JPH0526877B2 - - Google Patents
Info
- Publication number
- JPH0526877B2 JPH0526877B2 JP60113101A JP11310185A JPH0526877B2 JP H0526877 B2 JPH0526877 B2 JP H0526877B2 JP 60113101 A JP60113101 A JP 60113101A JP 11310185 A JP11310185 A JP 11310185A JP H0526877 B2 JPH0526877 B2 JP H0526877B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- ethyl
- substituted
- formula
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical class OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 19
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 18
- 229920002866 paraformaldehyde Polymers 0.000 claims description 18
- 239000003115 supporting electrolyte Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 150000007513 acids Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 5
- 229960003424 phenylacetic acid Drugs 0.000 claims description 5
- 239000003279 phenylacetic acid Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- -1 phenyloxy group Chemical group 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- DOCCDOCIYYDLGJ-UHFFFAOYSA-N ethyl 2-(4-methoxyphenyl)acetate Chemical compound CCOC(=O)CC1=CC=C(OC)C=C1 DOCCDOCIYYDLGJ-UHFFFAOYSA-N 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 229940049953 phenylacetate Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- QWJXGHJGOKFREC-UHFFFAOYSA-N ethyl 3-hydroxy-2-(4-methoxyphenyl)propanoate Chemical compound CCOC(=O)C(CO)C1=CC=C(OC)C=C1 QWJXGHJGOKFREC-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- NVWZHTVEPJITPR-UHFFFAOYSA-N ethyl 3-hydroxy-2-phenylpropanoate Chemical compound CCOC(=O)C(CO)C1=CC=CC=C1 NVWZHTVEPJITPR-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 2
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- QTMILHTUDCGNJF-UHFFFAOYSA-N ethyl 2-(2,5-dihydroxyphenyl)acetate Chemical compound CCOC(=O)CC1=CC(O)=CC=C1O QTMILHTUDCGNJF-UHFFFAOYSA-N 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- XGDZEDRBLVIUMX-UHFFFAOYSA-N methyl 2-(4-hydroxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(O)C=C1 XGDZEDRBLVIUMX-UHFFFAOYSA-N 0.000 description 2
- ZQYLDVNTWDEAJI-UHFFFAOYSA-N methyl 2-(4-methoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(OC)C=C1 ZQYLDVNTWDEAJI-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VNANKKHTFBNUCV-UHFFFAOYSA-N 1-piperidin-4-yl-2-(trifluoromethyl)benzimidazole Chemical compound FC(F)(F)C1=NC2=CC=CC=C2N1C1CCNCC1 VNANKKHTFBNUCV-UHFFFAOYSA-N 0.000 description 1
- KWAHADSKPFGJQF-UHFFFAOYSA-N 2-iodoprop-1-ene Chemical compound CC(I)=C KWAHADSKPFGJQF-UHFFFAOYSA-N 0.000 description 1
- CWSWWBPJNKCKBO-UHFFFAOYSA-N 2-methoxybut-3-en-1-ol Chemical compound COC(CO)C=C CWSWWBPJNKCKBO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PZVWKCGKIADPAU-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)aniline Chemical compound C1=CC(N)=CC=C1SC1=NC2=CC=CC=C2S1 PZVWKCGKIADPAU-UHFFFAOYSA-N 0.000 description 1
- VCYWCSZLXMMLLE-UHFFFAOYSA-N 4-Methoxybenzyl phenylacetate Chemical compound C1=CC(OC)=CC=C1COC(=O)CC1=CC=CC=C1 VCYWCSZLXMMLLE-UHFFFAOYSA-N 0.000 description 1
- NRPFNQUDKRYCNX-UHFFFAOYSA-N 4-methoxyphenylacetic acid Chemical compound COC1=CC=C(CC(O)=O)C=C1 NRPFNQUDKRYCNX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LDOXTQYWWYXYSQ-UHFFFAOYSA-N Butyl phenylacetate Chemical compound CCCCOC(=O)CC1=CC=CC=C1 LDOXTQYWWYXYSQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 1
- MIYFJEKZLFWKLZ-UHFFFAOYSA-N Phenylmethyl benzeneacetate Chemical compound C=1C=CC=CC=1COC(=O)CC1=CC=CC=C1 MIYFJEKZLFWKLZ-UHFFFAOYSA-N 0.000 description 1
- GXXFZZLGPFNITM-UHFFFAOYSA-N Propyl phenylacetate Chemical compound CCCOC(=O)CC1=CC=CC=C1 GXXFZZLGPFNITM-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- MCJLGGZHLZDDGT-UHFFFAOYSA-N benzyl 2-(4-methoxyphenyl)acetate Chemical compound C1=CC(OC)=CC=C1CC(=O)OCC1=CC=CC=C1 MCJLGGZHLZDDGT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WZKCZNJTDZCNMH-UHFFFAOYSA-N ethyl 2-(3,4-dimethoxyphenyl)acetate Chemical compound CCOC(=O)CC1=CC=C(OC)C(OC)=C1 WZKCZNJTDZCNMH-UHFFFAOYSA-N 0.000 description 1
