JPH0551577B2 - - Google Patents
Info
- Publication number
- JPH0551577B2 JPH0551577B2 JP58046062A JP4606283A JPH0551577B2 JP H0551577 B2 JPH0551577 B2 JP H0551577B2 JP 58046062 A JP58046062 A JP 58046062A JP 4606283 A JP4606283 A JP 4606283A JP H0551577 B2 JPH0551577 B2 JP H0551577B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- reaction
- metals
- salts
- activated carbon
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000002739 metals Chemical class 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 19
- 150000001448 anilines Chemical class 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- 150000002475 indoles Chemical class 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 150000001661 cadmium Chemical class 0.000 claims description 9
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 description 18
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 150000005181 nitrobenzenes Chemical class 0.000 description 8
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 7
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 7
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 2
- YPKBCLZFIYBSHK-UHFFFAOYSA-N 5-methylindole Chemical compound CC1=CC=C2NC=CC2=C1 YPKBCLZFIYBSHK-UHFFFAOYSA-N 0.000 description 2
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methylindole Natural products CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical compound COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- WGYFINWERLNPHR-UHFFFAOYSA-N 3-nitroanisole Chemical compound COC1=CC=CC([N+]([O-])=O)=C1 WGYFINWERLNPHR-UHFFFAOYSA-N 0.000 description 1
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- NRGIRRZWCDKDMV-UHFFFAOYSA-H cadmium(2+);diphosphate Chemical compound [Cd+2].[Cd+2].[Cd+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O NRGIRRZWCDKDMV-UHFFFAOYSA-H 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Indole Compounds (AREA)
- Catalysts (AREA)
Description
産業上の利用分野
本発明はインドール類の製造法に関する。さら
に詳しくは、本発明はアニリン類と酸化エチレン
とを触媒の存在下に反応させることにより、イン
ドール類を製造する方法に関するものである。
インドールは化学工業原料として知られ、特に
近年、香料やアミノ酸合成原料として重要な物質
となつてきている。
従来の技術
従来、インドールを合成しようという試みはい
くつかあつたが、いずれも副生物が多いものや、
原料的にみて高価なものが多く、またインドール
に至るまでの工程が長く、操作が繁雑なものが多
い。
発明が解決しようとする課題
本発明の目的は安価な原料を用い、かつ一段の
工程でインドール類を選択率良く製造することに
ある。
本発明者らは、この目的を達成すべく鋭意検討
した結果、従来、知られていなかつた全く新規な
反応にもとづく方法、すなわち、アニリン類と酸
化エチレンとを接触反応させることにより、目的
物であるインドール類を選択率良く製造できるこ
とを見出し、本発明の製造法を完成した。
すなわち、本発明の製造法は、アニリン類と酸
化エチレンとを元素周期律表の第８族金属、第
1b族金属、亜鉛塩類、カドミウム塩類、マグネ
シウム塩類、酸化マグネシウムおよび活性炭から
なる群から選ばれた１種または２種以上を含有す
る触媒の存在下に液相反応させてインドール類を
製造する方法である。
したがつて、本発明の製造法によれば、たとえ
ば、アニリンと酸化エチレンを触媒反応させるこ
とによりインドールを、パラートルイジンと酸化
