŒã®åæ (a) ïŒâïŒïŒâã¡ããã·ãšããã·ïŒâïŒâããã
ãã³ãŒã³ã¹ã«ãã³é žãããªãŠã ã®åæ 300mlã¡ãã«ã»ããœã«ãäžã«7.3ïœæ°ŽçŽ åãããª
ãŠã ïŒ50ïŒ æµåãã©ãã€ã³æžæ¿ç©ã®åœ¢ã§14.6ïœïŒ
ãå ããŠèª¿è£œãããããªãŠã âïŒâã¡ããã·âãš
ãã©ãŒã液ã«æ¹æãã€ã€ïŒâã¯ããâïŒâããã
ãã³ãŒã³ã¹ã«ãã³é žãããªãŠã ã55ïœå ãããå
å¿æ··åç©ãã湯济ã§30åé80ã85âã§å ç±æ¹æã
ããç±ãéãè¡ã€ãŠåŸãæ¯æ¶²ã«ã€ãœãããã«ã¢ã«
ã³ãŒã«1.5ãå ããŠæ¶æããããæåºçµæ¶ãã
éåŸãã€ãœãããã«ã¢ã«ã³ãŒã«100mlã«ãŠæŽæµã
ãã åé59ïœ m.p.238ã239â (b) ïŒâã¢ããâïŒâïŒïŒâã¡ããã·ãšããã·ïŒ
ãã³ãŒã³ã¹ã«ãã³é žã®åæ ïŒâïŒïŒâã¡ããã·ãšããã·ïŒâïŒâãããã
ã³ãŒã³ã¹ã«ãã³é ž30ïœãéå é30ïœãå¡©åã¢ã³ã¢
ããŠã 0.6ïœããã³æ°Ž60mlã®æ··å溶液ã80ã85â
ã«ä¿ã€ãŠïŒæéå ç±æ¹æãããåå¿çµäºåŸãäžæº¶
ç©ããå¥ãã液ã«ã€ãœãããã«ã¢ã«ã³ãŒã«200
mlå ããŠæ°·å·ãããææ¶ããçµæ¶ãåããã€ãœ
ãããã«ã¢ã«ã³ãŒã«50mlã«ãŠæŽæµãã颚也ããã åé23ïœ m.p.250âä»¥äž (c) ïŒâã·ã¢ãâïŒâïŒïŒâã¡ããã·ãšããã·â
ïŒâã¹ã«ãããšãã«ã¢ãŸïŒâïŒâããšãã«âïŒ
âãã©ãŸãã³ã®åæ æ°Žé žåãããªãŠã 8.0ïœãæ°Ž200mlãããªã溶液
ã«ãïŒâã¢ããâïŒâïŒïŒâã¡ããã·ãšããã·ïŒ
ãã³ãŒã³ã¹ã«ãã³é ž49.4ïœãå ããããã«äºç¡é ž
ãœãŒã13.8ïœã®æ°Žæº¶æ¶²ïŒ50mlïŒãå ãããå¥ã«æ¿
å¡©é ž60mlãæ°Ž400mlã§åžéããå¡©é žã調補ããïŒ
â以äžã§äžèšå¡©é žã滎äžããããã®åŸäžèšã®æ··å
液ãïŒâ以äžã§30åéæ¹æãåå¿ãå®çµããã
ïŒãã®æº¶æ¶²ããžã¢ãŸæ¶²ãšç§°ããïŒã å¥ã«æ°Žé žåãããªãŠã 16.0ïœãæ°Ž200mlãé ¢é ž
ãããªãŠã 33.0ïœããã³ã¡ã¿ããŒã«200mlãããª
ãæ··å溶液ã«ãïŒâã·ã¢ãâïŒâããšãã«âïŒâ
ãã©ãŸãã³37.0ïœãå ãã10â以äžã§äžèšèª¿è£œæž
ã®ãžã¢ãŸæ¶²ã滎äžããã滎äžçµäºåŸ10â以äžã§30
åéæ¹æããã€ãã§å®€æž©ã§ïŒæéæ¹æããåŸãæ
åºããçµæ¶ãåããã¢ã»ãã³200mlã§æŽæµãã
颚也ããã åé52.0ïœ m.p.263ã265â (d) ïŒâã·ã¢ãâïŒâïŒïŒâã¡ããã·ãšããã·â
ïŒâã¯ããã¹ã«ããã«ããšãã«ã¢ãŸïŒâïŒâã
ãšãã«âïŒâãã©ãŸãã³ã®åæ äžèš(1)ã§åŸãïŒâã·ã¢ãâïŒâïŒïŒâã¡ããã·
ãšããã·âïŒâã¹ã«ãããšãã«ã¢ãŸïŒâïŒâããš
ãã«âïŒâãã©ãŸãã³51.0ïœãã¢ã»ãã³250mlã
ãã³ãªãã·å¡©åãªã³50mlãããªãæ··å溶液ã«ïŒ®ïŒ
âãžã¡ãã«ã¢ã»ãã¢ãã50mlã50â以äžã§æ»Žäž
ããã滎äžåŸçŽïŒæéæ¹æããæ°·æ°Ž1.0ã®äžã«
åŸã ã«æ³šãã ãæåºããçµæ¶ãå¥åŸãã¢ã»ãã
ããªã«100mlã§æŽæµã颚也ããã åé46.7ïœ m.p. 181ã183â (e) ååç©DRRâïŒã®åæ ïŒïŒ®âãžã¡ãã«ã¢ã»ãã¢ãã20mlã«ãåèå
æäŸïŒã§åŸã4.4ïœã®ïŒâã¢ããâïŒâïœâãã
ã«âïŒâãããµãã·ã«ãªãã·âïŒâã¡ãã«âããš
