TWI410401B - 製備２，４-二羥苯基４-甲氧基苄基酮之方法 - Google Patents
製備２，４-二羥苯基４-甲氧基苄基酮之方法 Download PDFInfo
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- XHBZOAYMBBUURD-UHFFFAOYSA-N 1-(2,4-Dihydroxyphenyl)-2-(4-methoxyphenyl)ethanone Chemical class C1=CC(OC)=CC=C1CC(=O)C1=CC=C(O)C=C1O XHBZOAYMBBUURD-UHFFFAOYSA-N 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- NRPFNQUDKRYCNX-UHFFFAOYSA-N 4-methoxyphenylacetic acid Chemical compound COC1=CC=C(CC(O)=O)C=C1 NRPFNQUDKRYCNX-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- -1 4-methoxybenzene Ethyl chloride Chemical compound 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 8
- PMIAMRAWHYEPNH-UHFFFAOYSA-N 1-(2-chloroethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCCl)C=C1 PMIAMRAWHYEPNH-UHFFFAOYSA-N 0.000 claims 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- 229930003935 flavonoid Natural products 0.000 claims 1
- 150000002215 flavonoids Chemical class 0.000 claims 1
- 235000017173 flavonoids Nutrition 0.000 claims 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical class OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 125000005415 substituted alkoxy group Chemical group 0.000 abstract description 6
- 125000000547 substituted alkyl group Chemical group 0.000 abstract description 2
- GNJTUNGQOITXTK-UHFFFAOYSA-N 1,3-bis(2,4-dihydroxyphenyl)-1,3-bis(4-methoxyphenyl)propan-2-one Chemical class C1=CC(OC)=CC=C1C(C=1C(=CC(O)=CC=1)O)C(=O)C(C=1C(=CC(O)=CC=1)O)C1=CC=C(OC)C=C1 GNJTUNGQOITXTK-UHFFFAOYSA-N 0.000 abstract 2
- 150000002989 phenols Chemical class 0.000 abstract 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZZIALNLLNHEQPJ-UHFFFAOYSA-N coumestrol Chemical compound C1=C(O)C=CC2=C1OC(=O)C1=C2OC2=CC(O)=CC=C12 ZZIALNLLNHEQPJ-UHFFFAOYSA-N 0.000 description 2
- ZQSIJRDFPHDXIC-UHFFFAOYSA-N daidzein Chemical compound C1=CC(O)=CC=C1C1=COC2=CC(O)=CC=C2C1=O ZQSIJRDFPHDXIC-UHFFFAOYSA-N 0.000 description 2
- HKQYGTCOTHHOMP-UHFFFAOYSA-N formononetin Chemical compound C1=CC(OC)=CC=C1C1=COC2=CC(O)=CC=C2C1=O HKQYGTCOTHHOMP-UHFFFAOYSA-N 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- JAUFWTSSYRTLLB-UHFFFAOYSA-N (2-phenylacetyl) 2-phenylacetate Chemical compound C=1C=CC=CC=1CC(=O)OC(=O)CC1=CC=CC=C1 JAUFWTSSYRTLLB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NYYINZYOPBQRIU-UHFFFAOYSA-N FC(F)(F)N(S(=O)=O)C(F)(F)F Chemical compound FC(F)(F)N(S(=O)=O)C(F)(F)F NYYINZYOPBQRIU-UHFFFAOYSA-N 0.000 description 1
- 238000003309 Hoesch reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910004013 NO 2 Inorganic materials 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000007240 daidzein Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- RIKPNWPEMPODJD-UHFFFAOYSA-N formononetin Natural products C1=CC(OC)=CC=C1C1=COC2=CC=CC=C2C1=O RIKPNWPEMPODJD-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- TZBJGXHYKVUXJN-UHFFFAOYSA-N genistein Natural products C1=CC(O)=CC=C1C1=COC2=CC(O)=CC(O)=C2C1=O TZBJGXHYKVUXJN-UHFFFAOYSA-N 0.000 description 1
