JPH01157941A - Novel aromatic hydroxy compound and production thereof - Google Patents
Novel aromatic hydroxy compound and production thereofInfo
- Publication number
- JPH01157941A JPH01157941A JP62315375A JP31537587A JPH01157941A JP H01157941 A JPH01157941 A JP H01157941A JP 62315375 A JP62315375 A JP 62315375A JP 31537587 A JP31537587 A JP 31537587A JP H01157941 A JPH01157941 A JP H01157941A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- formula
- aromatic hydroxy
- general formula
- hydroxy compound
- 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 hydroxy compound Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 9
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 50
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- KSBOJNMIXMQGEH-UHFFFAOYSA-N 4-[2-[4-(4-nitrophenoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OC=2C=CC(=CC=2)[N+]([O-])=O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KSBOJNMIXMQGEH-UHFFFAOYSA-N 0.000 description 1
- HNWSTMJONUXJDN-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenyl]phenol Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(O)=CC=2)C=C1 HNWSTMJONUXJDN-UHFFFAOYSA-N 0.000 description 1
- XVABQXXXQIESRH-UHFFFAOYSA-N 4-[4-(4-nitrophenoxy)phenyl]phenol Chemical group C1=CC(O)=CC=C1C(C=C1)=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 XVABQXXXQIESRH-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- CISXHPLNQINGMO-UHFFFAOYSA-N C1=CC=C(C(=C1)C2=CC=C(C=C2)N)OC3=CC=C(C=C3)O Chemical group C1=CC=C(C(=C1)C2=CC=C(C=C2)N)OC3=CC=C(C=C3)O CISXHPLNQINGMO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 230000035484 reaction time Effects 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- 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、新規な芳香族ヒドロキシ化合物およびその製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel aromatic hydroxy compound and a method for producing the same.
更に詳しくは、−船蔵（Ｉｔ）
（式中、Ｘは炭素数１〜１０の２価の炭化水素基、ある
いは−Ｃ（Ｃｈ）ｚ−、−ＣＯ−１−５−１、−５Ｏ−
１−ＳＯｔ−または−〇−の２価の基を示す、またＸが
単結合で直接結合していてもよい、）で表されるビフェ
ノール類のジアルカリ金属塩１〜１．２当量をｐ−ハロ
ゲノニトロベンゼン１当量と非プロトン性極性溶媒中で
縮合させて、−船蔵（Ｉ［［）（式中、Ｘは一般式（Ｉ
ｌ）の場合と同じ意味である）で表される芳香族ヒドロ
キシ化合物を得、ついでこれを還元することを特徴とす
る一般式Ｎ）（式中、Ｘは一般式（ＩＩ）の場合と同じ
意味である）で表される新規な芳香族ヒドロキシ化合物
の製造方法に関する。More specifically, -Funezo (It) (wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, or -C(Ch)z-, -CO-1-5-1, -5O-
1 to 1.2 equivalents of the dialkali metal salt of biphenols represented by 1-SOt- or -0-, which represents a divalent group, and where X may be directly bonded with a single bond, are added to p- It is condensed with 1 equivalent of halogenonitrobenzene in an aprotic polar solvent, -Funazura (I[[) (wherein X is the general formula (I
The aromatic hydroxy compound represented by the general formula N) (which has the same meaning as in the case of general formula (II)) is obtained, and then this is reduced. The present invention relates to a method for producing a novel aromatic hydroxy compound represented by the following meaning.
前記−船蔵（１）で表される新規な芳香族ヒドロキシ化
合物はかって製造された例がなく、その用途も知られて
いない、しかしながら、その構造上、高分子の原料およ
び染料、顔料、農医薬等の中間原料として有用な化合物
である。The novel aromatic hydroxy compound represented by Funakura (1) has never been produced before, and its uses are unknown. However, due to its structure, it cannot be used as a polymer raw material, dye, pigment, or agricultural It is a compound useful as an intermediate raw material for pharmaceuticals, etc.
（従来の技術）
前記−船蔵（１）で表される新規な芳香族ヒドロキシ化
合物は同一分子内にアミノ基と水酸基を有しており、高
分子の原料として有用であるが、従来その一般的製造法
は知られていない、一方、本発明の化合物の製造にあた
り中間体として考えられる一般式（Ｉ［［）で表される
化合物の製造が可能であれば、これを還元することによ
り一般式（Ｉ）で表される新規な芳香族ヒドロキシ化合
物も容易に製造出来ると考えられる。しかしながら、−
船蔵（Ｉ［［）で表される化合物の製造法に関して従来
知られていることは次のようである。即ち、フェノール
類とｐ−ハロゲノニトロベンゼンよりジフェニルエーテ
ル類を製造する方法は数多く知られている。一方、ビフ
ェノール類の二つの水酸基のうち一つだけをｐ−ハロゲ
ノニトロベンゼンと反応させる方法として、一つのベン
ゼン環に二つの水酸基を有するハイドロキノンを用いた
例は公知であるが（西独、特許第２．１５７．７８１）
、本発明の一般式（ｎ）のように、−価のフェノールが
Ｘで表される連結基で結合した化合物に関しては従来全
く知られていない。(Prior Art) The novel aromatic hydroxy compound represented by - Funazo (1) has an amino group and a hydroxyl group in the same molecule and is useful as a raw material for polymers, but conventional On the other hand, if it is possible to produce a compound represented by the general formula (I It is believed that the novel aromatic hydroxy compound represented by formula (I) can also be easily produced. However, −
What is conventionally known regarding the method for producing the compound represented by Funazo (I[[) is as follows. That is, many methods are known for producing diphenyl ethers from phenols and p-halogenonitrobenzene. On the other hand, as a method for reacting only one of the two hydroxyl groups of biphenols with p-halogenonitrobenzene, an example using hydroquinone having two hydroxyl groups in one benzene ring is known (West Germany, Patent No. 2 .157.781)
A compound in which a -valent phenol is bonded to a linking group represented by X, as shown in the general formula (n) of the present invention, has not been known at all.
（発明が解決しようとする問題点）
このような従来技術より判断して、本発明の課題は、高
分子の原料および各種中間体として有用な前記−船蔵（
［）で表される新規な芳香族ヒドロキシ化合物の製造方
法を提供することである。(Problems to be Solved by the Invention) Judging from such prior art, the problem of the present invention is to solve the above-mentioned problems that are useful as polymer raw materials and various intermediates.
An object of the present invention is to provide a method for producing a novel aromatic hydroxy compound represented by [).
