JPS63179834A - Dimerization of aromatic halogen compound - Google Patents
Dimerization of aromatic halogen compoundInfo
- Publication number
- JPS63179834A JPS63179834A JP62010758A JP1075887A JPS63179834A JP S63179834 A JPS63179834 A JP S63179834A JP 62010758 A JP62010758 A JP 62010758A JP 1075887 A JP1075887 A JP 1075887A JP S63179834 A JPS63179834 A JP S63179834A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- aromatic
- compound
- halogen
- salt
- 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.)
- Granted
Links
- -1 aromatic halogen compound Chemical class 0.000 title claims abstract description 31
- 238000006471 dimerization reaction Methods 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019253 formic acid Nutrition 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 230000000447 dimerizing effect Effects 0.000 claims description 7
- 150000001339 alkali metal compounds Chemical group 0.000 claims description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004305 biphenyl Substances 0.000 abstract description 4
- 235000010290 biphenyl Nutrition 0.000 abstract description 4
- 235000011187 glycerol Nutrition 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920001721 polyimide Polymers 0.000 abstract description 2
- 239000009719 polyimide resin Substances 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- RLCCWSGPYQLVSW-UHFFFAOYSA-M sodium;3-chlorophthalate;hydron Chemical compound [Na+].OC(=O)C1=CC=CC(Cl)=C1C([O-])=O RLCCWSGPYQLVSW-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- BLNVISNJTIRAHF-UHFFFAOYSA-N 4-chlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1 BLNVISNJTIRAHF-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- FPWNLURCHDRMHC-UHFFFAOYSA-N 4-chlorobiphenyl Chemical group C1=CC(Cl)=CC=C1C1=CC=CC=C1 FPWNLURCHDRMHC-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 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
- 238000004811 liquid chromatography Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- XLKHCFJHGIAKFX-UHFFFAOYSA-M sodium;4-chlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(Cl)C=C1 XLKHCFJHGIAKFX-UHFFFAOYSA-M 0.000 description 1
- IZUPJOYPPLEPGM-UHFFFAOYSA-M sodium;hydron;phthalate Chemical compound [Na+].OC(=O)C1=CC=CC=C1C([O-])=O IZUPJOYPPLEPGM-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は芳香族ハロゲン化合物を脱ハロゲン二量化して
、ビフェニル化合物＠を製造する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a biphenyl compound @ by dehalogenating and dimerizing an aromatic halogen compound.
芳香族化合物の二量化により得られるビフェニル化合物
類は、種々の工業原料として有用表ものであシ、例えば
３．μ、３′、μ′−ビフェニルテトラカルボン酸アル
カリ金属塩は耐熱性ポリイミド樹脂製造用原料として有
用な物質である。Biphenyl compounds obtained by dimerization of aromatic compounds are useful as various industrial raw materials, such as 3. μ, 3', μ'-biphenyltetracarboxylic acid alkali metal salts are useful substances as raw materials for producing heat-resistant polyimide resins.
従来、芳香族ハロゲン化合物を脱ハロゲン二量化してビ
フェニル化合物を製造する方法としては、例えば、水酸
化アルカリ水溶液中で金属パラジウムを担持した触媒及
びメタノールの存在下に脱ハロゲン二量化せしめる方法
（Ｊ、Ａｍ。Conventionally, as a method for producing biphenyl compounds by dehalogenating and dimerizing aromatic halogenated compounds, for example, a method of dehalogenating and dimerizing aromatic halogenated compounds in the presence of methanol and a catalyst supporting metal palladium in an aqueous alkali hydroxide solution (J , Am.
Ｏｈ６ｍｍ ８０（１，互 ７７６（ｉｙａり）、特公
昭！ター／４ＡＯ１Ｊ号）等が知られている。しかしな
がら、これら公知の方法によると脱ハロゲンした芳香族
化合物が多量に副生ずるため、所望のビフェニル化合物
の収率が低い問題が有）、ビフェニル化合物を高収率で
得るためには、脱ハロゲン副生物を抑制することが課題
であった。Oh6mm 80 (1, 776 (iyari), Tokuko Sho! Tar/4AO1J No.) etc. are known. However, according to these known methods, a large amount of dehalogenated aromatic compounds are produced as a by-product, resulting in a low yield of the desired biphenyl compound).In order to obtain a high yield of biphenyl compounds, it is necessary to The challenge was to suppress the organisms.