ããŒã«å¡©é žå¡©ãšäžèš(d)ã§åŸãïŒâã·ã¢ãâïŒâ
ïŒïŒâã¡ããã·ãšããã·âïŒâã¯ããã¹ã«ããã«
ããšãã«ã¢ãŸïŒâïŒâããšãã«âïŒâãã©ãŸãã³
4.6ïœãšãå ãããäžèšã®æ··å溶液ãæ¹æãã€ã€
ããã«ããªãžã³4.7mlã滎äžãã滎äžåŸããã«å®€
æž©ã§ïŒæéæ¹æãããæ¹æããåŸãã¡ã¿ããŒã«30
mlãæ°Ž10mlãåå¿æ¶²ã«å ãããæåºããæ²¹ç¶ç©ã«
ãšã¿ããŒã«çŽ20mlãå ãããšçµæ¶ãæåºããã®ã§
åãããåé4.8ïœã
Claims (1)
- ãç¹èš±è«æ±ã®ç¯å²ã ïŒ äžè¬åŒïŒ ãã ã R1ããã³R2ã¯ãåãã§ãç°ãªã€ãŠããŠãããã
ããããã¢ã«ãã«åºãŸãã¯è³éŠæåºãè¡šããïŒ
R1ãšR2ãšãçµåããŠç°ã圢æããŠãããïŒ R3ã¯ãæ°ŽçŽ ååãã¢ã«ãã«åºãŸãã¯è³éŠæåºã
è¡šããïŒ R4ã¯ãã¢ã«ãã«åºãŸãã¯è³éŠæåºãè¡šããïŒ R5ã¯æ°ŽçŽ ååãã¢ã«ãã«åºãè¡šããïŒãã€R1ïŒ
R2ïŒR3ïŒR4ããã³R5ã®åèšççŽ æ°ã¯ïŒä»¥äžã§ã
ãã R6ã¯ã¡ãã«åºãè¡šããã ã§è¡šããããïœâã¢ã·ã«ã¢ããããšããŒã«èªå°
äœã ïŒ äžè¬åŒïŒïŒã§è¡šããããïœâã¢ã·ã«ã¢ãã
ããšããŒã«èªå°äœã®åææ³ã«ãããŠãåŒïŒïŒã®
ååç©ã«ãåŒïŒïŒã§è¡šããããååŠçš®ãäœçšã
ããããšãç¹åŸŽãšããåææ³ã ïŒãã ãR4ïŒR5ããã³R6ã¯åŒïŒïŒãšåçŸ©ïŒ ïŒãã ãR1ïŒR2ïŒããã³R3ã¯åŒïŒïŒãšå
矩ïŒ
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9118579A JPS5616452A (en) | 1979-07-18 | 1979-07-18 | O-acylaminophenol derivative and its preparation |
DE19803027128 DE3027128A1 (de) | 1979-07-18 | 1980-07-17 | O-aminophenolverbindungen |
GB8023571A GB2058051B (en) | 1979-07-18 | 1980-07-18 | 4,5-substituted o-aminophenol compounds |
US06/170,234 US4310693A (en) | 1979-07-18 | 1980-07-18 | o-Aminophenol compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9118579A JPS5616452A (en) | 1979-07-18 | 1979-07-18 | O-acylaminophenol derivative and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5616452A JPS5616452A (en) | 1981-02-17 |
JPS621386B2 true JPS621386B2 (ja) | 1987-01-13 |
Family
ID=14019383
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9118579A Granted JPS5616452A (en) | 1979-07-18 | 1979-07-18 | O-acylaminophenol derivative and its preparation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5616452A (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH044384Y2 (ja) * | 1986-11-21 | 1992-02-07 |
-
1979