- WIHVUBABONOVSO-UHFFFAOYSA-N ethyl 2-(3-chloro-4-cyclohexylphenyl)acetate Chemical compound ClC1=CC(CC(=O)OCC)=CC=C1C1CCCCC1 WIHVUBABONOVSO-UHFFFAOYSA-N 0.000 description 1
- PUIBRHJUTVHVPI-UHFFFAOYSA-N ethyl 2-(4-butoxyphenyl)acetate Chemical compound CCCCOC1=CC=C(CC(=O)OCC)C=C1 PUIBRHJUTVHVPI-UHFFFAOYSA-N 0.000 description 1
- CJSMRVHLBFFKMK-UHFFFAOYSA-N ethyl 2-(4-cyclohexylphenyl)acetate Chemical compound C1=CC(CC(=O)OCC)=CC=C1C1CCCCC1 CJSMRVHLBFFKMK-UHFFFAOYSA-N 0.000 description 1
- VMWJHHAOVXQCLE-UHFFFAOYSA-N ethyl 2-(4-fluorophenyl)acetate Chemical compound CCOC(=O)CC1=CC=C(F)C=C1 VMWJHHAOVXQCLE-UHFFFAOYSA-N 0.000 description 1
- RZKOHSYWTLEMBY-UHFFFAOYSA-N ethyl 2-(4-formylphenyl)acetate Chemical compound CCOC(=O)CC1=CC=C(C=O)C=C1 RZKOHSYWTLEMBY-UHFFFAOYSA-N 0.000 description 1
- HYUPPKVFCGIMDB-UHFFFAOYSA-N ethyl 2-(4-hydroxyphenyl)acetate Chemical compound CCOC(=O)CC1=CC=C(O)C=C1 HYUPPKVFCGIMDB-UHFFFAOYSA-N 0.000 description 1
- WPDHTKJCJJCOAZ-UHFFFAOYSA-N ethyl 2-(4-propoxyphenyl)acetate Chemical compound CCCOC1=CC=C(CC(=O)OCC)C=C1 WPDHTKJCJJCOAZ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- KHBWTRFWQROKJZ-UHFFFAOYSA-N methyl 2-(2-chlorophenyl)acetate Chemical compound COC(=O)CC1=CC=CC=C1Cl KHBWTRFWQROKJZ-UHFFFAOYSA-N 0.000 description 1
- BNQRSYFOIRGRKV-UHFFFAOYSA-N methyl 2-(2-methoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=CC=C1OC BNQRSYFOIRGRKV-UHFFFAOYSA-N 0.000 description 1
- UGFILLIGHGZLHE-UHFFFAOYSA-N methyl 2-(3,4-dihydroxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(O)C(O)=C1 UGFILLIGHGZLHE-UHFFFAOYSA-N 0.000 description 1
- QTXILVCSTXQKLF-UHFFFAOYSA-N methyl 2-(3-benzoylphenyl)acetate Chemical compound COC(=O)CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 QTXILVCSTXQKLF-UHFFFAOYSA-N 0.000 description 1
- DEVITRVUTHLYIP-UHFFFAOYSA-N methyl 2-(3-phenoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=CC(OC=2C=CC=CC=2)=C1 DEVITRVUTHLYIP-UHFFFAOYSA-N 0.000 description 1
- PYSYDGVIWZCWSC-UHFFFAOYSA-N methyl 2-(4-acetylphenyl)acetate Chemical compound COC(=O)CC1=CC=C(C(C)=O)C=C1 PYSYDGVIWZCWSC-UHFFFAOYSA-N 0.000 description 1
- ILHSYAQZDNDPIL-UHFFFAOYSA-N methyl 2-(4-benzylphenyl)acetate Chemical compound C1=CC(CC(=O)OC)=CC=C1CC1=CC=CC=C1 ILHSYAQZDNDPIL-UHFFFAOYSA-N 0.000 description 1
- JJJSFAGPWHEUBT-UHFFFAOYSA-N methyl 2-(4-hydroxy-3-methoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(O)C(OC)=C1 JJJSFAGPWHEUBT-UHFFFAOYSA-N 0.000 description 1
- LSAGWGNECLEVPE-UHFFFAOYSA-N methyl 2-(4-methylphenyl)acetate Chemical compound COC(=O)CC1=CC=C(C)C=C1 LSAGWGNECLEVPE-UHFFFAOYSA-N 0.000 description 1
- SRIBJRZQDFBVQC-UHFFFAOYSA-N methyl 2-(4-phenylphenyl)acetate Chemical group C1=CC(CC(=O)OC)=CC=C1C1=CC=CC=C1 SRIBJRZQDFBVQC-UHFFFAOYSA-N 0.000 description 1
- NVJAXNOSRPVIIT-UHFFFAOYSA-N methyl 2-[4-(2-methylpropyl)phenyl]acetate Chemical compound COC(=O)CC1=CC=C(CC(C)C)C=C1 NVJAXNOSRPVIIT-UHFFFAOYSA-N 0.000 description 1
- LLDQUDYCTIKKFV-UHFFFAOYSA-N methyl 2-[4-(hydroxymethyl)phenyl]acetate Chemical compound COC(=O)CC1=CC=C(CO)C=C1 LLDQUDYCTIKKFV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- USVNNHYNCCJCCP-UHFFFAOYSA-N phenyl 2-phenylacetate Chemical compound C=1C=CC=CC=1OC(=O)CC1=CC=CC=C1 USVNNHYNCCJCCP-UHFFFAOYSA-N 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- RIEKNUTZBRBQRY-UHFFFAOYSA-N propyl 2-(4-methoxyphenyl)acetate Chemical compound CCCOC(=O)CC1=CC=C(OC)C=C1 RIEKNUTZBRBQRY-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- FLYWOGRYUZXTIZ-UHFFFAOYSA-N tetraazanium;tetrabromide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Br-].[Br-].[Br-].