エチレンを接触反応させることにより５−メチル
インドールを得ることができる。
本発明の触媒は元素周期律表の第８族金属、第
1b族金属、亜鉛塩類、カドミウム塩類、マグネ
シウム塩類、酸化マグネシウムおよび活性炭から
なる群から選ばれた１種または２種以上を含有す
る触媒である。すなわち、第８族金属、第1b金
属、亜鉛塩類、カドミウム塩類、マグネシウム塩
類、酸化マグネシウムまたは活性炭のそれぞれ単
独、または２種以上の混合、さらにこれらのそれ
ぞれに他の化合物をあわせて含有するものであ
る。
たとえば、粉末状、粒状、塊状、鱗片状、成形
品等の鉄、コバルト、ニツケル、ルテニウム、ロ
ジウム、パラジウム、オスミウム、イリジウム、
白金、銅、銀、金、塩化亜鉛、硫酸亜鉛、硝酸亜
鉛、リン酸亜鉛、塩化カドミウム、硫酸カドミウ
ム、硝酸カドミウム、リン酸カドミウム、塩化マ
グネシウム、塩基性塩化マグネシウム、硫酸マグ
ネシウム、酸化マグネシウム、活性炭；担体に周
期律表の第８族金属、第1b族金属、亜鉛塩類、
カドミウム塩類、マグネシウム塩類、酸化マグネ
シウムおよび／または活性炭、あるいは第８族金
属、第1b族金属、カドミウム塩類、マグネシウ
ム塩類、酸化マグネシウムおよび／または活性炭
とその他の化合物との混合物を担持させて成る第
８族金属、第1b族金属、亜鉛塩類、カドミウム
塩類、マグネシウム塩類、酸化マグネシウムおよ
び／または活性炭を含有する触媒である。
触媒物質（以下、元素周期律表の第８族金属、
第1b族金属、亜鉛塩類、カドミウム塩類、マグ
ネシウム塩類、酸化マグネシウムおよび活性炭を
示す）と併用されるその他の化合物としてはリチ
ウム、カリウム、マグネシウム、カルシウム、ス
トロンチウム、バリウム、銅、銀、水銀、アルミ
ニウム、錫、鉄、コバルト、ニツケル、クロム、
マンガン、亜鉛、モリブテン等のハロゲン化物、
硝酸塩、硫酸塩、炭酸塩、有機酸塩、酸化物、水
酸化物または金属等である。前記触媒物質または
前記触媒物質とその他の化合物を担持させる担体
としては、一般に担持触媒の担体として使用され
ているものがいずれも使用できるが、通常、ケイ
ソウ土、軽石、チタニア、シリカ−アルミナ、ア
ルミナ、マグネシア、シリカゲル、活性炭、活性
白土、石綿等が用いられる。
これらの担体に前記触媒物質を常法により担持
させて担持触媒を調製する。浸漬法によれば、た
とえば活性炭またはアルミナ等の担体に水溶性の
第８族または第1b族の金属塩を水に溶かして浸
漬し、乾燥、熱分解、還元の操作を行うことによ
り製造する。沈殿法によれば、たとえば１種また
は２種以上の第８族または第1b族金属の硝酸塩
の水溶液に活性炭またはシリカゲル等の担体を加
え、攪拌しながらアルカリ物質を加えて沈殿を生
成させる。その沈殿を濾別、洗浄、乾燥、焼成お
よび還元することにより調製する。その他種々の
触媒調製法があり、触媒の調製法に限定はない。
また、前記触媒物質の担体に対する担持量にはと
くに制限はなく、通常、担体に応じて適当量、た
とえば0.01〜50％の前記触媒物質を担持させてよ
い。
本発明において触媒として活性炭単独にても使
用可能であるが、活性炭に元素周期律表の第８族
金属、第1b族金属、亜鉛塩類、カドミウム塩類、
マグネシウム塩類および／または酸化マグネシウ
ムを担持つさせるとその触媒活性は増大する。
本発明において使用する活性炭は各種の活性炭
ほ含む。たとえば、ヤシ殻、木材、おがくず、リ
グニン、石炭、血炭、石油系カーボン等から製造
した活性炭を含む。活性炭として市販されている
ものは通常、粉末炭、破砕炭、球形または円筒形
等に成形された成形炭であり、本発明では使用活
性炭の形状は特に限定しない。
本発明で用いられるアニリン類は、アニリン、
およびオルト−トルイジン、メタ−トルイジン、
パラ−トルイジン、オルト−アミノフエノール、
メタ−アミノフエノール、パラ−アミノフエノー
ル、オルト−アニシジン、メタ−アニシジン、パ
ラ−アニシジン等のアニリンの核置換誘導体を含
む。
本発明の方法は、液相または気液混相のいずれ
の方法でも実施することができる。
液相で実施する場合、固定層、流動層または移
動層反応器のいずれでも実施でき、アニリン類お
よび酸化エチレンの混合物を前記触媒物質含有触
媒の存在下に加熱昇温する。この際、原料の希釈
剤として、種々の不活性ガスおよび／または溶剤
を共存させることができる。このような不活性ガ
ス状物質として、例えば、窒素ガス、炭酸ガス、
水蒸気および本反応に不活性な化合物の蒸気があ
げられる。前記希釈剤として、水素ガスまたは水
素含有ガスを使用するのが好ましい。本発明に用
いることのできる溶剤は、本発明による反応を妨
げない溶剤である。たとえば、水、ベンゼン、ト
ルエン、キシレン、メタノール、エタノール、イ
ソプロパノール、ジオキサン、ジメチルホルムア
ミド、ジメチルスルホキシド、ピリジン、Ｎ−メ
チルピロリドン、トリメチルアミン、ジエチルア
ミン、トリエチルアミン、トリプロピルアミン、
トリブチルアミン、ジフエニルアミン、トリフエ
ニルアミン等のアミン類等を含む。好ましくは水
である。
アニリン類と酸化エチレンを原料として用いる
液相反応において、反応装置に装入するアニリン
類と酸化エチレンは、アニリン類１モルに対して
酸化エチレン0.05〜５モルの割合で混合し、前記
触媒と共に加熱する。
反応温度は200〜500℃の範囲、好ましくは250
〜400℃である。200℃以下では反応がほとんど進
行せず、400℃以上では副生物の生成が多くなり
好ましくない。
反応圧力は加圧または常圧のいずれでもよい。
本発明に用いる反応装置に関しては特に制限は
なく、一般に回分式または連続式の液相用の反応
装置が用いられる。
これらの種々の方法において、反応生成物から
インドール類は適当な方法、たとえば蒸留のよう
な常法によつて容易に分離精製できる。
本発明の方法は、上記のようにアニリン類を原
料として使用する。しかし、アニリン類の素原料