（問題点を解決するための手段）
本発明の課題を解決するため、本発明者らは一般式（１
）で表される新規な芳香族ヒドロキシ化合物の製造方法
について鋭意検討した。その結果前記−船蔵（ＩＩ）で
表されるビフェノール類のジアルカリ金属塩１−１．２
当量をｐ−ハロゲノニトロベンゼン１当量と非プロトン
性極性溶媒中で縮合させると前記−船蔵（ＩＩＩ）で表
される芳香族ヒドロキシ化合物が得られ、更にこの化合
物を還元すると、前記−船蔵（Ｉ）で表される新規な芳
香族ヒドロキシ化合物が工業的に有利に製造できること
を見出し、本発明を完成した。(Means for Solving the Problems) In order to solve the problems of the present invention, the present inventors have developed the general formula (1
) We have conducted intensive studies on a method for producing a novel aromatic hydroxy compound represented by As a result, the dialkali metal salt of biphenols represented by Funazo (II) 1-1.2
When the equivalent of p-halogenonitrobenzene is condensed with 1 equivalent of p-halogenonitrobenzene in an aprotic polar solvent, an aromatic hydroxy compound represented by the above-mentioned -Funazo (III) is obtained, and when this compound is further reduced, the above-mentioned -Funazo (III) is obtained. The present invention was completed based on the discovery that the novel aromatic hydroxy compound represented by I) can be produced industrially advantageously.
本発明の方法で製造される化合物は、前記−船蔵（１）
で表される新規な芳香族ヒドロキシ化合物である。具体
的には、４−（４−アミノフェノキシ）−４′−ヒドロ
キシビフェニル、４− （４−アミノフェノキシ）−４
”−ヒドロキシジフェニルメタン、２− （４−（４−
アミノフェノキシ）フェニル）−２−（４−ヒドロキシ
フェニル）プロパン、２− （４−（４−アミノフェノ
キシ）フェニル） −２−（４−ヒドロキシフェニル）
−１，１゜１．３．３．３−へキサフルオロプロパン
、４−（４−アミノフェノキシ）−４゛−ヒドロキシベ
ンゾフェノン、４−（４−アミノフェノキシ）−４゛−
ヒドロキシジフェニルスルフィド、４−（４−アミノフ
ェノキシ）−４°−ヒドロキシジフェニルスルホキシド
、４−（４−アミノフェノキシ）−４゛−ヒドロキシジ
フェニルスルホン、４−（４−アミノフェノキシ）−４
°−ヒドロキシジフェニルエーテルなどが挙げられる。The compound produced by the method of the present invention is
This is a novel aromatic hydroxy compound represented by Specifically, 4-(4-aminophenoxy)-4'-hydroxybiphenyl, 4-(4-aminophenoxy)-4
”-Hydroxydiphenylmethane, 2- (4-(4-
aminophenoxy)phenyl)-2-(4-hydroxyphenyl)propane, 2-(4-(4-aminophenoxy)phenyl)-2-(4-hydroxyphenyl)
-1,1゜1.3.3.3-hexafluoropropane, 4-(4-aminophenoxy)-4゛-hydroxybenzophenone, 4-(4-aminophenoxy)-4゛-
Hydroxy diphenyl sulfide, 4-(4-aminophenoxy)-4°-hydroxydiphenyl sulfoxide, 4-(4-aminophenoxy)-4′-hydroxydiphenyl sulfone, 4-(4-aminophenoxy)-4
Examples include °-hydroxydiphenyl ether.
本発明の方法で中間体として製造される化合物は、前記
−船蔵（Ｉ）で表される芳香族ヒドロキシ化合物である
。具体的には、４−ヒドロキーシー４’−（４−ニトロ
フェノキシ）ビフェニル、４−ヒドロキシ−４’−（４
−ニトロフェノキシ）ジフェニルメタン、２−（４−ヒ
ドロキシフェニル）−２−［４−（４−ニトロフェノキ
シ）フェニル］プロパン、２−（４−ヒドロキシフェニ
ル）−２−（４−（４−ニトロフェノキシ）フェニル〕
−１，１，１，３，３，３−へキサフルオロプロパン、
４−ヒドロキシ−４°−（４−ニトロフェノキシ）ベン
ゾフェノン、４−ヒドロキシ−４’−（４−ニトロフェ
ノキシ）ジフェニルスルフィド、４−ヒドロキシ−４’
−（４−ニトロフェノキシ）ジフェニルスルフィド、４
−ヒドロキシ−４’−（４−ニトロフェノキシ）ジフェ
ニルスルホン、４−ヒドロキシ−４’−（４−ニトロフ
ェノキシ）ジフェニルエーテルなどが挙げられる。The compound produced as an intermediate in the method of the present invention is an aromatic hydroxy compound represented by the above-mentioned -Funazo (I). Specifically, 4-hydroxy-4'-(4-nitrophenoxy)biphenyl, 4-hydroxy-4'-(4
-nitrophenoxy)diphenylmethane, 2-(4-hydroxyphenyl)-2-[4-(4-nitrophenoxy)phenyl]propane, 2-(4-hydroxyphenyl)-2-(4-(4-nitrophenoxy) Phenyl]
-1,1,1,3,3,3-hexafluoropropane,
4-Hydroxy-4°-(4-nitrophenoxy)benzophenone, 4-hydroxy-4'-(4-nitrophenoxy)diphenyl sulfide, 4-hydroxy-4'
-(4-nitrophenoxy)diphenyl sulfide, 4
-Hydroxy-4'-(4-nitrophenoxy) diphenyl sulfone, 4-hydroxy-4'-(4-nitrophenoxy) diphenyl ether, and the like.
本発明の方法で使用される出発物質は、ｐ−ハロゲノニ
トロベンゼンと前記−船蔵（Ｉｆ）で表されるビフェノ
ールである。ビフェノール類とじて具体的には、４，４
゛−ジヒドロキシビフェニル、４゜４°−ジヒドロキシ
ジフェニルメタン、２．２−ビス（４−ヒドロキシフェ
ニル）プロパン、２．２−ビス（４−ヒドロキシフェニ
ル） −１，１，１，３，３，３−ヘキサフルオロプロ
パン、４，４°−ジヒドロキシベンゾフェノン、４．４
′−ジヒドロキシジフェニルスルフィド、４．４′−ジ
ヒドロキシジフェニルスルホキシド、４．４’−ジヒド
ロキシジフェニルスルホン、４．４°−ジヒドロキシジ
フェニルエーテルなどが挙げられる。The starting materials used in the process of the invention are p-halogenonitrobenzene and the biphenol represented by If. Specifically, biphenols include 4,4
゛-Dihydroxybiphenyl, 4゜4゜-dihydroxydiphenylmethane, 2.2-bis(4-hydroxyphenyl)propane, 2.2-bis(4-hydroxyphenyl) -1,1,1,3,3,3- Hexafluoropropane, 4,4°-dihydroxybenzophenone, 4.4
Examples include '-dihydroxydiphenyl sulfide, 4.4'-dihydroxydiphenyl sulfoxide, 4.4'-dihydroxydiphenyl sulfone, and 4.4°-dihydroxydiphenyl ether.