[Br-] FLYWOGRYUZXTIZ-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- KRRBFUJMQBDDPR-UHFFFAOYSA-N tetrabutylazanium;cyanide Chemical compound N#[C-].CCCC[N+](CCCC)(CCCC)CCCC KRRBFUJMQBDDPR-UHFFFAOYSA-N 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- PCZOZSATUTWXIC-UHFFFAOYSA-N tetraethylazanium;cyanide Chemical compound N#[C-].CC[N+](CC)(CC)CC PCZOZSATUTWXIC-UHFFFAOYSA-N 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- OSXXGBUMRXAAFP-UHFFFAOYSA-N tetramethylazanium;cyanide Chemical compound N#[C-].C[N+](C)(C)C OSXXGBUMRXAAFP-UHFFFAOYSA-N 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZCPSWAFANXCCOT-UHFFFAOYSA-N trichloromethanesulfonyl chloride Chemical compound ClC(Cl)(Cl)S(Cl)(=O)=O ZCPSWAFANXCCOT-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
産業上の利用分野
本発明は置換トロパ酸類の製造方法に関する。
更に詳しくは置換フエニル酢酸類とパラホルムア
ルデヒドを、支持電解質の存在下電解還元するか
または、パラホルムアルデヒドを支持電解質の存
在下電解還元し、得られた還元生成物に置換フエ
ニル酢酸類を反応させることを特徴とする置換ト
ロパ酸類の製造方法に関する。
従来の技術
置換トロパ酸類は医薬品の中間体として有用な
化合物である。しかしながらその製造方法に関し
ては工業的に有利な方法は未だ見出されていな
い。即ち置換トロパ酸類の製法としては４−メト
キシフエニル酢酸エチルにDMSO（ジメチルスル
ホキシド）中、ナトリウムエトキシドの存在下
で、パラホルムアルデヒドを反応させて４−メト
キシトロパ酸エチルを41％の収率で得ている方法
〔Arch.Pharm.（Weinheim、Ger.）第305巻、839
頁（1972）；CA78.42988u〕、また置換フエニル酢
酸エステル誘導体に前記と同様にアルカリ金属ア
ルコラートの存在下で、DMSO中パラホルムア
ルデヒドを反応させて置換トロパ酸類を得る方法
〔Czech.CS195、615（CA97.144582s）、特開昭54−
103830号〕等数例が知られているが、これらの化
学的方法は強力な塩基であるアルカリ金属アルコ
ラートを触媒として用いること、かつこの触媒は
空気中の水分によつて容易に分解されるのでその
調製、保管に特別の注意を払う必要がある等の点
で難がある。さらに転化率を上げるために反応温
度を高くとる必要があり望ましくない副反応が同
時に進行し、目的の置換トロパ酸類の収率および
選択率が低いという欠点がある。
発明が解決しようとする問題点
取扱いの面倒なアルコラート系触媒を用いるこ
となく、収率よく置換トロパ酸類を製造する方法
の開発が望まれている。
問題点を解決するための手段
本発明者らは従来の製造方法にみられる前記し
た欠点を改良し効率よく置換トロパ酸類を製造す
る方法に関して鋭意研究した結果本発明に達した
ものである。即ち、本発明は一般式(1)
〔式(1)中、R1はC1〜4のアルキル基、アリール基、
アルケニル基、アラルキル基を、R2およびR3は
水素原子、ハロゲン原子、置換、非置換のC1〜4の
アルキル基、C1〜4のアルコキシ基、シクロアルキ
ル基、アラルキル基、アリール基、アリーロキシ
基、アシル基、アルケニロキシ基、水酸基から成
る群から選ばれた同一もしくは異なる基を表わ
す〕で示される置換フエニル酢酸類とパラホルム
アルデヒドとを、支持電解質の存在下電解還元す
るかまたは、パラホルムアルデヒドを支持電解質
の存在下電解還元し（電解反応）、次いで得られ
た還元生成物に前記式(1)で示される置換フエニル
酢酸類を反応させ（付加反応）、式(2)
〔式(2)中、R1、R2およびR3は前記と同じ意味を
表わす〕で示される置換トロパ酸類を製造すると
いうものである。前記したように従来のアルコラ
ート類を用いる方法では転化率ならびに収率を高
める為に種々の工夫を施しているのに比べ本発明
の方法は簡便な電解方法で収率良くしかも室温付
近の反応温度で置換トロパ酸類が容易に得られる
ことは驚くべきことである。
本発明の方法で用いられる式(1)の化合物におい
て、R1はメチル基、エチル基、プロピル基、イ
ソプロピル基、ブチル基、イソブチル基などの
C1〜4のアルキル基；フエニル基、トリル基、キシ
リル基、ナフチル基などのアリール基；アリル
基、イソプロペニル基、ブテニル基、クロチル基
などのアルケニル基；ベンジル基、置換ベンジル
基、フエネチル基などのアラルキル基であり、
R2およびR3は水素原子；クロル、ブロム、ヨー
ド、フツ素などのハロゲン原子；メチル基、エチ
ル基、プロピル基、イソプロピル基、ブチル基、
イソブチル基などのアルキル基；水酸基、ハロゲ
ン原子などで置換した置換アルキル基；メトキシ
基、エトキシ基、プロポキシ基、ブトキシ基など
のアルコキシ基；シクロヘキシル基、シクロペン
チル基などのシクロアルキル基；ベンジル基、置
換ベンジル基、フエネチル基などのアラルキル
基；フエニル基、置換フエニル基などのアリール
基；フエニロキシ基などのアリーロキシ基；ホル
ミル基、アセチル基、プロピオニル基、ベンゾイ
ル基などのアシル基；アリロキシ基などのアルケ
ニロキシ基または水酸基から成る群から選ばれた
同一もしくは異なる基である。一般式(1)で表わさ
れる置換フエニル酢酸類の具体例としてはフエニ
ル酢酸メチル、フエニル酢酸エチル、フエニル酢
酸ブチル、フエニル酢酸プロピル、フエニル酢酸
フエニル、フエニル酢酸−４−トリル、フエニル
酢酸−２−ブテニル、フエニル酢酸ナフチル、フ
エニル酢酸アリール、フエニル酢酸ベンジル、フ
エニル酢酸−４−ニリロベンジル、フエニル酢酸
−４−メトキシベンジル、４−クロロフエニル酢
酸メチル、４−ブロモフエニル酢酸エチル、４−
ヨウドフエニル酢酸エチル、４−フルオロフエニ
ル酢酸エチル、２−クロロフエニル酢酸メチル、
４−メトキシフエニル酢酸メチル、４−メトキシ
フエニル酢酸エチル、４−メトキシフエニル酢酸
プロピル、４−メトキシフエニル酢酸ベンジル、
４−メトキシフエニル酢酸フエニル、４−メトキ
シフエニル酢酸イソプロペニル、４−メトキシフ
エニル酢酸フエネチル、４−メトキシフエニル酢
酸クロチル、４−エトキシフエニル酢酸エチル、
４−ブトキシフエニル酢酸エチル、４−プロポキ
シフエニル酢酸エチル、２−メトキシフエニル酢
酸メチル、４−ヒドロキシフエニル酢酸−４−ニ
トロベンジル、４−ヒドロキシフエニル酢酸メチ
ル、４−ヒドロキシフエニル酢酸エチル、４−ヒ
ドロキシフエニル酢酸−４−メトキシベンジル、
４−メチルフエニル酢酸メチル、４−イソプロピ
ルフエニル酢酸エチル、４−ヒドロキシメチルフ
エニル酢酸メチル、４−イソブチルフエニル酢酸
アリル、４−イソブチルフエニル酢酸メチル、４
−イソブチルフエニル酢酸ベンジル、４−アセチ
ルフエニル酢酸−４−トリル、４−クロロメチル
フエニル酢酸フエニル、４−アセチルフエニル酢
酸メチル、４−ホルミルフエニル酢酸エチル、４
−ベンゾイルフエニル酢酸エチル、４−シクロヘ
キシルフエニル酢酸エチル、４−シクロヘキシル
−３−クロロフエニル酢酸エチル、４−ベンジル
フエニル酢酸メチル、４−フエネチルフエニル酢
酸エチル、４−メトキシカルボニルメチルビフエ
ニル、４−（４−ニトロベンジル）フエニル酢酸
エチル、４−（４−ニトロフエニル）フエニル酢
酸エチル、３，４−ジメトキシフエニル酢酸エチ
ル、３，４−ジヒドロキシフエニル酢酸メチル、
２，４−ジクロロフエニル酢酸エチル、３，４−
ジクロロフエニル酢酸アリル、４−アリロキシ−
３−クロロフエニル酢酸エチル、３−ベンゾイル
フエニル酢酸メチル、３−フエニルオキシフエニ
ル酢酸メチル、４−ヒドロキシ−３−メトキシフ
エニル酢酸メチル、２，５−ジヒドロキシフエニ
ル酢酸エチル、３−フルオロ−４−ヒドロキシフ
エニル酢酸メチル等が挙げられる。本発明に用い
られる支持電解質としては、通常の電解反応に供
される塩類が使用できるが好ましいものは下記式
〔式中、R1、R2、R3およびR4は同一もしくは異
なる置換、非置換アルキル基を、X-は
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing substituted tropic acids.
