JPH0813759B2 - Method for producing alkoxybenzene derivative - Google Patents
Method for producing alkoxybenzene derivativeInfo
- Publication number
- JPH0813759B2 JPH0813759B2 JP62218498A JP21849887A JPH0813759B2 JP H0813759 B2 JPH0813759 B2 JP H0813759B2 JP 62218498 A JP62218498 A JP 62218498A JP 21849887 A JP21849887 A JP 21849887A JP H0813759 B2 JPH0813759 B2 JP H0813759B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- copper
- added
- general formula
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000005224 alkoxybenzenes Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000010949 copper Substances 0.000 claims description 33
- 150000001412 amines Chemical class 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000005749 Copper compound Substances 0.000 claims description 7
- 150000001880 copper compounds Chemical class 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 150000005045 1,10-phenanthrolines Chemical class 0.000 claims description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 150000002843 nonmetals Chemical group 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- -1 silver halide Chemical class 0.000 description 54
- 150000001875 compounds Chemical class 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 239000000203 mixture Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 26
- 239000013078 crystal Substances 0.000 description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 17
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 17
- 239000002585 base Substances 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 150000001879 copper Chemical class 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 7
- 150000004699 copper complex Chemical class 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 229960003280 cupric chloride Drugs 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- FKFCNFNWFJYIJU-UHFFFAOYSA-N 8-bromonaphthalen-1-amine Chemical compound C1=CC(Br)=C2C(N)=CC=CC2=C1 FKFCNFNWFJYIJU-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 5
- 229940045803 cuprous chloride Drugs 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- MIWPRBLEIBNZCI-UHFFFAOYSA-N COC1=CC=CC2=CC=CC(=C12)NS(=O)(=O)C Chemical compound COC1=CC=CC2=CC=CC(=C12)NS(=O)(=O)C MIWPRBLEIBNZCI-UHFFFAOYSA-N 0.000 description 4
- 229910020366 ClO 4 Inorganic materials 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- FVFPNSRKNRGYMY-UHFFFAOYSA-N OC(C)OC1=C(C=CC=C1)C(NC1=CC=CC=C1)=O Chemical compound OC(C)OC1=C(C=CC=C1)C(NC1=CC=CC=C1)=O FVFPNSRKNRGYMY-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- YXGZTNUNHBXFAX-UHFFFAOYSA-N copper;1,10-phenanthroline Chemical compound [Cu+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YXGZTNUNHBXFAX-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000010446 mirabilite Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- BHHGABOCAHPYMA-UHFFFAOYSA-N 2-bromo-N-phenylbenzamide Chemical compound BrC1=CC=CC=C1C(=O)NC1=CC=CC=C1 BHHGABOCAHPYMA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- MGEPFYUANOTGDE-UHFFFAOYSA-N C(=O)(OCC)NC1=CC=CC2=CC=CC(=C12)OCCO Chemical compound C(=O)(OCC)NC1=CC=CC2=CC=CC(=C12)OCCO MGEPFYUANOTGDE-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- HCWJMLZCVUEYPO-UHFFFAOYSA-N 2-naphthalen-1-yloxyethanol Chemical compound C1=CC=C2C(OCCO)=CC=CC2=C1 HCWJMLZCVUEYPO-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- PNORPNVSXFRWLF-UHFFFAOYSA-N BrC1=CC=CC2=CC=CC(=C12)NS(=O)(=O)C Chemical compound BrC1=CC=CC2=CC=CC(=C12)NS(=O)(=O)C PNORPNVSXFRWLF-UHFFFAOYSA-N 0.000 description 2
- MHSPVGITSHFBQN-UHFFFAOYSA-N C(=O)(OCC)NC1=C2C(=CC(=C(C2=CC=C1)O)C(NCCCOCCCCCCCCCCCC)=O)OCCO Chemical compound C(=O)(OCC)NC1=C2C(=CC(=C(C2=CC=C1)O)C(NCCCOCCCCCCCCCCCC)=O)OCCO MHSPVGITSHFBQN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
- ORUGHLFJLOOKSH-UHFFFAOYSA-N OC(C)OC1=CC=CC2=CC=CC(=C12)NS(=O)(=O)C Chemical compound OC(C)OC1=CC=CC2=CC=CC(=C12)NS(=O)(=O)C ORUGHLFJLOOKSH-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- CSMDMSPUGRVWIG-UHFFFAOYSA-N ethyl N-[6-(3-dodecoxypropylcarbamoyl)-5-hydroxynaphthalen-1-yl]carbamate Chemical compound C(=O)(OCC)NC1=C2C=CC(=C(C2=CC=C1)O)C(NCCCOCCCCCCCCCCCC)=O CSMDMSPUGRVWIG-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000400 lauroyl group Chemical group O=C([*])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 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MOIWUTXHVRECSZ-UHFFFAOYSA-N n-(8-bromonaphthalen-1-yl)acetamide Chemical compound C1=CC(Br)=C2C(NC(=O)C)=CC=CC2=C1 MOIWUTXHVRECSZ-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 description 2
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- HMMPCBAWTWYFLR-UHFFFAOYSA-N n-pyridin-2-ylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=N1 HMMPCBAWTWYFLR-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001117 oleyl 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])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000006503 p-nitrobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1[N+]([O-])=O)C([H])([H])* 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 208000011906 peptic ulcer disease Diseases 0.000 description 1
- ABOYDMHGKWRPFD-UHFFFAOYSA-N phenylmethanesulfonamide Chemical compound NS(=O)(=O)CC1=CC=CC=C1 ABOYDMHGKWRPFD-UHFFFAOYSA-N 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 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
- 238000001308 synthesis method Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、アルコキシベンゼン誘導体の製造方法に関
するものである。TECHNICAL FIELD The present invention relates to a method for producing an alkoxybenzene derivative.
（従来の技術） 本発明の目的化合物としてのアルコキシベンゼン誘導
体は後記一般式（II）で表わされる。このアルコキシベ
ンゼン誘導体において、ＹとR2が閉環したものとして示
される、１−アルコキシ−８−アミドナフタレン誘導体
から得られる５−アミド−1,4−ナフトハイドロキノン
誘導体は置換基R1及びR2を変更することによりその還元
性を調整することができ種々の還元剤や酸化防止剤とし
ての用途があり、さらに１−アルコキシ−８−アミドナ
フタレン誘導体やこれから誘導される８−アミド−１−
ナフトール誘導体、８−アルコキシ−１−ナフチルアミ
ン誘導体、８−アミノ−１−ナフトール誘導体等は染料
や生理活性を有する化合物（医薬・農薬等）へ誘導する
合成中間体としての広い用途が期待されている。(Prior Art) The alkoxybenzene derivative as the object compound of the present invention is represented by the following general formula (II). In this alkoxybenzene derivative, a 5-amido-1,4-naphthohydroquinone derivative obtained from a 1-alkoxy-8-amidonaphthalene derivative, which is shown as a ring of Y and R 2 closed, has substituents R 1 and R 2 Its reducibility can be adjusted by changing it, and it can be used as various reducing agents and antioxidants. Furthermore, 1-alkoxy-8-amidonaphthalene derivatives and 8-amido-1-
Naphthol derivatives, 8-alkoxy-1-naphthylamine derivatives, 8-amino-1-naphthol derivatives, and the like are expected to be widely used as synthetic intermediates for deriving dyes and compounds having physiological activity (pharmaceuticals, agricultural chemicals, etc.). .
さらに１−アルコキシ−８−アミドナフタレン誘導体
は写真化学分野においてシアン発色カプラーの合成中間
体として近年注目されつつある。５−アミド−１−ナフ
トール系シアン発色カプラーが、現像時の疲労現像液に
よる還元退色を受けにくく、しかも生成色素の暗熱堅牢
性にも優れていることが見出された（特開昭60−237448
号及び特開昭61−153640号）。Furthermore, 1-alkoxy-8-amidonaphthalene derivatives have recently been attracting attention as a synthetic intermediate for cyan color couplers in the field of photographic chemistry. It has been found that the 5-amide-1-naphthol cyan color coupler is less susceptible to reduction and discoloration by a fatigue developer during development, and is also excellent in the dark heat fastness of the resulting dye (JP-A-60). −237448
And JP-A-61-153640).
ところで、写真用カプラーはその発色色素の色相によ
って大別され（例えばイエロー発色カプラー、マゼンタ
発色カプラー、シアン発色カプラー等）、さらに発色反
応の化学量論から４当量カプラー及び２当量カプラーの
２種に大別される。４当量カプラーは理論的にはハロゲ
ン化銀４モルの消費によって色素１モルが生成するのに
対し、２当量カプラーはカプラーのカップリング位に離
脱基を有しており、ハロゲン化銀２モルの消費によって
色素１モルが生成するため省資源（節銀）の立場から有
利であることが知られている。さらに２当量カプラーは
その発色速度が大きいため写真感度の向上や現像時間の
短縮が可能となる（米国特許第3,476,563号、同第3,61
7,291号、同第3,880,661号、同第4,052,212号、同第4,1
47,766号、英国特許第1,531,927号、同第2,006,755号、
特開昭55−32071号、同56−1938号、同56−27147号など
参照）。By the way, photographic couplers are roughly classified according to the hue of the color forming dye (for example, yellow color forming coupler, magenta color forming coupler, cyan color forming coupler, etc.), and from the stoichiometry of the color forming reaction, they are classified into two types of 4 equivalent couplers and 2 equivalent couplers. Broadly divided. The 4-equivalent coupler theoretically produces 1 mole of the dye by consuming 4 moles of silver halide, while the 2-equivalent coupler has a leaving group at the coupling position of the coupler, It is known that it is advantageous from the standpoint of resource saving (silver saving) because 1 mol of the dye is produced by consumption. Further, since the 2-equivalent coupler has a high coloring speed, it is possible to improve the photographic sensitivity and shorten the developing time (US Pat. Nos. 3,476,563 and 3,61).
No. 7,291, No. 3,880,661, No. 4,052,212, No. 4,1
47,766, British Patent No. 1,531,927, No. 2,006,755,
See JP-A-55-32071, 56-1938, 56-27147, etc.).
こうして近年のカラーネガフィルムの高感度化に伴っ
て、カップリング位に離脱基を導入した２当量カプラー
が多用されるようになってきており、前記５−アミド−
１−ナフトール系シアン発色カプラーについてもその例
外ではなく２当量カプラー化が望まれていた。１−ナフ
トール系シアン発色カプラーを２当量化する一般的な方
法はカップリング位すなわち４位にアルコキシ基を導入
するものであり、（特開昭52−18315号、同54−66129
号、同54−14736号、同55−32071号、同56−1938号、同
56−12643号、同56−27147号など参照）、５−アミド−
１−ナフトール系シアン発色カプラーでは４−アルコキ
シ−５−アミド−１−ナフトール誘導体すなわち１−ア
ルコキシ−８−アミドナフタレン誘導体となる。Thus, with the recent increase in the sensitivity of color negative films, 2-equivalent couplers in which a leaving group is introduced at the coupling position have been frequently used.
The 1-naphthol-based cyan color couplers are no exception to this, and conversion to 2-equivalent couplers has been desired. A general method for converting a 1-naphthol cyan color coupler into two equivalents is to introduce an alkoxy group at the coupling position, that is, at the 4-position (JP-A Nos. 52-18315 and 54-66129).
No. 54-14736, No. 55-32071, No. 56-1938, No.
56-12643, 56-27147, etc.), 5-amide-
The 1-naphthol cyan color coupler is a 4-alkoxy-5-amido-1-naphthol derivative, that is, a 1-alkoxy-8-amidonaphthalene derivative.
また一般式（II）において、Ｙがカルボニル基である
として示される、１−アルコキシ−２−カルバモイルベ
ンゼン化合物は、生理活性物質｛例えば下熱、鎮痛作用
（特開昭49−124043号）、抗消化性潰瘍作用（特開昭57
−62263号、特公昭58−33866号）、血糖降下作用（特開
昭58−69812号）など｝、感熱記録材料用の非画像部の
光安定性改良剤（特開昭58−136490号）など、工業的に
極めて有用な化合物として知られている。Further, in the general formula (II), 1-alkoxy-2-carbamoylbenzene compound represented by Y as a carbonyl group is a physiologically active substance (for example, lower heat, analgesic action (JP-A-49-124043), Peptic ulcer action (JP-A-57
-62263, JP-B-58-33866), hypoglycemic action (JP-A-58-69812), etc., and light stability improving agent for non-image area for heat-sensitive recording material (JP-A-58-136490). Etc. are known as industrially extremely useful compounds.