- 235000006539 genistein Nutrition 0.000 description 1
- 229940045109 genistein Drugs 0.000 description 1
- ZCOLJUOHXJRHDI-CMWLGVBASA-N genistein 7-O-beta-D-glucoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=C2C(=O)C(C=3C=CC(O)=CC=3)=COC2=C1 ZCOLJUOHXJRHDI-CMWLGVBASA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- CJWQYWQDLBZGPD-UHFFFAOYSA-N isoflavone Natural products C1=C(OC)C(OC)=CC(OC)=C1C1=COC2=C(C=CC(C)(C)O3)C3=C(OC)C=C2C1=O CJWQYWQDLBZGPD-UHFFFAOYSA-N 0.000 description 1
- 150000002515 isoflavone derivatives Chemical class 0.000 description 1
- 235000008696 isoflavones Nutrition 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本發明係關於藉由佛瑞德-克來福特醯化作用於氟化氫(HF)中製備式(I)之化合物之方法。
式(I)之化合物為製備異黄酮(例如刺芒柄花素或染料木素、大豆苷元及香豆雌酚)(式(IV))之重要的合成單元。
2,4-二羥苯基4-甲氧基苄基酮已藉由苯乙腈、間苯二酚及氯化氫所進行的耗時霍本-赫施反應(Hoeben-Hoesch reaction)得到非常有限的產率(W.Baker等人，J.Chem.Soc 1929,2902)。
具67%產率之間苯二酚與苯基乙酸酐或游離酸在三氟化硼合乙醚存在下之反應亦已有描述(S.Mohaty等人，Current Science,May 20,1988,vol.57,N.10及US 5,981,775)。
此外，以間苯二酚及4-甲氧基苯乙酸在40莫耳當量之BF3/Et2O複合物存在下之去氧安息香合成已有描述(T.A.Hase於J.Chem Soc.Perkin Trans.1,1991,3005中)。
再者，由酚及苯乙酸使用二環己基碳二亞胺(DCC)及4-二甲基胺基吡啶(DMAP)之2-苯基苯乙酮衍生物合成已有描述(WO 2005/054169)。
亦已知，安息香可藉由佛瑞德-克來福特醯化作用在AlCl3的存在下製得(Indian J.Chem.vol.6,1968,p.482)。
再者，已知聚羥基安息香係藉由離子液體之微波合成在雙(三氟甲基)磺醯胺或BF3/OEt2之存在下所製得(Tetrahedron Letters,47,2006,8375)。
所有的這些方法具有一系列的缺點。這些缺點為產率低、反應時間長或使用昂貴的試劑(例如DCC及DMAP)。使用催化劑(例如BF3及AlCl3)產生大量的廢水，其必須以繁複的方法來處理。
因為BF3/Et2O複合物燃點非常低，其實際上甚至不適用於工業級合成。
目前已發現式(I)之化合物之合成，
其中R1及R2 各為氫、氯、氟、溴、碘、CF3、甲基、甲氧基、視需要經取代之烷氧基、-OCF3、-C(CH3)3、-CH2(CH3)、-CH(CH3)2，R3 為氫、Cl、F、Br、視需要經取代之烷基、視需要經取代之烷氧基、-C(CH3)3，及X 為羥基、F、Cl、視需要經取代之烷氧基或Br，藉由式(II)之化合物與式(III)之酚在液態氟化氫(HF)中反
應，而可具高產率及高純度。
此方法另一項優點為HF具有20℃之沸點，可藉由蒸餾容易地從產物中移除且因此可完全回收。HF同時為非常便宜的原料並可製備及用於千噸量的工業上。
R1及R2 較佳地為氫、甲基、甲氧基、C1-C6-烷氧基、-OCF3、-C(CH3)3、-CH2(CH3)、-CH(CH3)2或氯、氟、溴、碘、CF3。
R1及R2 更佳地為氫、甲基、甲氧基、C1-C4-烷氧基、-C(CH3)3、-CH2(CH3)、-CH(CH3)2或氯、氟、溴、碘、-CF3。
R1 最佳地為甲氧基。
R2 最佳地為氫。
R3 較佳地為氫、C1-C6-烷基、氯、氟、溴、C1-C6-烷氧基、-C(CH3)3。
R3 更佳地為氫、C1-C4-烷基、Cl、F、Br、C1-C4-烷氧基、-C(CH3)3。
R3 最佳地為氫。
X 較佳地為羥基、氟、氯、C1-C6-烷氧基及更佳地為羥基、氟、氯、C1-C4-烷氧基。
X 亦較佳地為溴。
烷基及烷氧基之可能的取代基有：氟、氯、溴、碘、NO2、CN、SCN、NCO。
視需要可藉由添加另外的催化劑加速反應。例如，催化劑，例如可使用路易斯酸如BF3、SbF5、PF5、BiF3、AsF3、AlCl3、SbCl5、TiCl4、NbCl5、SnCl4、SiCl4及InCl3。較佳催化劑有：BF3、SbCl5、AlCl3、SiCl4、PF5。特佳的催化劑有BF3、AlCl3、SbCl5。
當進行本發明方法時，反應溫度可在相當廣的範圍中變化。一般而言，溫度係介於-10℃至120℃間。溫度較佳地係介於0℃至50℃間。特佳的反應溫度係介於20℃至40℃間。
氟化氫與式(III)酚之莫耳比率可在廣泛的範圍中變化。一般而言，本發明之方法係以介於1：1至100：1之氟化氫與式(III)酚的莫耳比率來進行。較佳的莫耳比率為50：1至10：1。
本發明之方法可視需要在另外的稀釋劑存在下進行。適合的此等稀釋劑有，例如乙醚、氟氯烷(Freon)、二氯甲烷、二氯乙烷、甲苯及氯苯。
較佳的係在無另外的稀釋劑下進行此方法。
