CN1075075C - 氯化(3－烷氧基苯基)镁的制备和用途 - Google Patents
氯化(3－烷氧基苯基)镁的制备和用途Info
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- CN1075075C CN1075075C CN97102454A CN97102454A CN1075075C CN 1075075 C CN1075075 C CN 1075075C CN 97102454 A CN97102454 A CN 97102454A CN 97102454 A CN97102454 A CN 97102454A CN 1075075 C CN1075075 C CN 1075075C
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- magnesium
- alkyl
- chlorination
- represent
- phenyl
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 title claims description 11
- 235000011147 magnesium chloride Nutrition 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 31
- 239000011777 magnesium Substances 0.000 claims description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 28
- 238000005660 chlorination reaction Methods 0.000 claims description 24
- -1 magnesium halide Chemical class 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 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
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- RIFKADJTWUGDOV-UHFFFAOYSA-N 1-cyclohexylethanone Chemical compound CC(=O)C1CCCCC1 RIFKADJTWUGDOV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010022998 Irritability Diseases 0.000 description 1
- 102000005262 Sulfatase Human genes 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical class O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 108060007951 sulfatase Proteins 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B49/00—Grignard reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C217/74—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with rings other than six-membered aromatic rings being part of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本文描述了一个制备氯化(3-烷氧苯基)镁的方法及其与某些羰基化合物反应的用途。
Description
本发明涉及氯化(3-烷氧基苯基)镁的制备方法以及这些化合物的用途。
大量的药物和农药的有效成分含有间茴香基基团。比较好的是借助于有机金属间茴香基化合物、尤其是借助于间茴香基Grignard化合物将间茴香基基团引入要合成的化合物中。通过间茴香基溴与金属镁在溶液中反应得到的溴化间茴香基镁，在这里用作Grignard化合物(Arzn.Forsch./Drug Res.28(Ⅰ),107(1978)).
活泼溴通常用于Grignard化合物的制备。然而，从经济和生态学的观点来看，由于氯化物第一比较便宜，第二由于其分子量较小，生成的盐量较少，因此，在Grignard化合物的制备中用较不活泼的氯化物代替溴化物是有利的。此外，用氯化物时，生成的副产品较少。
从US2959596和J.Chem.Soc.1968,1265中可了解氯化邻茴香基镁和氯化对茴香基镁的制备和用途。Derwent WPI Acc No:85-137805/23中涉及的JP60/72833，揭示了氯化(4-乙氧基苯基)镁而未陈述所用的制备方法。然而，氯化(3-甲氧基苯基)镁和氯化(3-乙氧基苯基)镁的制备和应用至今尚未见描述。这可以用由间位的烷氧基基团引起芳香族化合物的电子失活来解释。
因此，本发明的潜在目的包括研制出氯化(3-烷氧基苯基)镁的制备方法。
令人惊讶的是，发现通过相应的3-烷氧基苯基氯与活性镁反应，可高产量地得到烷氧基中含有1至5个碳原子的氯化(3-烷氧基苯基)镁。
因此，本发明涉及烷氧基中含有1至5个碳原子的氯化(3-烷氧基苯基)镁的制备方法，即通过(3-烷氧基苯基)氯与用碱金属还原卤化镁得到的活性镁反应来制备。
特别适用于本发明方法的活性镁是通过用锂、钠或钾还原卤化镁、特别是氯化镁来得到的(J.Org.Chem.52,3674,(1987)；J.Am.Chem.Soc.96,1775(1974))。还原通常用过量1至5％摩尔的卤化镁，在溶剂或溶剂混合物中，如在诸如四氢呋喃、取代的四氢呋喃、二甲氧基乙烷和/或二甲基二甘醇的脂族醚中，在65℃和162℃之间的温度下进行。在有诸如碱性碘化物、碱性硫酸盐和/或碱土金属硫酸盐的碱金属盐和碱土金属盐存在的情况下，进行反应是有利的。通过还原得到的活性镁最好不进行分离，再与烷氧基中含有1至5个碳原子的(3-烷氧基苯基)氯进行反应，生成相应的Grignard化合物。氯苯化合物中的C1-5烷氧基可以是直链、支链或环状基团。氯苯化合物最好是那些含有间位烷氧基而且是选自甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基和环戊氧基的烷氧基的氯苯化合物。特别推荐用3-甲氧基苯基氯和3-乙氧基苯基氯与活性镁反应。