さらに一般式（II）において、Ｙがスルホニル基であ
るとして示される、１−アルコキシ−２−スルファモイ
ルベンゼン化合物は、除草剤として有用であることが知
られている（米国特許第4,661,146号参照）。Further, in the general formula (II), 1-alkoxy-2-sulfamoylbenzene compounds represented by Y as a sulfonyl group are known to be useful as herbicides (see US Pat. No. 4,661,146). ).
このように、一般式（II）で表わされるアルコキシベ
ンゼン誘導体が、工業的に有用な化合物であることは明
らかである。これらのアルコキシベンゼン誘導体の合成
法として、従来用いられている方法は下記スキーム１に
代表される。Thus, it is clear that the alkoxybenzene derivative represented by the general formula (II) is an industrially useful compound. A conventionally used method for synthesizing these alkoxybenzene derivatives is represented by the following scheme 1.
すなわち、１−アルコキシ−２−カルバモイルベンゼ
ン化合物の場合を例にとって説明すると、その合成法と
しては、一般に下記スキーム１に示すように入手可能な
２−アルコキシ安息香酸誘導体の酸クロリドあるいは酸
無水物とアミンとの縮合反応が用いられる。That is, the case of a 1-alkoxy-2-carbamoylbenzene compound will be described as an example. As a synthetic method thereof, an acid chloride or acid anhydride of a 2-alkoxybenzoic acid derivative generally available as shown in the following scheme 1 is used. A condensation reaction with an amine is used.
（上記各一般式中、R11はベンゼン環上に置換可能な基
を示し、R12、R13はアキル基などを示し、ｎは０〜４の
整数を示す。） しかし、入手可能な２−アルコキシ安息香酸誘導体
（（IV）又は（Ｖ））は、単純な直鎖の２−アルコキシ
化合物がほとんどであり、アルコキシ基をさらに修飾
し、ポリマー等に担持させるのは不可能である。仮に、
２−ヒドロキシ安息香酸（サリチル酸）誘導体を出発原
料とし、修飾可能な２−（２−ヒドロキシエトキシ）安
息香酸誘導体等に変換したとしても、その酸クロリドあ
るいは酸無水物への変換、アミンとの縮合反応におい
て、さらに修飾可能な置換基（例えばヒドロキシ基）の
関与によって、反応が複雑になってしまう。 (In each of the above general formulas, R 11 represents a substitutable group on the benzene ring, R 12 and R 13 represent an alkyl group and the like, and n represents an integer of 0 to 4.) However, 2 available Most of the -alkoxybenzoic acid derivatives ((IV) or (V)) are simple linear 2-alkoxy compounds, and it is impossible to further modify the alkoxy group and to carry it on a polymer or the like. what if,
Even if a 2-hydroxybenzoic acid (salicylic acid) derivative is used as a starting material and converted into a modifiable 2- (2-hydroxyethoxy) benzoic acid derivative or the like, its conversion into an acid chloride or acid anhydride and condensation with an amine Involvement of further modifiable substituents (eg hydroxy groups) in the reaction complicates the reaction.
以上、述べた問題は、１−アルコキシ−２−カルバモ
イルベンゼン化合物に限られない。例えば、米国特許第
4,661,146号にあるように、１−アルコキシ−２−スル
ファモイルベンゼン類についても同様であり、アルコキ
シ基が、さらに修飾可能な２−ヒドロキシエトキシ基の
場合には、一旦、ヒドロキシ基を保護した後、縮合反応
を行っている。The problems described above are not limited to 1-alkoxy-2-carbamoylbenzene compounds. For example, US Patent No.
As described in 4,661,146, the same applies to 1-alkoxy-2-sulfamoylbenzenes. When the alkoxy group is a 2-hydroxyethoxy group which can be further modified, once the hydroxy group is protected, , A condensation reaction is performed.
そのため、下記スキーム２に示すような、アミド結合
を形成した後、アルコキシ基を導入するルートが検討さ
れている。Therefore, a route for introducing an alkoxy group after forming an amide bond as shown in the following scheme 2 is being studied.
（上記各一般式中、X11はハロゲン原子などの置換基を
示し、R11、R12及びR13とｎは前記と同じ意味をも
つ。） ここで、置換基X11がハロゲン原子の場合を考えてみ
ると、一般にハロゲノベンゼン類のハロゲン原子をアル
コキシ基に変換するには、アルコールと金属ナトリウム
から調製したナトリウムアルコキシドをアルコール及び
アミド（例えばジメチルホルムアミド）との混合溶媒中
で銅塩と共に加熱する方法が用いられている（例えば、
特開昭55−94329号参照）。 (In the above general formulas, X 11 represents a substituent such as a halogen atom, and R 11 , R 12 and R 13 and n have the same meanings as described above.) Here, when the substituent X 11 is a halogen atom In general, in order to convert a halogen atom of a halogenobenzene to an alkoxy group, a sodium alkoxide prepared from an alcohol and metallic sodium is heated with a copper salt in a mixed solvent of an alcohol and an amide (eg, dimethylformamide). Is used (for example,
See JP-A-55-94329).
（発明が解決しようとする問題点） しかし、このような従来の方法では、ナトリウムアル
コキシドなどのアルコキシドを必要とし、このものの調
製には、取扱いに注意を要するナトリウム金属などが用
いられている。そのため、その改良法として、より取扱
いの容易な酸化バリウムを用いる方法が提案されている
が（特開昭55−69536号、J.Org.Chem.,44,3305（197
9）；アルコキシフェノール類の合成法）他の基質に対
してもそのまま適用できるわけではなく、化合物の種
類、求核剤の種類、反応条件によって異なるが、還元的
脱ハロゲン化反応が目的とする置換反応と競争的に進行
する場合が多く、アルコキシドを用いる従来法と比べて
大きなメリットを有する合成法ではない。さらに、触媒
としてギ酸エステルを第一銅塩とともに用いるという改
良法も提案されているが（特開昭57−150442号）、この
場合、完全に禁水の条件が必要なこと、さらに不活性ガ
スとして一酸化炭素を用いるのが望ましいなど、工業的
スケールではかなり高度な技術を必要とする。(Problems to be Solved by the Invention) However, in such a conventional method, an alkoxide such as sodium alkoxide is required, and sodium metal or the like, which requires careful handling, is used for the preparation of the alkoxide. Therefore, as an improved method, a method using barium oxide, which is easier to handle, has been proposed (JP-A-55-69536, J. Org. Chem., 44, 3305 (197
9); Method for synthesizing alkoxyphenols) This method cannot be applied to other substrates as it is, but it depends on the type of compound, the type of nucleophile, and the reaction conditions. In many cases, it proceeds competitively with the substitution reaction, and is not a synthetic method having a great merit in comparison with the conventional method using an alkoxide. Further, an improved method has been proposed in which a formate ester is used as a catalyst together with a cuprous salt (JP-A-57-150442), but in this case, a condition of completely prohibiting water is required, and further, an inert gas is not used. As a result, it is desirable to use carbon monoxide as a material, which requires a fairly high level of technology on an industrial scale.
さらに、これらの改良法を含めて、従来のウルマン
（U11mann）縮合反応において、導入されるアルコキシ
基（一般式（IX）における−OR13）は、その炭素鎖の短
い無置換のもの（例えばメトキシ基、エトキシ基など）
がほとんどであり、置換アルコキシ基（例えば２−ヒド
ロキシエトキシ基）が導入できた例はない（例えば、J.
Chem.Soc.（Ｃ）312（1969）参照）。In addition, in the conventional U11mann condensation reaction including these improved methods, the introduced alkoxy group (-OR 13 in the general formula (IX)) has a short carbon chain (eg, methoxy). Group, ethoxy group, etc.)
In most cases, a substituted alkoxy group (for example, 2-hydroxyethoxy group) has not been introduced (for example, J.
Chem. Soc. (C) 312 (1969)).
したがって本発明の目的は、アルコキシベンゼン誘導
体を対応するハロゲノベンゼン誘導体より、温和な条件
にて収率よく合成しうる方法を提供することにある。加
えて、導入後容易に修飾しうるような置換アルコキシ基
（例えば２−ヒドロキシエトキシ基、３−ヒドロキシエ
トキシ基等）を収率よく導入しうる合成法を確立するこ
とにある。Therefore, an object of the present invention is to provide a method capable of synthesizing an alkoxybenzene derivative from a corresponding halogenobenzene derivative under mild conditions with good yield. In addition, it is to establish a synthetic method capable of introducing a substituted alkoxy group (for example, a 2-hydroxyethoxy group, a 3-hydroxyethoxy group, etc.) that can be easily modified after the introduction in a high yield.
（問題点を解決するための手段） 本発明者らは、こうした従来法の欠点を克服すべく、
種々の検討を重ねた結果、銅または銅塩とアミン類及び
塩基の存在下、ハロゲノベンゼン誘導体とアルコール類
とを反応させることにより、温和な条件下で収率よく、
かつ、高選択率で、目的とするアルコキシベンゼン誘導
体を得ることが可能であることを見出した。(Means for Solving Problems) In order to overcome the drawbacks of the conventional methods, the present inventors have
As a result of various studies, by reacting a halogenobenzene derivative with an alcohol in the presence of copper or a copper salt, an amine and a base, a good yield can be obtained under mild conditions.
It was also found that the desired alkoxybenzene derivative can be obtained with high selectivity.
すなわち本発明は、ハロゲノベンゼン誘導体とアルコ
ール類とを、銅もしくは銅化合物、アミン類及び塩基の
存在下で反応させることを特徴とするアルコキシベンゼ
ン誘導体の製造方法を提供するものである。That is, the present invention provides a method for producing an alkoxybenzene derivative, which comprises reacting a halogenobenzene derivative with an alcohol in the presence of copper or a copper compound, an amine and a base.
本発明の反応は次式で表わすことができる。 The reaction of the present invention can be represented by the following formula.
一般式（Ｉ）において、Ｘはハロゲン原子を表わし、
Ｙは−CO−、−SO2、R2と結合してナフタレン環を形成
する非金属原子群又はR1と結合して５員の含窒素ヘテロ
環基を形成する非金属原子群を表わし、R1は、アリール
基、アルキルカルボニル基、アルキルスルホニル基、ア
ルコキシカルボニル基又はＹと結合して５員の含窒素ヘ
テロ環基を形成する基を表わし、R2は芳香族環に置換可
能な基を表わし、ｍは０〜４の整数を表わす。ｍが２以
上の場合、R2は互いに同じであっても異なっていてもよ
い。ただし、ＹとR2が結合してナフタレン環を形成する
場合に限りｍは０から６の整数を表わす。一般式（II）
において、R3は、アルキル基を表わす。 In the general formula (I), X represents a halogen atom,
Y is -CO -, - SO 2, R 2 combine with represents a non-metallic atomic group forming a nitrogen-containing heterocyclic group having 5-membered combined with non-metallic atomic group, or R 1 to form a naphthalene ring, R 1 represents an aryl group, an alkylcarbonyl group, an alkylsulfonyl group, an alkoxycarbonyl group, or a group forming a 5-membered nitrogen-containing heterocyclic group by bonding with Y, and R 2 is a group capable of substituting for an aromatic ring. And m represents an integer of 0 to 4. When m is 2 or more, R 2 s may be the same or different from each other. However, m represents an integer of 0 to 6 only when Y and R 2 combine to form a naphthalene ring. General formula (II)
In, R 3 represents an alkyl group.
一般式（Ｉ）においてＸは、塩素原子、臭素原子、ヨ
ウ素原子、フッ素原子などであるが好ましくは塩素原子
又は臭素原子である。一般式（Ｉ）においてＹは、好ま
しくは として表わされる、原子１個を介して連結する（Ｘが結
合している炭素原子から数えて、４番目にR1が結合する
窒素原子がある）二価の連結基を表わす。ここで、R6は
水素原子、アルキル基又はアリール基を表わし、R7はR2
と結合してナフタレン環を形成する非金属原子群を表わ
し、R8は、R1と結合して５員の含窒素ヘテロ環を形成す
る非金属原子群を表わす。In the general formula (I), X is a chlorine atom, a bromine atom, an iodine atom, a fluorine atom or the like, preferably a chlorine atom or a bromine atom. In the general formula (I), Y is preferably A divalent linking group represented by the formula (3) is a divalent linking group linked through one atom (the nitrogen atom to which R 1 is bonded is fourth at the fourth position from the carbon atom to which X is bonded). Here, R 6 represents a hydrogen atom, an alkyl group or an aryl group, and R 7 represents R 2
Represents a non-metal atom group forming a naphthalene ring, and R 8 represents a non-metal atom group forming a 5-membered nitrogen-containing heterocycle by combining with R 1 .