水出願人は、先に上記の公知方法に於いて、メタノール
の代わ）に多価アルコールおよび／またはホルムアルデ
ヒド類を用いる方法（特願昭４０−／ｌ！ｌｒｐ号）及
び一酸化炭素を用いる方法（特願昭２０−．２／／２？
を号）をみい出し、特許出願を行なった。The applicant has previously proposed a method using a polyhydric alcohol and/or formaldehyde (instead of methanol) in the above-mentioned known method (Japanese Patent Application No. 1972/1!lrp) and a method using carbon monoxide. (Special application 1949-.2//2?
(No.) and filed a patent application.
そして、上述の方法について更に検討を重ねた結果、芳
香族ハロゲン化合物の脱ハロゲン二量化反応に於いてア
ルコール又はギ酸もしくはその塩を存在させ、しかも、
少なくとも反応初期に一酸化炭素を存在させることによ
り、目的化合物の収率が一層向上することをみい出した
。As a result of further studies on the above-mentioned method, we found that alcohol or formic acid or a salt thereof is present in the dehalogen dimerization reaction of aromatic halogen compounds, and
It has been found that the yield of the target compound can be further improved by allowing carbon monoxide to exist at least at the initial stage of the reaction.
即ち、本発明は、芳香族ハロゲン化合物を脱ハロゲン二
量化してビフェニル化合物類を高収率で製造することが
できる方法を提供しようとするものである。That is, the present invention aims to provide a method capable of producing biphenyl compounds in high yield by dehalogenating and dimerizing aromatic halogen compounds.
ｃ問題点を解決するための手段〕
本発明の要旨は、少なくとも１個のハロゲン原子を芳香
核炭素に有する芳香族化合物を白金族金属触媒、および
ハロゲン受容体の存在下に脱ハロゲン二量化する方法に
おいて、アルコール又はギ酸もしくはその塩を存在させ
、かつ少なくとも、反応初期に一酸化炭素全存在ぢせる
ことを特徴とする芳香族ハロゲン化合物の脱ハロゲン副
生物法に存する。Means for Solving Problems] The gist of the present invention is to dehalogenate and dimerize an aromatic compound having at least one halogen atom in the aromatic carbon in the presence of a platinum group metal catalyst and a halogen acceptor. The present invention relates to a method for dehalogenating by-products of aromatic halogen compounds, which is characterized in that alcohol or formic acid or a salt thereof is present, and at least all carbon monoxide is present in the initial stage of the reaction.
以下に、本発明につき詳細に説明する。The present invention will be explained in detail below.
本発明方法における出発物質としては、少なくとも１個
のハロゲン原子を芳香核炭素に有する芳香族化合物が使
用される。Aromatic compounds having at least one halogen atom on the aromatic carbon are used as starting materials in the process of the invention.
芳香核炭素にある少なくともｌａのハロゲン原子として
は、通常塩素、臭素、沃素が挙げられるが、ガかでも臭
素および塩素が好ましい。The halogen atom of at least 1 a in the aromatic nuclear carbon usually includes chlorine, bromine, and iodine, with bromine and chlorine being preferred.
芳香核炭素に結合するハロゲン原子数は／−ｊ個が可能
であるが、好ましくは１〜３個であ）、ハロゲン原子が
２個以上の場合これらハロゲン原子は互いに同一でも異
なっていてもよい。The number of halogen atoms bonded to the aromatic nuclear carbon can be /-j, but preferably 1 to 3), and when there are 2 or more halogen atoms, these halogen atoms may be the same or different from each other. .
この芳香族ハロゲン化合物の核炭素は脱ハロゲン二量化
反応に悪影響を与えないハロゲン原子以外の置換基で置
換されていてもかまわないが、ハロゲン原子を有する芳
香核炭素の隣接炭素に置換基を有する場合は目的二量体
のビフェニル化合物類の収率が低下する傾向がある。The core carbon of this aromatic halogen compound may be substituted with a substituent other than a halogen atom that does not adversely affect the dehalogen dimerization reaction, but the aromatic core carbon having a halogen atom has a substituent on the adjacent carbon. In this case, the yield of the desired dimeric biphenyl compounds tends to decrease.