反應可在周圍壓力於氫氣壓下或於保護氣體的壓力下進行。
根據下列流程，式(I)化合物可轉變為式(IV)化合物。
適合此反應之化合物為CH(OEt)3、且為CH結構單元以及具有親核性離子基團之一般化合物(Pivovarenko等人，Klim.Pirod.Soed.(Ukraine)5(1989),639-643)。
1-(2,4-二羥苯基)-2-(4-甲氧基苯基)-乙酮之製備
將4-甲氧基苯乙酸(83.9克)、間苯二酚(55克)及氟化氫(450克)於-10℃先裝入殺菌釜中，並將混合物於20℃攪拌12小時。隨後於40℃將氟化氫蒸發出，及以水清洗沉澱並乾燥。
由此得到123克(91%之理論值)純度96%及沸點(m.p.)160-162℃之產物。
將4-甲氧基苯乙醯氯(93克)、間苯二酚(55克)及氟化氫(450克)於-10℃先裝入殺菌釜中，並將混合物於20℃攪拌12小時。隨後於40℃將氟化氫蒸發出，及以水清洗沉澱並和乾燥。
由此得到125克(92%之理論值)純度96%之產物。
將4-甲氧基苯乙酸(83.9克)、間苯二酚(55克)及氟化氫(300克)於-10℃先裝入殺菌釜中，並將混合物於20℃攪拌12小時。隨後於40℃將氟化氫蒸發出，及以水清洗沉澱並乾燥。
由此得到120克(89%之理論值)純度93%之產物。
Claims (8)
- 一種用於製備式(I)之化合物之方法，
- 如申請專利範圍第1項之方法，其中R1及R2 各為氫、氯、氟、溴、碘、CF3、甲基、C1-C6-烷氧基、-OCF3、-C(CH3)3、-CH2(CH3)、-CH(CH3)2，R3 為氫、Cl、F、Br、C1-C6-烷基、C1-C6-烷氧基、-C(CH3)3及X 為羥基、F、Cl、Br、C1-C6-烷氧基。
- 如申請專利範圍第1項之方法，其中R1及R2 各為氫、氯、氟、溴、碘、CF3、甲基、C1-C4-烷氧基、-C(CH3)3、-CH2(CH3)、-CH(CH3)2，R3 為氫、Cl、F、Br、C1-C6-烷基、C1-C4-烷氧基、-C(CH3)3及X 為羥基、F、Cl、C1-C4-烷氧基。
- 一種製備1-(2,4-二羥苯基)-2-(4-甲氧基苯基)乙酮之方法，其特徵為係將4-甲氧基苯乙酸或4-甲氧基苯乙醯氯與間苯二酚及與氟化氫反應，且無其他稀釋劑。
- 如申請專利範圍第1項之方法，其特徵為氟化氫與式(III)酚之莫耳比率係在50：1至10：1之範圍內。
- 如申請專利範圍第1項之方法，其特徵為反應溫度係介於10℃至50℃間。
- 一種製備1-(2,4-二羥苯基)-2-(4-甲氧基苯基)乙酮之方法，其特徵為係以50：1至10：1範圍內之氟化氫與間苯二酚之莫耳比率及於0℃至40℃的溫度範圍內，且無其他稀釋劑，將4-甲氧基苯乙酸或4-甲氧基 苯乙醯氯與間苯二酚及與氟化氫反應。
- 一種製備式(IV)化合物之方法，
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07003860A EP1961727A1 (de) | 2007-02-26 | 2007-02-26 | Verfahren zur Herstellung von 2,4-Dihydroxyphenyl-4-methoxybenzyl-ketonen |
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| Publication Number | Publication Date |
|---|---|
| TW200846313A TW200846313A (en) | 2008-12-01 |
| TWI410401B true TWI410401B (zh) | 2013-10-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| TW097106390A TWI410401B (zh) | 2007-02-26 | 2008-02-25 | 製備２，４-二羥苯基４-甲氧基苄基酮之方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US8324431B2 (zh) |
| EP (2) | EP1961727A1 (zh) |
| JP (1) | JP5352477B2 (zh) |
| CN (1) | CN101610989B (zh) |
| ES (1) | ES2623432T3 (zh) |
| IL (1) | IL199931A (zh) |
| TW (1) | TWI410401B (zh) |
| WO (1) | WO2008104297A1 (zh) |
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| CN118063423B (zh) * | 2024-02-05 | 2024-09-06 | 宁夏明凌新材料科技有限公司 | 一种大豆苷元的提取方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225619A (en) * | 1976-04-14 | 1980-09-30 | Boehringer Ingelheim Gmbh | Substituted fluoracylresorcinols |
| US4269965A (en) * | 1979-09-17 | 1981-05-26 | E. I. Du Pont De Nemours And Company | Aromatic polyester which forms optically anisotropic melts and filaments thereof |
| US5981775A (en) * | 1998-09-16 | 1999-11-09 | Board Of Trustees Operating Michigan State University | Process for the preparation of isoflavones |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2616986A1 (de) * | 1976-04-17 | 1977-10-27 | Bayer Ag | Verfahren zur herstellung von hydroxyketonen |