R6は、より好ましくは、水素原子、炭素数１〜36のア
ルキル基、炭素数６〜36のアリール基を表わす。R 6 more preferably represents a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, or an aryl group having 6 to 36 carbon atoms.
R8は、R1と結合してイミダゾールのような５員含窒素
ヘテロ環を形成するがこれらはさらに芳香環、複素環と
縮合していてもよい。R 8 combines with R 1 to form a 5-membered nitrogen-containing heterocycle such as imidazole, which may be further condensed with an aromatic ring or a heterocycle.
一般式（Ｉ）において、R1は好ましくは、炭素数６〜
36のアリール基（例えば、フェニル、ｐ−トリル、ｐ−
アニシル、ｐ−ニトロフェニル、２−クロロ−５−エト
キシカルボニルフェニル）、炭素数２〜36のアルキルカ
ルボニル基｛例えば、アセチル、プロピオニル、ピバロ
イル、ドデカノイル、２−エチルヘキサノイル、２−
（2,4−ジ−ｔ−ペンチルフェノキシ）ブタノイル、ト
リフルオロアセチル、トリクロロアセチル｝、炭素数１
〜36のアルキルスルホニル基（例えばメタンスルホニ
ル、エタンスルホニル、ｎ−ブタンスルホニル、ベンジ
ルスルホニル、トリフルオロメタンスルホニル、ｎ−ド
デカンスルホニル、ｎ−ヘキサデカンスルホニル）、又
は炭素数２〜36のアルコキシカルボニル基（例えばメト
キシカルボニル、エトキシカルボニル、ｉ−ブトキシカ
ルボニル、ベンジルオキシカルボニル、ｔ−ブトキシカ
ルボニル、ドデシルオキシカルボニル）を表わす。一般
式（Ｉ）においてR2は好ましくは、ハロゲン原子（フッ
素原子、塩素原子、臭素原子）、炭素１〜18のアルキル
基（例えばメチル、エチル、ｉ−プロピル、ｔ−ブチ
ル、トリフルオロメチル、ベンジル、ｎ−ドデシル）、
カルボキシル、スルホ、ヒドロキシル、シアノ、炭素数
１〜37のカルバモイル基｛例えばカルバモイル、N,N−
ジメチルカルバモイル、N,N−ジエチルカルバモイル、
Ｎ−メチルカルバモイル、Ｎ−ブチルカルバモイル、Ｎ
−シクロヘキシルカルバモイル、N,N−ジヘキシルカル
バモイル、Ｎ−ドデシルカルバモイル、Ｎ−（３−ドデ
シルオキシプロピル）カルバモイル、Ｎ−〔３−（2,4
−ジ−ｔ−ペンチルフェノキシ）プロピル〕カルバモイ
ル、Ｎ−〔４−（2,4−ジ−ｔ−ペンチルフェノキシ）
ブチル〕カルバモイル｝、炭素数０〜36のスルフアモイ
ル基（例えばスルフアモイル、Ｎ−メチルスルフアモイ
ル、Ｎ−ブチルスルフアモイル、N,N−ジメチルスルフ
アモイル、N,N−ジエチルスルフアモイル、Ｎ−ドデシ
ルスルフアモイル）、炭素数１〜36のカルボンアミド基
（例えばホルムアミド、アセトアミド、トリフルオロア
セトアミド、プロパンアミド、ベンズアミド、ｐ−ニト
ロベンズアミド、ドデカンアミド）、炭素数１〜36のス
ルホンアミド基（例えばメタンスルホンアミド、エタン
スルホンアミド、ブタンスルホンアミド、トリフルオロ
メタンスルホンアミド、ベンゼンスルホンアミド、ｐ−
トルエンスルホンアミド、ベンジルスルホンアミド、ｎ
−ヘキサデカンスルホンアミド）、炭素数１〜36のアル
コキシ基（例えばメトキシ、エトキシ、メトキシエトキ
シ、ベンジルオキシ、ｎ−ドデシルオキシ）、炭素数２
〜36のアルコキシカルボニル基（例えばメトキシカルボ
ニル、エトキシカルボニル、ｎ−ドデシルオキシカルボ
ニル）、アミノ基（例えばアミノ、メチルアミノ、ジメ
チルアミノ、モルホリノ）、ニトロ基又は炭素数１〜24
のアシル基（例えばホルミル、アセチル、ベンゾイル、
ドデカノイル）を表わす。In the general formula (I), R 1 preferably has 6 to 6 carbon atoms.
36 aryl groups (eg phenyl, p-tolyl, p-
Anisyl, p-nitrophenyl, 2-chloro-5-ethoxycarbonylphenyl), an alkylcarbonyl group having 2 to 36 carbon atoms (for example, acetyl, propionyl, pivaloyl, dodecanoyl, 2-ethylhexanoyl, 2-
(2,4-di-t-pentylphenoxy) butanoyl, trifluoroacetyl, trichloroacetyl}, carbon number 1
To 36 alkylsulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, benzylsulfonyl, trifluoromethanesulfonyl, n-dodecanesulfonyl, n-hexadecanesulfonyl), or alkoxycarbonyl groups having 2 to 36 carbon atoms (eg, methoxy). Carbonyl, ethoxycarbonyl, i-butoxycarbonyl, benzyloxycarbonyl, t-butoxycarbonyl, dodecyloxycarbonyl). In formula (I), R 2 is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 18 carbon atoms (for example, methyl, ethyl, i-propyl, t-butyl, trifluoromethyl, Benzyl, n-dodecyl),
Carboxyl, sulfo, hydroxyl, cyano, a carbamoyl group having 1 to 37 carbon atoms {eg, carbamoyl, N, N-
Dimethylcarbamoyl, N, N-diethylcarbamoyl,
N-methylcarbamoyl, N-butylcarbamoyl, N
-Cyclohexylcarbamoyl, N, N-dihexylcarbamoyl, N-dodecylcarbamoyl, N- (3-dodecyloxypropyl) carbamoyl, N- [3- (2,4
-Di-t-pentylphenoxy) propyl] carbamoyl, N- [4- (2,4-di-t-pentylphenoxy)
Butyl] carbamoyl}, a sulfamoyl group having 0 to 36 carbon atoms (for example, sulfamoyl, N-methylsulfamoyl, N-butylsulfamoyl, N, N-dimethylsulfamoyl, N, N-diethylsulfamoyl, N -Dodecylsulfamoyl), a carbonamide group having 1 to 36 carbon atoms (for example, formamide, acetamide, trifluoroacetamide, propanamide, benzamide, p-nitrobenzamide, dodecaneamide), a sulfonamide group having 1 to 36 carbon atoms ( For example, methanesulfonamide, ethanesulfonamide, butanesulfonamide, trifluoromethanesulfonamide, benzenesulfonamide, p-
Toluenesulfonamide, benzylsulfonamide, n
-Hexadecanesulfonamide), an alkoxy group having 1 to 36 carbon atoms (eg, methoxy, ethoxy, methoxyethoxy, benzyloxy, n-dodecyloxy), 2 carbon atoms
To 36 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, n-dodecyloxycarbonyl), amino groups (eg amino, methylamino, dimethylamino, morpholino), nitro groups or 1 to 24 carbon atoms.
Acyl groups (eg formyl, acetyl, benzoyl,
Dodecanoyl).
一般式（Ｉ）で表わされる化合物は、より好ましく
は、一般式（Ｘ）〜（XIII）で表わされる化合物から選
ばれる。（一般式（Ｘ）〜（XIII）において、Ｘ、R1、
R2及びｍは、前記と同じ意味をもつ。） 一般式（Ｘ） 一般式（XI） 一般式（XII） 一般式（XIII） （Ｚは、 とともに５員環の複素環を形成するに必要な非金属原子
群を表わす。） 一般式（XIII）において、 とＺによって形成される５員環の複素環としてはピロー
ル、ピラゾール、イミダゾールなどが挙げられ、これら
は、さらに芳香環、複素環と縮合していてもよい。The compound represented by the general formula (I) is more preferably selected from the compounds represented by the general formulas (X) to (XIII). (In the general formulas (X) to (XIII), X, R 1 ,
R 2 and m have the same meaning as described above. ) General formula (X) General formula (XI) General formula (XII) General formula (XIII) (Z is Represents a nonmetallic atom group necessary for forming a 5-membered heterocycle. ) In the general formula (XIII), Examples of the 5-membered heterocycle formed by Z and Z include pyrrole, pyrazole, imidazole, and the like, and these may be further condensed with an aromatic ring or a heterocycle.
一般式（Ｉ）で表わされる化合物は、さらに好ましく
は一般式（Ｘ）、（XI）、（XII）、（XIII）から選ば
れる。The compound represented by the general formula (I) is more preferably selected from the general formulas (X), (XI), (XII) and (XIII).
一般式（II）において、R3はより好ましくは炭素数１
〜36の１級のアルキル基〔例えばメチル、エチル、プロ
ピル、ベンジル、２−ヒドロキシエチル、３−ヒドロキ
シプロピル、２−メトキシエチル、２−エチルヘキシ
ル、アリル、プロパルギル、フエネチル、２−フェノキ
シエチル、２−（ｐ−ニトロフェノキシ）エチル、２−
クロロエチル、２−ブロモエチル、ｎ−ヘキシル、２−
（２−ヒドロキシエトキシ）エチル、ｐ−ニトロベンジ
ル〕を表わす。In the general formula (II), R 3 more preferably has 1 carbon atom.
To 36 primary alkyl groups such as methyl, ethyl, propyl, benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethylhexyl, allyl, propargyl, phenethyl, 2-phenoxyethyl, 2- (P-Nitrophenoxy) ethyl, 2-
Chloroethyl, 2-bromoethyl, n-hexyl, 2-
(2-hydroxyethoxy) ethyl, p-nitrobenzyl].
本発明の反応は銅もしくは銅化合物、アミン類及び塩
基の存在下で行われる。銅化合物は酸化数１価〜２価の
ものいずれも用いることができる。銅化合物として好ま
しくは銅塩が用いられる。The reaction of the present invention is carried out in the presence of copper or a copper compound, amines and a base. As the copper compound, any of those having an oxidation number of 1 to 2 can be used. A copper salt is preferably used as the copper compound.
本発明において用いられる銅または銅塩としては既知
のものすべてが用いることができる。代表的なものは以
下の通りである。All known copper or copper salts used in the present invention can be used. The representative ones are as follows.
（イ）銅 粉末状、粉状、板状、鎖状または線状の銅 （ロ）１価の銅（無水物または水和物） 塩化第一銅、臭化第一銅、シアン化第一銅、沃化第一
銅、酸化第一銅、チオシアン酸第一銅等 （ハ）２価の銅（無水物または水和物） 酢酸銅、銅アセチルアセトネート、臭化第二銅、塩化
第二銅、クエン酸第二銅、塩化二アンモニウム銅、４−
シクロヘキシル酪酸銅、ギ酸銅、グルコン酸銅、水酸化
第二銅、硝酸銅、オレイン酸銅、酸化第二銅、リン酸第
二銅、塩化第二銅カリウム、硫酸銅、硫化第二銅、炭酸
銅、ドデカン酸銅、エチルアセト酢酸銅、フッ化銅、し
ゅう酸銅、過塩素酸銅、ピロリン酸銅、セレン酸銅、ス
テアリン酸銅、酒石酸銅、キサントゲン酸銅等 これらの銅または銅塩のうち本発明において好ましく
用いられるのは２価の銅塩（例えば酢酸銅、塩化第二
銅、臭化第二銅等）である。(A) Copper Powder, powder, plate, chain or linear copper (b) Monovalent copper (anhydrate or hydrate) Cuprous chloride, cuprous bromide, first cyanide Copper, cuprous iodide, cuprous oxide, cuprous thiocyanate, etc. (c) Divalent copper (anhydride or hydrate) Copper acetate, copper acetylacetonate, cupric bromide, cupric chloride Cupric, cupric citrate, copper diammonium chloride, 4-
Copper cyclohexylbutyrate, copper formate, copper gluconate, cupric hydroxide, copper nitrate, copper oleate, cupric oxide, cupric phosphate, potassium cupric chloride, copper sulfate, cupric sulfide, carbonic acid Copper, copper dodecanoate, copper ethylacetoacetate, copper fluoride, copper oxalate, copper perchlorate, copper pyrophosphate, copper selenate, copper stearate, copper tartrate, copper xanthate, etc. Of these copper or copper salts A divalent copper salt (eg, copper acetate, cupric chloride, cupric bromide, etc.) is preferably used in the present invention.