氯化镁化合物用本发明的方法可高产量地制备，而且不生成副产品。相反，如果3-烷氧基苯基氯与非活性镁，在有少量二溴乙烷存在的情况下，或是与非活性镁在乙基溴存在的情况下，用EP307106中描述的用于3-叔丁氧基苯基氯的方法进行反应，得到的相应的Grignard化合物的量不能令人满意，而且，生成大量的副产品。
醛和酮用按本发明制备的氯化(3-烷氧基苯基)镁，可高产量地转化为相应的醇。
因此，本发明也涉及烷氧基中含有1至5个碳原子的氯化(3-烷氧基苯基)镁用来与式Ⅰ的β-氨基醛或β-氨基酮反应的用途，这里R1代表H或C1-4烷基，R2代表H或C1-4烷基，或R2与R1一起代表-(CH2)4-，或R2与R3一起代表C4-7环烷基，或R2与R4一起代表C5-8环烷基，或R2与R5一起代表一个5至8员的杂环，而R3为H或一直链C1-4烷基，R4是H，而R5代表C1-3烷基，R6代表C1-3烷基，或用来与分子式Ⅱ
的醛或酮反应，这里R7和R8相同或不同，各自代表H、C1-6烷基或C3-6环烷基。
氯化(3-烷氧基苯基)镁最好用来与β-氨基醛或β-氨基酮反应，这里，烷氧基代表甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基或环戊氧基，最好使用氯化(3-甲氧基苯基)镁或氯化(3-乙氧基苯基)镁。特别合适的是那些式Ⅰ中R1是C1-4烷基、R2代表H或C1-4烷基、或R2与R1一起代表-(CH2)4-、R3代表H或一直链C1-4烷基、而R4为H、R5为CH3、R6为CH3的β-氨基醛或β-氨基酮。
按本发明制备的氯化镁化合物的反应以本领域熟知的方法进行，即Grignard化合物与含有分子式Ⅰ或Ⅱ的化合物，在溶剂或溶剂混合物中，如在四氢呋喃、取代的四氢呋喃、二烷基醚和/或二噁烷的脂族醚、和/或诸如苯、甲苯和/或二甲苯的芳香烃中，在-78℃和120℃之间的温度下进行反应。
实施例
所有的工作用干燥过的溶剂和试剂，在保护性气体中进行。
实施例1氯化(3-甲氧基苯基)镁的制备
将2.04g(21.4mmol)的氯化镁置于装有回流冷凝器、温度计和滴液漏斗的100ml三颈烧瓶中，用50ml四氢呋喃(THF)覆盖，将0.82g(21.0mmol)新鲜切割的钾分批加入其中，混合物边搅拌边回流加热90分钟。然后，在搅拌下用30分钟滴加溶于20ml THF的3.05g(21.4mmol)3-氯苯甲醚。滴加完毕后，将混合物在室温下搅拌20小时，得到的Grignard化合物用于进一步的反应。
实施例22-((二甲氨基)甲基)-1-(3-甲氧基苯基)-环己醇的制备
将溶于10ml THF中的3.32g(21.4mmol)2-(二甲氨基)甲基-环己酮，用40分钟的时间滴加到按照实例1得到的、冰浴中冷却的氯化(3-甲氧基苯基)镁溶液中。室温下搅拌24小时后，混合物用20ml20％的氯化铵溶液在冰浴中冷却水解。将有机相分离出来，水相用乙酸乙酯再提取两次。合并的有机相用硫酸镁干燥并过滤。通过蒸馏除去溶剂后，得到3.4g(理论值的60％)环己醇化合物。
Claims (8)
1．一种制备醇的方法，该方法是通过与先通过一相应的(3-烷氧基苯基)氯与用碱金属还原卤化镁得到的活性镁反应而制得的烷氧基中含有1至5个碳原子的氯化(3-烷氧基苯基)镁与式Ⅰ的β-氨基醛或β-氨基酮反应，式Ⅰ为：
其中R1代表H或C1-4烷基，R2代表H或C1-4烷基，或R2与R1一起代表-(CH2)4-，或R2与R3一起代表C4-7环烷基，或R2与R4一起代表C5-8环烷基，或R2与R5一起代表一个5至8员的杂环，而R3为H或一直链C1-4烷基，R4为H，R5为C1-3烷基，而R6代表C1-3烷基，或与式Ⅱ的醛或酮反应，式Ⅱ为：其中R7和R8相同或不同，每一个都代表H、C1-6烷基或C3-6环烷基。
2．按照权利要求1的方法，其特征在于用锂、钠或钾还原氯化镁来得到活性镁。
3．按照权利要求1的方法，其特征在于(3-烷氧基苯基)氯与活性镁反应，其中烷氧基代表甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基和环戊氧基。
4．按照权利要求1的方法，其特征在于(3-甲氧基苯基)氯或(3-乙氧基苯基)氯与活性镁反应。
5．按照权利要求1的方法，其特征在于，氯化(3-烷氧基苯基)镁是与β-氨基醛或β-氨基酮反应的。
6．按照权利要求1的方法，其特征在于，氯化(3-烷氧基苯基)镁是与式Ⅰ的β-氨基醛或β-氨基酮反应的，其中R1是C1-4烷基，R2代表H或C1-4烷基，或R2与R1一起构成-(CH2)4-，而R2为H或一直链C1-4烷基，R4为H,R5为CH3,R6为CH3。
7．按照权利要求1的方法，其特征在于，使用的烷氧基为甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基或环戊氧基的氯化(3-烷氧基苯基)镁。
8．按照权利要求1至7中任一项的方法，其特征在于使用的氯化(3-烷氧基苯基)镁是氯化(3-甲氧基苯基)镁或氯化(3-乙氧基苯基)镁。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19605778A DE19605778C1 (de) | 1996-02-16 | 1996-02-16 | Herstellung und Verwendung von (3-Alkoxyphenyl)magnesiumchloriden |
| DE19605778.7 | 1996-02-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1166491A CN1166491A (zh) | 1997-12-03 |
| CN1075075C true CN1075075C (zh) | 2001-11-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97102454A Expired - Fee Related CN1075075C (zh) | 1996-02-16 | 1997-02-14 | 氯化(3－烷氧基苯基)镁的制备和用途 |
Country Status (31)
| Country | Link |