ｐ−ハロゲノニトロベンゼンとして具体的には、ｐ−フ
ルオロニトロベンゼン、ｐ−クロロニトロベンゼン、ｐ
−ブロモニトロベンゼン、ｐ−ヨードニトロベンゼンな
どであり、工業的にはｐ−クロロニトロベンゼンが用い
られる。Specifically, p-halogenonitrobenzene includes p-fluoronitrobenzene, p-chloronitrobenzene, p-chloronitrobenzene, and p-fluoronitrobenzene.
-bromonitrobenzene, p-iodonitrobenzene, etc., and p-chloronitrobenzene is used industrially.
本発明の方法は、前記−船蔵（ＩＩ）で表されるビフェ
ノール類のジアルカリ金属塩をｐ−ハロゲノニトロベン
ゼンと、非プロトン性極性溶媒中で縮合して、前記−船
蔵（Ｉ［［）で表される芳香族ヒドロキシ化合物を製造
する反応（以下、第１段の反応という）と、更にこれを
還元して前記−船蔵（１）で表される新規な芳香族ヒド
ロキシ化合物を製造する反応（以下、第２段の反応とい
う）の２種の反応より成る。[ A reaction to produce an aromatic hydroxy compound represented by (hereinafter referred to as the first stage reaction), and further reduction to produce a novel aromatic hydroxy compound represented by -Funakura (1) above. The reaction consists of two types of reactions (hereinafter referred to as the second stage reaction).
第１段の反応における原料の使用量は、ビフェノール類
をｐ−ハロゲノニトロベンゼンに対して０．８〜２．０
モル、好ましくは１．０〜１．２モルとなるように用い
る。The amount of raw materials used in the first stage reaction is 0.8 to 2.0 of biphenols relative to p-halogenonitrobenzene.
It is used in an amount of 1.0 to 1.2 mol, preferably 1.0 to 1.2 mol.
第１段の反応において使用される塩基は、アルカリ金属
の酸化物、水酸化物、炭酸塩、炭酸水素塩、水素化物お
よびアルコキシド類であり、好ましくは水酸化物である
。具体的には、酸化ナトリ゛ウム、酸化リチウム、水酸
化カリウム、水酸化ナトリウム、水酸化リチウム、炭酸
カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水
素ナトリウム、水素化ナトリウム、カリウム−Ｌ−ブト
キシド、ナトリウムメトキシド、ナトリウムエトキシド
などが使用され、好ましくは、水酸化ナトリウム、水酸
化カリウムが使用される。使用量は、通常、原料のビフ
ェノール類に対して１〜３倍モルであり、好ましくは１
．８〜２．０倍モルである。The base used in the first stage reaction is an alkali metal oxide, hydroxide, carbonate, hydrogen carbonate, hydride, or alkoxide, preferably a hydroxide. Specifically, sodium oxide, lithium oxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydride, potassium-L-butoxide, sodium Methoxide, sodium ethoxide, etc. are used, preferably sodium hydroxide, potassium hydroxide. The amount used is usually 1 to 3 times the mole of the raw material biphenols, preferably 1
．． It is 8 to 2.0 times the mole.
この反応の際に４級アンモニウム塩、４級リン塩、クラ
ウンエーテルのような大環状ポリエーテル、クリプテー
トのような含窒素大環状ポリエーテル、含窒素鎖状ポリ
エーテル、ポリエチレングリコール及びそのアルキルエ
ーテルのような相間移動触媒、銅粉および銅塩などを反
応促進剤として加えてもよい。During this reaction, quaternary ammonium salts, quaternary phosphorus salts, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptate, nitrogen-containing chain polyethers, polyethylene glycol, and their alkyl ethers are used. Phase transfer catalysts such as copper powder, copper salts, etc. may be added as reaction promoters.
反応溶媒としては、非プロトン性極性溶媒が使用される
。具体的には、Ｎ−メチルホルムアミド、Ｎ、Ｎ−ジメ
チルホルムアミド、Ｎ、Ｎ−ジメチルアセトアミド、ジ
メチルスルホキシド、ジメチルスルホン、スルホラン、
１−メチル−２−ピロリジノン、１．３−ジメチル−２
−イミダゾリジノン、Ｎ、Ｎ、Ｎ’、Ｎ’−テトラメチ
ルウレア、ヘキサメチルホスホトリアミドおよび１，３
−ジメチル−３，４，５，６−チトラヒドロー２（ＬＨ
）−ピリミジンなどが挙げられる。これらの溶媒の使用
量は特に限定されないが、通常、原料に対して１〜１０
重量倍で十分である。As the reaction solvent, an aprotic polar solvent is used. Specifically, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane,
1-methyl-2-pyrrolidinone, 1,3-dimethyl-2
-imidazolidinone, N,N,N',N'-tetramethylurea, hexamethylphosphotriamide and 1,3
-dimethyl-3,4,5,6-titrahydro-2 (LH
)-pyrimidine and the like. The amount of these solvents used is not particularly limited, but usually 1 to 10
Double weight is sufficient.
反応の実施に際しては、通常、所定量のビフェノール類
、塩基および溶媒を装入して、あらかじめビフェノール
類のジアルカリ金属塩を調製した後、ｐ−ハロゲノニト
ロベンゼンを固体のまま、または溶媒に溶解して添加す
る。塩基としてアルカリ金属の酸化物、水酸化物などを
用いて反応系に生じた水は、特に除去する必要はない。When carrying out the reaction, a predetermined amount of biphenols, a base, and a solvent are usually charged to prepare a dialkali metal salt of biphenols in advance, and then p-halogenonitrobenzene is added as a solid or dissolved in a solvent. Added. There is no particular need to remove water generated in the reaction system using an alkali metal oxide, hydroxide, etc. as a base.
反応温度は、通常、２０〜２４０°Ｃ１好ましくは６０
〜１６０℃の範囲であり、反応時間は１〜１０時間の範
囲である。The reaction temperature is usually 20 to 240°C, preferably 60°C.
-160°C and reaction time ranges from 1 to 10 hours.
反応の終点は、薄層クロマトグラフィーおよび高速液体
クロマトグラフィーなどにより決定できる。The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography, and the like.
反応終了後、反応液をそのまま水中に排出し、塩酸を加
えて酸性にすると目的物の粗製品が得られる。この粗製
品は、再結晶またはアルカリ金属塩として精製すること
が出来、第２段の反応に使用する。After the reaction is complete, the reaction solution is directly discharged into water, and hydrochloric acid is added to make it acidic to obtain the target crude product. This crude product can be recrystallized or purified as an alkali metal salt and used in the second stage reaction.