本発明に用いられるアミン類は、2,2′−ジピリジル
類又は1,10−フェナントロリン類から選ばれる少なくと
も１種であり、下記式で表わされるアミン類に包含さ
れ、2,2′−ジピリジル類として、例えば、2,2′−ジピ
リジル、2,2′−ジピリジルアミン、2,2′−ジピリジル
メタン、2,2′−ジピリジルケトンがあり、1,10−フェ
ナントロリン類としては、例えば、1,10−フェナントロ
リン、2,4−ジメチル−1,10−フェナントロリン、2,9−
ジメチル−1,10−フェナントロリン、2,4,7,9−テトラ
メチル−1,10−フェナントロリンがある。The amines used in the present invention is at least one selected from 2,2′-dipyridyls and 1,10-phenanthrolines, and they are included in the amines represented by the following formulas, and are 2,2′-dipyridyls. As, for example, 2,2'-dipyridyl, 2,2'-dipyridylamine, 2,2'-dipyridylmethane, 2,2'-dipyridyl ketone, 1,10-phenanthrolines, for example, 1, 10-phenanthroline, 2,4-dimethyl-1,10-phenanthroline, 2,9-
There are dimethyl-1,10-phenanthroline and 2,4,7,9-tetramethyl-1,10-phenanthroline.
一般式（XV） 式中R14、R15、R16及びR17はそれぞれ独立に水素原
子、炭素数０〜36のアミノ基（例えばアミノ基、N,N−
ジメチルアミノ基、ピロリジノ基、ピペリジノ基、モル
ホリノ基、N,N−ジエチルアミノ基、アニリノ基等）、
ヒドロキシ基、メルカプト基、炭素数１〜36のアルコキ
シ基（例えばメトキシ基、エトキシ基、メトキシエトキ
シ基、オクチルオキシ基等）、炭素数１〜36のアルキル
基（例えばメチル基、エチル基、ｉ−プロピル基、ｔ−
ブチル基、ｎ−ドデシル基等）、炭素数２〜36のアルケ
ニル基（例えばビニル基、アリル基、オレイル基等）、
炭素数６〜36のアリール基（例えばフェニル基、ナフチ
ル基、ｐ−トリル基、ｐ−ヒドロキシフェニル基等）及
び炭素数１〜24の複素環基（例えばピリジル、キノリ
ル、フリル、チエニル、ピリミジル、イミダゾリル等）
を表わす。General formula (XV) In the formula, R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom, an amino group having 0 to 36 carbon atoms (for example, an amino group, N, N-
Dimethylamino group, pyrrolidino group, piperidino group, morpholino group, N, N-diethylamino group, anilino group, etc.),
Hydroxy group, mercapto group, C1-C36 alkoxy group (for example, methoxy group, ethoxy group, methoxyethoxy group, octyloxy group, etc.), C1-C36 alkyl group (for example, methyl group, ethyl group, i- Propyl group, t-
Butyl group, n-dodecyl group, etc.), alkenyl group having 2 to 36 carbon atoms (for example, vinyl group, allyl group, oleyl group, etc.),
An aryl group having 6 to 36 carbon atoms (eg phenyl group, naphthyl group, p-tolyl group, p-hydroxyphenyl group etc.) and a heterocyclic group having 1 to 24 carbon atoms (eg pyridyl, quinolyl, furyl, thienyl, pyrimidyl, (Imidazolyl etc.)
Represents
R14、R15、R16及びR17はまたそれぞれ独立に炭素原子
またはヘテロ原子（例えば窒素原子、酸素原子、イオウ
原子、セレン原子等）であってR14とR15、R15とR16また
はR16とR17により置換もしくは無置換の５〜20員環の炭
化水素環（例えばベンゼン環、ナフタレン環、シクロヘ
キサン環、シクロペンタン環、シクロヘキセン環、シク
ロヘキサジエン環等）または複素環（例えばピリジン、
キノリン、ピリミジン、トリアジン、フラン、チオフェ
ン等）を構成する要素であってもよい。R 14 , R 15 , R 16 and R 17 are each independently a carbon atom or a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, etc.) and R 14 and R 15 , R 15 and R 16 Or a hydrocarbon ring having 5 to 20 membered ring which is substituted or unsubstituted by R 16 and R 17 (eg, benzene ring, naphthalene ring, cyclohexane ring, cyclopentane ring, cyclohexene ring, cyclohexadiene ring, etc.) or heterocycle (eg, pyridine ,
Quinoline, pyrimidine, triazine, furan, thiophene, etc.).
本発明において用いられる塩基としては通常の有機反
応に用いられる塩基を用いることができる。塩基として
はその共役酸の水中での解離定数（pKa）が９以上のも
のが好ましい。塩基の例としては水酸化ナトリウム、水
酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸
カリウム、炭酸リチウム、炭酸水素ナトリウム、炭酸水
素カリウム、水素化ナトリウム、水素化カリウム、水素
化リチウム、ナトリウムアミド、酸化カルシウム、酸化
バリウム、ｔ−ブトキシカリウムなどのアルカリ金属も
しくはアルカリ土類金属化合物並びにグアニジン、1,8
−ジアザビシクロ［5,4,0］−７−ウンデセン（DBU）、
1,5−ジアザビシクロ［4,3,0］−５−ノネン（DBN）等
がある。本発明において好ましく用いられる塩基として
は水酸化ナトリウム、水酸化カリウム、炭酸ナトリウ
ム、炭酸カリウム、水素化ナトリウム、DBU等がある。As the base used in the present invention, a base used in ordinary organic reactions can be used. As the base, one having a dissociation constant (pKa) of the conjugate acid in water of 9 or more is preferable. Examples of bases are sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydride, sodium amide, oxidation Alkali metal or alkaline earth metal compounds such as calcium, barium oxide, potassium t-butoxide and guanidine, 1,8
-Diazabicyclo [5,4,0] -7-undecene (DBU),
Examples include 1,5-diazabicyclo [4,3,0] -5-nonene (DBN). Bases preferably used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, DBU and the like.
本発明においてアミン類と銅もしくは銅化合物は別々
に反応系に添加してもよいが、あらかじめアミン類の銅
錯体を調製して銅錯体として同時に添加することもでき
る。本発明に用いる銅錯体としては１価または２価の銅
塩と一般式（XV）で表わされるアミン類との錯体が好ま
しく、特に好ましい錯体としては下記一般式（XVI）で
表わされる錯体を挙げることができる。In the present invention, amines and copper or a copper compound may be added to the reaction system separately, but it is also possible to prepare a copper complex of amines in advance and add them simultaneously as a copper complex. As the copper complex used in the present invention, a complex of a monovalent or divalent copper salt and an amine represented by the general formula (XV) is preferable, and a particularly preferable complex is a complex represented by the following general formula (XVI). be able to.
一般式（XVI） 〔Cu（Ｌ）ｌ〕（Ｔ）ｐ 一般式（XVI）においてはＬは一般式（XV）で表わさ
れる化合物と同じ意味を示し、ｌは１〜４の整数を示
し、Ｔは錯体のアニオンまたは共有結合成分を示す。ｐ
はCuとＴのチャージバランスをとるために必要な数（例
えば1/2、１、２等）を示す。例えばCuが２価でＴが１
価のアニオンのときｐは２である。ｐが複数のときＴは
同じであっても異なっていてもよい。本発明に用いる銅
錯体一般式（XVI）で表わされる銅錯体に他の異なる塩
が複合した複塩の形であってもよい。Ｔの例をアニオン
形で以下に示す。General formula (XVI) [Cu (L) 1 ] (T) p In general formula (XVI), L has the same meaning as in the compound represented by general formula (XV), and l represents an integer of 1 to 4, T represents the anion or covalent bond component of the complex. p
Indicates the number (eg, 1/2, 1, 2, etc.) required to balance the charge of Cu and T. For example, Cu is divalent and T is 1
In the case of a valent anion, p is 2. When p is plural, T may be the same or different. The copper complex used in the present invention may be in the form of a double salt in which another different salt is complexed with the copper complex represented by the general formula (XVI). Examples of T are shown below in anionic form.
F-、Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、NO2 -、N
O3 -、N3 -、SCN-、OH-、CN-、SO4 2-、SO3 2-、HSO4 -、HSO
3 -、NaSO4 -、NaSO3 -、CO3 2- 本発明において用いられる銅錯体の例として以下のも
のを挙げることができる。 F -, Cl -, Br - , I -, ClO 4 -, BF 4 -, CH 3 COO -, NO 2 -, N
O 3 -, N 3 -, SCN -, OH -, CN -, SO 4 2-, SO 3 2-, HSO 4 -, HSO
3 -, NaSO 4 -, NaSO 3 -, may be mentioned the following examples of the copper complex used in the CO 3 2- present invention.
〔Cu（py）２〕Cl2 〔Cu（py）２〕Br2 〔Cu（bpy）〕Cl2 〔Cu（bpy）〕Br2 〔Cu（bpy）２〕Cl2 〔Cu（bpy）２〕Cl（ClO4 -） 〔Cu（bpy）２〕I2 〔Cu（bpy）〕（NO3）２ 〔Cu（bpy）２〕（NO3）２ 〔Cu（bpy）３〕（NO3）２ 〔Cu（bpy）〕（SCN）２ 〔CuCl2（terp）〕 〔Cu（phen）２〕Cl2 〔Cu（phen）２〕（ClO4） 〔Cu（phen）３〕（ClO4）２ 〔Cu（phen）２〕NO3 〔Cu（phen）３〕（NO3）２ （ただし、py＝ピリジン、bpy＝2,2′−ビピリジル、ph
en＝1,10−フェナントロリン、terp＝2,2′:6′,2″−
ターピリジル） これらの銅錯体は水またはアルコール系溶媒中対応す
る銅塩とピリジン類とを混合することにより容易に得る
ことができる。これらの銅錯体の合成法及び性質につい
ては新実験化学講座、第８巻、「無機化合物の合成II
I」（丸善株式会社）に詳しい。[Cu (py) 2 ] Cl 2 [Cu (py) 2 ] Br 2 [Cu (bpy)] Cl 2 [Cu (bpy)] Br 2 [Cu (bpy) 2 ] Cl 2 [Cu (bpy) 2 ] Cl (ClO 4 -) [Cu (bpy) 2] I 2 [Cu (bpy)] (NO 3) 2 [Cu (bpy) 2] (NO 3) 2 [Cu (bpy) 3] (NO 3) 2 [Cu (bpy)] (SCN) 2 [CuCl 2 (terp)] [Cu (phen) 2] Cl 2 [Cu (phen) 2] (ClO 4) [Cu (phen) 3] (ClO 4) 2 [ Cu (phen) 2 ] NO 3 [Cu (phen) 3 ] (NO 3 ) 2 (where py = pyridine, bpy = 2,2′-bipyridyl, ph
en = 1,10-phenanthroline, terp = 2,2 ': 6', 2 "-
Terpyridyl) These copper complexes can be easily obtained by mixing the corresponding copper salt and pyridine in water or an alcohol solvent. For the synthesis method and properties of these copper complexes, New Experimental Chemistry Course, Volume 8, "Synthesis of Inorganic Compounds II"
Details on "I" (Maruzen Co., Ltd.)
次に本発明の反応の反応条件について詳細に述べる。 Next, the reaction conditions of the reaction of the present invention will be described in detail.
本発明におけるアルコール類の反応基質すなわちハロ
ゲノベンゼン化合物に対するモル比は0.1〜1000であ
り、好ましくは1.0〜200、さらに好ましくは10〜100で
ある。In the present invention, the molar ratio of the alcohol to the reaction substrate, that is, the halogenobenzene compound is 0.1 to 1000, preferably 1.0 to 200, and more preferably 10 to 100.
本発明における銅、銅化合物または銅錯体の反応基質
に対するモル比は1.0×10-10〜10であり、好ましくは1.
0×10-6〜1.0、さらに好ましくは1.0×10-3〜0.1であ
る。Copper in the present invention, the molar ratio of the copper compound or the copper complex to the reaction substrate is 1.0 × 10 -10 ~ 10, preferably 1.
