JPH0780790B2 - Dimerization method of aromatic halogen compounds - Google Patents
Dimerization method of aromatic halogen compoundsInfo
- Publication number
- JPH0780790B2 JPH0780790B2 JP62103982A JP10398287A JPH0780790B2 JP H0780790 B2 JPH0780790 B2 JP H0780790B2 JP 62103982 A JP62103982 A JP 62103982A JP 10398287 A JP10398287 A JP 10398287A JP H0780790 B2 JPH0780790 B2 JP H0780790B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- aromatic
- chloroform
- acid
- 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
- -1 aromatic halogen compounds Chemical class 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 24
- 238000006471 dimerization reaction Methods 0.000 title claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 7
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 6
- 238000005695 dehalogenation reaction Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 229910001361 White metal Inorganic materials 0.000 claims description 2
- 239000010969 white metal Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 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
- 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
- 230000007423 decrease Effects 0.000 description 2
- 230000000447 dimerizing effect Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 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
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SODPIMGUZLOIPE-UHFFFAOYSA-N (4-chlorophenoxy)acetic acid Chemical class OC(=O)COC1=CC=C(Cl)C=C1 SODPIMGUZLOIPE-UHFFFAOYSA-N 0.000 description 1
- 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- IXLSVQMYQRAMEW-UHFFFAOYSA-N 1-chloro-4-ethoxybenzene Chemical compound CCOC1=CC=C(Cl)C=C1 IXLSVQMYQRAMEW-UHFFFAOYSA-N 0.000 description 1
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-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
- KHZYMPDILLAIQY-UHFFFAOYSA-N 3-(3-carboxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=C(C=CC=2)C(O)=O)=C1 KHZYMPDILLAIQY-UHFFFAOYSA-N 0.000 description 1
- FDOQKGWUMUEJLX-UHFFFAOYSA-N 4,5-dichlorophthalic acid Chemical compound OC(=O)C1=CC(Cl)=C(Cl)C=C1C(O)=O FDOQKGWUMUEJLX-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
- 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
- LZAPZSIPXRCLLP-FPYGCLRLSA-N 6-[(e)-3-(4-nitrophenyl)prop-2-enoyl]-3h-1,3-benzoxazol-2-one Chemical compound C1=CC([N+](=O)[O-])=CC=C1\C=C\C(=O)C1=CC=C(NC(=O)O2)C2=C1 LZAPZSIPXRCLLP-FPYGCLRLSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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
- 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
- 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
- JLJCKJXTAZLJMO-UHFFFAOYSA-N [N].ClC(Cl)Cl Chemical compound [N].ClC(Cl)Cl JLJCKJXTAZLJMO-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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 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
- 239000006227 byproduct 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000000539 dimer Substances 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
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 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
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical class [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 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
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
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)
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、ビアリール化合物類を製造する方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a method for producing a biaryl 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アリール化合物
類は、種々の工業原料として有用なものであり、例えば
3,4,3′,4′−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。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.Chem.Soc.71 776（1949）、特公昭59
−14015号）等が知られている。しかしながら、これら
の公知の方法によると脱ハロゲンした芳香族化合物が多
量に副生するため、所望のビフェニル化合物の収率が低
い問題があり、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。Biaryl compounds obtained by dimerization of aromatic compounds are useful as various industrial raw materials.
Alkali metal salt of 3,4,3 ', 4'-biphenyltetracarboxylic acid is a useful material as a raw material for producing a heat resistant polyimide resin. Conventionally, as a method of producing a biphenyl compound by dehalogenating an aromatic halogen compound, for example, a method of dehalogenating dimerization in the presence of a metal palladium-supported catalyst and methanol in an aqueous alkali hydroxide solution (J. Am.Chem.Soc.71 776 (1949), JPB 59
-14015) and the like are known. However, according to these known methods, since a large amount of dehalogenated aromatic compounds are by-produced, there is a problem in that the yield of the desired biphenyl compound is low. The challenge was to control by-products.
本発明は、芳香族ハロゲン化合物を脱ハロゲン二量化し
てビアリー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。The present invention aims to provide a method capable of producing a high yield of biaryl compounds by dehalogenating an aromatic halogen compound.