More specifically, substituted phenylacetic acids and paraformaldehyde are electrolytically reduced in the presence of a supporting electrolyte, or paraformaldehyde is electrolytically reduced in the presence of a supporting electrolyte, and the resulting reduction product is reacted with the substituted phenylacetic acids. The present invention relates to a method for producing substituted tropic acids characterized by: BACKGROUND OF THE INVENTION Substituted tropic acids are useful compounds as intermediates for pharmaceuticals. However, no industrially advantageous manufacturing method has yet been found. Specifically, the method for producing substituted tropic acids is to react ethyl 4-methoxyphenylacetate with paraformaldehyde in DMSO (dimethyl sulfoxide) in the presence of sodium ethoxide to obtain ethyl 4-methoxytropaate in a yield of 41%. [Arch.Pharm. (Weinheim, Ger.) Vol. 305, 839
(1972); CA78.42988u], and a method for obtaining substituted tropic acids by reacting a substituted phenyl acetate derivative with paraformaldehyde in DMSO in the presence of an alkali metal alcoholate as described above [Czech. CS195, 615 ( CA97.144582s), Japanese Patent Application Publication No. 1989-
103830], but these chemical methods use alkali metal alcoholates, which are strong bases, as catalysts, and this catalyst is easily decomposed by moisture in the air. There are difficulties in that special care must be taken in its preparation and storage. Furthermore, it is necessary to raise the reaction temperature to increase the conversion rate, and undesirable side reactions proceed simultaneously, resulting in a disadvantage that the yield and selectivity of the desired substituted tropic acids are low. Problems to be Solved by the Invention There is a desire for the development of a method for producing substituted tropic acids in good yields without using alcoholate catalysts that are difficult to handle. Means for Solving the Problems The present inventors have arrived at the present invention as a result of intensive research into a method for efficiently producing substituted tropic acids by improving the above-mentioned drawbacks found in conventional production methods. That is, the present invention is based on the general formula (1) [In formula (1), R 1 is a C 1-4 alkyl group, an aryl group,
alkenyl group, aralkyl group, R2 and R3 are hydrogen atoms, halogen atoms, substituted or unsubstituted C1-4 alkyl groups, C1-4 alkoxy groups, cycloalkyl groups, aralkyl groups, aryl groups, [representing the same or different groups selected from the group consisting of aryloxy group, acyl group, alkenyloxy group, and hydroxyl group]] and paraformaldehyde are electrolytically reduced in the presence of a supporting electrolyte, or paraformaldehyde is electrolytically reduced in the presence of a supporting electrolyte (electrolytic reaction), and then the resulting reduction product is reacted with the substituted phenylacetic acid represented by the above formula (1) (addition reaction), resulting in the reaction of formula (2). [In formula (2), R 1 , R 2 and R 3 have the same meanings as above] is produced. As mentioned above, in the conventional method using alcoholates, various measures are taken to increase the conversion rate and yield, but the method of the present invention is a simple electrolytic method with a high yield and a reaction temperature near room temperature. It is surprising that tropic acids substituted with are easily obtained. In the compound of formula (1) used in the method of the present invention, R 1 is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, etc.
C1-4 alkyl group; Aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group; Alkenyl group such as allyl group, isopropenyl group, butenyl group, crotyl group; benzyl group, substituted benzyl group, phenethyl group an aralkyl group such as
R 2 and R 3 are hydrogen atoms; halogen atoms such as chlorine, bromine, iodine, fluorine; methyl group, ethyl group, propyl group, isopropyl group, butyl group,
Alkyl groups such as isobutyl group; Substituted alkyl groups substituted with hydroxyl group, halogen atom, etc.; Alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; Cycloalkyl groups such as cyclohexyl group, cyclopentyl group; Benzyl group, substituted Aralkyl groups such as benzyl group and phenethyl group; Aryl groups such as phenyl group and substituted phenyl group; Aryloxy groups such as phenyloxy group; Acyl groups such as formyl group, acetyl group, propionyl group, and benzoyl group; Alkenyloxy groups such as allyloxy group or the same or different groups selected from the group consisting of hydroxyl groups. Specific examples of substituted phenylacetic acids represented by general formula (1) include methyl phenyl acetate, ethyl phenyl acetate, butyl phenyl acetate, propyl phenyl acetate, phenyl phenyl acetate, 4-tolyl phenyl acetate, and 2-butenyl phenyl acetate. , naphthyl phenyl acetate, aryl phenyl acetate, benzyl phenyl acetate, 4-nylilobenzyl phenyl acetate, 4-methoxybenzyl phenyl acetate, methyl 4-chlorophenylacetate, ethyl 4-bromophenyl acetate, 4-
Ethyl iodophenylacetate, ethyl 4-fluorophenylacetate, methyl 2-chlorophenylacetate,