本発明で用いられる前記芳香族化合物の具体例としては
、例えば、クロロベンゼン、ブロモベンゼン、ｐ−クロ
ロブロモベンゼン、ｐ−クロロジフェニル、ｐ−クロロ
フェノール、Ｐ −クロロアニソ−／ｌ／、Ｉ）−クロ
ロフェノ−ル、ｐ−クロロベンズアミド、ｐ−クロロア
ニリン、ｐ−クロロベンゾフェノン、ｐ−クロロアセト
フェノン、ｐ−クロロベンゾニトリル、ｐ−クロロベン
ゼンスルホン酸ナトリウム塩、α−クロロナフタレン、
μｍクロロオルソキシレン、ｐ−クロロ安息香酸、μｍ
クロロオルソフタル酸、グークロロオルソフタル酸のア
ルカリ金属塩、およびμ、ｊ−ジクロロフタル酸等が挙
げられるが、本発明に使用される芳香族ハロゲン化合物
は、上記のものに伺等限定されない。Specific examples of the aromatic compounds used in the present invention include chlorobenzene, bromobenzene, p-chlorobromobenzene, p-chlorodiphenyl, p-chlorophenol, P-chloroaniso-/l/, and I)-chlorophenol. p-chlorobenzamide, p-chloroaniline, p-chlorobenzophenone, p-chloroacetophenone, p-chlorobenzonitrile, p-chlorobenzenesulfonic acid sodium salt, α-chloronaphthalene,
μm chloroorthoxylene, p-chlorobenzoic acid, μm
Examples include chloroorthophthalic acid, alkali metal salts of goochloroorthophthalic acid, μ,j-dichlorophthalic acid, and the like, but the aromatic halogen compound used in the present invention is not limited to the above.
本発明方法では、これら芳香族ハロゲン化合物は、通常
、単一種で用いられるが、必要にょシ、異なる芳香族ハ
ロゲン化合物の混合物を使用することもできる。In the method of the present invention, these aromatic halogen compounds are usually used as a single type, but if necessary, a mixture of different aromatic halogen compounds can also be used.
本発明に用いる白金族金属触媒の中心金属としては、パ
ラジウム、ロジウム、ルテニウム、白金、イリジウムな
どが挙げられるが、なかでもパラジウム、ロジウムが好
適である。Examples of the central metal of the platinum group metal catalyst used in the present invention include palladium, rhodium, ruthenium, platinum, and iridium, with palladium and rhodium being particularly preferred.
これらの白金族金属触媒は、ハロゲン化物、硝酸塩、硫
酸塩等の無機酸塩、酢酸塩、安息香酸塩、フタル酸塩等
の有機酸塩、アセチルアセトン等のβ−ジケトン類を含
むキレート塩および単体として使用される。なかでも、
金属単体を活性炭、シリカ、アルミナ、シリカアルミナ
、ゼオライト、酸化チタン、マグネシア、珪藻土、グラ
ファイト、アスベスト、イオン交換樹脂、炭酸バリウム
、炭酸カルシウム等の担体に担持させたものが好ましく
、特に活性炭に担持した触媒が好適である。これら担持
金属触媒におりて金属は担体に対して通常０．／ −，
２０重量当、特ＫＯ，！−１０重量ｓ程度担持されてい
るのが好適である。白金族金属触媒の使用量は芳香族ハ
ロゲン化合物７モルに対し、金属原子換算で通常１０Ｏ
Ｎ０．００ ／ミリモル、好適には、３０−０．０／ミ
リモルである。These platinum group metal catalysts include halides, inorganic acid salts such as nitrates and sulfates, organic acid salts such as acetates, benzoates, and phthalates, chelate salts including β-diketones such as acetylacetone, and simple substances. used as. Among them,
It is preferable that a metal element is supported on a carrier such as activated carbon, silica, alumina, silica alumina, zeolite, titanium oxide, magnesia, diatomaceous earth, graphite, asbestos, ion exchange resin, barium carbonate, calcium carbonate, etc., and in particular supported on activated carbon. Catalysts are preferred. In these supported metal catalysts, the metal is usually 0.0% relative to the support. / −,
20 weight wins, special KO! -10 weight s is preferably supported. The amount of platinum group metal catalyst used is usually 10 O in terms of metal atoms per 7 moles of aromatic halogen compound.