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属金属触媒、アルカ
リ金属またはアルカリ土類金属化合物およびクロロホル
ムの存在下水性媒体中脱ハロゲン二量化させることを特
徴とする芳香族ハロゲン化合物の脱ハロゲン二量化法に
存する。The gist of the present invention is to dehalogenate and dimerize an aromatic compound having at least one halogen atom in an aromatic carbon atom in an aqueous medium in the presence of a white metal catalyst, an alkali metal or alkaline earth metal compound and chloroform. The method lies in the dehalogenation dimerization method of aromatic halogen compounds.
以下に、本発明につき詳細に説明する。The present invention will be described 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 in the aromatic nucleus 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１個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、なかでも臭
素および塩素が好ましい。芳香核炭素に結合するハロゲ
ン原子数は１〜６個が可能であるが、好ましくは１〜３
個であり、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。As the at least one halogen atom in the aromatic nucleus carbon, chlorine, bromine and iodine are usually mentioned. Among them, bromine and chlorine are preferable. The number of halogen atoms bonded to the aromatic nucleus carbon can be 1 to 6, but preferably 1 to 3
When there are two or more halogen atoms, these halogen atoms may be the same or different.
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
のビアリール化合物類の収率が低下する傾向がある。The nuclear carbon of this aromatic halogen compound may be substituted with a substituent other than a halogen atom that does not adversely affect the dehalogenation dimerization reaction, but has a substituent on the adjacent carbon of the aromatic nuclear carbon having a halogen atom. In this case, the yield of the target dimeric biaryl compound 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−クロロアニソール、ｐ−クロロフェ
ネトール、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、４−
クロロオルソキシレン、ｐ−クロロ安息香酸、４−クロ
ロオルソフタル酸、４−クロロオルソフタル酸のアルカ
リ金属塩、および4,5−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
記のものに何等限定されない。Specific examples of the aromatic compound used in the present invention include, for example, chlorobenzene, bromobenzene, p-chlorobromobenzene, p-chlorodiphenyl, p-chlorophenol, p-chloroanisole, p-chlorophenetol, p. -Chlorobenzamide, p-chloroaniline, p-chlorobenzophenone, p-chloroacetophenone, p-chlorobenzonitrile, p-chlorobenzenesulfonic acid sodium salt, α-chloronaphthalene, 4-
Examples include chloroorthoxylene, p-chlorobenzoic acid, 4-chloroorthophthalic acid, alkali metal salts of 4-chloroorthophthalic acid, and 4,5-dichlorophthalic acid, which are aromatic compounds used in the present invention. The halogen compound 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、必要により、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 kind, but if necessary, a mixture of different aromatic halogen compounds can 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. Of these, palladium and rhodium are preferable.
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
持金属触媒において金属は担体に対して通常0.1〜20重
量％特に0.5〜10重量％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
１モルに対し、金属原子換算で通常100〜0.001ミリモ
ル、好適には30〜0.01ミリモルである。These platinum group metal catalysts include inorganic acid salts such as halides, 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. Above all,
Activated carbon, silica, alumina, silica-alumina, zeolite, titanium oxide, magnesia, diatomaceous earth, graphite, asbestos, ion-exchange resin, barium carbonate, calcium carbonate, etc. are preferably supported on the carrier, and particularly supported on activated carbon. Catalysts are preferred. In these supported metal catalysts, it is preferable that the metal is usually supported on the carrier in an amount of 0.1 to 20% by weight, particularly 0.5 to 10% by weight. The amount of the platinum group metal catalyst used is usually 100 to 0.001 mmol, preferably 30 to 0.01 mmol, in terms of metal atom, based on 1 mol of the aromatic halogen compound.
本発明では、アルカリ金属化合物またはアルカリ土類金
属化合物を反応系に存在させることが必要である。アル
カリ金属化合物またはアルカリ土類金属化合物として
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、ホウ酸等の無機酸塩、酢酸等の有機酸塩、
水酸化物、およびアルコキシド類等が挙げられる。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、炭酸ナトリウ
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
ターシャリープチレート等のアルコキシドであるが炭酸
塩は、水酸化物に比べ反応収率がやゝ低い場合もあるの
で、水酸化物がより好ましい。In the present invention, it is necessary to allow an alkali metal compound or an alkaline earth metal compound to be present in the reaction system. The alkali metal compound or alkaline earth metal compound, carbonic acid of alkali metal or alkaline earth metal, nitric acid, phosphoric acid, inorganic acid salts such as boric acid, organic acid salts such as acetic acid,
Examples thereof include hydroxides and alkoxides. Particularly preferred specific examples include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide, carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate, sodium. Alkoxides such as methoxide, sodium ethoxide, potassium tertiary phthalate and the like are preferable, but carbonates are more preferable because carbonates sometimes have a slightly lower reaction yield than hydroxides.
