CN1262668A - 四丁基铵酚盐二苯酚加合物的制备方法 - Google Patents
四丁基铵酚盐二苯酚加合物的制备方法 Download PDFInfo
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- QQJSZUAIXZSBAV-UHFFFAOYSA-M phenol;tetrabutylazanium;phenoxide Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.[O-]C1=CC=CC=C1.CCCC[N+](CCCC)(CCCC)CCCC QQJSZUAIXZSBAV-UHFFFAOYSA-M 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940031826 phenolate Drugs 0.000 claims abstract description 6
- 239000008346 aqueous phase Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 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 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkali metal phenolate Chemical class 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000012153 distilled water Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FTDXCHCAMNRNNY-UHFFFAOYSA-N phenol Chemical class OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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Abstract
本发明涉及四丁基铵酚盐二苯酚加合物的制备及纯化方法,该方法是将碱金属的酚盐与四丁基铵盐在水相中反应,然后通过加入酚来沉淀加合物。
Description
本发明涉及四丁基铵酚盐二苯酚加合物的制备及纯化方法，该方法是将碱金属的酚盐与四丁基铵盐在水相中反应，然后通过加入酚来沉淀加合物。
四烷基铵的酚盐已经被数次披露而变为公知。例如J.Am.Chem.Soc.103(1983)475和Inorg.Chem.24(1985)3465公开了四乙基铵的酚盐的生产，由DE-OS 22 03 448可知四丁基铵的酚盐的制备方法，EP-A 244 799教导了含有四烷基铵酚盐的电解质的制备方法。
各种四烷基铵的酚盐的苯酚加合物也是已知的。J.Chem.Soc.Faraday Trans.89(1993)119公开了各种四烷基铵的酚盐的(一)苯酚加合物的制备方法，EP-A 362 854公开了四丁基铵(对叔丁基酚盐)的二(对叔丁基酚)加合物的制备方法。
Tetrahedron Lett.3(1982)607公开了一种制备四丁基铵的酚盐的二苯酚加合物的制备方法，该方法是将氢氧化四丁基铵与苯酚在水溶液中反应。然而，对于工业生产来说，使用昂贵的氢氧化四丁基铵是不能令人满意的。因此需要寻找造价可接受的、在技术规模上可以实施以及所得产物中碱金属离子含量低的方法。
本发明的主题是四丁基铵酚盐二苯酚加合物N(C4H9)4OC6H5 *2C6H5OH的制备方法，其中，在第一步中，使碱金属酚盐与化学计量量的四丁基铵盐在水相中反应，然后在第二步中，向反应混合物中加入两当量的苯酚，并将所得加合物沉淀出来。
在一个优选的实施方案中，在第三步，将所形成的沉淀分离，用水洗涤，直至沉淀中钠的含量达到＜1500ppm。
在另一个优选实施方案中，在第三步，用有机溶剂萃取反应混合物，分离有机相并除去溶剂。
使碱金属酚盐在水相中与四丁基铵盐反应。这些四丁基铵盐优选为一价阳离子的盐，例如氟化物、氯化物、碘化物、四氟硼酸盐、高氯酸盐、六氟磷酸盐。从经济角度考虑，特别优选使用溴化四丁基铵。
方便地用等摩尔量的碱金属盐与四丁基铵盐进行反应。当然，也可以过量使用其中一种组分。然而，这会使产率减少并且有损该方法的经济价值。
当实施本发明的方法时，首先优选制备碱金属酚盐的和四丁基铵盐的水溶液，然后将其混合。一般来说，各初始溶液的盐浓度为约0.6-1.3摩尔/升。也可以将一种组分溶解在水中，然后以固体形式加入第二种组分。在反应过程中优选将反应溶液冷却，这样溶液的温度就不会明显超出室温。