であるニトロベンゼン類を用いても同様の反応方
法でインドール類を製造することができる。すな
わち、水素とニトロベンゼン類が接触反応してア
ニリン類を生成するので、水素とニトロベンゼン
と酸化エチレンを接触反応させることによりイン
ドール類を、水素とパラ−ニトロトルエンと酸化
エチレンを接触反応させることにより５−メチル
インドールを得ることができる。
この方法で使用するニトロベンゼン類としては
ニトロベンゼンおよびオルト−ニトロトルエン、
メタ−ニトロトルエン、パラ−ニトロトルエン、
オルト−ニトロフエノール、メタ−ニトロフエノ
ール、パラ−ニトロフエノール、オルト−ニトロ
アニソール、メタ−ニトロアニソール、パラ−ニ
トロアニソール等のニトロベンゼンの核置換誘導
体を含む。
この方法の反応は、ニトロベンゼン類と酸化エ
チレンと水素ガス、および必要に応じて添加する
希釈剤との混合物を前記触媒物質含有触媒の存在
下に加熱して実施する。
反応器に装入するニトロベンゼン類と酸化エチ
レンは、ニトロベンゼン類１モルに対して酸化エ
チレン0.05〜５モルの割合で、触媒に対する液空
間速度が0.01〜51／１−触媒／hrとなるように反
応器に装入する。ニトロベンゼン類や酸化エチレ
ンと混合する水素ガスはニトロベンゼン類１モル
に対して0.1〜100モル、好ましくは１〜30モルの
割合で反応器に装入する。
反応系に水または水蒸気を添加する場合にはア
ニリン類１モルに対して水0.1〜100モルの割合で
反応器に装入する。
この方法において、とくに好ましい触媒は元素
周期律表第８族金属類含有触媒である。その他の
反応希釈剤、反応条件および生成物の取得法等は
本発明の前記方法と同様である。
実施例
以下、実施例をあげて、本発明の方法を詳述す
る。
実施例 １
内容200mlの攪拌機つきチタン合金製オートク
レーブ中にアニリン93.1g（１モル）と酸化エチレ
ン4.4g（0.1モル）と粉末状のルテニウム−炭素触
媒（Ru含量0.5％）1gを入れ、オートクレーブ中
の空気を窒素で置換し、窒素圧力10Kg／cm2を封入
した後、反応温度275℃、30分間オートクレーブ
を攪拌しながら反応させた。反応後、反応液から
触媒を濾別し、反応生成物をガスクロマトグラフ
で分析した。蒸留によつて生成物を単離し、IR
およびNMRでインドールの生成を確認した。そ
の結果、インドールが2.9g（酸化エチレンを基準
とした転化率33.8％、選択率72.5％）得られた。
副生物として少量のインドリンを得た。
実施例 ２〜24
実施例１においてルテニウム−炭素触媒の代わ
りに触媒を種々変えて、その他は実施例１と同様
に反応を行つた。その結果を第１表に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing indoles. More specifically, the present invention relates to a method for producing indoles by reacting anilines and ethylene oxide in the presence of a catalyst. Indole is known as a raw material for the chemical industry, and has become an important substance in recent years, particularly as a raw material for perfumery and amino acid synthesis. Conventional technology There have been several attempts to synthesize indole, but all of them produced many by-products,
Many of them are expensive in terms of raw materials, the process to reach indole is long, and many of them are complicated to operate. Problems to be Solved by the Invention An object of the present invention is to produce indoles with high selectivity using inexpensive raw materials and in a single step. As a result of intensive studies to achieve this objective, the inventors of the present invention have found that the desired product can be obtained by a method based on a completely new reaction that was previously unknown, that is, by causing a catalytic reaction between anilines and ethylene oxide. We have discovered that certain indoles can be produced with good selectivity, and have completed the production method of the present invention. That is, the production method of the present invention uses anilines and ethylene oxide as group 8 metals in the periodic table of elements.