これらアルカリ金属化合物またはアルカリ土類金属化合
物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
置換基の存在により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１モルに対し0.01〜100モ
ル、好適には0.1〜20モル用いられる。The amount of these alkali metal compounds or alkaline earth metal compounds used is not particularly limited and varies depending on the number of halogen atoms contained in the starting aromatic halogen compound and the presence of an acidic substituent such as a carboxyl group. It is used in an amount of 0.01 to 100 mol, preferably 0.1 to 20 mol, per 1 mol of the aromatic halogen compound.
本発明は、上述のような白金族金属触媒とアルカリ金属
化合物またはアルカリ土類金属化合物の存在下に芳香族
ハロゲン化合物を二量化歯脳させる反応に於いて、更に
クロホルムを存在させることを必須の要件とするもので
ある。The present invention, in the reaction for dimerizing the aromatic halogen compound in the presence of the platinum group metal catalyst and the alkali metal compound or the alkaline earth metal compound as described above, it is essential to further include chloroform. It is a requirement.
二量化反応系内に存在させるクロロホルムの量は、その
供給方法にかかわらず白金族金属1g原子あたり0.01〜20
000モル、特に１〜2000モルが好ましい。クロロホルム
の量が前記範囲を外れるとビアリール化合物の収率が低
下し好ましくない。The amount of chloroform present in the dimerization reaction system is 0.01 to 20 per 1 g atom of platinum group metal regardless of the supply method.
000 moles, especially 1 to 2000 moles are preferred. If the amount of chloroform deviates from the above range, the yield of the biaryl compound decreases, which is not preferable.
クロロホルムを反応系内に存在させる方法は特定される
ものではなく、例えば、反応系内に最初から前記範囲の
クロロホルムを添加しておく方法、あるいは、反応を開
始した後、反応液を十分撹拌しながらクロロホルムを断
続的、または連続的に前記範囲を保持するように添加す
ることもできる。この場合のクロロホルムの総使用量
は、芳香族ハロゲン化合物１モルに対し0.1〜20モル程
度の量であることが好ましい。The method of allowing chloroform to be present in the reaction system is not specified, and for example, a method of adding chloroform in the above range from the beginning into the reaction system or after starting the reaction, stirring the reaction solution sufficiently. While chloroform may be added intermittently or continuously so as to maintain the above range. In this case, the total amount of chloroform used is preferably about 0.1 to 20 mol per mol of the aromatic halogen compound.
一方、クロロホルムを反応系内に存在させる方法として
気体状のクロロホルムを反応系に流通させて行なうこと
もできる。この場合、必要ならばクロロホルムを窒素、
アルゴン、一酸化炭素等のキャリヤーガスと混合して用
いても良い。混合気体におけるクロロホルム濃度は、特
に限定されないが、通常は５容量％以上が好適である。
気体の供給速度は、クロロホルム濃度により一義的に決
められるものではないが、反応液１あたり５〜2000l/
hr（標準状態に換算）程度である。On the other hand, as a method for causing chloroform to exist in the reaction system, gaseous chloroform can be passed through the reaction system. In this case, if necessary, add chloroform to nitrogen,
You may use it, mixing with carrier gas, such as argon and carbon monoxide. The concentration of chloroform in the mixed gas is not particularly limited, but usually 5% by volume or more is suitable.
The gas supply rate is not uniquely determined by the chloroform concentration, but is 5 to 2000 l / reaction solution 1
It is about hr (converted to standard state).
尚、本発明の反応では、水単独または水を主体とし、反
応に不活性な溶媒、例えば、テトラヒドロフラン、ジオ
キサン等のエーテル類等とからなる水性媒体が溶媒とし
て用いられる。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0.1〜50容量倍程度である。In the reaction of the present invention, water is used alone or an aqueous medium containing water as a main component and an inert solvent for the reaction, for example, ethers such as tetrahydrofuran and dioxane is used as a solvent. In this case, the amount of the solvent used is usually about 0.1 to 50 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50〜2
00℃であり、また、反応応力は通常、常圧〜200kg/c
m2、好ましくは常圧〜100kg/cm2である。The reaction temperature of the present invention is usually 20 to 300 ° C., preferably 50 to 2
00 ℃, and the reaction stress is usually from atmospheric pressure to 200kg / c
m 2 , preferably atmospheric pressure to 100 kg / cm 2 .