N0.00/mmol, preferably 30-0.0/mmol.
更に、本発明方法では、ハロゲン受容体を併用すること
がビフェニル化合物知全高収率で得るために必要である
。ハロゲン受容体としては、脱ハロゲンニ量化の際に生
じるハロゲン原子を受答出来る物質であれば良く、通常
は、塩基性物質が用いられる。Furthermore, in the method of the present invention, it is necessary to use a halogen acceptor in combination in order to obtain a biphenyl compound in a high overall yield. The halogen acceptor may be any substance as long as it can accept halogen atoms generated during dehalogen dimerization, and usually a basic substance is used.
塩基性物質としては、アンモニア、アルカリ金属化合物
、アルカリ土類金属化合物等が挙げられる。これらの中
でもアルカリ金属化合物またはアルカリ土類金属化合物
が好適であシ、具体的にはアルカリ金属またはアルカリ
土類金属の炭酸、硝酸、リン酸、ホウ酸等との無機酸塩
、水酸化物、酢酸、フタル酸等の有機酸塩、およゝびア
ルコキシド類等が挙げられる。Examples of the basic substance include ammonia, alkali metal compounds, alkaline earth metal compounds, and the like. Among these, alkali metal compounds or alkaline earth metal compounds are preferred; specifically, inorganic acid salts of alkali metals or alkaline earth metals with carbonic acid, nitric acid, phosphoric acid, boric acid, etc., hydroxides, Examples include organic acid salts such as acetic acid and phthalic acid, and alkoxides.
特に好ましい具体例は、水酸化リチウム、水酸化ナトリ
ウム、水酸化カリウム、水酸化マグネシウム、水酸化カ
ルシウム、水酸化バリウム等の水酸化物、炭酸す） Ｉ
Ｊウム、炭酸カリウム、炭酸水素ナトリウム等の炭酸塩
、ナトリウムメトキシド、ナトリウムエトキシド、カリ
ウムターシャリ−ブチレート等のアルコキシドである１
、が炭酸塩は、水酸化物に比べ反応取置がや＼低い場合
もあるので、水酸化物がよシ好ましい。Particularly preferred examples include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and carbonic acid.
Carbonates such as potassium carbonate, sodium hydrogen carbonate, alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butyrate, etc.
However, since carbonates may have a slightly lower reaction reserve than hydroxides, hydroxides are more preferred.
これらハロゲン受容体の使用量は出発原料である芳香族
ハロゲン化合物中に含まれるハロゲン原子数およびカル
ボキシル基等の酸性置換基の存在によシ変化し特に限定
されないが、通常は、芳香族ハロゲン化合物７モルに対
し０．０ ／〜１００モル、好適にはθ、／−、３０モ
ル用いられる。The amount of these halogen acceptors used varies depending on the number of halogen atoms contained in the aromatic halogen compound as a starting material and the presence of acidic substituents such as carboxyl groups, and is not particularly limited. 0.0/-100 mol, preferably θ,/-, 30 mol per 7 mol.
本発明では上述のような白金族金属触媒、とハロゲン受
容体の存在下に芳香族ハロゲン化合物を二量化反応させ
る反応に於いて、更に、アルコール又はギ酸もしくはそ
の塩を存在させ、かつ少なくとも、この反応初期に一酸
化炭素を存在させることを必須の要件とするものである
。In the present invention, in the dimerization reaction of an aromatic halogen compound in the presence of a platinum group metal catalyst and a halogen acceptor as described above, alcohol or formic acid or a salt thereof is further present, and at least It is an essential requirement that carbon monoxide be present at the initial stage of the reaction.