It is 0 × 10 −6 to 1.0, and more preferably 1.0 × 10 −3 to 0.1.
本発明におけるアミン類の反応基質に対するモル比は
1.0×10-10〜1000、好ましくは1.0×10-6〜200、さらに
好ましくは1.0×10-3〜100である。ただしアミン類が一
般式（XV）で表わされる化合物であるときは反応基質に
対するモル比は好ましくは1.0×10-6〜1.0、さらに好ま
しくは1.0×10-3〜0.1である。The molar ratio of the amines to the reaction substrate in the present invention is
It is 1.0 × 10 −10 to 1000, preferably 1.0 × 10 −6 to 200, and more preferably 1.0 × 10 −3 to 100. However, when the amine is a compound represented by the general formula (XV), the molar ratio to the reaction substrate is preferably 1.0 × 10 −6 to 1.0, more preferably 1.0 × 10 −3 to 0.1.
本発明における塩基の反応基質に対するモル比は0.1
〜100、好ましくは0.5〜10、さらに好ましくは1.0〜3.0
である。In the present invention, the molar ratio of the base to the reaction substrate is 0.1.
~ 100, preferably 0.5-10, more preferably 1.0-3.0
Is.
アミン類がDBU、DBN、グアニジン等の強塩基であると
きは、アミン類は塩基の代わりとして用いることがで
き、この時アミン類の反応基質に対するモル比は前記塩
基のそれに準じる。ここで強塩基とはその共役酸の水中
での解離定数（pKa）が９以上の塩基のことを言う。When the amine is a strong base such as DBU, DBN or guanidine, the amine can be used as a substitute for the base, and the molar ratio of the amine to the reaction substrate is the same as that of the base. Here, the strong base means a base having a dissociation constant (pKa) of the conjugate acid in water of 9 or more.
本発明の反応における溶媒としてはアセトニトリル、
N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミ
ド、ジメチルスルホキシド、Ｎ−メチルピロリドン、テ
トラヒドロフラン、ジオキサン、ジメトキシエタン、ジ
グライム、エーテル、ヘキサメチルホスホリルトリアミ
ド、スルホラン、ジエチルカーボネート、1,3−ジメチ
ル−２−イミダゾリドン等を挙げることができるが、反
応に用いられるアルコール類またはアミン類（例えばピ
リジン、α−ピコリン、β−ピコリン、γ−ピコリン、
キノリン、2,6−ルチジン、2,4,6−コリジン、N,N,N′,
N′−テトラメチルエチレンジアミン、DBU、DBN等）を
過剰量用いて溶媒としても作用させるのがより好まし
い。As a solvent in the reaction of the present invention, acetonitrile,
N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, ether, hexamethylphosphoryltriamide, sulfolane, diethyl carbonate, 1,3-dimethyl- 2-imidazolidone and the like can be mentioned, but alcohols or amines used in the reaction (for example, pyridine, α-picoline, β-picoline, γ-picoline,
Quinoline, 2,6-lutidine, 2,4,6-collidine, N, N, N ′,
It is more preferable to use an excessive amount of N'-tetramethylethylenediamine, DBU, DBN, etc.) to act as a solvent.
反応温度は−78℃〜200℃、好ましくは−20℃〜100
℃、さらに好ましくは−10℃〜60℃である。The reaction temperature is -78 ° C to 200 ° C, preferably -20 ° C to 100 ° C.
C., more preferably -10.degree. C. to 60.degree.
（化合物の具体例） 以下に本発明の反応を適用する化合物の具体例を一般
式（Ｉ）及び（II）で示される化合物の組合せで示す
が、これらに限定されるものではない。なお、化合物１
−17）、２−（14）、２−（15）、２−（16）、２−
（17）、２−（19）、２−（20）、２−（21）、３−
（15）、３−（18）、３−（20）、３−（21）、３−
（22）は参考化合物である。(Specific Examples of Compounds) Specific examples of the compounds to which the reaction of the present invention is applied are shown below by a combination of compounds represented by the general formulas (I) and (II), but are not limited thereto. Compound 1
-17), 2- (14), 2- (15), 2- (16), 2-
(17), 2- (19), 2- (20), 2- (21), 3-
(15), 3- (18), 3- (20), 3- (21), 3-
(22) is a reference compound.
（発明の効果） 本発明方法によれば、アルコキシベンゼン誘導体を温
和な条件で収率よく、かつ高選択率で得ることができ
る。また本発明方法によればアルコキシ基を好収率で導
入することができ、さらに修飾して使用されるアルコキ
シベンゼン誘導体の合成方法として好適である。 (Effect of the Invention) According to the method of the present invention, an alkoxybenzene derivative can be obtained under mild conditions with good yield and high selectivity. Further, according to the method of the present invention, an alkoxy group can be introduced in a good yield, and it is suitable as a method for synthesizing an alkoxybenzene derivative which is further modified and used.
（実施例） 次に本発明を実施例に基づきさらに詳細に説明する。(Example) Next, the present invention will be described in more detail based on examples.
参考例１ １−アセトアミド−８−ヒドロキシエトキシナフタレ
ンの合成（例示化合物１−（８）の合成） L.H.Klemm,J.W.Sprague,E.Y.Mak,J.Org.Chem.,22,164
（1957）により８−ブロモ−１−ナフチルアミンを合成
した。すなわち、1,8−ジアミノナフタレン36gを2.4
の水に分散し、84mlの濃塩酸を加えスチームバス上で約
１時間加熱撹拌した。ろ過により不溶物を除去後氷−メ
タノール混合により冷却し、内温０〜５℃で亜硝酸ナト
リウム16gの水400ml溶液を約１時間で滴下した。さらに
１時間撹拌の後冷蔵庫にて１日静置した。生じたアズイ
ミノナフタレンの沈殿をろ過し、水洗し、次いで風乾
し、40gのアズイミノナフタレンを得た。Reference Example 1 Synthesis of 1-acetamido-8-hydroxyethoxynaphthalene (Synthesis of Exemplified Compound 1- (8)) LHKlemm, JWSprague, EYMak, J.Org.Chem., 22,164
8-Bromo-1-naphthylamine was synthesized according to (1957). That is, 36 g of 1,8-diaminonaphthalene is 2.4
Of water, 84 ml of concentrated hydrochloric acid was added, and the mixture was heated and stirred on a steam bath for about 1 hour. After removing the insoluble matter by filtration, the mixture was cooled with ice-methanol mixture, and a solution of 16 g of sodium nitrite in 400 ml of water was added dropwise at an internal temperature of 0 to 5 ° C. in about 1 hour. After stirring for an additional 1 hour, the mixture was allowed to stand in the refrigerator for 1 day. The resulting aziminonaphthalene precipitate was filtered, washed with water, and then air-dried to obtain 40 g of aziminonaphthalene.
濃臭化水素酸240mlに110℃で加熱撹拌下銅粉末16gを
加え30分間加熱した。アズイミノナフタレン40gを徐々
に加え、発泡が収まってからさらに30分間加熱した。50
0mlの水を加え加熱後熱時ろ過した。ろ液を冷却し、水
酸化ナトリウムで中和し、析出した結晶をろ過、水洗、
乾燥することにより８−ブロモ−１−ナフチルアミンを
24g得た。To 240 ml of concentrated hydrobromic acid, 16 g of copper powder was added with heating and stirring at 110 ° C., and the mixture was heated for 30 minutes. Azimino naphthalene (40 g) was gradually added, and after the foaming stopped, the mixture was heated for another 30 minutes. 50
After adding 0 ml of water and heating, the mixture was filtered while hot. The filtrate was cooled, neutralized with sodium hydroxide, and the precipitated crystals were filtered, washed with water,
8-Bromo-1-naphthylamine was obtained by drying.
I got 24g.
８−ブロモ−１−ナフチルアミン11.1gをN,N−ジメチ
ルホルムアミド50mlに溶解し、ピリジン8g及び無水酢酸
7.7gを加え80℃で３時間撹拌した。室温に冷却後500ml
の水を加え析出した結晶をろ過した。結晶を酢酸エチル
−トルエン混合溶媒より再結晶することにより１−アセ
トアミド−８−ブロモナフタレンを11.1g得た。11.1 g of 8-bromo-1-naphthylamine was dissolved in 50 ml of N, N-dimethylformamide to give 8 g of pyridine and acetic anhydride.
7.7 g was added and the mixture was stirred at 80 ° C. for 3 hours. 500 ml after cooling to room temperature
Water was added and the precipitated crystals were filtered. The crystals were recrystallized from a mixed solvent of ethyl acetate-toluene to obtain 11.1 g of 1-acetamido-8-bromonaphthalene.
エチレングリコール15.5gに60％水素化ナトリウム0.9
g、ピリジン19.8g、塩化第１銅25mgを順次加え、次いで
１−アセトアミド−８−ブロモナフタレン2.64gを少し
ずつ加えた。添加後さらに５時間室温で撹拌の後200ml
の水を加え析出した結晶をろ過した。結晶をトルエンよ
り再結晶することにより目的とする１−アセトアミド−
８−ヒドロキシエトキシナフタレンを2.11g（収率80
％）、融点177〜180℃ 参考例２ １−ヒドロキシエトキシ−８−メタンスルホンアミド
ナフタレンの合成（例示化合物１−（９）の合成） ８−ブロモ−１−ナフチルアミン11.1gをピリジン50m
lに溶解し、室温でメチルスルホニルクロリド8.6gを滴
下した。50℃で５時間反応の後室温に冷却し、300mlの
水を加え濃塩酸で中和し、析出した結晶をろ過、水洗、
乾燥した。結晶をトルエンより再結晶することにより１
−ブロモ−８−メタンスルホンアミドナフタレンを10.8
g得た。60% sodium hydride 0.9 in 15.5 g ethylene glycol
g, 19.8 g of pyridine and 25 mg of cuprous chloride were sequentially added, and then 2.64 g of 1-acetamido-8-bromonaphthalene was added little by little. 200 ml after stirring at room temperature for 5 hours after addition
Water was added and the precipitated crystals were filtered. By recrystallizing the crystal from toluene, the desired 1-acetamide-
2.11 g of 8-hydroxyethoxynaphthalene (yield 80
%), Melting point 177 to 180 ° C. Reference Example 2 Synthesis of 1-hydroxyethoxy-8-methanesulfonamidonaphthalene (Synthesis of Exemplified Compound 1- (9)) 8-Bromo-1-naphthylamine 11.1 g of pyridine 50 m
It was dissolved in 1 and 8.6 g of methylsulfonyl chloride was added dropwise at room temperature. After reacting at 50 ° C for 5 hours, the mixture was cooled to room temperature, 300 ml of water was added, the mixture was neutralized with concentrated hydrochloric acid, and the precipitated crystals were filtered, washed with water,
Dried. 1 by recrystallizing the crystal from toluene
-Bromo-8-methanesulfonamide naphthalene 10.8
g got.