本発明方法は回分式、半回分式、連続式のいずれでも行
なうことができる。The method of the present invention can be performed in a batch system, a semi-batch system, or a continuous system.
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り
反応液から分離回収される。担持金属触媒を用いた場合
は、過により容易に分離回収され、再び脱ハロゲン二
量化反応に使用することが出来る。The platinum group metal catalyst used in the reaction is separated and recovered from the reaction solution by a method generally used in the past, such as an extraction method, a crystallization method or a reduction method. When a supported metal catalyst is used, it can be easily separated and recovered and can be used again in the dehalogenation dimerization reaction.
本発明で得られた、ビアリール化合物類は、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。The biaryl compounds obtained in the present invention are separated and obtained from the reaction solution by an evaporation method, a distillation method, a crystallization method, an acid precipitation method or the like according to their physical properties.
次に、本発明を実施例により更に詳細に説明するが本発
明はその要旨を超えない限り、以下の実施例に限定され
るものではない。Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
実施例−１ 還流冷却器、攪拌機、滴下ロートを備えた内容積100ml
のガラス製四つ口フラスコに、メタクロル安息香酸（以
下ｍ−CBAと略す）2.0g、水酸化ナトリウム6.0g、水20m
lおよび２重量％パラジウムカーボン（日本エンゲルハ
ルト社製）0.2gを仕込み、撹拌しながら加熱還流させ
た。次いで、滴下ロートより、クロロホルム0.25mlを15
分ごとに継続的に添加した。合計4mlのクロロホルムを
添加した後15分間還流を続けた。反応後、高速液体クロ
マトグラフにより分析したところ、反応液中には、脱ハ
ロゲンした安息香酸ナトリウム塩および所望のビフェニ
ル−3.3′−ジカルボン酸ナトリウム塩（以下BDC塩と略
す）が生成していた。結果を表−１に示す。Example-1 Internal volume 100 ml equipped with a reflux condenser, stirrer and dropping funnel
In a four-necked glass flask made of glass, 2.0 g of metachlorobenzoic acid (hereinafter abbreviated as m-CBA), 6.0 g of sodium hydroxide, 20 m of water.
1 g and 0.2 g of 2 wt% palladium carbon (manufactured by Nippon Engelhardt) were charged and heated to reflux with stirring. Then, from the dropping funnel, add 0.25 ml of chloroform to 15
It was added continuously every minute. Reflux was continued for 15 minutes after adding a total of 4 ml of chloroform. After the reaction, analysis by high performance liquid chromatography revealed that dehalogenated sodium benzoate and the desired sodium salt of biphenyl-3.3'-dicarboxylic acid (hereinafter abbreviated as BDC salt) were formed in the reaction solution. The results are shown in Table-1.
比較例−１ クロロホルムを添加しなかった以外は実施例−１同じに
行なった。結果を表−１に示す。Comparative Example-1 The procedure of Example-1 was repeated except that chloroform was not added. The results are shown in Table-1.
比較例−２ クロロホルムの代わりにメタノール2mlを添加し1.5時間
反応させた以外は実施例−１と同じに行なった。結果を
表−１に示す。Comparative Example-2 The procedure of Example-1 was repeated, except that 2 ml of methanol was added instead of chloroform and the reaction was carried out for 1.5 hours. The results are shown in Table-1.