Methyl 4-methoxyphenylacetate, ethyl 4-methoxyphenylacetate, propyl 4-methoxyphenylacetate, benzyl 4-methoxyphenylacetate,
Phenyl 4-methoxyphenyl acetate, isopropenyl 4-methoxyphenyl acetate, phenethyl 4-methoxyphenyl acetate, crotyl 4-methoxyphenyl acetate, ethyl 4-ethoxyphenyl acetate,
Ethyl 4-butoxyphenylacetate, ethyl 4-propoxyphenylacetate, methyl 2-methoxyphenylacetate, 4-nitrobenzyl 4-hydroxyphenylacetate, methyl 4-hydroxyphenylacetate, ethyl 4-hydroxyphenylacetate, 4-hydroxyphenylacetate-4-methoxybenzyl,
Methyl 4-methylphenylacetate, ethyl 4-isopropylphenylacetate, methyl 4-hydroxymethylphenylacetate, allyl 4-isobutylphenylacetate, methyl 4-isobutylphenylacetate, 4
-Benzyl isobutylphenyl acetate, 4-tolyl 4-acetylphenyl acetate, phenyl 4-chloromethylphenylacetate, methyl 4-acetylphenyl acetate, ethyl 4-formylphenyl acetate, 4
-ethyl benzoylphenyl acetate, ethyl 4-cyclohexylphenylacetate, ethyl 4-cyclohexyl-3-chlorophenylacetate, methyl 4-benzylphenylacetate, ethyl 4-phenethylphenyl acetate, 4-methoxycarbonylmethylbiphenyl, ethyl 4-(4-nitrobenzyl)phenylacetate, ethyl 4-(4-nitrophenyl)phenylacetate, ethyl 3,4-dimethoxyphenylacetate, methyl 3,4-dihydroxyphenylacetate,
Ethyl 2,4-dichlorophenylacetate, 3,4-
Allyl dichlorophenyl acetate, 4-allyloxy-
Ethyl 3-chlorophenylacetate, methyl 3-benzoylphenylacetate, methyl 3-phenyloxyphenylacetate, methyl 4-hydroxy-3-methoxyphenylacetate, ethyl 2,5-dihydroxyphenylacetate, 3-fluoro- Examples include methyl 4-hydroxyphenylacetate. As the supporting electrolyte used in the present invention, salts that are subjected to ordinary electrolytic reactions can be used, but preferred ones are those of the following formula: [In the formula, R 1 , R 2 , R 3 and R 4 are the same or different substituted or unsubstituted alkyl groups, and X - is
【式】ハライドイオン、
HSO3 -、CN6またはBF4 -などのアンモニウムイ
オンと対をなし、第４級アンモニウム塩を形成す
る陰イオンを意味する〕で示される第４級アンモ
ニウム塩でありその具体的な例としては次のよう
なものがある。テトラメチルアンモニウムパラト
ルエンスルホネート、テトラエチルアンモニウム
パラトルエンスルホネート、テトラブチルアンモ
ニウムパラトルエンスルホネート等の第４級アン
モニウム塩パラトルエンスルホン酸エステル類；
過塩素酸テトラメチルアンモニウム、過塩素酸テ
トラエチルアンモニウム、過塩素酸テトラブチル
アンモニウム等の過塩素酸第４級アンモニウム塩
類；テトラアンモニウムブロミド、テトラエチル
アンモニウムブロミド、ｎ−ドデシルトリメチル
アンモニウムブロミド、セチルトリメチルアンモ
ニウムブロミド、テトラエチルアンモニウムアイ
オダイド等のハロゲン化第４級アンモニウム塩
類；テトラメチルアンモニウムシアニド、テトラ
エチルアンモニウムシアニド、テトラブチルアン
モニウムシアニド等の第４級アンモニウム塩；テ
トラエチルアンモニウムテトラフルオロボレート
等の第４級アンモニウム塩等が挙げられる。支持
電解質として使用されるその他の化合物として
は、過塩素酸ナトリウム、過塩素酸カリウム等の
過塩素酸アルカリ金属塩；ヨウ化ナトリウム、ヨ
ウ化カリウム等のハロゲン化アルカリ金属塩等が
挙げられる。これらの支持電解質の使用量は反応
媒質や反応槽の形状などにより一定しないが、通
常置換フエニル酢酸類に対して重量比で0.1〜30
倍、好ましくは0.3〜10倍の範囲である。またパ
ラホルムアルデヒドの使用量は式(1)の反応基質の
種類により一定しないが通常0.1〜10倍モル、好
ましくは0.5〜3.0倍モルの範囲である。本発明の
方法は有機溶媒中で行われ、有機溶媒としては、
非プロトン性極性溶媒または非プロトン性極性溶
媒とそれ以外の溶媒との混合溶媒が使用出来る。
非プロトン性極性溶媒としては、ジメチルホルム
アミド、ジメチルスルホキシド、テトラヒドロフ
ラン、ヘキサメチルホスホトリアミド、ジメチル
アセトアミド、ジオキサン、ジメトオキシエタ
ン、アセトニトリル、プロピオニトリル等が用い
られる。必要に応じてこれらとメタノール、エタ
ノール、イソプロピルアルコール、第３級ブチル
アルコール等の脂肪族アルコール等との混合溶媒
も用いることができる。特にジメチルホルムアミ
ド、ジメチルホルムアミドを主溶媒とする混合溶
媒が好ましい。これらの溶媒の使用量は置換フエ
ニル酢酸類に対して重量比で１〜100倍、好まし
くは３〜30倍の範囲である。
本発明の電解反応には通常の電解用電極、即ち
白金、炭素、ニツケル、鉛、銅、ステンレス、亜
鉛、アルミニウム等を素材に用いた電極や白金で
表面処理したチタン極が使用できる。本発明にお
いては単一セルもしくは陽、陰極室を分離した分
離セルが用いられるが、好ましいのは分離セルで
ある。この際、陽、陰極室を分離する隔膜は特に
限定はないが、ガラスフイルター、素焼きの磁性
材料、イオン交換膜などが用いられる。また電解
反応およびその付加反応の際の反応温度は通常０
〜100℃、好ましくは５〜40℃、全反応時間は0.1
〜10時間、好ましくは0.3〜５時間である。電解
反応では定電解方法または定電流方法が採用出
る。電流密度は0.1〜100ｍＡ／cm2の範囲で、また
通電電気量は、反応槽の形状や用いる基質の種類
により一定しないが通常は置換フエニル酢酸類
（基質）１モルに対して0.005〜2F、好ましくは
0.01〜1.0Fの通電でよい。陰極室における基質の
濃度は通常重量％で溶媒に対して１〜50％、好ま
しくは５〜30％の範囲である。
本発明の方法は以上のように電解反応を利用し
て支持電解質の存在下、置換フエニル酢酸類をパ
ラホルムアルデヒドを室温付近で反応させ置換ト
ロパ酸類を製造するか、もしくはパラホルムアル
デヒドを支持電解質の存在下電解還元し次いで陰
極室に置換フエニル酢酸類を加えて反応させる
か、または陰極液を別の容器に移し、そこに置換
フエニル酢酸類を加えて反応させることにより副
生物を生成することなく高収率で置換トロパ酸類
を製造することを可能ならしめたものである。生
成した置換トロパ酸類は反応混合物から公知の方
法例えば蒸留、抽出などの方法で容易に分離、精
製される。
実施例
実施例により本発明を更に詳細に説明する。
実施例 １
陽、陰極室分離セルの陰極室に４−メトキシフ
エニル酢酸エチル300mg（1.5ｍmol）、パラホル
ムアルデヒド56mg（ホルムアルデヒドとして1.9
ｍmol）を量りとり、これに支持電解質としてテ
トラエチルアンモニウムパラトルエンスルホネー
ト（Et4NOTs）300mgを溶かしたジメチルホルム
アミド（DMF）6.0mlを加える。一方陽極室に
Et4NOTs300mgを溶かしたDMF6.0mlを加える。
陽、陰両極室に撹拌子、温度計ならびに白金電極
（大きさ1.5×1.0cm2）を反応溶液に充分浸して取
り付ける。反応温度を20〜26℃に保ち、電流密度
3.3ｍＡ／cm2、端子電圧７〜9Vの条件で電解を行
い、0.03F／molの電気量を流したところで電解
を中止した。次に陰極液を飽和食塩水に注ぎ、５
％塩酸水溶液にて液性をPH4.5にした。酢酸エチ
ルで数回抽出し、抽出液を水洗したのち乾燥、濃
縮した。得られた粗生成物をシリカゲルカラムを
用い、ベンゼン流出さらにｎ−ヘキサン−酢酸エ
チル（５：１）の混合溶媒で展開すると４−メト
キシトロパ酸エチルが298.4mg（86.5％）得られ
た。本反応の変換率は94.8％であつた。
４−メトキシトロパ酸エチルの物性
IR（neat） 3400、2980、2950、2840、1735、
1620、1595、1525、1476、1380、1310、1257、
1183、1080、1040、837、800、756cm-1
NMR（CDCl3、ppm）
δ1.18（ｔ、3H、−CH3）
δ2.96（br.s、1H、−OH）
δ3.71（ｓ、3H、−OCH3）
δ3.55〜4.15（ｍ、3H、−CHCH2−）
δ3.80〜4.35（ｑ、2H、−CH2−）
δ6.64〜7.27（ｍ、4H、Ar−Ｈ）
実施例 ２
陽、陰極分離セルの陰極室にパラホルムアルデ
ヒド68mg（ホルムアルデヒドとして2.3ｍmol）
を量りとり、これに支持電解質として
Et4NOTs400mgを溶かしたDMF6.0mlを加える。
一方陽極室にEt4NOTs400mgを溶かしたDMF6.0
mlを加える。陽陰両極室に撹拌子、温度計ならび
に白金電極（大きさ1.5×1.0cm2）を反応溶液に充
分浸して取り付ける。反応温度を18〜25℃に保
ち、電流密度3.3ｍＡ／cm2、端子電圧９〜10Vの
条件で電解を行い、0.04F／molの電気量を流し
たところで電解を中止した。次に陰極室に４−メ
トキシフエニル酢酸エチル330mg（1.7ｍmol）を
加え、反応温度を20〜25℃に保ち0.5時間かきま
ぜた。次に陰極室の反応液を飽和食塩水に注ぎ５
％塩酸水溶液にて液性をPH4.5にした。酢酸エチ
ルで数回抽出し、抽出液を水洗したのち乾燥、濃
縮した。得られた粗生成物をシリカゲルカラムを
用い、ベンゼン流出さらにｎ−ヘキサン−酢酸エ
チル（５：１）の混合溶媒で展開すると４−メト
キシトロパ酸エチルが312.3mg（82.0％）得られ
た。本反応の変換率は93.6％であつた。IR、
NMRは実施例１のそれと同一であつた。
実施例 ３〜９
実施例１とほぼ同様な操作で陰極の種類を変え
