CN1040429C - 制备硫代乙酰胺的改进方法 - Google Patents
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- CN1040429C CN1040429C CN93119701A CN93119701A CN1040429C CN 1040429 C CN1040429 C CN 1040429C CN 93119701 A CN93119701 A CN 93119701A CN 93119701 A CN93119701 A CN 93119701A CN 1040429 C CN1040429 C CN 1040429C
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- thioacetamide
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- 238000000034 method Methods 0.000 title claims abstract description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- -1 poly(4-vinylpyridine) Polymers 0.000 abstract description 3
- LWZDSXONSDJDOH-UHFFFAOYSA-N n-benzyl-n-methylpyridin-4-amine Chemical compound C=1C=NC=CC=1N(C)CC1=CC=CC=C1 LWZDSXONSDJDOH-UHFFFAOYSA-N 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 229920006037 cross link polymer Polymers 0.000 abstract 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- FKNJDCSKTSRSSW-UHFFFAOYSA-N ethyl 2-methyl-4-(trifluoromethyl)-1,3-thiazole-5-carboxylate Chemical compound CCOC(=O)C=1SC(C)=NC=1C(F)(F)F FKNJDCSKTSRSSW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- PKDGEPVOLLFDIP-UHFFFAOYSA-N CCCCCCCCCCCCCC[ClH]CC(C(O)=O)F Chemical class CCCCCCCCCCCCCC[ClH]CC(C(O)=O)F PKDGEPVOLLFDIP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- LSOWZKPNRJYLSR-UHFFFAOYSA-N acetonitrile;ethanethioamide Chemical compound CC#N.CC(N)=S LSOWZKPNRJYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZLRKALPKQZIMPF-UHFFFAOYSA-N ethanethiohydrazide Chemical compound CC(=S)NN ZLRKALPKQZIMPF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FOOHWUQIWMQCQA-UHFFFAOYSA-N n-phenyl-1,3-thiazole-2-carboxamide Chemical compound N=1C=CSC=1C(=O)NC1=CC=CC=C1 FOOHWUQIWMQCQA-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
- C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/42—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of a saturated carbon skeleton
-
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种用乙腈和硫化氢反应来制备硫代乙酰胺的改进方法，其中使用了一种附于聚合物载体上的胺催化剂。这种附于聚合物载体上的胺催化剂包括聚二甲基氨基吡啶树脂，用二乙烯苯交联的聚(4-乙烯吡啶)和载有4-(N-苯甲基-N-甲基氨基)吡啶的交联聚合物。
Description
本发明提供以硫化氢和乙腈为原料进行硫代乙酰胺制造的改进方法。
硫代乙酰胺是具有多种工业用途并已商业化生产的一种化学品。它是一种通用试剂，可用于进一步的化学合成。用硫化氢和乙腈来制取硫代乙酰氨的反应已为大家所熟悉。美国专利2421031公开了在500°F左右温度下，以8-14目的SiO2Al2O3胶为催化剂，得到按照硫化氢计算85％的产率。这种反应也可用各种碱催化。Jaworski等公开了在苯或甲苯中用三乙胺催化一个220小时的反应的情况(Polish J.Chem.，52(10)：2067-8，1978)。Girgis公开了胺类催化剂包括仲胺的使用情况(加拿大专利946392，1974；美国专利3852287，1974；美国专利3700664，1972)。不久前，公开了用烷基金属硫化物和氢硫化物催化氨基乙腈与硫化氢反应以制备氨基硫代乙酰胺(Moder等，EP0272909)。Moder等更喜欢用这类催化剂的原因是因为先前所用的胺类碱催化剂在反应完成后很难除掉。