第２段の反応で用いられる還元方法は特に制限はなく、
通常ニトロ基をアミノ基に還元する方法（例えば、新実
験化学講座、１５巻、酸化と還元〔■〕、丸善（１９７
７） ）を適用できるが、工業的には接触還元またはヒ
ドラジン還元が好ましい、接触還元の場合、使用される
還元触媒としては、一般に接触還元に用いられている金
属触媒、例えばニッケル、パラジウム、白金、ロジウム
、ルテニウム、コバルト、銅などを使用することができ
る。There are no particular restrictions on the reduction method used in the second stage reaction.
Usually, a method for reducing a nitro group to an amino group (for example, New Experimental Chemistry Course, Volume 15, Oxidation and Reduction [■], Maruzen (197
7) ) can be applied, but catalytic reduction or hydrazine reduction is preferred industrially. In the case of catalytic reduction, the reduction catalyst used is a metal catalyst generally used for catalytic reduction, such as nickel, palladium, platinum. , rhodium, ruthenium, cobalt, copper, etc.
工業的にはパラジウム触媒を使用するのが好ましい、こ
れらの触媒は、金属の状態でも使用することができるが
、通常は、カーボン、硫酸バリウム、シリカゲル、アル
ミナ、セライトなどの担体表面に担持させて用いたり、
また、ニッケル、コバルト、銅などはラネー触媒として
も用いられる。触媒の使用量は特に制限はないが、原料
の一般式（■）で表される芳香族ヒドロキシ化合物に対
して０．０１〜１０重量％の範囲であり、通常、金属の
状態で使用する場合は２〜８重量％、担体に担持させた
場合では０．１〜５重量％の範囲である。Industrially, it is preferable to use palladium catalysts. Although these catalysts can be used in the metallic state, they are usually supported on the surface of a carrier such as carbon, barium sulfate, silica gel, alumina, or celite. Use or
Nickel, cobalt, copper, etc. are also used as Raney catalysts. The amount of the catalyst used is not particularly limited, but it is in the range of 0.01 to 10% by weight based on the aromatic hydroxy compound represented by the general formula (■) of the raw material, and is usually used in the metal state. is in the range of 2 to 8% by weight, and in the case of supported on a carrier, it is in the range of 0.1 to 5% by weight.
反応溶媒としては、反応に不活性なものであれば特に限
定されるものでなく、例えば、メタノール、エタノール
、イソプロピルアルコール等のアルコール類、エチレン
グリコール、プロピレングリコール等のグリコール類、
エーテル、ジオキサン、テトラヒドロフラン、メチルセ
ロソルブ等のエーテル類、ヘキサノ、シクロヘキサン等
の脂肪族炭化水素類、ベンゼン、トルエン、キシレン等
の芳香族炭化水素類、酢酸エチル、酢酸ブチル等のエス
テル類、ジクロロメタン、クロロホルム、四塩化炭素、
１．２−ジクロロエタン、１，１．２−トリクロロエタ
ン、テトラクロロエタン等のハロゲン化炭化水素類およ
びＮ、Ｎ−ジメチルホルムアミド、ジメチルスルホキシ
ド等が使用できる。なお、水と混和しない反応溶媒を使
用した際に、反応の進行が遅い場合は四級アンモニウム
塩、四級ホスホニウム塩のような一般に使用されている
相間移動触媒を加えることによって速めることができる
。The reaction solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol, glycols such as ethylene glycol and propylene glycol,
Ethers such as ether, dioxane, tetrahydrofuran, methyl cellosolve, aliphatic hydrocarbons such as hexano, cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, esters such as ethyl acetate, butyl acetate, dichloromethane, chloroform ,Carbon tetrachloride,
Halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,2-trichloroethane, and tetrachloroethane, N,N-dimethylformamide, dimethylsulfoxide, and the like can be used. Note that when using a reaction solvent that is immiscible with water, if the reaction progresses slowly, it can be accelerated by adding a commonly used phase transfer catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt.
溶媒の使用量は、原料を懸濁させるかあるいは完全に溶
解させるに足る量で十分であり特に限定されないが、通
常、原料に対して０．５〜１０重量倍で十分である。The amount of the solvent to be used is not particularly limited as it is sufficient to suspend or completely dissolve the raw materials, but usually 0.5 to 10 times the weight of the raw materials is sufficient.
反応温度は、特に限定はない、−船釣には２０〜２００
℃の範囲、特に２０〜１００℃が好ましい、また反応圧
力は、通常、常圧〜５０Ｋｇ／ｃｄＧ程度である。The reaction temperature is not particularly limited - 20-200℃ for boat fishing
The temperature range is preferably from 20 to 100°C, and the reaction pressure is usually from normal pressure to about 50 kg/cdG.
反応は、通常、原料を溶媒に溶解もしくは懸濁させた状
態で触媒を加え、ついで撹拌下に所定の温度で水素を導
入して還元反応を行う０反応の終点は水素吸収量によっ
ても、あるいは薄層クロマトグラフィーや高速液体クロ
マトグラフィーなどによっても決定できる。The reaction is usually carried out by adding a catalyst to the raw materials dissolved or suspended in a solvent, and then introducing hydrogen at a predetermined temperature under stirring to carry out a reduction reaction.The end point of the reaction depends on the amount of hydrogen absorbed, or It can also be determined by thin layer chromatography or high performance liquid chromatography.
一方、ヒドラジン還元の場合には、ヒドラジンを通常、
理論量に対して少過剰で良く、好ましくは１．２〜２倍
量用いて還元反応を実施する。On the other hand, in the case of hydrazine reduction, hydrazine is usually
The reduction reaction may be carried out in a small excess of the theoretical amount, preferably 1.2 to 2 times the amount.
触媒としては、−ａに接触還元に用いられている前記の
金属触媒を使用する。工業的には、パラジウム／カーボ
ン、白金／カーボンまたは塩化第２鉄を活性炭に吸着さ
せた触媒が好ましい、 触媒の使用量は特に制限はな（
、通常、前記−船蔵（Ｉ［）で表される芳香族ヒドロキ
シ化合物に対して、金属として０．０１〜３０重量％の
範囲である。As the catalyst, the above-mentioned metal catalyst used for catalytic reduction in -a is used. Industrially, catalysts with palladium/carbon, platinum/carbon, or ferric chloride adsorbed on activated carbon are preferred; there are no particular restrictions on the amount of catalyst used (
Usually, the metal content is in the range of 0.01 to 30% by weight based on the aromatic hydroxy compound represented by -Funazura (I[).
反応溶媒としては、接触還元の場合と同様の溶媒を用い
ることができる０反応温度は特に限定はなく、−船釣に
は２０〜１５０’Ｃの範囲、特に４０〜１００°Ｃが好
ましい。As the reaction solvent, the same solvent as in the case of catalytic reduction can be used.The reaction temperature is not particularly limited, and - for boat fishing, a range of 20 to 150'C, particularly 40 to 100C is preferred.