A method for producing indoles through a liquid phase reaction in the presence of a catalyst containing one or more selected from the group consisting of group 1b metals, zinc salts, cadmium salts, magnesium salts, magnesium oxide, and activated carbon. be. Therefore, according to the production method of the present invention, for example, indole can be obtained by catalytically reacting aniline and ethylene oxide, and 5-methylindole can be obtained by catalytically reacting para-toluidine and ethylene oxide. The catalyst of the present invention is a group 8 metal of the periodic table of elements.
A catalyst containing one or more selected from the group consisting of Group 1b metals, zinc salts, cadmium salts, magnesium salts, magnesium oxide, and activated carbon. That is, it contains Group 8 metals, Group 1B metals, zinc salts, cadmium salts, magnesium salts, magnesium oxide, or activated carbon, each alone or in combination of two or more, and each of these together with other compounds. be. For example, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, etc.
Platinum, copper, silver, gold, zinc chloride, zinc sulfate, zinc nitrate, zinc phosphate, cadmium chloride, cadmium sulfate, cadmium nitrate, cadmium phosphate, magnesium chloride, basic magnesium chloride, magnesium sulfate, magnesium oxide, activated carbon; Group 8 metals of the periodic table, group 1b metals, zinc salts,
8, which is supported by cadmium salts, magnesium salts, magnesium oxide and/or activated carbon, or mixtures of group 8 metals, group 1b metals, cadmium salts, magnesium salts, magnesium oxide and/or activated carbon, and other compounds; Catalysts containing group metals, group 1b metals, zinc salts, cadmium salts, magnesium salts, magnesium oxide and/or activated carbon. Catalytic substances (hereinafter referred to as Group 8 metals of the periodic table of elements,
Other compounds used in combination with Group 1b metals, zinc salts, cadmium salts, magnesium salts, magnesium oxide and activated carbon include lithium, potassium, magnesium, calcium, strontium, barium, copper, silver, mercury, aluminum, tin, iron, cobalt, nickel, chromium,
Halides such as manganese, zinc, molybdenum,
These include nitrates, sulfates, carbonates, organic acid salts, oxides, hydroxides, or metals. As the carrier for supporting the catalyst substance or the catalyst substance and other compounds, any carrier that is generally used as a carrier for supported catalysts can be used, but diatomaceous earth, pumice, titania, silica-alumina, and alumina are usually used. , magnesia, silica gel, activated carbon, activated clay, asbestos, etc. are used. A supported catalyst is prepared by supporting the catalyst substance on these carriers by a conventional method. According to the immersion method, a water-soluble group 8 or group 1b metal salt is dissolved in water and immersed in a carrier such as activated carbon or alumina, followed by drying, thermal decomposition, and reduction. According to the precipitation method, a carrier such as activated carbon or silica gel is added to an aqueous solution of nitrate of one or more Group 8 or Group 1b metals, and an alkaline substance is added while stirring to form a precipitate. The precipitate is prepared by filtering, washing, drying, calcination and reduction. There are various other catalyst preparation methods, and the method for preparing the catalyst is not limited.