本发明的目的是提供高收率、有效的制备硫代乙酰胺的方法，该方法的反应后处理程序最少，而且催化剂可重复使用。
本发明提供在聚合物载体上的胺催化剂的存在下用硫化氢和乙腈制备硫代乙酰胺的方法。由于使用硫化氢气体，这种反应是在加压下进行的。反应温度并不重要，但是为了节约时间降低成本，尽管在比较高的温度下所需的产品有一些分解，还是宁愿将反应温度维持在100至200℃。因此，最好使反应温度不超过150℃，如果能维持在120至130℃之间则更好。
本发明所用的反应物均是常规商品。使用时基本上是等摩尔数的，或者乙腈摩尔用量多于硫化氢摩尔用量。乙腈摩尔过量将使产品成为硫代乙酰胺的乙腈溶液，这种溶液产品处理方便，而且对于象下面谈到的一些后继反应正需要这种状态下的硫代乙酰胺。
这种反应可以在管式反应器中分批进行，也可以连续进行。催化剂的用量应能满足反应的需要，它取决于反应器大小和结构，同时也取决于混合和热交换的效率。本发明所用的聚合物载体上的胺催化剂具有一定的效力范围。这需要用本领域技术人员所熟知的常规探索实验来测定最佳条件；不管怎样，下在的实例提供了关于有效组合的指南。
聚合物载体上的胺催化剂可以是带有氨基官能团的任何聚合物，这种胺可以是烷基胺、芳香胺或者是如吡啶之类的杂环胺。聚合物载体上的胺也可以与第二种类型聚合物进行交联。为了方便进行去除和重新循环使用，最好这种聚合物载体上的胺催化剂是不溶于乙腈的。这种催化剂的例子有多相凝胶或大网格状树脂如用二乙烯苯交联的聚(4-乙烯基吡啶)，已发现在本发明中25％的交联是比较有效的。其它例子还有带有4-二甲基氨基吡啶(DMAP)基团或4-(N-苯甲基-N-甲基氨基)吡啶的聚合物。它也可以是主链聚合物如聚苯乙烯。在本发明中，优选的聚合物是具有DMAP基团的聚合物。
适用的聚合物载体上的胺催化剂来源广泛，存在形式众多。其中一个来源是Reilly Tar & Chemical Corporation(印第安纳波利斯)。有关如何制备这种聚合物载体上的胺催化剂的论述可参见PCT申请WO 90/03368(1990年4月)，此文也作为参考文献并入本文。欧洲专利申请0277824也公开了这种聚合物载体上的胺催化剂和它们在乙酸产中的使用情况。
聚合物载体上的胺催化剂具有众多优点。首先，它不溶于乙腈中，因此可用过滤的方法从反应物中进行回收。或者将反应物放入装有催化剂的容器，反应物可以自出入，而客器内的催化剂则不能掉出容器外，这种篮子式的容器可以悬挂在反应罐中，也可以装在器壁或折流板上。
第二，这种催化剂无需再生就可重新使用。反应物或硫代乙酰胺的污染并不降低其在下次反应中的催化活性。第三，这种催化剂催化的反应在适当的温度下可以使收率基本上达到100％，基本没有或完全没有分解的发生。
实施例1
将500毫升乙腈和10克Reilex425或Reilly Poly-DMAP树脂(Reilly Tar & Chemicals)的混合物放入一升的压热器中。将溶液进行搅拌并加热到110至130℃。加入硫化氢气体(34克，1.0摩尔)。随着硫化氢与乙腈反应的进行，压力从约145Psi降低至40Psi。反应2至18小时后，将混合物倒出反应器并进行过滤。滤出液是浓度为2M的硫代乙酰胺的乙腈溶液。本反应在不同条件下的收率见下表。该收率是按照反应中硫化氢的消耗量的百分数来报告的。
催化剂 时间(小时) 温度(℃) 收率(％)
Reilex425 18 120 100
Reilex425 3 130 100
Reilly poly-DMAP 2.25 120 100
在本发明中，每一种催化剂均已用在三次连续的反应中，但均没有催化效力上的损失。因此可以认为在本发明方法中聚合物载体上的胺催化剂可以使用多次而不会有催化效力上的实际损失。
硫代乙酰胺乙腈溶液的用途之一是用于制备噻唑和它的衍生物。下面就是这种反应的一个例子，硫代乙酰胺与4，4，4-三氟-2-氯乙酰醋酸乙酸反应生成2-甲基-4-(三氟甲基)噻唑-5-羧酸乙酯，产物还可继续制成杀菌剂噻唑羧酰替苯胺。在下面例子中所用的这种制备方法会有更详尽的描述，该法公开在共同未决的美国申请号......(与本案同时申请，代理人案号41-21(2951)A)，该文被引为参考文献。
实施例2
噻唑衍生物的制备
将按例1方法制备的硫代乙酰胺的乙腈(6.66摩尔)溶液放入一个烧瓶中，加入2-氯-4，4，4-三氟乙酰醋酸乙酯(5.06摩尔)，可以观察到有放热反应产生。加入三乙胺(13.64摩尔)并将混合物加热(约76℃)回流一小时。然后将所得溶液冷却，用标准方法将2-甲基-4-(三氟甲基)-噻唑-5-羧酸乙酯分离出来。
Claims (6)
1.硫代乙酰胺的制备方法，它包括在足够量的于一种聚合物载体上带有氨基功能团的催化剂的存在下，将乙腈与硫化氢进行反应。
2.权利要求1的方法，其中反应温度为100至150℃。
3.权利要求2的方法，其中反应温度为120至130℃。
4.权利要求1的方法，其中乙腈的摩尔数超过硫化氢的摩尔数。
5.权利要求1的方法，其中所述的聚合物载体上的胺催化剂包括接在聚合物的4-二甲基氨吡啶基团。
6.权利要求1的方法，其中所述的聚合物载体上的胺催化剂是一种大网格状的树脂颗粒。
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/927,997 US5284974A (en) | 1992-08-11 | 1992-08-11 | Process for the preparation of thioacetamide |
| CA002108227A CA2108227A1 (en) | 1992-08-11 | 1993-10-12 | Process for the preparation of thioacetamide |