反応は、通常、原料を溶媒に溶解または懸濁させた状態
で触媒を加え、ついで撹拌下に所定の温度でヒドラジン
を滴下して還元反応を行う０反応路点は薄層クロマトグ
ラフィーや高速液体クロマトグラフィーなどにより決定
できる。The reaction is usually carried out by adding a catalyst to the raw materials dissolved or suspended in a solvent, and then adding hydrazine dropwise at a predetermined temperature with stirring to carry out the reduction reaction. It can be determined by chromatography etc.
反応終了後、反応液を熱濾過して触媒を除去した後、必
要に応じて溶媒を留去すると目的とする新規な芳香族ヒ
ドロキシ化合物が好収率で得られる。After the reaction is completed, the catalyst is removed by hot filtration of the reaction solution, and then the solvent is distilled off if necessary to obtain the desired novel aromatic hydroxy compound in good yield.
（作用および効果）
本発明の方法によれば、ビフェノール類のジアルカリ金
属塩１．０〜１．２当量をｐ−ハロゲノニトロベンゼン
１当量と縮合させた後、更に還元することにより新規な
芳香族ヒドロキシ化合物が好収率かつ容易に製造できる
。(Functions and Effects) According to the method of the present invention, 1.0 to 1.2 equivalents of dialkali metal salts of biphenols are condensed with 1 equivalent of p-halogenonitrobenzene, and then further reduced to form a novel aromatic hydroxyl. The compound can be easily produced with good yield.
（実施例）
以下、本発明の方法を実施例により更に具体的に説明す
る。(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
実施例１
撹拌機、温度計、冷却管を装備した反応フラスコに４．
４′−ジヒドロキシビフェニル１８６．２ｇ （１，１
モル）と１．３′−ジメチル−２−イミダゾリジノン９
３１．０ ｇを装入し、窒素を通気させながら昇温し、
６０°Ｃで溶解する。これに９６％水酸化ナトリウム９
１．７ｇ （２，２モル）を装入し、昇温し、１００〜
１２０°Ｃで２時間撹拌した。内温を８０°Ｃ以下に下
げたのち、ｐ−ニトロクロルベンゼン１５７．６ｇ （
１，０モル）を１．３−ジメチル−２−イミダゾリジノ
ン２３６．３ ｇに溶解した溶液を８０〜９０°Ｃで２
時間かけて滴下し、更に同温度で２時間撹拌した。Example 1 A reaction flask equipped with a stirrer, a thermometer, and a condenser was charged with 4.
4'-dihydroxybiphenyl 186.2g (1,1
mole) and 1,3'-dimethyl-2-imidazolidinone9
31.0 g was charged, and the temperature was raised while nitrogen was bubbled through.
Dissolve at 60°C. Add to this 96% sodium hydroxide9
Charge 1.7 g (2.2 mol) and raise the temperature to 100~
Stirred at 120°C for 2 hours. After lowering the internal temperature to below 80°C, 157.6g of p-nitrochlorobenzene (
A solution of 1.0 mol) dissolved in 236.3 g of 1,3-dimethyl-2-imidazolidinone was heated at 80 to 90°C for 2 hours.
The mixture was added dropwise over time and further stirred at the same temperature for 2 hours.
反応終了後、反応液を冷却し、氷水２．４１に排出し、
３５％塩酸水１３７．７ ｇを滴下すると、黄色結晶が
析出した。これを濾過、洗浄後乾燥して、４−ヒドロキ
シ−４” −ニトロフェノキシビフェニルを得た。After the reaction was completed, the reaction solution was cooled and drained into ice water at 2.4 mL.
When 137.7 g of 35% hydrochloric acid water was added dropwise, yellow crystals were precipitated. This was filtered, washed and dried to obtain 4-hydroxy-4''-nitrophenoxybiphenyl.
収量２４０．０ｇ （収率７８．０％）糟ｐ２６０〜２
６２°Ｃ
元素分析（Ｃ＋ｓＨ＋ＪＯ４）
ＣＩＮＮ
計算値（χ） ７０．３５ ４．２６ ４．５６
分析値（χ） ７０．８５ ４．００ ４．７２
ＩＲ（ＫＢｒ、 ｃｍ″’） ３４２５ ：水酸基１５
９０．１３４０ ：ニトロ基
１２４０ ：エーテル結合
次に撹拌機二温度計を装備した田閉型還元容器に上記４
−ヒドロキシ−４″ −ニトロフェノキシビフェニル１
８４ｇ （０，６モル）と５０％Ｐｄ／Ｃ触媒３．６８
ｇおよびイソプロピルアルコール９２０ ｇを装入し、
激しく撹拌しながら水素ガスを導入した。Yield 240.0g (Yield 78.0%) Peel p260~2
62°C Elemental analysis (C+sH+JO4) CINN Calculated value (χ) 70.35 4.26 4.56
Analysis value (χ) 70.85 4.00 4.72
IR (KBr, cm'') 3425: hydroxyl group 15
90.1340: Nitro group 1240: Ether bond Next, add the above 4 to a Ta-close type reduction vessel equipped with a stirrer and two thermometers.
-hydroxy-4″-nitrophenoxybiphenyl 1
84 g (0.6 mol) and 50% Pd/C catalyst 3.68
g and 920 g of isopropyl alcohol,
Hydrogen gas was introduced with vigorous stirring.
２０〜３０°Ｃで４時間反応を行ワたところ、理論量の
水素を吸収し、これ以上の吸収が認められなくなったの
で反応を終了した。液温を６０〜７０°Ｃに昇温し、熱
濾過後、冷却すると結晶が析出した。結晶を濾過、洗浄
後乾燥して、４−ヒドロキシ−４′−アミノフェノキシ
ビフェニルを得た。When the reaction was carried out at 20 to 30°C for 4 hours, the theoretical amount of hydrogen was absorbed and no further absorption was observed, so the reaction was terminated. The liquid temperature was raised to 60 to 70°C, and after hot filtration, the mixture was cooled to precipitate crystals. The crystals were filtered, washed and dried to obtain 4-hydroxy-4'-aminophenoxybiphenyl.