て反応を行つた結果を表１に示した。[Formula] refers to an anion that forms a quaternary ammonium salt by pairing with an ammonium ion such as a halide ion, HSO 3 - , CN 6 or BF 4 - . Specific examples include: Quaternary ammonium salt paratoluenesulfonic acid esters such as tetramethylammonium paratoluenesulfonate, tetraethylammonium paratoluenesulfonate, and tetrabutylammonium paratoluenesulfonate;
Quaternary ammonium perchlorate salts such as tetramethylammonium perchlorate, tetraethylammonium perchlorate, and tetrabutylammonium perchlorate; tetraammonium bromide, tetraethylammonium bromide, n-dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide, Halogenated quaternary ammonium salts such as tetraethylammonium iodide; Quaternary ammonium salts such as tetramethylammonium cyanide, tetraethylammonium cyanide, and tetrabutylammonium cyanide; Quaternary ammonium salts such as tetraethylammonium tetrafluoroborate etc. Other compounds used as the supporting electrolyte include alkali metal perchlorates such as sodium perchlorate and potassium perchlorate; alkali metal halides such as sodium iodide and potassium iodide. The amount of these supporting electrolytes to be used varies depending on the reaction medium and the shape of the reaction tank, but is usually 0.1 to 30% by weight relative to the substituted phenylacetic acid.
times, preferably in the range of 0.3 to 10 times. The amount of paraformaldehyde to be used varies depending on the type of reaction substrate of formula (1), but is usually in the range of 0.1 to 10 times the mole, preferably 0.5 to 3.0 times the mole. The method of the present invention is carried out in an organic solvent, and the organic solvent is
An aprotic polar solvent or a mixed solvent of an aprotic polar solvent and another solvent can be used.
As the aprotic polar solvent, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, hexamethylphosphotriamide, dimethylacetamide, dioxane, dimethoxyethane, acetonitrile, propionitrile, etc. are used. If necessary, a mixed solvent of these and an aliphatic alcohol such as methanol, ethanol, isopropyl alcohol, tertiary butyl alcohol, etc. can also be used. Particularly preferred are dimethylformamide and a mixed solvent containing dimethylformamide as the main solvent. The amount of these solvents to be used is in the range of 1 to 100 times, preferably 3 to 30 times, the weight of the substituted phenylacetic acid. For the electrolytic reaction of the present invention, ordinary electrodes for electrolysis, ie, electrodes made of materials such as platinum, carbon, nickel, lead, copper, stainless steel, zinc, aluminum, etc., and titanium electrodes surface-treated with platinum, can be used. In the present invention, a single cell or a separate cell with separate anode and cathode chambers is used, but a separate cell is preferred. At this time, the diaphragm that separates the anode and cathode chambers is not particularly limited, but glass filters, unglazed magnetic materials, ion exchange membranes, etc. are used. In addition, the reaction temperature during the electrolytic reaction and its addition reaction is usually 0.
~100°C, preferably 5-40°C, total reaction time 0.1
-10 hours, preferably 0.3-5 hours. For electrolytic reactions, constant electrolytic method or constant current method is adopted. The current density is in the range of 0.1 to 100 mA/ cm2 , and the amount of electricity applied varies depending on the shape of the reaction tank and the type of substrate used, but it is usually 0.005 to 2F per mole of substituted phenylacetic acid (substrate). Preferably
A current of 0.01 to 1.0F is sufficient. The concentration of the substrate in the cathode chamber is usually in the range of 1 to 50%, preferably 5 to 30% by weight, based on the solvent. As described above, the method of the present invention utilizes an electrolytic reaction to produce substituted tropic acids by reacting substituted phenylacetic acids with paraformaldehyde at around room temperature in the presence of a supporting electrolyte, or by reacting paraformaldehyde with paraformaldehyde in the presence of a supporting electrolyte. Substituted phenylacetic acids can be electrolytically reduced and then reacted by adding substituted phenylacetic acids to the cathode chamber, or the catholyte can be transferred to another container and substituted phenylacetic acids can be added thereto and reacted to achieve a high concentration without producing by-products. This makes it possible to produce substituted tropic acids with high yield. The generated substituted tropic acids can be easily separated and purified from the reaction mixture by known methods such as distillation and extraction. Examples The present invention will be explained in more detail by examples. Example 1 300 mg (1.5 mmol) of ethyl 4-methoxyphenyl acetate and 56 mg of paraformaldehyde (1.9 mg as formaldehyde) were added to the cathode chamber of the positive and cathode chamber separation cell.
mmol), and add 6.0 ml of dimethylformamide (DMF) in which 300 mg of tetraethylammonium paratoluene sulfonate (Et 4 NOTs) is dissolved as a supporting electrolyte. On the other hand, in the anode chamber
Add 6.0ml of DMF containing 300mg of Et 4 NOTs.