エチレングリコール15.5gに水酸化ナトリウム1gを加
えスチームバス上で加熱撹拌して均一溶液とし室温に冷
却し、ピリジン19.8g及び塩化第二銅二水和物34mgを加
え、さらに１−ブロモ−８−メタンスルホンアミドナフ
タレンを3.00g徐々に加えた。３時間撹拌の後300mlの水
を加え濃塩酸で中和し、析出した結晶をろ過した。結晶
をトルエンより再結晶することにより目的とする１−ヒ
ドロキシエトキシ−８−メタンスルホンアミドナフタレ
ンを2.56g（収率91％）得た。融点84〜85℃ 参考例３ １−ヒドロキシエトキシ−８−メタンスメホンアミド
ナフタレンの合成（合成例２と異なる反応条件による例
示化合物１−（９）の合成） エチレングリコール7.8にDBU1.9g及び塩化第二銅二水
和物21mgを加えさらに１−ブロモ−８−メタンスルホン
アミドナフタレン1.5gを徐々に加えた。８時間室温で撹
拌の後300mlの水を加え、濃塩酸で中和し、析出した結
晶をろ過した。結晶をトルエンより再結晶することによ
り目的とする１−ヒドロキシエトキシ−８−メタンスル
ホンアミドナフタレンを1.25g（収率89％）得た。融点8
4.5〜85℃ 実施例１ １−カルボエトキシアミノ−８−ヒドロキシエトキシ
ナフタレンの合成（例示化合物１−（10）の合成） ８−ブロモ−１−ナフチルアミン11.1gをN,N−ジメチ
ルアセトアミド50mlに溶解し、80℃で撹拌しながらクロ
ロ炭酸エチル5.5gを滴下した。５時間撹拌の後冷却し、
500mlの水を加え、200mlの酢酸エチルにより抽出した。
酢酸エチル溶液を300mlの水で２回水洗の後硫酸ナトリ
ウムで乾燥し、濃縮した。残渣にチルエン−ｎ−ヘキサ
ン混合溶媒を加え晶析することにより１−ブロモ−８−
カルボエトキシアミノナフタレンの結晶を12.1g（収率8
2％）得た。Sodium hydroxide (1 g) was added to ethylene glycol (15.5 g), and the mixture was heated and stirred on a steam bath to form a uniform solution, which was cooled to room temperature. Pyridine (19.8 g) and cupric chloride dihydrate (34 mg) were added, and 1-bromo-8- 3.00 g of methanesulfonamide naphthalene was gradually added. After stirring for 3 hours, 300 ml of water was added, the mixture was neutralized with concentrated hydrochloric acid, and the precipitated crystals were filtered. By recrystallizing the crystals from toluene, 2.56 g (yield 91%) of the target 1-hydroxyethoxy-8-methanesulfonamidenaphthalene was obtained. Melting point 84-85 ° C Reference Example 3 Synthesis of 1-hydroxyethoxy-8-methanesmephonamide naphthalene (synthesis of Exemplified Compound 1- (9) under different reaction conditions from Synthesis Example 2) 1.9 g of DBU and chlorination of ethylene glycol 7.8. 21 mg of cupric dihydrate was added, and 1.5 g of 1-bromo-8-methanesulfonamidonaphthalene was gradually added. After stirring at room temperature for 8 hours, 300 ml of water was added, the mixture was neutralized with concentrated hydrochloric acid, and the precipitated crystals were filtered. The crystals were recrystallized from toluene to obtain 1.25 g (yield 89%) of the target 1-hydroxyethoxy-8-methanesulfonamidonaphthalene. Melting point 8
4.5-85 ° C. Example 1 Synthesis of 1-carboethoxyamino-8-hydroxyethoxynaphthalene (Synthesis of Exemplified Compound 1- (10)) 11.1 g of 8-bromo-1-naphthylamine was dissolved in 50 ml of N, N-dimethylacetamide. Then, 5.5 g of ethyl chlorocarbonate was added dropwise with stirring at 80 ° C. After stirring for 5 hours, cool down,
500 ml of water was added, and the mixture was extracted with 200 ml of ethyl acetate.
The ethyl acetate solution was washed twice with 300 ml of water, dried over sodium sulfate and concentrated. 1-Bromo-8- was obtained by adding tylene-n-hexane mixed solvent to the residue for crystallization.
12.1 g of crystals of carboethoxyaminonaphthalene (yield 8
2%) obtained.
DBU3.8gをエチレングリコール7.8gに溶解し、室温で
［Cu（bpy）２］Cl245mgを加えた。次いで１−ブロモ−
８−カルボエトキシアミノナフタレン2.94gを徐々に加
え、さらに２時間撹拌した。反応液に100mlを加え濃塩
酸で中和し析出した結晶をろ過した。結晶をトルエより
再結晶することにより目的とする１−カルボエトキシア
ミノ−８−ヒドロキシエトキシナフタレンを2.56g（収
率93％）得た。融点122〜123℃ 実施例２ １−カルボエトキシアミノ−８−ヒドロキシエトキシ
ナフタレンの合成（実施例４と異なる反応条件による例
示化合物１−（10）の合成） エチレングリコール25gに炭酸カリウム3.5gを加え、
スチームバス上で加熱撹拌して溶解し室温に冷却した。
［Cu（bpy）２］Cl245mgを加え、次いで１−ブロモ−８
−カルボエトキシアミノナフタレン2.94gを徐々に加
え、さらに２時間撹拌した。反応液に水200mlを加え析
出した結晶をろ過した。結晶をトルエンより再結晶する
ことにより目的とする１−カルボンエトキシアミノ−８
−ヒドロキシエトキシナフタレンを2.45g（収率89％）
得た。融点122〜123℃ 実施例３ １−メトキシ−８−メタンスルホンアミドナフタレン
の合成（例示化合物１−（３）の合成） 水酸化カリウム0.84をメタノール13gに加え、スチー
ムバス上で加熱撹拌して溶解し、室温に冷却した。2,
2′−ビピリジル31mg及び塩化第二銅二水和物17mgを加
え、次いで１−ブロモ−８−メタンスルホンアミドナフ
タレン3.00gを徐々に加え、さらに２時間撹拌した。反
応液に水100mlを加え、濃塩酸で中和し析出した結晶を
ろ過した。結晶をトルエンより再結晶することにより目
的とする１−メトキシ−８−メタンスルホンアミドナフ
タレンを2.16g（収率86％）得た。融点98〜100℃） 実施例４ １−メトキシ−８−メタンスルホンアミドナフタレン
の合成（実施例３と異なる反応条件による例示化合物１
−（３）の合成） ｔ−ブトキシカリウム1.7gをメタノール8gに分散し室
温で撹拌しながら ［Cu（phen）２］Cl249mgを加えた。１−ブロモ−８−
メタンスルホンアミドナフタレン3.00gを徐々に加えさ
らに２時間撹拌の後水100mlを加え析出した結晶をろ過
した。結晶をトルエンより再結晶することにより目的と
する１−メトキシ−８−メタンスルホンアミドナフタレ
ンを2.06g（収率82％）得た。融点99〜100℃ 実施例５ 種々の1.8−ジ置換ナフタレン類を用い、下記式によ
り下記第４表の反応条件でアルコール類を反応させた。
その結果を第４表にまとめた。3.8 g of DBU was dissolved in 7.8 g of ethylene glycol, and 45 mg of [Cu (bpy) 2 ] Cl 2 was added at room temperature. Then 1-bromo-
2.94 g of 8-carbethoxyaminonaphthalene was gradually added, and the mixture was further stirred for 2 hours. 100 ml was added to the reaction solution, which was neutralized with concentrated hydrochloric acid and the precipitated crystals were filtered. The crystals were recrystallized from tolue to obtain 2.56 g (yield 93%) of the target 1-carboethoxyamino-8-hydroxyethoxynaphthalene. Melting point 122-123 ° C. Example 2 Synthesis of 1-carboethoxyamino-8-hydroxyethoxynaphthalene (synthesis of Exemplified compound 1- (10) under different reaction conditions from Example 4) 3.5 g of potassium carbonate was added to 25 g of ethylene glycol. ,
The mixture was heated and stirred on a steam bath for dissolution and cooled to room temperature.
[Cu (bpy) 2 ] Cl 2 45 mg was added, followed by 1-bromo-8
-2.94 g of carboethoxyaminonaphthalene was gradually added, and the mixture was further stirred for 2 hours. 200 ml of water was added to the reaction solution, and the precipitated crystals were filtered. By recrystallizing the crystals from toluene, the desired 1-carboxylicethoxyamino-8
2.45 g of hydroxyethoxynaphthalene (yield 89%)
Obtained. Melting point 122-123 ° C. Example 3 Synthesis of 1-methoxy-8-methanesulfonamidonaphthalene (synthesis of Exemplified compound 1- (3)) 0.84 potassium hydroxide was added to 13 g of methanol, and the mixture was heated with stirring on a steam bath to be dissolved. And cooled to room temperature. 2,
31 mg of 2'-bipyridyl and 17 mg of cupric chloride dihydrate were added, and then 3.00 g of 1-bromo-8-methanesulfonamidonaphthalene was gradually added, and the mixture was further stirred for 2 hours. 100 ml of water was added to the reaction solution, which was neutralized with concentrated hydrochloric acid and the precipitated crystals were filtered. The crystals were recrystallized from toluene to obtain 2.16 g (yield 86%) of the target 1-methoxy-8-methanesulfonamidonaphthalene. Melting point 98 to 100 ° C.) Example 4 Synthesis of 1-methoxy-8-methanesulfonamidonaphthalene (Exemplified Compound 1 under reaction conditions different from those in Example 3)
- (3) Synthesis of) t-butoxy potassium 1.7g was added with stirring [Cu (phen) 2] Cl 2 49mg at room temperature were dispersed in methanol 8 g. 1-bromo-8-
Methanesulfonamide naphthalene (3.00 g) was gradually added, and the mixture was stirred for 2 hours, then 100 ml of water was added, and the precipitated crystals were filtered. The crystals were recrystallized from toluene to obtain 2.06 g (yield: 82%) of the target 1-methoxy-8-methanesulfonamidonaphthalene. Melting point 99-100 ° C. Example 5 Using various 1.8-disubstituted naphthalenes, alcohols were reacted according to the following formula under the reaction conditions shown in Table 4 below.
The results are summarized in Table 4.
第４表から明らかなように反応基質の１−ハロゲノナ
フタレンにおいてハロゲン原子のペリ位のアミド基（一
般式（Ｉ）においてR2NH−と規定した）の存在が本発明
の反応において必須である。すなわち本反応は１−アミ
ド−８−ハロゲノフタレン誘導体について基質特異的で
ある。また本反応において塩基、アミン及び銅または銅
塩のいずれもが必須であることが第４表より明らかであ
る。 As is apparent from Table 4, the presence of the amide group at the peri position of the halogen atom (defined as R 2 NH- in the general formula (I)) in the reaction substrate 1-halogenonaphthalene is essential in the reaction of the present invention. . That is, this reaction is substrate-specific for the 1-amido-8-halogenophthalene derivative. Further, it is clear from Table 4 that all of the base, amine and copper or copper salt are essential in this reaction.
実施例６ ５−カルボエトキシアミノ−２−［Ｎ−（３−ドデシ
ルオキシプロピル）カルバモイル］−４−ヒドロキシエ
トキシ−１−ナフトール（特開昭61−153640号特許請求
の範囲に包含されるシアン色素形成カプラー、例示化合
物１−（29））の合成 ５−カルボエトキシアミノ−２−［Ｎ−（３−ドデシ
ルオキシプロピル）カルバモイル］−１−ナフトール
（特開昭61−153640号明細書に記載の例示カプラー
（８））を同明細書に記載の方法に従って合成した。融
点79〜81℃ 次に５−カルボエトキシアミノ−２−［Ｎ−（３−ド
デシルオキシプロピル）カルバモイル］−１−ナフトー
ル50gをクロロホルム350mlに溶解し、水冷下撹拌しなが
ら臭素を16.4g約30分で滴下した。１時間撹拌の後反応
液を500mlの水で３回水洗し濃縮した。残渣にアセトニ
トリル400mlを加え溶解、晶析次いでろ過することによ
り４−ブロモ−５−カルボエトキシアミノ−２−［Ｎ−
（３−ドデシルオキシプロピル）カルバモイル］−１−
ナフトールを51.9g（収率90％）得た。融点94〜96℃ エチレングリコール120mlに水酸化ナトリウム2gを加
え、スチームバス上で加熱、溶解後水冷した。［Cu（dp
y）２］Cl290mgを加え、次いで４−ブロモ−５−カルボ
エトキシアミノ−２−［Ｎ−（３−ドデシルオキシプロ
ピル）カルバモイル］−１−ナフトール11.6gを加え
た。３時間撹拌の後水240mlを加え濃塩酸で中和した。
酢酸エチル200mlを加えて抽出し酢酸エチル溶液を300ml
の水で２回水洗した。酢酸エチル溶液を硫酸ナトリウム
で乾燥後約1/5量に濃縮しアセトニトリルを加えて晶析
した。析出した結晶をろ過、アセトニトリル洗浄次いで
乾燥することにより目的とする５−カルボエトキシアミ
ノ−２−［Ｎ−（３−ドデシルオキシプロピル）カルバ
モイル］−４−ヒドロキシエトキシ−１−ナフトールを
9.9g（収率88％）得た。融点133〜134℃ 同様にして下記反応に従い合成した化合物群を第５表
に示した。Example 6 5-Carboethoxyamino-2- [N- (3-dodecyloxypropyl) carbamoyl] -4-hydroxyethoxy-1-naphthol (Cyan dye within the scope of the patent application No. 61-153640) Forming Coupler, Synthesis of Exemplified Compound 1- (29)) 5-Carboethoxyamino-2- [N- (3-dodecyloxypropyl) carbamoyl] -1-naphthol (described in JP-A-61-153640). Exemplified coupler (8)) was synthesized according to the method described in the specification. Melting point 79-81 ° C. Next, 50 g of 5-carboethoxyamino-2- [N- (3-dodecyloxypropyl) carbamoyl] -1-naphthol was dissolved in 350 ml of chloroform, and 16.4 g of bromine was added while stirring under cooling with water. Dropped in minutes. After stirring for 1 hour, the reaction solution was washed with 500 ml of water three times and concentrated. To the residue was added 400 ml of acetonitrile, dissolved, crystallized and then filtered to give 4-bromo-5-carbethoxyamino-2- [N-
(3-Dodecyloxypropyl) carbamoyl] -1-
51.9 g (yield 90%) of naphthol was obtained. Melting point 94-96 ° C. 2 g of sodium hydroxide was added to 120 ml of ethylene glycol, heated on a steam bath, dissolved and cooled with water. [Cu (dp
y) 90 mg of 2 ] Cl 2 was added, followed by 11.6 g of 4-bromo-5-carbethoxyamino-2- [N- (3-dodecyloxypropyl) carbamoyl] -1-naphthol. After stirring for 3 hours, 240 ml of water was added and neutralized with concentrated hydrochloric acid.