| EP93870201A EP0648742B1 (en) | 1992-08-11 | 1993-10-14 | Improved process for the preparation of thioacetamide |
| ES93870201T ES2097484T3 (es) | 1992-08-11 | 1993-10-14 | Procedimiento mejorado para la preparacion de tioacetamida. |
| DE69307708T DE69307708T2 (de) | 1992-08-11 | 1993-10-14 | Verbessertes Verfahren zur Herstellung von Thioacetamid |
| AT93870201T ATE148107T1 (de) | 1992-08-11 | 1993-10-14 | Verbessertes verfahren zur herstellung von thioacetamid |
| JP5261017A JPH07126244A (ja) | 1992-08-11 | 1993-10-19 | チオアセトアミド製造の改良方法 |
| CN93119701A CN1040429C (zh) | 1992-08-11 | 1993-10-28 | 制备硫代乙酰胺的改进方法 |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/927,997 US5284974A (en) | 1992-08-11 | 1992-08-11 | Process for the preparation of thioacetamide |
| CA002108227A CA2108227A1 (en) | 1992-08-11 | 1993-10-12 | Process for the preparation of thioacetamide |
| EP93870201A EP0648742B1 (en) | 1992-08-11 | 1993-10-14 | Improved process for the preparation of thioacetamide |
| JP5261017A JPH07126244A (ja) | 1992-08-11 | 1993-10-19 | チオアセトアミド製造の改良方法 |
| CN93119701A CN1040429C (zh) | 1992-08-11 | 1993-10-28 | 制备硫代乙酰胺的改进方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1102182A CN1102182A (zh) | 1995-05-03 |
| CN1040429C true CN1040429C (zh) | 1998-10-28 |
Family
ID=36930207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93119701A Expired - Fee Related CN1040429C (zh) | 1992-08-11 | 1993-10-28 | 制备硫代乙酰胺的改进方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5284974A (zh) |
| EP (1) | EP0648742B1 (zh) |
| JP (1) | JPH07126244A (zh) |
| CN (1) | CN1040429C (zh) |
| AT (1) | ATE148107T1 (zh) |
| CA (1) | CA2108227A1 (zh) |
| DE (1) | DE69307708T2 (zh) |
| ES (1) | ES2097484T3 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145639A (zh) * | 2011-12-07 | 2013-06-12 | 中化蓝天集团有限公司 | 2-甲基-4-(三氟甲基)噻唑-5-甲酸的制备方法 |
| CN105777597A (zh) * | 2016-04-08 | 2016-07-20 | 张俊杰 | 一种硫代乙酰胺的制备方法 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE376020T1 (de) * | 2001-08-22 | 2007-11-15 | Bioartificial Gel Technologies Inc | Verfahren zu herstellung von aktivierten polyethylenglykolen |
| CN106083678A (zh) * | 2016-06-01 | 2016-11-09 | 张俊杰 | 一种负载催化剂制备硫代乙酰胺的方法 |
| FR3079909B1 (fr) | 2018-04-05 | 2022-10-14 | Microoled | Dispositif electroluminescent a resolution et fiabilite ameliorees |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852287A (en) * | 1970-03-26 | 1974-12-03 | Uniroyal Ltd | Preparation of thionamides |