在该方法的第二步中，将两当量的苯酚加入反应混合物中。当然，也可以偏离精确的化学计量量；但是这对于产率和产物的纯度有不利影响。优选将苯酚缓缓滴加至反应混合物中，优选用约1-2小时，小心地进行反应以确保反应混合物和苯酚很好地混合。从反应混合物中分离出复合的盐N(C4H9)4OC6H5 *2C6H5OH。为了使反应完全，优选再继续搅拌约60-120分钟。
在一个优选的实施方案中，之后分离所形成的沉淀。这可以通过本领域专业人员公知的常规方法进行，例如过滤、沉积或离心。然后用水洗涤沉淀，直至沉淀中钠的含量达到＜1500ppm，优选＜750ppm，特别优选＜500ppm。由此还使得该产物在对碱金属离子的存在敏感的方法中应用变为可能。然后有利地将所得产物干燥。在干燥过程中，优选采用低于该化合物熔点温度。
在另一个优选实施方案中，在第三步中，用有机溶剂萃取反应混合物，分离有机相并除去溶剂。优选使用的萃取剂是卤代烃，特别优选二氯甲烷。分离有机相后，优选用水洗涤该有机相，以除去残留的水溶性杂质。然后按照本领域专业人员公知的方法除去有机相中的溶剂，例如减压蒸馏。由此方法获得的产物具有特别低的钠含量。一般来说，产物中的钠含量低于检测限，也就是说，约为＜1ppm。
按照本发明方法制备的四丁基铵的酚盐二苯酚加合物特别适于用作催化剂体系的组分，例如用于制备酚树脂。因此，本发明的另一个主题是N(C4H9)4OC6H5 *2C6H5OH作为催化剂组分的应用。
实施例实施例1
在一个6000毫升装有内置挡板、精密玻璃搅拌器、可加热的加液漏斗和回流冷凝器的三颈圆底烧瓶中，将510.6克(3.0摩尔)苯酚钠三水合物溶解在1800毫升蒸馏水中(溶液A)。在一只3升玻璃烧杯中，将967.20克(3.0摩尔)溴化四丁基铵溶解在1800毫升蒸馏水中(溶液B)。
冷却，然后将溶液B加入到溶液A中。之后进行剧烈搅拌，用120分钟向其中滴加535.8克(5.7摩尔)苯酚，并继续搅拌120分钟。将所形成的沉淀吸滤，并用30升蒸馏水洗涤。将滤出的残余物在真空干燥器中干燥。
产量：1147克(理论值的73％)
干燥固体中钠的含量：570ppm实施例2
重复实施例1的方法。不同的是通过将120.0克(3.0摩尔)NaOH溶解在1800毫升蒸馏水中，并加入282.3克(3.0摩尔)熔融的苯酚，进行冷却，就地制备苯酚钠。
产量：1028克(理论值的65％)
干燥固体中钠的含量：430ppm实施例3
在一个500毫升装有内置挡板、精密玻璃搅拌器、可加热的加液漏斗和回流冷凝器的三颈圆底烧瓶中，用72毫升蒸馏水稀释113.5克(0.18摩尔)40％氢氧化四丁基铵溶液。然后用60分钟向其中滴加49.4克(0.53摩尔)苯酚，并继续搅拌60分钟。将所形成的沉淀吸滤，用少量水洗涤，然后在真空干燥器中干燥，直至恒重。
产量：71克(理论值的77％)
干燥固体中钠的含量：约3ppm实施例4
在一个500毫升装有内置挡板、精密玻璃搅拌器、可加热的加液漏斗和回流冷凝器的三颈圆底烧瓶中，将29.8克(0.18摩尔)苯酚钠溶解在80毫升蒸馏水中(溶液A)。在一只250毫升玻璃烧杯中，将48.6克(0.18摩尔)氯化四丁基铵溶解在200毫升蒸馏水中(溶液B)。
冷却，将溶液B加入到溶液A中。剧烈搅拌，然后用60分钟向其中滴加32.9克(0.35摩尔)苯酚；滴加完成后，继续搅拌60分钟。将所形成的沉淀吸滤，用水洗涤，然后在真空干燥器中干燥。
产量：66.2克(理论值的72％)
干燥固体中钠的含量：250ppm实施例5
在一个2升装有内置挡板、精密玻璃搅拌器、可加热加的液漏斗和回流冷凝器的三颈圆底烧瓶中，通过将40.0克(1.0摩尔)氢氧化钠溶解在500毫升水中并加入94.1克(1.0摩尔)苯酚，在500毫升蒸馏水中制备1摩尔苯酚钠(溶液A)。
在一只2升玻璃烧杯中，将322.4克(1.0摩尔)溴化四丁基铵溶解在700毫升蒸馏水中(溶液B)。
将溶液B加入到溶液A中。剧烈搅拌，用60分钟向其中滴加188.2克(2摩尔)苯酚。将所得悬浮液再搅拌60分钟。然后用200毫升二氯甲烷萃取三次。合并的有机相用150毫升洗涤一次，用旋转蒸发器浓缩，最好用油泵干燥，得到固体结晶饼。
产量：514.0克(理论值的98％)
固体中钠的含量：＜1ppm
溴含量为约3.8％(重量)，以溴化四丁基铵计算，其含量相当于15.3％(重量)。实施例6
在一个由搪瓷制造的100升装有冷却水水门、蒸馏头、真空/氮气阀门和可加热的计量罐的搅拌容器中，将19.7千克(61.6摩尔)溴化四丁基铵溶解在30.5升充分软化水中，并且为了临时贮藏，将其装入一只衬有Valenthene的大桶中(溶液A)。
在类似的装置中，将1.22千克(30.5摩尔)NaOH溶解在15.3千克充分软化水中，并将该溶液与2.83千克(30.1摩尔)熔融苯酚混合(溶液B)。