A stirrer, a thermometer, and a platinum electrode (size 1.5 x 1.0 cm 2 ) are fully immersed in the reaction solution and attached to the positive and negative polarity chambers. Keep the reaction temperature at 20-26℃ and reduce the current density
Electrolysis was performed under the conditions of 3.3 mA/cm 2 and a terminal voltage of 7 to 9 V, and the electrolysis was stopped when an amount of electricity of 0.03 F/mol was passed. Next, pour the catholyte into saturated saline solution and
% aqueous hydrochloric acid solution to pH 4.5. It was extracted several times with ethyl acetate, and the extract was washed with water, dried, and concentrated. The obtained crude product was developed using a silica gel column with benzene flowing out and a mixed solvent of n-hexane-ethyl acetate (5:1) to obtain 298.4 mg (86.5%) of ethyl 4-methoxytropate. The conversion rate of this reaction was 94.8%. Physical properties of ethyl 4-methoxytropate IR (neat) 3400, 2980, 2950, 2840, 1735,
1620, 1595, 1525, 1476, 1380, 1310, 1257,
1183, 1080, 1040, 837, 800, 756 cm -1 NMR (CDCl 3 , ppm) δ1.18 (t, 3H, -CH 3 ) δ2.96 (br.s, 1H, -OH) δ3.71 (s , 3H, −OCH 3 ) δ3.55 to 4.15 (m, 3H, −CHCH 2 −) δ3.80 to 4.35 (q, 2H, −CH 2 −) δ6.64 to 7.27 (m, 4H, Ar−H ) Example 2 68 mg of paraformaldehyde (2.3 mmol as formaldehyde) in the cathode chamber of the positive and cathode separation cell
Weigh out and use this as a supporting electrolyte.
Add 6.0ml of DMF containing 400mg of Et 4 NOTs.
Meanwhile, DMF6.0 with 400 mg of Et 4 NOTs dissolved in the anode chamber
Add ml. A stirrer, a thermometer, and a platinum electrode (size 1.5 x 1.0 cm 2 ) are fully immersed in the reaction solution and attached to the positive and negative electrode chambers. The reaction temperature was maintained at 18 to 25° C., and electrolysis was carried out under the conditions of a current density of 3.3 mA/cm 2 and a terminal voltage of 9 to 10 V, and the electrolysis was stopped when an amount of electricity of 0.04 F/mol was passed. Next, 330 mg (1.7 mmol) of ethyl 4-methoxyphenylacetate was added to the cathode chamber, and the mixture was stirred for 0.5 hour while maintaining the reaction temperature at 20 to 25°C. Next, pour the reaction solution in the cathode chamber into saturated saline solution.
% aqueous hydrochloric acid solution to pH 4.5. It was extracted several times with ethyl acetate, and the extract was washed with water, dried, and concentrated. The obtained crude product was developed using a silica gel column with benzene flowing out and a mixed solvent of n-hexane-ethyl acetate (5:1) to obtain 312.3 mg (82.0%) of ethyl 4-methoxytropate. The conversion rate of this reaction was 93.6%. IR,
NMR was the same as that of Example 1. Examples 3 to 9 Table 1 shows the results of reactions conducted in substantially the same manner as in Example 1, but with different types of cathodes.
【表】【table】
【表】
反応条件
原料、４−メトキシフエニル酢酸エチル；300
mg（1.5ｍmol）、パラホルムアルデヒド；56mg
（1.9ｍmol）、支持電解質、Et4NOts；300mg×２、
DMF；6.0ml×２、陽電極；白金電極（1.0×1.5
cm2）、反応温度；20〜25℃、電流；0.5ｍＡ、電気
量；0.03〜0.05F／Ｍ
実施例 10〜25
実施例１とほぼ同様な操作で支持電解質を変え
て反応を行つた結果を表２に示した。[Table] Reaction conditions Raw material, ethyl 4-methoxyphenyl acetate; 300
mg (1.5 mmol), paraformaldehyde; 56 mg
(1.9 mmol), supporting electrolyte, Et 4 NOts; 300 mg x 2,
DMF; 6.0ml x 2, positive electrode; platinum electrode (1.0 x 1.5
cm 2 ), reaction temperature: 20 to 25°C, current: 0.5 mA, quantity of electricity: 0.03 to 0.05 F/M Examples 10 to 25 Results of reactions carried out in almost the same manner as in Example 1 by changing the supporting electrolyte. are shown in Table 2.
【表】【table】
【表】
原料、４−メトキシトロパ酸エチル；300mg
（1.5ｍmol）、パラホルムアルデヒド；56mg（1.9
ｍmol）、DMF：6.0ml×２、陽、陰極；白金電極
（1.0×1.5cm2）、反応温度；20〜29℃、電流；0.5ｍ
Ａ、電気量；0.3〜0.4F／Ｍ
なお表中、Meはメチル、Etはエチル、Buはブ
チル、Ptはフエニルを表わす。
実施例 26〜34
実施例１とほゞ同様な操作で溶媒を変えて反応
を行つた結果を表３に示した。[Table] Raw material, ethyl 4-methoxytropate; 300mg
(1.5 mmol), paraformaldehyde; 56 mg (1.9
mmol), DMF: 6.0ml x 2, anode, cathode; platinum electrode (1.0 x 1.5cm 2 ), reaction temperature: 20-29℃, current: 0.5m
A. Electricity; 0.3 to 0.4 F/M In the table, Me represents methyl, Et represents ethyl, Bu represents butyl, and Pt represents phenyl. Examples 26 to 34 Table 3 shows the results of reactions carried out in substantially the same manner as in Example 1, but with different solvents.