本発明で反応系丙に存在させるアルコールとしては、例
えば、メタノール、エタノール、プロパノ−ルナ８０１
価アルコール、エチレングリコール、プロピレングリコ
ール、八−−ブタンジオール、ｌ、３−フロパンジオー
ル、ｌ、≠−ブタンジオール等の２価アルコール、グリ
セリン等の３価アルコール、ペンタエリスリトール等の
μ価アルコールが挙げられ、中でもエチレングリコール
、プロピレングリコール、ノ、−一ブタンジオール、グ
リセリン等のコ価又は３価アルコールが好適である。ま
た、ギ酸塩としては、例えば、ナ） ＩＪウム塩、カリ
ウム塩が挙げられる。これら化合物の使用量は通常、芳
香族ハロゲン化合物１モルに対し、 Ｄ、θ／ −ｊ
０モル、好ましくは０．３−１０モルである。Examples of the alcohol present in reaction system C in the present invention include methanol, ethanol, and propanol Luna 801.
dihydric alcohols such as ethylene glycol, propylene glycol, 8-butanediol, l,3-furopanediol, l,≠-butanediol, trihydric alcohols such as glycerin, and μ-hydric alcohols such as pentaerythritol. Among them, covalent or trihydric alcohols such as ethylene glycol, propylene glycol, monobutanediol, and glycerin are preferred. Further, examples of the formate include sodium salt and potassium salt. The amount of these compounds used is usually D, θ/-j per 1 mole of aromatic halogen compound.
0 mol, preferably 0.3-10 mol.
一酸化炭素は二量化反応の全期間を通して存在させても
良いが、少なくとも反応初期に存在させることが必要で
あ）、通常、反応開始時から芳香族化合物の転換惠が少
なくともｊ％に達するまで、好ましくは、少なくとも７
０％に達するまでの間は必ず、一酸化炭素が存在するよ
うに調節する。一酸化炭素の使用量は例えば、芳香族ハ
ロゲン化合物に対して、θ、／−−θそル２でアシ、通
常、この際の一酸化炭素分圧はθ、ｔ−ＡＯｋＱ／Ｃ１
／ｌ程度である。なお、反応の進行に伴なって、一酸化
炭素分圧は次第に低下することとなる。尚、一酸化炭素
は、純粋でも、例えば、窒素ガスなどの不活性ガスで希
釈して使用しても差し支えない。Carbon monoxide may be present throughout the entire period of the dimerization reaction, but it is necessary to be present at least at the beginning of the reaction), and usually from the start of the reaction until the conversion of the aromatic compound reaches at least j%. , preferably at least 7
Adjust so that carbon monoxide is always present until it reaches 0%. The amount of carbon monoxide used is, for example, θ, /--θ so2 for aromatic halogen compounds, and the carbon monoxide partial pressure in this case is usually θ, t-AOkQ/C1
/l. Note that as the reaction progresses, the carbon monoxide partial pressure will gradually decrease. Note that carbon monoxide may be used either pure or diluted with an inert gas such as nitrogen gas.
本発明の反応は溶媒の存在下または不存在下で実施する
ことができるが、通常、水または水を主体とする水性媒
体を用いるのが好ましい。Although the reaction of the present invention can be carried out in the presence or absence of a solvent, it is usually preferable to use water or an aqueous medium mainly composed of water.
この際の溶媒の使用量は通常、芳香族ハロゲン化合物に
対して、Ｏ１ｌ〜３θ容量倍程度である。The amount of solvent used in this case is usually about 011 to 3θ times the volume of the aromatic halogen compound.
本発明の反応温度は通常、２０〜３００℃、好ましくは
ｊＯ−２００℃であ夛、また、反応圧力は通常、常圧〜
−θθＪＣＱ／Ｃｄ、好ましくは常圧〜１００＃Ｉ／Ｃ
１ｄである。The reaction temperature of the present invention is usually 20 to 300°C, preferably -200°C, and the reaction pressure is usually normal pressure to
-θθJCQ/Cd, preferably normal pressure to 100#I/C
It is 1d.
本発明方法は回分式、半回分式、連続式のいずれでも行
なりことができる。The method of the present invention can be carried out in a batch, semi-batch or continuous manner.
反応に使用した白金族金属触媒は従来一般に行なわれて
いる方法、例えば抽出法、結晶法もしくは還元法によシ
反応液から分離回収される。The platinum group metal catalyst used in the reaction is separated and recovered from the reaction solution by a conventional method, such as an extraction method, a crystallization method, or a reduction method.