Further, there is no particular restriction on the amount of the catalyst substance supported on the carrier, and usually an appropriate amount, for example 0.01 to 50%, of the catalyst substance may be supported depending on the carrier. In the present invention, activated carbon can be used alone as a catalyst, but activated carbon may include metals from group 8 of the periodic table of elements, metals from group 1b, zinc salts, cadmium salts,
When magnesium salts and/or magnesium oxide are supported, the catalytic activity increases. The activated carbon used in the present invention includes various types of activated carbon. Examples include activated carbon made from coconut shells, wood, sawdust, lignin, coal, blood charcoal, petroleum carbon, and the like. Commercially available activated carbon is usually powdered carbon, crushed carbon, or molded carbon shaped into a spherical or cylindrical shape, and the shape of the activated carbon used in the present invention is not particularly limited. The anilines used in the present invention include aniline,
and ortho-toluidine, meta-toluidine,
para-toluidine, ortho-aminophenol,
Includes nuclear substituted derivatives of aniline such as meta-aminophenol, para-aminophenol, ortho-anisidine, meta-anisidine, para-anisidine. The method of the present invention can be carried out in either a liquid phase or a gas-liquid mixed phase method. When carried out in a liquid phase, it can be carried out in a fixed bed, fluidized bed or moving bed reactor, in which a mixture of anilines and ethylene oxide is heated to an elevated temperature in the presence of the catalyst containing the above-mentioned catalytic substance. At this time, various inert gases and/or solvents can be used as diluents for the raw materials. Examples of such inert gaseous substances include nitrogen gas, carbon dioxide gas,
Examples include water vapor and the vapor of compounds inert to this reaction. Preferably, hydrogen gas or hydrogen-containing gas is used as the diluent. Solvents that can be used in the present invention are those that do not interfere with the reaction according to the present invention. For example, water, benzene, toluene, xylene, methanol, ethanol, isopropanol, dioxane, dimethylformamide, dimethyl sulfoxide, pyridine, N-methylpyrrolidone, trimethylamine, diethylamine, triethylamine, tripropylamine,
Contains amines such as tributylamine, diphenylamine, and triphenylamine. Preferably it is water. In a liquid phase reaction using anilines and ethylene oxide as raw materials, the anilines and ethylene oxide charged into the reaction apparatus are mixed at a ratio of 0.05 to 5 moles of ethylene oxide per 1 mole of aniline, and heated together with the catalyst. do. The reaction temperature is in the range of 200-500℃, preferably 250℃
~400℃. If the temperature is below 200°C, the reaction will hardly proceed, and if it is above 400°C, a large amount of by-products will be produced, which is not preferable. The reaction pressure may be either elevated pressure or normal pressure. There are no particular restrictions on the reactor used in the present invention, and generally a batch or continuous liquid phase reactor is used. In these various methods, indoles can be easily separated and purified from the reaction product by a suitable method, for example, a conventional method such as distillation. The method of the present invention uses anilines as raw materials as described above. However, indoles can also be produced by the same reaction method using nitrobenzenes, which are raw materials for anilines. That is, hydrogen and nitrobenzenes undergo a catalytic reaction to produce anilines, so by catalytically reacting hydrogen, nitrobenzene, and ethylene oxide, indoles are produced, and by catalytically reacting hydrogen, para-nitrotoluene, and ethylene oxide, 5- Methylindole can be obtained. The nitrobenzenes used in this method include nitrobenzene and ortho-nitrotoluene;
Meta-nitrotoluene, para-nitrotoluene,
Includes nuclear substituted derivatives of nitrobenzene such as ortho-nitrophenol, meta-nitrophenol, para-nitrophenol, ortho-nitroanisole, meta-nitroanisole, para-nitroanisole. The reaction in this method is carried out by heating a mixture of nitrobenzenes, ethylene oxide, hydrogen gas, and optionally added diluent in the presence of the catalyst containing the above-mentioned catalytic material. The nitrobenzenes and ethylene oxide charged into the reactor are reacted at a ratio of 0.05 to 5 moles of ethylene oxide per mole of nitrobenzene, so that the liquid hourly space velocity relative to the catalyst is 0.01 to 51/1-catalyst/hr. Pour into the container. Hydrogen gas to be mixed with nitrobenzenes and ethylene oxide is charged into the reactor at a ratio of 0.1 to 100 moles, preferably 1 to 30 moles, per mole of nitrobenzenes. When water or steam is added to the reaction system, it is charged into the reactor at a ratio of 0.1 to 100 moles of water per mole of aniline. In this method, particularly preferred catalysts are catalysts containing metals from Group 8 of the Periodic Table of Elements. Other reaction diluents, reaction conditions, method for obtaining products, etc. are the same as in the above-mentioned method of the present invention. Examples Hereinafter, the method of the present invention will be explained in detail with reference to Examples. Example 1 93.1 g (1 mol) of aniline, 4.4 g (0.1 mol) of ethylene oxide, and 1 g of powdered ruthenium-carbon catalyst (Ru content 0.5%) were placed in a 200 ml titanium alloy autoclave equipped with a stirrer, and the contents were placed in the autoclave. After replacing the air with nitrogen and enclosing a nitrogen pressure of 10 Kg/cm 2 , the autoclave was reacted at a reaction temperature of 275° C. for 30 minutes with stirring. After the reaction, the catalyst was filtered off from the reaction solution, and the reaction product was analyzed by gas chromatography. Isolate the product by distillation and IR
The formation of indole was confirmed by NMR. As a result, 2.9 g of indole (conversion rate 33.8%, selectivity 72.5% based on ethylene oxide) was obtained.