然后泵入25千克溶液A(＝30.5摩尔溴化四丁基铵)并充分混合。然后在室温下，用140分钟，通过可加热的加液漏斗滴加5.6千克(59.5摩尔)苯酚，充分混合。再搅拌90分钟，然后经盖有Dralon布的大吸滤器过滤。用水洗涤，然后在25℃于真空干燥器中，在金属片上干燥残余物直至恒重。
产量：10.1千克(理论值的63％)
钠含量：150ppm；溴含量：0.12％(重量)；水含量：400ppm实施例7(比较实施例)
在一只250毫升玻璃烧杯中，将8.1克(0.09摩尔)苯酚溶解在100毫升水中。在一只100毫升玻璃烧杯中，用25毫升蒸馏水稀释55毫升40％氢氧化四丁基铵溶液(＝0.085摩尔)。在振摇漏斗中将两种溶液合并，充分混合约5分钟，并分离各相。有机相用MgSO4干燥，过滤，然后蒸发浓缩。将粘稠的残余物溶解在11毫升乙酸乙酯中。但是，不可能从溶液中分离结晶的产物。甚至在大约0℃加入晶种也不能形成结晶。
Claims (4)
1.四丁基铵酚盐二苯酚加合物的制备方法，其中，在第一步中，使碱金属酚盐与化学计量量的四丁基铵盐在水相中反应，然后第二步，向反应混合物中加入两当量的苯酚，并将加合物沉淀。
2.权利要求1的方法，其中在第三步，将所形成的沉淀分离，用水洗涤，直至沉淀中钠的含量达到＜1500ppm。
3.权利要求1的方法，其中在第三步，用有机溶剂萃取反应混合物，分离有机相并除去溶剂。
4.四丁基铵酚盐二苯酚加合物作为催化剂组分的应用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19730022A DE19730022A1 (de) | 1997-07-11 | 1997-07-11 | Verfahren zur Herstellung von Tetrabutylammoniumphenolat-Diphenoladdukt |
| DE19730022.7 | 1997-07-11 |
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| Publication Number | Publication Date |
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| CN1262668A true CN1262668A (zh) | 2000-08-09 |
| CN1107045C CN1107045C (zh) | 2003-04-30 |
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| US (1) | US6177538B1 (zh) |
| EP (1) | EP1000004B1 (zh) |
| JP (1) | JP2001509494A (zh) |
| KR (1) | KR20010021646A (zh) |
| CN (1) | CN1107045C (zh) |
| AU (1) | AU8803198A (zh) |
| DE (2) | DE19730022A1 (zh) |
| ES (1) | ES2184313T3 (zh) |
| HK (1) | HK1029580A1 (zh) |
| IL (1) | IL133482A0 (zh) |
| TW (1) | TW409116B (zh) |
| WO (1) | WO1999002474A2 (zh) |
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| WO2020119595A1 (zh) * | 2018-12-13 | 2020-06-18 | 中国科学院上海有机化学研究所 | 一种酚盐及其应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19858967C1 (de) * | 1998-12-21 | 2000-07-13 | Bayer Ag | Flüssige Formulierung von Tetrabutylammoniumphenolat |
| DE10164142A1 (de) * | 2001-12-27 | 2003-07-10 | Bayer Ag | Verfahren zur Herstellung von Quartärsalzphenolatlösungen und zur Regenerierung und Rückführung von Quartärsalzphenolatlösungen aus Reaktionsgemischen |
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| GB1381272A (en) | 1971-01-26 | 1975-01-22 | Glaxo Lab Ltd | Cephalosporin compounds |