担持金属触媒を用Ａた場合は、濾過によシ容易に分離回
収され、再び脱ハロゲン二蓋化反応に使用することが出
来る。When a supported metal catalyst is used, it can be easily separated and recovered by filtration and used again in the dehalogenation reaction.
本発明で得られた、ビフェニル化合物類は、その物理的
性状に従って蒸発法、蒸留法、結晶法、酸析法等によっ
て反応液から分離取得されるＯ
〔実施例〕
次に、本発明を実施例によ少更に詳細に説明するが本発
明はその要旨を超えない限シ、以下の実施例に限定され
るものではない。The biphenyl compounds obtained in the present invention can be separated and obtained from the reaction solution by evaporation, distillation, crystallization, acid precipitation, etc. according to their physical properties. [Example] Next, the present invention will be carried out. Although the present invention will be explained in more detail by way of example, the present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例−７
内容量／３００ｒｒｔｌのステンレス製誘導攪拌式オー
トクレーブに１−重ｉ′鴬パラジウムカーボン／ ６．
９１７およびμｍクロルフタル酸モノナトリウム塩（以
下、ｇ−ＯＰＡ塩と略す）Ｊ−７・２ｍ０１ｘ′に含有
する白色粉末ｊ ｔ ３．Ｐ 、Ｆ （４−クロル体以
外は３−クロルフタル酸モノナトリウム塩（以下、Ｊ−
ＯＰＡ塩と略す） ／ 、２．／ ｍ０１％、フタル酸
モノナトリウム塩、２４ｔ、Ｏｍｏｌ Ｘ％μ、！−ジ
クロルフタル酸モノナトリウム塩（以下、ｌｌ、ｊ−Ｄ
ＯＰＡ塩と略す） ３．３ｍｏ１％、３、クージクロル
フタル酸モノナトリウム塩（以下、３．４ｌ−ＤＯＰＡ
塩と略す） ３．ｓ ｍ０１％）、り５％水酸化ナトリ
ウム／９１．タ ｙ１エチレングリコール−〇、３９．
脱塩水乙り７．２ｍ１ｔ−入れ攪拌しつつ一酸化炭素雰
囲気下でｌｌｏ℃迄昇温した後、系内を一酸化炭素でハ
！ ｋｇ ／ ｃｒｌ Ｇ迄昇圧し消費した一酸化炭素
を供給しつつ一定圧力で５時間反応を行った。反応終了
後７０℃迄降温し、脱塩水で希釈した後、系中のパラジ
ウムカーボンｔ−Ｆ別し九。液体クロマトグラフィーに
て分析した結果を表−ノに示す。Example-7 In a stainless steel induction stirring autoclave with an internal capacity of 300 rrtl, 1-heavy i'homugi palladium carbon/6.
White powder j t contained in 917 and μm chlorphthalic acid monosodium salt (hereinafter abbreviated as g-OPA salt) J-7.2m01x' 3. P, F (other than the 4-chlor form is 3-chlorophthalic acid monosodium salt (hereinafter referred to as J-
(abbreviated as OPA salt) / , 2. / m01%, phthalic acid monosodium salt, 24t, Omol X%μ,! -dichlorophthalic acid monosodium salt (hereinafter ll, j-D
(abbreviated as OPA salt) 3.3 mo1%, 3, cudichlorophthalic acid monosodium salt (hereinafter referred to as 3.4 l-DOPA
(abbreviated as salt) 3. s m01%), 5% sodium hydroxide/91. Ta y1 ethylene glycol-〇, 39.
After adding 7.2 ml of desalinated water and raising the temperature to 10°C under a carbon monoxide atmosphere while stirring, the system was filled with carbon monoxide. The reaction was carried out at a constant pressure for 5 hours while increasing the pressure to kg/crl G and supplying the consumed carbon monoxide. After the reaction was completed, the temperature was lowered to 70°C, diluted with demineralized water, and the palladium carbon t-F in the system was separated. The results of liquid chromatography analysis are shown in Table No.
トラカルボン酸−ｔナトリウム塩を衣わす。Coat with tracarboxylic acid-t sodium salt.