|---|---|
| US (1) | US5852216A (zh) |
| EP (1) | EP0790251B1 (zh) |
| JP (1) | JP3893180B2 (zh) |
| KR (2) | KR100521062B1 (zh) |
| CN (1) | CN1075075C (zh) |
| AR (1) | AR005775A1 (zh) |
| AT (1) | ATE229025T1 (zh) |
| AU (1) | AU707621B2 (zh) |
| BR (1) | BR9700208A (zh) |
| CA (1) | CA2197616C (zh) |
| CO (1) | CO4770991A1 (zh) |
| CZ (1) | CZ290270B6 (zh) |
| DE (2) | DE19605778C1 (zh) |
| DK (1) | DK0790251T3 (zh) |
| ES (1) | ES2187690T3 (zh) |
| HK (1) | HK1004812A1 (zh) |
| HU (1) | HU219060B (zh) |
| IL (1) | IL120224A (zh) |
| IN (1) | IN192277B (zh) |
| MY (1) | MY113636A (zh) |
| NO (1) | NO315943B1 (zh) |
| NZ (1) | NZ299965A (zh) |
| PE (1) | PE1098A1 (zh) |
| PL (1) | PL185309B1 (zh) |
| PT (1) | PT790251E (zh) |
| RU (1) | RU2177931C2 (zh) |
| SI (1) | SI0790251T1 (zh) |
| SK (1) | SK282190B6 (zh) |
| UA (1) | UA46740C2 (zh) |
| UY (1) | UY24460A1 (zh) |
| ZA (1) | ZA971232B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19757499A1 (de) * | 1997-12-23 | 1999-06-24 | Studiengesellschaft Kohle Mbh | Verfahren zur Synthese von Organomagnesium-Verbindungen unter Einsatz von Katalysatoren |
| US6531597B2 (en) * | 2001-02-13 | 2003-03-11 | Hoffmann-La Roche Inc. | Process for preparation of 2-phenyl acetic acid derivatives |
| EP1785412A1 (en) * | 2005-11-14 | 2007-05-16 | IPCA Laboratories Limited | Tramadol recovery process |
| US9882245B2 (en) | 2013-08-23 | 2018-01-30 | Ut-Battelle, Llc | Alkoxide-based magnesium electrolyte compositions for magnesium batteries |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0307106A1 (en) * | 1987-09-11 | 1989-03-15 | Hokko Chemical Industry Co., Ltd | P- or m-tert butoxyphenethyl alcohol and process for preparing the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2959596A (en) | 1957-11-22 | 1960-11-08 | Metal & Thermit Corp | Aryl chloride-cyclic ether grignard reagents |
| US3706809A (en) * | 1970-09-17 | 1972-12-19 | Takasago Perfumery Co Ltd | Process for preparing highly reactive organo-magnesium compounds |
| US4133824A (en) * | 1977-08-17 | 1979-01-09 | Texas Alkyls, Inc. | Organo-magnesium complexes and process for their preparation |
| JPS6072833A (ja) * | 1983-09-29 | 1985-04-24 | Hokko Chem Ind Co Ltd | 芳香族ビニル化合物の改良製造法 |
| US4731203A (en) * | 1983-11-09 | 1988-03-15 | Studiengesellschaft Kohle Mbh | Process for using finely divided highly reactive magnesium |
| US5273686A (en) * | 1987-07-11 | 1993-12-28 | Studiengesellschaft Kohle Mbh | Soluble magnesium hydrides, method of preparing them, and use thereof |
| JP3107920B2 (ja) | 1992-08-28 | 2000-11-13 | 花王株式会社 | 歯磨剤の製造方法 |
| US5358670A (en) * | 1993-07-02 | 1994-10-25 | Ferro Corporation | Process for preparing grignard reagents in diethylene glycol dibutyl ether |
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1996