【表】
反応条件
原料、４−メトキシフエニル酢酸エチル；300
mg（1.5ｍmol）、パラホルムアルデヒド；56mg
（1.9ｍmol）、陽、陰極；白金電極（1.0×1.5cm2）、
Et4NOTs；1.0〜1.3ｍmol×２〔*THFの場合、
Bu4NClO4（0.9ｍmol）を用いた。〕反応温度；20
〜29℃、電流；５ｍＡ、電気量；0.1F／Ｍ
実施例 35
原料として４−メトキシフエニル酢酸エチルの
代わりにフエニル酢酸エチル330mg（2.0ｍmol）
を使用した以外は実施例１とほぼ同様に反応を行
うとトロパ酸エチル300.7mg（77.5％）が得られ
た。
本反応の変換率は88.2％であつた。
トロパ酸エチルの物性
IR（neat）
3400、2965、2920、1730、1602、1497、
1455、1372、1200、1173、1045、1028、735、
698cm-1
NMR（CDCl3）
δ1.18（ｔ、3H、−CH3）
δ2.47（br.s、1H、−OH）
δ3.60〜4.30（ｍ、3H、−CHCH2−）
δ3.87〜4.40（ｑ、2H、−CH2−）
δ7.26（ｓ、5H、Ar−Ｈ）
実施例 36
原料として４−メトキシフエニル酢酸エチルの
代わりにフエニル酢酸エチル330mg（2.0ｍmol）
を使用した以外は実施例２とほぼ同様に反応を行
うと、トロパ酸エチル291mg（75.0％）が得られ
た。本反応の変換率は87.4％であつた。またIR、
NMRは実施例35のそれと同一であつた。
実施例 37〜70
実施例１（Ａ法）及び実施例２（Ｂ法）とほぼ同
様な操作で原料、陰電極及び支持電解質を変えて
反応を行つた結果を表４に示した。[Table] Reaction conditions Raw material, ethyl 4-methoxyphenyl acetate; 300
mg (1.5 mmol), paraformaldehyde; 56 mg
(1.9 mmol), anode, cathode; platinum electrode (1.0 x 1.5 cm 2 ),
Et 4 NOTs; 1.0-1.3 mmol×2 [ * For THF,
Bu 4 NClO 4 (0.9 mmol) was used. ]Reaction temperature; 20
~29°C, current: 5 mA, electricity: 0.1 F/M Example 35 330 mg (2.0 mmol) of ethyl phenyl acetate instead of ethyl 4-methoxyphenylacetate as a raw material
The reaction was carried out in substantially the same manner as in Example 1 except that 300.7 mg (77.5%) of ethyl tropate was obtained. The conversion rate of this reaction was 88.2%. Physical properties of ethyl tropate IR (neat) 3400, 2965, 2920, 1730, 1602, 1497,
1455, 1372, 1200, 1173, 1045, 1028, 735,
698cm -1 NMR (CDCl 3 ) δ1.18 (t, 3H, −CH 3 ) δ2.47 (br.s, 1H, −OH) δ3.60~4.30 (m, 3H, −CHCH 2 −) δ3. 87-4.40 (q, 2H, -CH 2 -) δ7.26 (s, 5H, Ar-H) Example 36 330 mg (2.0 mmol) of ethyl phenyl acetate instead of ethyl 4-methoxyphenylacetate as a raw material
The reaction was carried out in substantially the same manner as in Example 2 except that 291 mg (75.0%) of ethyl tropate was obtained. The conversion rate of this reaction was 87.4%. Also IR,
NMR was the same as that of Example 35. Examples 37 to 70 Table 4 shows the results of reactions conducted in substantially the same manner as in Example 1 (Method A) and Example 2 (Method B), but with different raw materials, negative electrodes, and supporting electrolytes.
【表】【table】
【表】
反応条件
原料；２ｍmol、パラホルムアルデヒド；80mg
（2.7ｍmol）、支持電解質；1.0〜1.5ｍmol×２、
DMF；6.0ml×２、陽電極；白金電極（1.0×1.5
cm2）、反応温度：20〜29℃、電流；５ｍＡ、電気
量；0.1〜0.3F／Ｍ反応時間（Ｂ法）；１時間、反
応温度（Ｂ法）；20〜29℃
発明の効果
取扱いの面倒なアルコラート系触媒を用いるこ
となく効率よく置換トロパ酸類を得ることができ
る。[Table] Reaction conditions Raw materials: 2 mmol, paraformaldehyde: 80 mg
(2.7 mmol), supporting electrolyte; 1.0-1.5 mmol x 2,
DMF; 6.0ml x 2, positive electrode; platinum electrode (1.0 x 1.5
cm 2 ), reaction temperature: 20-29°C, current: 5mA, quantity of electricity: 0.1-0.3F/M reaction time (Method B): 1 hour, reaction temperature (method B): 20-29°C Effects of the invention Handling Substituted tropic acids can be efficiently obtained without using troublesome alcoholate catalysts.
Claims (1)
アルケニル基、アラルキル基を、R2およびR3は
水素原子、ハロゲン原子、置換、非置換のC1〜4の
アルキル基C1〜4のアルコキシ基、シクロアルキル
基、アラルキル基、アリール基、アリーロキシ
基、アシル基、アルケニロキシ基、水酸基から成
る群から選ばれた同一もしくは異なる基を表わ
す〕で示される置換フエニル酢酸類とパラホルム
アルデヒドとを、支持電解質の存在下電解還元す
るかまたは、パラホルムアルデヒドを支持電解質
の存在下電解還元し、次いで得られた還元生成物
に前記式(1)で示される置換フエニル酢酸類を反応
させることを特徴とする式(2) 〔式(2)中、R1、R2およびR3は前記と同じ意味を
表わす〕で示される置換トロパ酸類の製造方法。[Claims] 1 General formula (1) [In formula (1), R 1 is a C 1-4 alkyl group, an aryl group,
Alkenyl group, aralkyl group, R2 and R3 are hydrogen atom, halogen atom, substituted or unsubstituted C1-4 alkyl group, C1-4 alkoxy group, cycloalkyl group, aralkyl group, aryl group, aryloxy [representing the same or different groups selected from the group consisting of acyl group, alkenyloxy group, and hydroxyl group] and paraformaldehyde are electrolytically reduced in the presence of a supporting electrolyte, or paraformaldehyde is reduced by electrolysis in the presence of a supporting electrolyte. Formula (2), which is characterized by electrolytically reducing the product in the presence of a supporting electrolyte, and then reacting the obtained reduction product with a substituted phenylacetic acid represented by the above formula (1). [In formula (2), R 1 , R 2 and R 3 have the same meanings as above] A method for producing substituted tropic acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60113101A JPS61271250A (en) | 1985-05-28 | 1985-05-28 | Production of substituted tropic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60113101A JPS61271250A (en) | 1985-05-28 | 1985-05-28 | Production of substituted tropic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61271250A JPS61271250A (en) | 1986-12-01 |
| JPH0526877B2 true JPH0526877B2 (en) | 1993-04-19 |
Family
ID=14603504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60113101A Granted JPS61271250A (en) | 1985-05-28 | 1985-05-28 | Production of substituted tropic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61271250A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101052620B1 (en) * | 2008-08-28 | 2011-07-29 | 한국과학기술연구원 | Novel phenylacetate derivative or pharmaceutically acceptable salt thereof, preparation method thereof and composition for the prevention or treatment of diseases caused by the activity of T-type calcium ion channel containing the same as an active ingredient |
| CN105985241A (en) * | 2015-01-27 | 2016-10-05 | 邵阳学院 | Inhibition effect of [alpha]-substituted phenyl acetate compounds on [alpha]-glycosidase and application of the compounds |
-
1985
- 1985-05-28 JP JP60113101A patent/JPS61271250A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61271250A (en) | 1986-12-01 |
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