| US3979452A (en) * | 1973-08-10 | 1976-09-07 | Merck & Co., Inc. | Thioformamide improved process |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2421031A (en) * | 1945-09-10 | 1947-05-27 | Phillips Petroleum Co | Process for synthesis of thioamides |
| US3700664A (en) * | 1970-03-26 | 1972-10-24 | Uniroyal Ltd | Preparation of thionamides |
| CA946392A (en) * | 1970-03-26 | 1974-04-30 | Uniroyal Ltd. | Preparation of thionamides |
| EP0272909A3 (en) * | 1986-12-24 | 1989-11-08 | Eli Lilly And Company | Synthesis of aminothioacetamides |
| EP0277824B1 (en) * | 1987-02-05 | 1994-04-27 | Reilly Industries, Inc. | Process for acetic acid preparation and heterogeneous catalyst for same |
| US5015706A (en) * | 1988-09-21 | 1991-05-14 | Reilly Industries, Inc., | Polymer-supported 4-(N-benzyl-N-methylamino)pyridine catalyst and process for same |
-
1992
- 1992-08-11 US US07/927,997 patent/US5284974A/en not_active Expired - Fee Related
-
1993
- 1993-10-12 CA CA002108227A patent/CA2108227A1/en not_active Abandoned
- 1993-10-14 ES ES93870201T patent/ES2097484T3/es not_active Expired - Lifetime
- 1993-10-14 AT AT93870201T patent/ATE148107T1/de not_active IP Right Cessation
- 1993-10-14 EP EP93870201A patent/EP0648742B1/en not_active Expired - Lifetime
- 1993-10-14 DE DE69307708T patent/DE69307708T2/de not_active Expired - Fee Related
- 1993-10-19 JP JP5261017A patent/JPH07126244A/ja active Pending
- 1993-10-28 CN CN93119701A patent/CN1040429C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852287A (en) * | 1970-03-26 | 1974-12-03 | Uniroyal Ltd | Preparation of thionamides |
| US3979452A (en) * | 1973-08-10 | 1976-09-07 | Merck & Co., Inc. | Thioformamide improved process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145639A (zh) * | 2011-12-07 | 2013-06-12 | 中化蓝天集团有限公司 | 2-甲基-4-(三氟甲基)噻唑-5-甲酸的制备方法 |
| CN103145639B (zh) * | 2011-12-07 | 2016-01-06 | 中化蓝天集团有限公司 | 2-甲基-4-(三氟甲基)噻唑-5-甲酸的制备方法 |
| CN105777597A (zh) * | 2016-04-08 | 2016-07-20 | 张俊杰 | 一种硫代乙酰胺的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0648742A1 (en) | 1995-04-19 |
| DE69307708D1 (de) | 1997-03-06 |
| CA2108227A1 (en) | 1995-04-13 |
| ATE148107T1 (de) | 1997-02-15 |
| JPH07126244A (ja) | 1995-05-16 |
| DE69307708T2 (de) | 1997-08-21 |
| EP0648742B1 (en) | 1997-01-22 |
| US5284974A (en) | 1994-02-08 |
| CN1102182A (zh) | 1995-05-03 |
| ES2097484T3 (es) | 1997-04-01 |
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