収量１５３ｇ（収率９２．０％）
Ｉｌｐ ２５０〜２５１“Ｃ
元素分析（Ｃ＋Ｊ＋５Ｎ（ｈ）
ＣＨＮ
計算値（χ） ７７．９６ ５．４５ ５．０５
分析値（χ） ？７．９４ ５．３４ ４．９５
ＩＲ（ＫＢｒ、 ｃｍ−リ３４２０ ：水酸基３３６０
．３３００ ニアミノ基
１２３０ ：エーテル結合
実施例２
撹拌機、温度計、冷却管を装備した反応フラス：７ニ４
．４″−ジヒドロキシビフェニル１８６．２ｇ （１，
１モル）とジメチルスルホキシド９３１．０ ｇを装入
した。窒素を通気させながら昇温し、６０”Ｃで溶解す
る。これに９６％水酸化ナトリうム９１．７ｇ （２，
２モル）を装入後、昇温し、１００〜１２０″Ｃで２時
間撹拌した。内温を８０″Ｃ以下に下げたのち、ｐ−ニ
トロクロルベンゼン１５７．６ｇ （Ｌｏモ／ｌｚ）を
１，３−ジメチル−２−イミダゾリジノン２３６．３
ｇに溶解した溶液を８０〜９０”Ｃで２時間かけて滴下
し、更に同温度で２時間撹拌した。Yield 153g (yield 92.0%) Ilp 250-251"C Elemental analysis (C+J+5N(h) CHN Calculated value (χ) 77.96 5.45 5.05
Analysis value (χ)? 7.94 5.34 4.95
IR (KBr, cm-3420: hydroxyl group 3360
．． 3300 Niamino group 1230: Ether bond Example 2 Reaction flask equipped with a stirrer, thermometer, and cooling tube: 7 Ni4
．． 4″-dihydroxybiphenyl 186.2g (1,
1 mol) and 931.0 g of dimethyl sulfoxide were charged. Raise the temperature while bubbling nitrogen and dissolve at 60"C. To this, add 91.7g of 96% sodium hydroxide (2,
After charging 2 mol), the temperature was raised and stirred at 100-120"C for 2 hours. After lowering the internal temperature to 80"C or less, 157.6 g (Lomo/lz) of p-nitrochlorobenzene was added. 1,3-dimethyl-2-imidazolidinone 236.3
A solution dissolved in 50 g was added dropwise at 80 to 90''C over 2 hours, and the mixture was further stirred at the same temperature for 2 hours.
反応終了後、反応液を冷却し、氷水２．４１に排出し、
３５％塩酸水１３７．７ ｇを滴下すると、黄色結晶が
析出した。これを濾過、洗浄後乾燥して、４−ヒドロキ
シ−４°−ニトロフェノキシビフェニルを得た。After the reaction was completed, the reaction solution was cooled and drained into ice water at 2.4 mL.
When 137.7 g of 35% hydrochloric acid water was added dropwise, yellow crystals were precipitated. This was filtered, washed and dried to obtain 4-hydroxy-4°-nitrophenoxybiphenyl.
収量２２３ｇ（収率７２．５％）
８ｐ２６０〜２６２℃
次に撹拌機、温度計を装備した密閉型還元容器に上記４
−ヒドロキシ−４゛−ニトロフェノキシビフェニル１８
４ｇ （０，６モル）と５０％Ｐｄ／Ｃ触媒３．６８ｇ
およびイソプロピルアルコール９２０ ｇを装入し、激
しく撹拌しながら水素ガスを導入した。Yield 223g (yield 72.5%) 8p 260-262℃ Next, the above 4 was placed in a closed reduction container equipped with a stirrer and a thermometer.
-Hydroxy-4゛-nitrophenoxybiphenyl 18
4 g (0.6 mol) and 3.68 g of 50% Pd/C catalyst
and 920 g of isopropyl alcohol were charged, and hydrogen gas was introduced while stirring vigorously.
２０〜３０℃で４時間反応を行ったところ、理論量の水
素を吸収し、これ以上の吸収が認められなくなったので
反応を終了した。液温を６０〜７０℃に昇温し、熱濾過
後、冷却すると結晶が析出した。濾過、洗浄後乾燥して
、４−ヒドロキシ−４°−アミノフェノキシビフェニル
を得た。When the reaction was carried out at 20 to 30°C for 4 hours, the theoretical amount of hydrogen was absorbed, and no further absorption was observed, so the reaction was terminated. The liquid temperature was raised to 60 to 70°C, and after hot filtration, the mixture was cooled to precipitate crystals. After filtration, washing, and drying, 4-hydroxy-4°-aminophenoxybiphenyl was obtained.
収量１４７ｇ（収率８８．２％）
８９２５０〜２５１℃
実施例３
撹拌機、温度計、冷却管を装備した反応フラスコに４，
４°−ジヒドロキシビフェニル１８６．２ｇ （１，１
モル）と１．３−ジメチル−２−イミダゾリジノン９３
１．０ ｇを装入し、窒素を通気させながら昇温し、６
０℃で溶解する。これに９６％水酸化カリウム１２９ｇ
（２，２モル）を装入し、次いで、１００〜１２０℃
で２時間撹拌した。内温を８０℃以下に下げたのち、ｐ
−ニトロクロルベンゼン１５７．６ｇ （１，０モル）
を１．３−ジメチル−２−イミダゾリジノン２３６．３
ｇに溶解した溶液を８０〜９０℃で２時間かけて滴下
し、更に同温度で２時間撹拌した。Yield: 147 g (yield: 88.2%) 89250-251°C Example 3 Into a reaction flask equipped with a stirrer, thermometer, and condenser tube, 4.
4°-dihydroxybiphenyl 186.2g (1,1
mol) and 1,3-dimethyl-2-imidazolidinone93
Charge 1.0 g, heat up while bubbling with nitrogen, and heat to 6.
Dissolve at 0°C. Add to this 129g of 96% potassium hydroxide
(2.2 mol) and then at 100-120℃
The mixture was stirred for 2 hours. After lowering the internal temperature to below 80℃, p
-Nitrochlorobenzene 157.6g (1.0 mol)
1,3-dimethyl-2-imidazolidinone 236.3
A solution dissolved in g was added dropwise at 80 to 90°C over 2 hours, and the mixture was further stirred at the same temperature for 2 hours.
反応終了後、反応液を冷却し、氷水２．４１に排出し、
３５％塩酸水１３７．７ ｇを滴下すると、黄色結晶が
析出した。これを濾過、洗浄後乾燥して、４−ヒドロキ
シ−４°−ニド６フエノキシビフエニルを得た。After the reaction was completed, the reaction solution was cooled and drained into ice water at 2.4 mL.
When 137.7 g of 35% hydrochloric acid water was added dropwise, yellow crystals were precipitated. This was filtered, washed, and dried to obtain 4-hydroxy-4°-nido-6phenoxybiphenyl.
収量２５３ｇ（収率７５．０％）
次に撹拌機、温度計を装備した密閉型還元容器に上記４
−ヒドロキシ−４゛−ニトロフェノキシビフェニル１８
４ｇ （０，６モル）と５０％Ｐｄ／Ｃ触媒３．６８
ｇおよびイソプロピルアルコール９２０ｇを装入し、激
しく撹拌しながら水素ガスを導入した。Yield 253g (yield 75.0%) Next, the above 4 was placed in a closed reduction container equipped with a stirrer and a thermometer.
-Hydroxy-4゛-nitrophenoxybiphenyl 18
4g (0.6 mol) and 50% Pd/C catalyst 3.68
g and 920 g of isopropyl alcohol were charged, and hydrogen gas was introduced while vigorously stirring.