実施例−一
エチレングリコールを反応前に添加せず、反応中に、２
１ ／ ｈ ｒで連続的に添加した以外は、実施例−７
と同様の方法で反応を行った。結果を表−１に示す。Example - 1 ethylene glycol was not added before the reaction and during the reaction, 2
Example-7 except that it was added continuously at 1/hr.
The reaction was carried out in the same manner. The results are shown in Table-1.
参考例−／
エチレングリコールの添加をしなかった以外は実施例−
ｌと同様の方法で反応を行つな。結果を表−７に示す。Reference example - / Example except that ethylene glycol was not added -
Do not carry out the reaction in the same manner as in 1. The results are shown in Table-7.
参考例−！
一酸化炭素を用いずに窒素を用いた以外は実施例−λと
同様の方法で反応を行った。結果を表−７に示す。Reference example-! The reaction was carried out in the same manner as in Example-λ, except that nitrogen was used instead of carbon monoxide. The results are shown in Table-7.
表 −７
１）Ｓ−ＢＴ口塩収藁（ｍ ｏ １！Ａ’ ）実施例−
３
内容／ ｊ ００．ｇのジルコニウム製誘導攪拌式オー
トクレーブに、２重量％パラジウムカーボン／ １＜、
りｌおよび、４ｔ−ＯＰ＆塩を含む白色粉末３乙３．り
、９（成分組成は実施例−７と同様である）、９′！Ｘ
水酸化ナトリウムツタＩ−９１ｓギ酸ナトリウム塩μ３
．３ｇ、脱塩水ｔ！３．２ｄ迄昇圧し、一定容積で５時
間反応を行った。尚、反応スタート後約１時間で００分
圧はＯＩｃｇＺｃｒｌＧとなった。その時点での芳香族
ノ・ロゲン化合物の転化基は約Ｊ Ｄ １０１％程度で
あった。反応終了後実施例−ノと同様の後処理を行い、
分析を行った結果ｔ−表一１に示す。Table-7 1) S-BT mouth salt collection straw (m o 1!A') Example-
3 Contents/j 00. In a zirconium induction-stirring autoclave with 2 wt% palladium on carbon/1<,
White powder containing 1 and 4t-OP & salt 3. 9 (composition is the same as Example-7), 9'! X
Sodium hydroxide ivy I-91s sodium formate salt μ3
．． 3g, demineralized water! The pressure was increased to 3.2 d, and the reaction was carried out at a constant volume for 5 hours. Note that the 00 partial pressure became OIcgZcrlG about 1 hour after the start of the reaction. At that point, the converted group of the aromatic compound was approximately J D 101%. After the reaction was completed, the same post-treatment as in Example No. was carried out.
The results of the analysis are shown in Table 1.
実施例−弘
ギ酸ナトリウム塩を反応前に添加せず、＜Ｚｊ重量Ｓの
水溶液とじ／り、２ｇ（水溶液） ／ ｈ ｒで反応中
連続的に添加した以外は、実施例−３と同様の方法で反
応を行つ九。結果を表−λに示す。Example - Same as Example 3, except that sodium proformate was not added before the reaction, but was added continuously during the reaction at a rate of 2 g (aqueous solution) / hr of an aqueous solution of <Zj weight S. 9. How to conduct a reaction. The results are shown in Table-λ.
比較例−ノ
内容量ｊ００−のステンレス製セパラブルフラスコに２
重量％パラジウムカーボン≠、ｏ ｊ ｌ ｓ＄ −Ｏ
Ｐ Ａ塩を含む白色粉末９θ、９Ｉｉ（成分組成は実施
例−／［同じ）、９１Ｎ水酸化ナトリウム１２．７ｇ、
ギ酸ナトリウムｌθ、ＩＪＩ、脱塩水／ｌｊ、！−を入
れ攪拌しつつ、遺留温度（約／１０℃）迄昇温した後、
一時間反応を行った。反応終了後実施例−７と同様の後
処理を行い、分析を行った。結果を表−コに示す。Comparative Example - In a stainless steel separable flask with an internal capacity of j00 - 2
Weight% palladium carbon≠, o j l s$ −O
White powder 9θ, 9Ii containing PA salt (composition is the same as Example), 12.7 g of 91N sodium hydroxide,
Sodium formate lθ, IJI, demineralized water/lj,! - was added and heated to the residual temperature (approx. /10°C) while stirring,
The reaction was carried out for one hour. After the reaction was completed, the same post-treatment as in Example 7 was performed and analysis was performed. The results are shown in Table-C.