- 1979-07-18 JP JP9118579A patent/JPS5616452A/ja active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH044384Y2 (ja) * | 1986-11-21 | 1992-02-07 |
Also Published As
Publication number | Publication date |
---|---|
JPS5616452A (en) | 1981-02-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS62262047A (ja) | åçèŠçŽ | |
US4009035A (en) | Process for forming cyan dye photographic images | |
JPS60218645A (ja) | ããã²ã³åéåçæå ææ | |
US4336322A (en) | Color photographic light-sensitive material | |
US4594426A (en) | Benzoxazole derivative intermediates for synthesis of dye releasing redox compounds | |
US4310693A (en) | o-Aminophenol compounds | |
EP0193051B1 (en) | 2-equivalent cyan dye-forming 5-hydroxy-6-acylamino-benzoxazole-2-one couplers, silver halide photographic elements and processes employing them | |
JPS621386B2 (ja) | ||
US4439518A (en) | Process for the production of a photographic image | |
US3770446A (en) | Color photographic silver halide material containing acetanilide couplers | |
US3337344A (en) | Color photographic silver halide emulsion | |
JPH02120737A (ja) | åçããã²ã³åéçµæç© | |
US4204867A (en) | Process for the production of color photographic images using new white coupler substances | |
US2979405A (en) | Light-sensitive photographic element containing a 1-hydroxy-2-naphthoic acid anilidecolor coupler | |
JPS633855B2 (ja) | ||
US2694718A (en) | Sulfobenzamides | |
JPH02148A (ja) | ã¢ãŸååç©ã®è£œæ³ | |
US2897079A (en) | Production of colored photographic images with oxodiazole couplers | |
US3652286A (en) | Color photographic silver halide multi-layer material containing cyan-forming couplers | |
JPH03369B2 (ja) | ||
US3890364A (en) | {60 -Aryl-b-(amino-phenyl)acrylonitriles with an O-dialkyl sulphamidoxy or sulfuric acid semi-ester group | |
JPS6361650B2 (ja) | ||
JPS6147412B2 (ja) | ||
JPS5950977B2 (ja) | ã«ã©âåçæå ææ | |
US5041605A (en) | Method of synthesizing phenolic cyan-dye-forming photographic couplers |