実施例−２ 還流冷却器、撹拌器、およびガス導入管を備えた内容積
300mlのガラス製四つ口フラスコ４−クロルオルソフタ
ル酸モノナトリウム塩76.3ミリモル（以下４−CPA塩略
す。）、３−クロルオルソフタル酸モノナトリウム塩1
4.8ミリモル。ジクロルオルソフタル酸モノナトリウム
塩9.7ミリモル、オルソフタル酸モノナトリウム塩24.7
ミリモルからなる混合物、水酸化ナトリウム45gおよび
水160mlを仕込み、粗ハロゲン化オルソフタル酸塩と水
酸化ナトリウムの水溶液を調製した。次いで、２重量％
パラジウムカーボン3gを加え、常圧下撹拌しながら加熱
還流し、ガス導入管より、25℃においてクロロホルム蒸
気を飽和せしめた窒素ガスを700ml/minの流速で水溶液
中に連続的に供給しながら15時間反応させた。反応後、
高速液体クロマトグラフにより分析したところ、反応液
中には脱ハロゲンにより生成したオルソフタル酸ナトリ
ウム塩および所望の3,4,3′,4′−ビフェニルテトラカ
ルボン酸ナトリウム塩（以下Ｓ−BTCと略す）が生成し
ていた。結果を表−２に示す。 Example-2 Internal volume equipped with reflux condenser, stirrer, and gas introduction pipe
300 ml glass four-necked flask 4-chloroorthophthalic acid monosodium salt 76.3 mmol (hereinafter 4-CPA salt abbreviated), 3-chloroorthophthalic acid monosodium salt 1
4.8 mmol. Dichloroorthophthalic acid monosodium salt 9.7 mmol, orthophthalic acid monosodium salt 24.7
A mixture of millimoles, 45 g of sodium hydroxide and 160 ml of water were charged to prepare an aqueous solution of a crude halogenated orthophthalic acid salt and sodium hydroxide. Then 2% by weight
Add 3 g of palladium carbon, heat to reflux with stirring under normal pressure, and react for 15 hours while continuously supplying nitrogen gas saturated with chloroform vapor at 25 ° C into the aqueous solution at a flow rate of 700 ml / min from the gas inlet tube. Let After the reaction
Analysis by high performance liquid chromatography revealed that the reaction solution contained orthophthalic acid sodium salt produced by dehalogenation and the desired sodium salt of 3,4,3 ', 4'-biphenyltetracarboxylic acid (hereinafter abbreviated as S-BTC). Was being generated. The results are shown in Table-2.
比較例−３ ガス導入管よりクロロホルム−窒素の混合ガスを供給す
る代わりにメタノール16mlを加え４時間反応させた以外
は実施例−２と同じに行なった。結果を表−２に示す。Comparative Example-3 The procedure of Example-2 was repeated, except that 16 ml of methanol was added and the reaction was carried out for 4 hours instead of supplying the mixed gas of chloroform-nitrogen from the gas inlet tube. The results are shown in Table-2.
〔効果〕 本発明によれば、白金族金属触媒およびアルカリ金属化
合物またはアルカリ土類金属化合物の存在したに水性媒
体中芳香族ハロゲン化合物を脱ハロゲン二量化する方法
に於いてクロロホルムを存在させることにより、高収率
で選択性良く芳香族化合物の二量体を得ることができ、
工業的に極めて有利な方法である。 [Effect] According to the present invention, the presence of chloroform in the method of dehalogenating an aromatic halogen compound in an aqueous medium in the presence of a platinum group metal catalyst and an alkali metal compound or an alkaline earth metal compound causes the presence of chloroform. , A dimer of an aromatic compound can be obtained with high yield and good selectivity,
This is an industrially extremely advantageous method.
Claims (1)
素に有する芳香族化合物を白金属金属触媒、アルカリ金
属化合物または、アルカリ土類金属化合物およびクロロ
ホルムの存在下、水性媒体中で脱ハロゲン二量化させる
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. Dehalogenation dimerization of an aromatic compound having at least one halogen atom in an aromatic nucleus carbon in an aqueous medium in the presence of a white metal metal catalyst, an alkali metal compound or an alkaline earth metal compound and chloroform. A dehalogenation dimerization method of an aromatic halogen compound, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103982A JPH0780790B2 (en) | 1987-04-27 | 1987-04-27 | Dimerization method of aromatic halogen compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103982A JPH0780790B2 (en) | 1987-04-27 | 1987-04-27 | Dimerization method of aromatic halogen compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63267735A JPS63267735A (en) | 1988-11-04 |
| JPH0780790B2 true JPH0780790B2 (en) | 1995-08-30 |
Family
ID=14368519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62103982A Expired - Lifetime JPH0780790B2 (en) | 1987-04-27 | 1987-04-27 | Dimerization method of aromatic halogen compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780790B2 (en) |
-
1987
- 1987-04-27 JP JP62103982A patent/JPH0780790B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63267735A (en) | 1988-11-04 |
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