A small amount of indoline was obtained as a by-product. Examples 2 to 24 The reaction was carried out in the same manner as in Example 1 except that various catalysts were used in place of the ruthenium-carbon catalyst in Example 1. The results are shown in Table 1.
【表】
発明の効果
本発明の方法の利点は次のようである。第１に
原料がアニリンおよび酸化エチレンのように非常
に安価である。第２に原料からインドール類が一
段で製造される。第３に副生物が非常に少なく、
選択率が非常に良く、したがつて高純度のインド
ールを得ることができる。[Table] Effects of the invention The advantages of the method of the present invention are as follows. First, the raw materials are very cheap, such as aniline and ethylene oxide. Second, indoles are produced in one step from raw materials. Thirdly, there are very few by-products.
The selectivity is very good and therefore high purity indole can be obtained.
Claims (1)
第８族金属類、第1b族金属類、亜鉛塩類、カド
ミウム塩類、マグネシウム塩類、酸化マグネシウ
ムおよび活性炭からなる群から選ばれた１種また
は２種以上を含有する触媒の存在下に液相反応さ
せることを特徴とするインドール類の製造法。 ２ 反応を水素の存在下で行う特許請求の範囲第
１項記載の製造法。 ３ 反応を水の存在下で行う特許請求の範囲第１
項記載の製造法。[Claims] 1. Anilines and ethylene oxide are selected from the group consisting of Group 8 metals of the Periodic Table of Elements, Group 1B metals, zinc salts, cadmium salts, magnesium salts, magnesium oxide, and activated carbon. A method for producing indoles, which comprises performing a liquid phase reaction in the presence of one or more catalysts. 2. The production method according to claim 1, wherein the reaction is carried out in the presence of hydrogen. 3 Claim 1 in which the reaction is carried out in the presence of water
Manufacturing method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58046062A JPS59172467A (en) | 1983-03-22 | 1983-03-22 | Production of indole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58046062A JPS59172467A (en) | 1983-03-22 | 1983-03-22 | Production of indole compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59172467A JPS59172467A (en) | 1984-09-29 |
| JPH0551577B2 true JPH0551577B2 (en) | 1993-08-03 |
Family
ID=12736519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58046062A Granted JPS59172467A (en) | 1983-03-22 | 1983-03-22 | Production of indole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59172467A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57206656A (en) * | 1981-06-12 | 1982-12-18 | Mitsui Toatsu Chem Inc | Preparation of indole compound |
| JPS5829762A (en) * | 1981-08-18 | 1983-02-22 | Mitsui Toatsu Chem Inc | Preparation of indole |
| JPS5846067A (en) * | 1981-09-14 | 1983-03-17 | Mitsui Toatsu Chem Inc | Preparation of indole |
-
1983
- 1983-03-22 JP JP58046062A patent/JPS59172467A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57206656A (en) * | 1981-06-12 | 1982-12-18 | Mitsui Toatsu Chem Inc | Preparation of indole compound |
| JPS5829762A (en) * | 1981-08-18 | 1983-02-22 | Mitsui Toatsu Chem Inc | Preparation of indole |
| JPS5846067A (en) * | 1981-09-14 | 1983-03-17 | Mitsui Toatsu Chem Inc | Preparation of indole |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59172467A (en) | 1984-09-29 |
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