表 −２
〔発明の効果〕
本発明によれば、白金族金属触媒およびハロゲン受容体
の存在下に芳香族ノ・ロゲン化合物を脱ハロゲン二量化
する方法に於いて、アルコール、又はギ酸もしくはその
塩を存在させ、かつ少なくとも反腑期に一酸化炭素を存
在させるととＫより、２量化反応の転換藁及び選択基を
共に高いレベルに保持し、高収嘉で目的化合物を得るこ
とができるのである。Table 2 [Effects of the Invention] According to the present invention, in the method for dehalogenating and dimerizing an aromatic compound in the presence of a platinum group metal catalyst and a halogen acceptor, alcohol, or formic acid or a salt thereof is used. If carbon monoxide is present at least in the anaerobic stage, both the conversion straw and the selective group in the dimerization reaction can be maintained at a high level, and the target compound can be obtained with high yield. be.
Claims (4)
する芳香族化合物を白金族金属触媒、およびハロゲン受
容体の存在下に脱ハロゲン二量化する方法において、ア
ルコール又はギ酸もしくはその塩を存在させ、かつ少な
くとも、反応初期に一酸化炭素を存在させることを特徴
とする芳香族ハロゲン化合物の脱ハロゲン二量化法。(1) In a method for dehalogenating and dimerizing an aromatic compound having at least one halogen atom in the aromatic carbon in the presence of a platinum group metal catalyst and a halogen acceptor, alcohol or formic acid or a salt thereof is present; A method for dehalogenating and dimerizing an aromatic halogen compound, which is characterized in that carbon monoxide is present at least in the initial stage of the reaction.
カリ土類金属化合物である特許請求の範囲第１項記載の
二量化法。(2) The dimerization method according to claim 1, wherein the halogen acceptor is an alkali metal compound or an alkaline earth metal compound.
囲第２項記載の二量化法。(3) The dimerization method according to claim 2, wherein the alcohol is a polyhydric alcohol.
化合物の転換率が５％に達するまでの間、存在させるこ
とを特徴とする特許請求の範囲第１項記載の二量化法。(4) The dimerization method according to claim 1, characterized in that carbon monoxide is present at least from the start of the reaction until the conversion of the aromatic compound reaches 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62010758A JP2512456B2 (en) | 1987-01-20 | 1987-01-20 | Dimerization method of aromatic halogen compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62010758A JP2512456B2 (en) | 1987-01-20 | 1987-01-20 | Dimerization method of aromatic halogen compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63179834A true JPS63179834A (en) | 1988-07-23 |
| JP2512456B2 JP2512456B2 (en) | 1996-07-03 |
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ID=11759226
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62010758A Expired - Lifetime JP2512456B2 (en) | 1987-01-20 | 1987-01-20 | Dimerization method of aromatic halogen compounds |
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| Country | Link |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5520705A (en) * | 1978-07-31 | 1980-02-14 | Ube Ind Ltd | Preparation of 3,3',4,4'-biphenyltetracarboxylic acid salt |
| JPS61293932A (en) * | 1985-06-14 | 1986-12-24 | インペリアル ケミカル インダストリ−ズパブリツク リミテイド カンパニ− | Aromatic compound and manufacture |
-
1987
- 1987-01-20 JP JP62010758A patent/JP2512456B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5520705A (en) * | 1978-07-31 | 1980-02-14 | Ube Ind Ltd | Preparation of 3,3',4,4'-biphenyltetracarboxylic acid salt |
| JPS61293932A (en) * | 1985-06-14 | 1986-12-24 | インペリアル ケミカル インダストリ−ズパブリツク リミテイド カンパニ− | Aromatic compound and manufacture |
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| Publication number | Publication date |
|---|---|
| JP2512456B2 (en) | 1996-07-03 |
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