- 1996-02-16 DE DE19605778A patent/DE19605778C1/de not_active Expired - Fee Related
- 1996-12-18 NZ NZ299965A patent/NZ299965A/en not_active IP Right Cessation
- 1996-12-26 MY MYPI96005468A patent/MY113636A/en unknown
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1997
- 1997-01-28 PT PT97101270T patent/PT790251E/pt unknown
- 1997-01-28 SI SI9730477T patent/SI0790251T1/xx unknown
- 1997-01-28 EP EP97101270A patent/EP0790251B1/de not_active Expired - Lifetime
- 1997-01-28 ES ES97101270T patent/ES2187690T3/es not_active Expired - Lifetime
- 1997-01-28 AT AT97101270T patent/ATE229025T1/de active
- 1997-01-28 DE DE59708849T patent/DE59708849D1/de not_active Expired - Lifetime
- 1997-01-28 DK DK97101270T patent/DK0790251T3/da active
- 1997-02-04 PE PE1997000069A patent/PE1098A1/es not_active Application Discontinuation
- 1997-02-06 BR BR9700208A patent/BR9700208A/pt not_active Application Discontinuation
- 1997-02-10 AR ARP970100524A patent/AR005775A1/es active IP Right Grant
- 1997-02-11 CO CO97006908A patent/CO4770991A1/es unknown
- 1997-02-12 CZ CZ1997430A patent/CZ290270B6/cs not_active IP Right Cessation
- 1997-02-12 SK SK202-97A patent/SK282190B6/sk not_active IP Right Cessation
- 1997-02-13 UA UA97020620A patent/UA46740C2/uk unknown
- 1997-02-13 IN IN247CA1997 patent/IN192277B/en unknown
- 1997-02-13 ZA ZA9701232A patent/ZA971232B/xx unknown
- 1997-02-14 UY UY24460A patent/UY24460A1/es not_active IP Right Cessation
- 1997-02-14 PL PL97318486A patent/PL185309B1/pl not_active IP Right Cessation
- 1997-02-14 CN CN97102454A patent/CN1075075C/zh not_active Expired - Fee Related
- 1997-02-14 HU HU9700441A patent/HU219060B/hu not_active IP Right Cessation
- 1997-02-14 RU RU97102339/04A patent/RU2177931C2/ru not_active IP Right Cessation
- 1997-02-14 CA CA002197616A patent/CA2197616C/en not_active Expired - Fee Related
- 1997-02-14 KR KR1019970004335A patent/KR100521062B1/ko not_active IP Right Cessation
- 1997-02-14 IL IL12022497A patent/IL120224A/en not_active IP Right Cessation
- 1997-02-14 US US08/800,879 patent/US5852216A/en not_active Expired - Lifetime
- 1997-02-14 JP JP03083397A patent/JP3893180B2/ja not_active Expired - Fee Related
- 1997-02-14 AU AU14715/97A patent/AU707621B2/en not_active Ceased
- 1997-02-14 NO NO19970698A patent/NO315943B1/no not_active IP Right Cessation
-
1998
- 1998-05-08 HK HK98104001A patent/HK1004812A1/xx not_active IP Right Cessation
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2005
- 2005-04-20 KR KR1020050032652A patent/KR100541786B1/ko not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0307106A1 (en) * | 1987-09-11 | 1989-03-15 | Hokko Chemical Industry Co., Ltd | P- or m-tert butoxyphenethyl alcohol and process for preparing the same |
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