| FR2519975A1 (fr) * | 1982-01-21 | 1983-07-22 | Rhone Poulenc Spec Chim | Procede de preparation de trifluoromethoxy ou trifluoromethylthiophenylcetones |
| JPS60188343A (ja) * | 1984-03-07 | 1985-09-25 | Mitsubishi Gas Chem Co Inc | 芳香族ケトンの製造法 |
| IT1196264B (it) * | 1984-09-24 | 1988-11-16 | Blaschim Spa | Procedimento per preparare arilalchilchetoni |
| IL86747A (en) * | 1987-06-19 | 1992-06-21 | Lilly Co Eli | Process for the preparation of 4-alkanoylresorcinol from resorcinol |
| DK0478559T3 (da) * | 1990-04-18 | 1996-02-19 | Chinoin Gyogyszer Es Vegyeszet | Forbedret fremgangsmåde til fremstilling af kentonforbindelser |
| WO2005054169A1 (en) | 2003-12-08 | 2005-06-16 | Hanbul Cosmetic Co., Ltd. | Preparation method of 2-phenylacetophenone derivatives |
| US20060129002A1 (en) * | 2004-12-15 | 2006-06-15 | Honeywell International Inc. | Process for the synthesis of alkylresorcinols |
-
2007
- 2007-02-26 EP EP07003860A patent/EP1961727A1/de not_active Ceased
-
2008
- 2008-02-16 JP JP2009550235A patent/JP5352477B2/ja not_active Expired - Fee Related
- 2008-02-16 EP EP08715804.4A patent/EP2114847B1/de not_active Not-in-force
- 2008-02-16 US US12/525,023 patent/US8324431B2/en not_active Expired - Fee Related
- 2008-02-16 CN CN200880004683.0A patent/CN101610989B/zh not_active Expired - Fee Related
- 2008-02-16 ES ES08715804.4T patent/ES2623432T3/es active Active
- 2008-02-16 WO PCT/EP2008/001203 patent/WO2008104297A1/de not_active Ceased
- 2008-02-25 TW TW097106390A patent/TWI410401B/zh not_active IP Right Cessation
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2009
- 2009-07-16 IL IL199931A patent/IL199931A/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225619A (en) * | 1976-04-14 | 1980-09-30 | Boehringer Ingelheim Gmbh | Substituted fluoracylresorcinols |
| US4269965A (en) * | 1979-09-17 | 1981-05-26 | E. I. Du Pont De Nemours And Company | Aromatic polyester which forms optically anisotropic melts and filaments thereof |
| US5981775A (en) * | 1998-09-16 | 1999-11-09 | Board Of Trustees Operating Michigan State University | Process for the preparation of isoflavones |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101610989B (zh) | 2013-05-15 |
| US20100121082A1 (en) | 2010-05-13 |
| US8324431B2 (en) | 2012-12-04 |
| ES2623432T3 (es) | 2017-07-11 |
| EP1961727A1 (de) | 2008-08-27 |
| JP2010519231A (ja) | 2010-06-03 |
| IL199931A (en) | 2012-12-31 |
| EP2114847B1 (de) | 2017-03-22 |
| TW200846313A (en) | 2008-12-01 |
| EP2114847A1 (de) | 2009-11-11 |
| WO2008104297A1 (de) | 2008-09-04 |
| CN101610989A (zh) | 2009-12-23 |
| JP5352477B2 (ja) | 2013-11-27 |
| IL199931A0 (en) | 2010-04-15 |
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