| JPS62259418A (ja) | 1986-05-02 | 1987-11-11 | 日本ケミコン株式会社 | 電解コンデンサ用電解液 |
| US4939112A (en) * | 1988-10-06 | 1990-07-03 | James River Paper Company, Inc. | Catalyst for synthesis of vesicular phenoxy resins |
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- 1998-06-30 IL IL13348298A patent/IL133482A0/xx unknown
- 1998-06-30 US US09/446,999 patent/US6177538B1/en not_active Expired - Fee Related
- 1998-06-30 EP EP98939566A patent/EP1000004B1/de not_active Expired - Lifetime
- 1998-06-30 DE DE59805837T patent/DE59805837D1/de not_active Expired - Fee Related
- 1998-06-30 AU AU88031/98A patent/AU8803198A/en not_active Abandoned
- 1998-06-30 WO PCT/EP1998/003987 patent/WO1999002474A2/de not_active Application Discontinuation
- 1998-06-30 JP JP2000502004A patent/JP2001509494A/ja active Pending
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- 1998-06-30 KR KR1020007000204A patent/KR20010021646A/ko not_active Application Discontinuation
- 1998-06-30 CN CN98806955A patent/CN1107045C/zh not_active Expired - Fee Related
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020119595A1 (zh) * | 2018-12-13 | 2020-06-18 | 中国科学院上海有机化学研究所 | 一种酚盐及其应用 |
| CN111318303A (zh) * | 2018-12-13 | 2020-06-23 | 中国科学院上海有机化学研究所 | 一种酚盐及其应用 |
| CN111318303B (zh) * | 2018-12-13 | 2023-08-11 | 中国科学院上海有机化学研究所 | 一种酚盐及其应用 |
Also Published As
| Publication number | Publication date |
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| WO1999002474A2 (de) | 1999-01-21 |
| WO1999002474A3 (de) | 1999-04-01 |
| DE19730022A1 (de) | 1999-01-14 |
| HK1029580A1 (en) | 2001-04-06 |
| KR20010021646A (ko) | 2001-03-15 |
| ES2184313T3 (es) | 2003-04-01 |
| CN1107045C (zh) | 2003-04-30 |
| EP1000004A2 (de) | 2000-05-17 |
| JP2001509494A (ja) | 2001-07-24 |
| TW409116B (en) | 2000-10-21 |
| IL133482A0 (en) | 2001-04-30 |
| US6177538B1 (en) | 2001-01-23 |
| AU8803198A (en) | 1999-02-08 |
| DE59805837D1 (de) | 2002-11-07 |
| EP1000004B1 (de) | 2002-10-02 |
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