200 ml of ethyl acetate was added for extraction, and 300 ml of ethyl acetate solution was extracted.
It was washed twice with water. The ethyl acetate solution was dried over sodium sulfate, concentrated to about 1/5 volume, and acetonitrile was added for crystallization. The precipitated crystals were filtered, washed with acetonitrile and then dried to give the desired 5-carbethoxyamino-2- [N- (3-dodecyloxypropyl) carbamoyl] -4-hydroxyethoxy-1-naphthol.
9.9 g (88% yield) was obtained. Melting point 133-134 ° C. Table 5 shows compounds similarly synthesized according to the following reaction.
参考例４ １−ヒドロキシエトキシ−２−フェニルカルバモイル
ベンゼン（例示化合物２−（２））の合成 ２−ブロモ安息香酸20.1gをトルエン200mlに分散し、
これに塩化チオニル14.5mlを加え、内温80〜90℃にて２
時間反応した。トルエンを留去して得られた油状物をア
ニリン8.4g、ジメチルアセトアミド120mlの溶液に滴下
し、室温にて１時間撹拌した。これに酢酸エチル300ml
を加え、２回水洗し、芒硝にて乾燥した。溶媒を留去し
た後、ｎ−ヘキサン−酢酸エチル系で晶析を行い、１−
ブロモ−２−フェニルカルバモイルベンゼン22.0gを得
た。 Reference Example 4 Synthesis of 1-Hydroxyethoxy-2-phenylcarbamoylbenzene (Exemplified Compound 2- (2)) 2-Bromobenzoic acid (20.1 g) was dispersed in toluene (200 ml),
Thionyl chloride (14.5 ml) was added to this, and the internal temperature was adjusted to 80-90 ° C.
Reacted for hours. The oily substance obtained by distilling off toluene was added dropwise to a solution of 8.4 g of aniline and 120 ml of dimethylacetamide, and the mixture was stirred at room temperature for 1 hour. 300 ml of ethyl acetate
Was added, and the mixture was washed twice with water and dried over Glauber's salt. After distilling off the solvent, crystallization was carried out in an n-hexane-ethyl acetate system to give 1-
22.0 g of bromo-2-phenylcarbamoylbenzene was obtained.
エチレングリコール15.6gにDBU1.9g、塩化第一銅50m
g、１−ブロモ−２−フェニルカルバモイルベンゼン1.3
8g、さらにピリジン14mlを順次加え、室温にて30分撹拌
した。これに酢酸エチル、水を加え、塩酸にて酸性化し
た後、有機層を２回水洗した。芒硝乾燥後、溶媒を留去
し、これにｎ−ヘキサンを加えて晶析を行い、目的とす
る１−ヒドロキシエトキシ−２−フェニルカルバモイル
ベンゼンを1.05g（収率81％）得た。融点114〜116.5℃ 実施例７ １−ヒドロキシエトキシ−２−フェニルカルバモイル
ベンゼン（例示化合物２−（２））の合成 エチレングリコール15.6gに水酸化ナトリウム0.5gを
加え、スチームバス上で加熱撹拌して均一溶液とした
後、室温に冷却し、塩化第二銅二水和物21mg、2,2′−
ビピリジル20mg、さらに１−ブロモ−２−フェニルカル
バモイルベンゼン1.38gを順次加え、室温で３時間撹拌
した。その後、実施例10と同様の後処理を行い、目的と
する１−ヒドロキシエトキシ−２−フェニルカルバモイ
ルベンゼンを1.20g（収率93％）得た。融点114.5〜116
℃ 参考例５ 例示化合物２−（16）の合成 ２−ブロモ安息香酸20.1gをトルエン200mlに分散し、
これに塩化チオニル14.5mlを加え、内温80〜90℃にて２
時間反応した。トルエンを留去して得られた油状物を３
−アミノピリジン9.4g、ジメチルアセトアミド120mlの
溶液に滴下し、室温にて１時間撹拌した。これに酢酸エ
チル300mlを加え、２回水洗し、芒硝にて乾燥した。溶
媒を留去した後、ヘキサン−酢酸エチルにて晶析を行
い、１−ブロモ−２−ピリジカルバモイルベンゼン20.1
gを得た。DBU 1.9g, cuprous chloride 50m to ethylene glycol 15.6g
g, 1-bromo-2-phenylcarbamoylbenzene 1.3
8 g and 14 ml of pyridine were sequentially added, and the mixture was stirred at room temperature for 30 minutes. Ethyl acetate and water were added to this, and after acidifying with hydrochloric acid, the organic layer was washed twice with water. After drying with Glauber's salt, the solvent was distilled off, and n-hexane was added thereto for crystallization to obtain 1.05 g (yield 81%) of 1-hydroxyethoxy-2-phenylcarbamoylbenzene of interest. Melting point 114 to 116.5 ° C. Example 7 Synthesis of 1-hydroxyethoxy-2-phenylcarbamoylbenzene (Exemplified compound 2- (2)) 0.56 g of sodium hydroxide was added to 15.6 g of ethylene glycol, and the mixture was heated with stirring on a steam bath. After forming a homogeneous solution, it was cooled to room temperature and cupric chloride dihydrate 21 mg, 2,2'-
Bipyridyl 20 mg and 1-bromo-2-phenylcarbamoylbenzene 1.38 g were sequentially added, and the mixture was stirred at room temperature for 3 hours. Then, the same post-treatment as in Example 10 was carried out to obtain 1.20 g (yield 93%) of the target 1-hydroxyethoxy-2-phenylcarbamoylbenzene. Melting point 114.5-116
C. Reference Example 5 Synthesis of Exemplified Compound 2- (16) 2-Bromobenzoic acid (20.1 g) was dispersed in toluene (200 ml),
Thionyl chloride (14.5 ml) was added to this, and the internal temperature was adjusted to 80-90 ° C.
Reacted for hours. The oily substance obtained by distilling off the toluene was 3
-Aminopyridine was added dropwise to a solution of 9.4 g and dimethylacetamide 120 ml, and the mixture was stirred at room temperature for 1 hour. To this, 300 ml of ethyl acetate was added, washed twice with water, and dried with sodium sulfate. After distilling off the solvent, crystallization was carried out with hexane-ethyl acetate to give 1-bromo-2-pyridicarbamoylbenzene 20.1.
got g.
メタノール20mlに、DBU 1.9g、CuCl2（bpy）２・2H2
O 44mg、１−ブロモ−２−ピリジルカルバモイルベン
ゼン1.39g、さらにピリジン10mlを順次加え、室温に
て、２時間撹拌した。これに酢酸エチル、水を加え、塩
酸にて中和した後、有機層を２回水洗した。芒硝乾燥
後、溶媒を留去し、メタノールから再結晶し、目的とす
る例示化合物２−（16）を0.92g（収率85％）得た。融
点112〜114℃ 実施例８ 例示化合物２−（６）の合成 エチレングリコール15.6mlとピリジン15mlの混合溶媒
に金属銅310mg、炭酸カリウム3.5gを加え、スチームバ
ス上で30分加熱撹拌した。室温まで冷却した後１−ブロ
モ−２−（４−ニトロフェニルカルバモイル）ベンゼン
1.60g、2.2′−ビピリジル20mgを加え、室温にて30分間
撹拌した。これに酢酸エチル、水を加え、塩酸にて中和
した後、分液を行い、有機層を２回水洗した。芒硝乾燥
後、溶媒を留去し、ヘキサン−イソプロパノールより晶
析して、例示化合物２−（６）1.30g（収率87％）を得
た。融点185〜187℃ 参考例６〜14 ２−カルバモイル−１−ハロゲンベンゼン化合物とア
ルコール類を第１表に示した化合物に代えた以外は参考
例５と同様にして１−アルコキシ−２−カルバモイルベ
ンゼン化合物を合成した。その結果を第６表に示した。Methanol 20ml, DBU 1.9g, CuCl 2 ( bpy) 2 · 2H 2
O 44 mg, 1-bromo-2-pyridylcarbamoylbenzene 1.39 g, and pyridine 10 ml were sequentially added, and the mixture was stirred at room temperature for 2 hours. Ethyl acetate and water were added to this, and after neutralizing with hydrochloric acid, the organic layer was washed twice with water. After drying with Glauber's salt, the solvent was distilled off and the residue was recrystallized from methanol to obtain 0.92 g (yield 85%) of the target Exemplified Compound 2- (16). Melting point 112-114 ° C. Example 8 Synthesis of Exemplified Compound 2- (6) To a mixed solvent of 15.6 ml of ethylene glycol and 15 ml of pyridine, 310 mg of metallic copper and 3.5 g of potassium carbonate were added, and the mixture was heated and stirred on a steam bath for 30 minutes. After cooling to room temperature 1-bromo-2- (4-nitrophenylcarbamoyl) benzene
1.60 g and 2.2'-bipyridyl 20 mg were added, and the mixture was stirred at room temperature for 30 minutes. After adding ethyl acetate and water thereto and neutralizing with hydrochloric acid, liquid separation was performed, and the organic layer was washed twice with water. After drying with Glauber's salt, the solvent was distilled off and the product was crystallized from hexane-isopropanol to obtain 1.30 g (yield 87%) of Exemplified compound 2- (6). Melting point 185 to 187 ° C Reference Examples 6 to 14 1-Alkoxy-2-carbamoylbenzene in the same manner as in Reference Example 5 except that the compounds shown in Table 1 were used instead of the 2-carbamoyl-1-halogenbenzene compounds and alcohols. The compound was synthesized. The results are shown in Table 6.
比較例１〜３ 塩基（NaOH）、アミン（2,2′−ビピリジン）及び銅
塩（CuCl2・2H2O）のいずれかを省いた以外は実施例７
と同様にして反応を行わせて１ヒドロキシエトキシ−２
−フェニルカルバモイルベンゼンを合成した。その結果
を第７表に示した。 Comparative Examples 1 to 3 bases (NaOH), amines (2,2'-bipyridine) and copper salts (CuCl 2 · 2H 2 O) except omitting one of Example 7
1 Hydroxyethoxy-2
-Phenylcarbamoylbenzene was synthesized. The results are shown in Table 7.
上記表の結果より、本反応において、塩基、アミン及
び銅または銅塩のいずれも必要であることがわかる。 From the results in the above table, it can be seen that the base, amine and copper or copper salt are all required in this reaction.
実施例９ 例示化合物３−（12）の合成 下記スキームに従い、原料Ｇを合成し、さらに銅塩を
用いる今回の反応を行った。Example 9 Synthesis of Exemplified Compound 3- (12) Starting material G was synthesized according to the following scheme, and this reaction using a copper salt was performed.
−１）原料Ｇの合成 ｏ−ニトロアニリン（Ｃ）4.1gをジメチルアセトアミ
ド50mlに溶かし、これに、ｏ−ブロモベンゾイルクロリ
ド（Ｄ）6.7gを滴下し、さらにアセトニトリル30mlを加
え、内温90℃にて３時間撹拌した。室温にもどし、酢酸
エチル200mlを加え、２回水洗した。少量残存するｏ−
ニトロアニリンを蒸留にて除去した後（b.p.85〜95℃/
0.3mmHg）、残渣をｎ−ヘキサン/i−プロパノールから
晶析して、化合物Ｅを7.0g得た。収率73％ 還元鉄12.8g、塩化アンモニウム0.7gに酢酸0.7ml、水
16ml、ｉ−プロパノール80mlを加え、窒素雰囲気下、１
時間加熱還流し、これに化合物Ｅ6.4gを加えて、さらに
30分加熱還流した。熱時に鉄粉をろ別後、ろ液を濃縮
し、水を加えて、結晶化させ、化合物Ｆをろ取した。4.