２０〜３０℃で４時間反応を行ったところ、理論量の水
素を吸収し、これ以上の吸収が認められなくなったので
反応を終了した。液温を６０〜７０℃に昇温し、熱濾過
後、冷却すると結晶が析出した。結晶を濾過、洗浄後乾
燥して、４−ヒドロキシ−４゜−アミノフェノキシビフ
ェニルを得た。When the reaction was carried out at 20 to 30°C for 4 hours, the theoretical amount of hydrogen was absorbed, and no further absorption was observed, so the reaction was terminated. The liquid temperature was raised to 60 to 70°C, and after hot filtration, the mixture was cooled to precipitate crystals. The crystals were filtered, washed and dried to obtain 4-hydroxy-4°-aminophenoxybiphenyl.
収量１４１ｇ（収率８５．０％）
ｍＰ ２５０〜２５１℃
実施例４
撹拌機、温度計、冷却管を装備した反応フラスコに２．
２−ビス（４“−ヒドロキシフェニル）プロパン１００
．４ｇ （０，４４モル）と１．３−ジメチル−２−イ
ミダゾリジノン５０２ｇを装入し、窒素を通気させなが
ら昇温し、６０℃で溶解する。これに９６％水酸化カリ
ウム５１．４ｇ （０，８８モル）を装入後、昇温し、
１００〜１２０℃で２時間撹拌した。内温を８０℃以下
に下げたのち、ｐ−ニトロクロルベンゼン６３．０ｇ
（０，４モル）を１．３−ジメチル−２−イミダゾリジ
ノン９４．５ ｇに溶解した溶液を８０〜９０℃で２時
間かけて滴下し、更に同温度で２時間撹拌した。Yield 141 g (yield 85.0%) mP 250-251°C Example 4 2.
2-bis(4″-hydroxyphenyl)propane 100
．． 4 g (0.44 mol) and 502 g of 1,3-dimethyl-2-imidazolidinone were charged, the temperature was raised while nitrogen was bubbled through, and the mixture was dissolved at 60°C. After charging 51.4 g (0.88 mol) of 96% potassium hydroxide to this, the temperature was raised,
Stirred at 100-120°C for 2 hours. After lowering the internal temperature to below 80℃, 63.0g of p-nitrochlorobenzene
A solution of (0.4 mol) dissolved in 94.5 g of 1,3-dimethyl-2-imidazolidinone was added dropwise at 80 to 90°C over 2 hours, and the mixture was further stirred at the same temperature for 2 hours.
反応終了後、反応液を冷却し、氷水１．２１に排出し、
３５％塩酸水４５．９ｇを滴下すると、黄色結晶が析出
した。これを濾過、洗浄後乾燥して、２−（４−ヒドロ
キシフェニル）−２−（４−（４−ニトロフェノキシ）
フェニル〕プロパンを得た。After the reaction was completed, the reaction solution was cooled and drained into 1.21 g of ice water.
When 45.9 g of 35% hydrochloric acid water was added dropwise, yellow crystals were precipitated. This was filtered, washed and dried to produce 2-(4-hydroxyphenyl)-2-(4-(4-nitrophenoxy)
phenyl]propane was obtained.
収量１０７ｇ（収率７６．５％）
ｒｓ９１１８〜１２０°Ｃ
元素分析（Ｃ□１１９ＮＯ４）
ＣＨＮ
計算値（χ’） ７２．１９ ５．４８ ４．０
１分析値（χ）７２，４３ ５．６１ ３．７６ＩＲ
（ＫＢｒ、 ｃｍ−’） ３４２０：水酸基１３４Ｇ
：二トロ基
１２４０ ：エーテル結合
次に撹拌機、温度計を装備した密閉型還元容器に上記２
−（４−ヒドロキシフェニル）−２−（４−（４−ニト
ロフェノキシ）フェニル〕プロパン１０５ｇ （０，３
モル）と５０％Ｐｄ／Ｃ触媒２．１ｇおよびイソプロピ
ルアルコール５２５ｇを装入し、激しく撹拌しながら水
素ガスを導入した。２０〜３０’Ｃで４時間反応を行っ
たところ、理論量の水素を吸収し、これ以上の吸収が認
められなくなったので反応を終了した。液温を６０〜７
０°Ｃに昇温し、熱濾過後、冷却すると結晶が析出した
。濾過、洗浄後乾燥して、２− （４−（４−アミノフ
ェノキシ）フェニル）−２−（４−ヒドロキシフェニル
］プロパンを得た。Yield 107g (yield 76.5%) rs9118~120°C Elemental analysis (C□119NO4) CHN Calculated value (χ') 72.19 5.48 4.0
1 analysis value (χ) 72,43 5.61 3.76IR
(KBr, cm-') 3420: hydroxyl group 134G
: Nitro group 1240 : Ether bond Next, put the above 2 into a closed reduction vessel equipped with a stirrer and a thermometer.
-(4-hydroxyphenyl)-2-(4-(4-nitrophenoxy)phenyl)propane 105g (0,3
mol), 2.1 g of 50% Pd/C catalyst, and 525 g of isopropyl alcohol were charged, and hydrogen gas was introduced with vigorous stirring. When the reaction was carried out at 20-30'C for 4 hours, the theoretical amount of hydrogen was absorbed and no further absorption was observed, so the reaction was terminated. Set the liquid temperature to 60-7
The temperature was raised to 0°C, and after hot filtration, crystals were precipitated when cooled. After filtration, washing, and drying, 2-(4-(4-aminophenoxy)phenyl)-2-(4-hydroxyphenyl]propane was obtained.
収量８５．２ｇ （収率８９，０％）
ｍｐ １５０〜１５２°Ｃ
元素分析（ＣｚＪｚ＋Ｎ０ｘ）
ＣＩＩＮ
計算値（χ） ７８．９７ ６．６３ ４．３９
分析値（χ） ７８．７０ ６．３１ ４．３９
ＩＲ（ＫＢｒ、 ｅｌｌ−’） ３３８０．３３００
ニアミノ基３２００ ：水酸基
１２３０ ：エーテル結合
実施例５
撹拌機、温度計、冷却管を装備した反応フラスコに２．
２−ビス（４°−ヒドロキシフェニル）プロパン１００
．４ｇ （０，４４モル）とジメチルスルホキシド５０
２ｇを装入し、窒素を通気させながら昇温し、６０°Ｃ
で溶解する。これに９６％水酸化カリウム５１．４ｇ
（０，８８モル）を装入後、昇温し、１００〜１２０℃
で２時間撹拌した。内温を８０°Ｃ以下に下げたのち、
ｐ−ニトロクロルベンゼン６３．０ｇ （０，４モル）
ヲ１．３−ジメチル−２−イミダゾリジノン９４．５ｇ
に溶解した溶液を８０〜９０°Ｃで２時間かけて滴下し
、更に同温度で２時間撹拌した。Yield 85.2g (yield 89.0%) mp 150-152°C Elemental analysis (CzJz+N0x) CIIN Calculated value (χ) 78.97 6.63 4.39
Analysis value (χ) 78.70 6.31 4.39
IR (KBr, ell-') 3380.3300
Niamino group 3200: Hydroxyl group 1230: Ether bond Example 5 2.