8g（収率82％） 次いで化合物Ｆ4.7g,p−トルエンスルホン酸0.3gをト
ルエン30mlに分散し、脱水しながら加熱還流を３時間行
った。室温にもどし、酢酸エチル100mlを加え、２回水
洗した。溶媒を留去後、カラムクロマトグラフィー（ク
ロロホルム）にて精製後、アセトニトリルより晶析し
て、化合物G2.8gを得た。収率64％ −２）例示化合物３−（12）の合成 ジエチレングリコール50mlに水素化ナトリウム（40
％）1.0gを少量ずつ加え、これに、塩化第一銅1.0g、2.
2′−ビピリジル1.6g、化合物Ｇ2.7gを順次加え、さら
にピリジン50mlを加え、12時間室温にて撹拌した。反応
混合物を、リン酸−カリウム水溶液に注ぎ、食塩を飽和
させた後、酢酸エチルで抽出した。溶媒留去後、カラム
クロマトグラフィー（クロロホルム／酢酸エチル＝1/
3）にて精製し、化合物３−（12）1.6gを得た。収率54
％、融点143.5〜146℃ 実施例10 例示化合物３−（４）の合成 下記スキームに従い、原料Ｊを合成し、さらに銅塩を
用いる今回の反応を行った。 -1) Synthesis of raw material G o-Nitroaniline ( C ) 4.1 g was dissolved in dimethylacetamide 50 ml, o-bromobenzoyl chloride ( D ) 6.7 g was added dropwise thereto, and acetonitrile 30 ml was added, and the internal temperature was 90 ° C. It was stirred for 3 hours. The mixture was returned to room temperature, 200 ml of ethyl acetate was added, and the mixture was washed twice with water. A small amount remains o-
After removing nitroaniline by distillation (bp85-95 ℃ /
0.3 mmHg) and the residue was crystallized from n-hexane / i-propanol to obtain 7.0 g of Compound E. Yield 73% Reduced iron 12.8 g, ammonium chloride 0.7 g, acetic acid 0.7 ml, water
16 ml, 80 ml of i-propanol were added, and under nitrogen atmosphere, 1
The mixture was heated under reflux for an hour, 6.4 g of Compound E was added thereto, and
The mixture was heated under reflux for 30 minutes. After iron powder was filtered off while hot, the filtrate was concentrated, water was added to crystallize, and compound F was collected by filtration. Four.
8 g (yield: 82%) Next, 4.7 g of compound F and 0.3 g of p-toluenesulfonic acid were dispersed in 30 ml of toluene, and heated under reflux for 3 hours while dehydrating. After returning to room temperature, 100 ml of ethyl acetate was added, and the mixture was washed twice with water. After the solvent was distilled off, the residue was purified by column chromatography (chloroform) and crystallized from acetonitrile to obtain compound G2.8g. Yield 64% -2) Synthesis of Exemplified Compound 3- (12) 50 ml of diethylene glycol was added with sodium hydride (40
%) 1.0 g in small portions, and cuprous chloride 1.0 g, 2.
1.6 g of 2'-bipyridyl and 2.7 g of compound G were sequentially added, 50 ml of pyridine was further added, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured into an aqueous solution of potassium phosphate-potassium to saturate the sodium chloride and then extracted with ethyl acetate. After distilling off the solvent, column chromatography (chloroform / ethyl acetate = 1 /
Purification in 3) yielded 1.6 g of compound 3- (12). Yield 54
%, Melting point 143.5 to 146 ° C. Example 10 Synthesis of Exemplified Compound 3- (4) Raw material J was synthesized according to the following scheme, and this reaction was further performed using a copper salt.
−１）原料Ｊの合成 ｐ−ジブロモベンゼン（Ｈ）80gにクロロスルホン酸9
0mlを加え、内温60℃にて１時間撹拌後、室温にもど
し、氷水に少量ずつ加えた。析出した結晶を水洗後、送
風乾燥を行い、化合物Ｉを90.1g得た。化合物Ｉ3.34g、
3,4−ジクロロアニリン1.62gをアセトニトリル30mlに分
散し、これにピリジン0.8mlを加えた後、２時間加熱還
流した。室温にもどし、酢酸エチル100mlを加え、水洗
を２回行った後、芒硝にて乾燥した。溶媒を留去後、ｎ
−ヘキサン／酢酸エチルにて晶析を行い、化合物Ｊ3.2g
を得た。融点176〜179℃ −２）例示化合物３−（４）の合成 ジエチレングリコール10mlに水素化ナトリウム0.1gを
加え、さらに塩化第一銅10mg、1,10−フェナントロリン
18mg、化合物Ｊ460mgを順次加えた後、ピリジン5mlを加
え、室温にて15時間撹拌した。酢酸エチル100mlを加
え、２回水洗後、溶媒を留去して得られた油状物をシリ
カゲル分取用薄層クロマトグラフィー（展開溶媒：クロ
ロホルム／酢酸エチル＝1/3）にて精製し、例示化合物
３−（４）を油状物として85mg得た。精製前の油状物中
に副生成物は検出されなかった。ｎ−ヘキサン−酢酸エ
チルにて結晶化し、例示化合物３−（４）を結晶として
67mg得た。融点111.5〜114℃ -1) Synthesis of Raw Material J 80 g of p-dibromobenzene ( H 2 ) was mixed with 9 g of chlorosulfonic acid.
0 ml was added, and the mixture was stirred at an internal temperature of 60 ° C for 1 hr, returned to room temperature, and added little by little to ice water. The precipitated crystals were washed with water and then air-dried to obtain 90.1 g of Compound I. Compound I 3.34 g,
1.62 g of 3,4-dichloroaniline was dispersed in 30 ml of acetonitrile, 0.8 ml of pyridine was added thereto, and the mixture was heated under reflux for 2 hours. The mixture was returned to room temperature, 100 ml of ethyl acetate was added, washed twice with water, and then dried with sodium sulfate. After distilling off the solvent, n
-Crystallization with hexane / ethyl acetate gave compound J 3.2g
I got Melting point 176 to 179 ° C -2) Synthesis of Exemplified Compound 3- (4) To 10 ml of diethylene glycol, 0.1 g of sodium hydride was added, and further 10 mg of cuprous chloride and 1,10-phenanthroline.
18 mg and Compound J ( 460 mg) were sequentially added, pyridine (5 ml) was added, and the mixture was stirred at room temperature for 15 hr. 100 ml of ethyl acetate was added, washed twice with water, the solvent was distilled off, and the resulting oil was purified by silica gel preparative thin layer chromatography (developing solvent: chloroform / ethyl acetate = 1/3). 85 mg of the compound 3- (4) was obtained as an oil. No by-products were detected in the oil before purification. Crystallization with n-hexane-ethyl acetate gave Exemplified Compound 3- (4) as crystals.
67 mg was obtained. Melting point 111.5-114 ° C
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｄ 213/81 // Ｂ０１Ｊ 31/02 １０２ Ｘ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area C07D 213/81 // B01J 31/02 102 X C07B 61/00 300
Claims (1)
ンゼン誘導体とR3OHで表わされるアルコール類とを、銅
もしくは銅化合物、2,2′−ジピリジル類及び1,10−フ
ェナントロリン類から選ばれるアミン類並びに塩基の存
在下で反応させ、下記一般式（II）で表わされるアルコ
キシベンゼン誘導体を得ることを特徴とするアルコキシ
ベンゼン誘導体の製造方法。 一般式（Ｉ） （式中、Ｘはハロゲン原子を表わし、Ｙは−CO−、SO2
−、R2と結合してナフタレン環を形成するのに必要な原
子群又はR1と結合して５員の含窒素ヘテロ環基を形成す
る非金属原子群を表わし、R1はアリール基、アルキルカ
ルボニル基、アルキルスルホニル基、アルコキシカルボ
ニル基又はＹと結合して５員の含窒素ヘテロ環基を形成
する非金属原子群を表わし、R2は芳香族環に置換可能な
基を表わし、ｍは０〜４の整数を表わす。ｍが２以上の
場合、R2は互いに同じであっても異なっていてもよい。
ただし、ＹとR2が結合してナフタレン環を形成する場合
に限り、ｍは０〜６の整数を表わす。） 一般式（II） （式中、R3はアルキル基を表わし、R1、R2、Ｙ、ｍはそ
れぞれ一般式（Ｉ）におけるものと同義である。1. A halogenobenzene derivative represented by the following general formula (I) and alcohols represented by R 3 OH are selected from copper or copper compounds, 2,2′-dipyridyls and 1,10-phenanthrolines. A method for producing an alkoxybenzene derivative, which comprises reacting in the presence of an amine and a base to obtain an alkoxybenzene derivative represented by the following general formula (II). General formula (I) (In the formula, X represents a halogen atom, Y represents —CO—, SO 2
- represents a non-metallic atomic group forming a bond to 5-membered nitrogen-containing heterocyclic group with the atom group or R 1 necessary to form a naphthalene ring bonded to R 2, R 1 is an aryl group, An alkylcarbonyl group, an alkylsulfonyl group, an alkoxycarbonyl group or a non-metal atom group forming a 5-membered nitrogen-containing heterocyclic group by bonding with Y, R 2 represents a group substitutable on an aromatic ring, and m Represents an integer of 0 to 4. When m is 2 or more, R 2 s may be the same or different from each other.
However, m represents an integer of 0 to 6 only when Y and R 2 combine to form a naphthalene ring. ) General formula (II) (In the formula, R 3 represents an alkyl group, and R 1 , R 2 , Y, and m each have the same meaning as in formula (I).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62218498A JPH0813759B2 (en) | 1986-09-01 | 1987-09-01 | Method for producing alkoxybenzene derivative |
| DE3819025A DE3819025A1 (en) | 1987-09-01 | 1988-06-03 | Process for the preparation of alkoxybenzene compounds |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20534486 | 1986-09-01 | ||
| JP61-205344 | 1986-09-01 | ||
| JP61-279608 | 1986-11-26 | ||
| JP27960886 | 1986-11-26 | ||
| JP62218498A JPH0813759B2 (en) | 1986-09-01 | 1987-09-01 | Method for producing alkoxybenzene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63258446A JPS63258446A (en) | 1988-10-25 |
| JPH0813759B2 true JPH0813759B2 (en) | 1996-02-14 |
Family
ID=27328484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62218498A Expired - Fee Related JPH0813759B2 (en) | 1986-09-01 | 1987-09-01 | Method for producing alkoxybenzene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813759B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5182296A (en) * | 1989-10-26 | 1993-01-26 | Tanabe Seiyaky Co., Ltd. | Naphthyloxazolidone derivatives |
| GB9119932D0 (en) * | 1991-09-18 | 1991-10-30 | Glaxo Group Ltd | Chemical compounds |
| GEP20135847B (en) | 2008-06-17 | 2013-06-10 | Millennium Pharm Inc | Boronate ester compounds and pharmaceutical compositions containing them |
| JP2013006855A (en) * | 2012-09-03 | 2013-01-10 | Millennium Pharmaceuticals Inc | Proteasome inhibitor |
| SG10202003693RA (en) | 2014-05-20 | 2020-05-28 | Millennium Pharm Inc | Boron-containing proteasome inhibitors for use after primary cancer therapy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5032144A (en) * | 1973-07-12 | 1975-03-28 | ||
| JPS5775948A (en) * | 1980-10-28 | 1982-05-12 | Ihara Chem Ind Co Ltd | Production of 2-(substituted phenoxy)phenylacetic acid |
| JPS5931755A (en) * | 1972-07-03 | 1984-02-20 | ライカ− ラボラトリ−ス インコ−ポレ−テツド | Substituted diphenyl ethers |
-
1987
- 1987-09-01 JP JP62218498A patent/JPH0813759B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5931755A (en) * | 1972-07-03 | 1984-02-20 | ライカ− ラボラトリ−ス インコ−ポレ−テツド | Substituted diphenyl ethers |
| JPS5032144A (en) * | 1973-07-12 | 1975-03-28 | ||
| JPS5775948A (en) * | 1980-10-28 | 1982-05-12 | Ihara Chem Ind Co Ltd | Production of 2-(substituted phenoxy)phenylacetic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63258446A (en) | 1988-10-25 |
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