2-bis(4°-hydroxyphenyl)propane 100
．． 4 g (0.44 mol) and dimethyl sulfoxide 50
Charge 2g and raise the temperature while bubbling nitrogen to 60°C.
Dissolve with. Add to this 51.4g of 96% potassium hydroxide
After charging (0.88 mol), the temperature was raised to 100-120℃
The mixture was stirred for 2 hours. After lowering the internal temperature to below 80°C,
p-Nitrochlorobenzene 63.0g (0.4 mol)
1.3-dimethyl-2-imidazolidinone 94.5g
was added dropwise over 2 hours at 80 to 90°C, and further stirred at the same temperature for 2 hours.
反応終了後、反応液を冷却し、氷水１．２１！、に排出
し、３５％塩酸水４５．９ ｇを滴下すると、黄色結晶
が析出した。これを濾過、洗浄後乾燥して、２−（４−
ヒドロキシフェニル）−２−（４−（４−ニトロフェノ
キシ）フェニル）プロパンを得た。After the reaction is completed, the reaction solution is cooled down to 1.21 cm in ice water. , and 45.9 g of 35% hydrochloric acid solution was added dropwise to precipitate yellow crystals. This was filtered, washed and dried, and the 2-(4-
Hydroxyphenyl)-2-(4-(4-nitrophenoxy)phenyl)propane was obtained.
収量１０５ｇ（収率７５．０％）
＠Ｐ １１８〜１２０°Ｃ
次に撹拌機、温度計を装備した密閉型還元容器に上記２
−（４−ヒドロキシフェニル）−２−（４−（４−ニト
ロフェノキシ）フェニル〕プロパン１４０ｇ （０，４
モル）と５０％Ｐｄ／Ｃ触媒２．１ｇおよびイソプロピ
ルアルコール５２５ｇを装入し、激しく撹拌しながら水
素ガスを導入した。 ２０〜３０℃で４時間反応を行っ
たところ、理論量の水素を吸収し、これ以上の吸収が認
められな（なったので反応を終了した。６０〜７０℃に
昇温し、熱濾過後、冷却すると結晶が析出した。濾過、
洗浄後乾燥して、２− （４−（４−アミノフェノキシ
）フェニル）−２−（４−ヒドロキシフェニル〕プロパ
ンを得た。Yield 105g (yield 75.0%) @P 118-120°C Next, add the above 2 to a closed reduction container equipped with a stirrer and a thermometer.
-(4-hydroxyphenyl)-2-(4-(4-nitrophenoxy)phenyl)propane 140g (0,4
mol), 2.1 g of 50% Pd/C catalyst, and 525 g of isopropyl alcohol were charged, and hydrogen gas was introduced with vigorous stirring. When the reaction was carried out at 20 to 30°C for 4 hours, the theoretical amount of hydrogen was absorbed, and no further absorption was observed, so the reaction was terminated.The temperature was raised to 60 to 70°C, and after hot filtration. , When cooled, crystals precipitated.Filtration,
After washing and drying, 2-(4-(4-aminophenoxy)phenyl)-2-(4-hydroxyphenyl)propane was obtained.
収量１１６ｇ （収率９１．０％） ｓｐ １５０〜１５２℃Yield 116g (yield 91.0%) sp 150~152℃
Claims (1)
いは−Ｃ（ＣＦ＿３）＿２−、−ＣＯ−、−Ｓ−、−Ｓ
Ｏ−、−ＳＯ＿２−または−Ｏ−の２価の基を示す。ま
たＸが単結合で直接結合していてもよい。）で表される
新規な芳香族ヒドロキシ化合物。 ２）一般式（II） ▲数式、化学式、表等があります▼（II） （式中、Ｘは一般式（ I ）の場合と同じ意味である）
で表されるビフェノール類のジアルカリ金属塩１〜１．
２当量をｐ−ハロゲノニトロベンゼン１当量と非プロト
ン性極性溶媒中で縮合させて、一般式（III） ▲数式、化学式、表等があります▼（III） （式中、Ｘは一般式（III）の場合と同じ意味である）
で表される芳香族ヒドロキシ化合物を得、ついでこれを
還元することを特徴とする一般式（ I ）▲数式、化学
式、表等があります▼（ I ） （式中、Ｘは一般式（ I ）の場合と同じ意味である）
で表される新規な芳香族ヒドロキシ化合物の製造方法。[Claims] 1) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, or -C(CF_3 )_2-, -CO-, -S-, -S
Indicates a divalent group of O-, -SO_2- or -O-. Moreover, X may be directly bonded with a single bond. ) A novel aromatic hydroxy compound represented by 2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, X has the same meaning as in general formula (I))
Dialkali metal salts of biphenols represented by 1 to 1.
2 equivalents of p-halogenonitrobenzene are condensed with 1 equivalent of p-halogenonitrobenzene in an aprotic polar solvent to form the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (wherein, X is the general formula (III) )
The general formula (I) is characterized by obtaining an aromatic hydroxy compound represented by and then reducing it ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (wherein, X is the general formula (I) )
A method for producing a novel aromatic hydroxy compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62315375A JP2622136B2 (en) | 1987-12-15 | 1987-12-15 | Novel aromatic hydroxy compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62315375A JP2622136B2 (en) | 1987-12-15 | 1987-12-15 | Novel aromatic hydroxy compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01157941A true JPH01157941A (en) | 1989-06-21 |
| JP2622136B2 JP2622136B2 (en) | 1997-06-18 |
Family
ID=18064647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62315375A Expired - Fee Related JP2622136B2 (en) | 1987-12-15 | 1987-12-15 | Novel aromatic hydroxy compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2622136B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115093345A (en) * | 2022-08-23 | 2022-09-23 | 天津辰欣药物研究有限公司 | Synthesis method of Kelibaro impurity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618727A (en) * | 1984-11-05 | 1986-10-21 | The Dow Chemical Company | Nitro substituted diphenyl ethers |
-
1987
- 1987-12-15 JP JP62315375A patent/JP2622136B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618727A (en) * | 1984-11-05 | 1986-10-21 | The Dow Chemical Company | Nitro substituted diphenyl ethers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115093345A (en) * | 2022-08-23 | 2022-09-23 | 天津辰欣药物研究有限公司 | Synthesis method of Kelibaro impurity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2622136B2 (en) | 1997-06-18 |
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