CN1161354C - 制备杂环化合物的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims description 17
- 150000002391 heterocyclic compounds Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical group CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- WTUAWWLVVCGTRG-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-ylcyanamide Chemical compound N#CNC1=NCCS1 WTUAWWLVVCGTRG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CNDPJIYEKZBFEZ-UHFFFAOYSA-N 2,5-dichloro-2-methyl-1H-pyridine Chemical compound ClC1(NC=C(C=C1)Cl)C CNDPJIYEKZBFEZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- -1 Ethylidene Chemical group 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SKCNYHLTRZIINA-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)pyridine Chemical compound ClCC1=CC=C(Cl)N=C1 SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/416—2,5-Pyrrolidine-diones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Pyridine Compounds (AREA)
- Hydrogenated Pyridines (AREA)
- Saccharide Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
本申请涉及通式(I)化合物的制备方法，其中R1，A，X和Z分别如说明书中定义，包括使通式(II)化合物，其中A和X分别如说明书中定义，与通式(III)化合物反应，其中Z，R1和M1分别如说明书中定义。
Description
技术领域
本发明涉及通过对适宜前体烷基化而制备已知杂环化合物的新方法。
背景技术
在非质子传递溶剂中进行的该烷基化反应是已知的(EP A2 0235 725)。
通过在醇中使未取代的环氮原子烷基化而制备不饱和的杂环化合物也是已知的(EP A2 0259 738)。
在这些例子中，产品需要随后纯化以达到足够的纯度；而且用已知方法获得的收率是不够的。
发明内容
现在发现通式(I)化合物
其中
R1代表氢原子或烷基，
A代表亚乙基，该亚乙基可以被烷基取代，或代表可以被烷基取代的三亚甲基，
X代表氧或硫原子或下式基团
其中
R3代表氢原子或烷基，和
Z代表任选取代的含有至少两个选自氧原子，硫原子和氮原子的杂原子的5-或6-元杂环基，或代表任选取代的3-或4-吡啶基，
可以通过使式(II)化合物
其中
A和X分别定义如上
与式(III)化合物
其中
R1和Z分别定义如上，且
M1代表卤子或基团-OSO2-M2
其中
M2代表低级烷基，芳基或OM3，
其中
M3代表低级烷基或碱金属，
在质子溶剂存在下，如果合适，在碱存在下反应，然后用醇结晶而制备。
本发明方法避免了重结晶的纯化步骤，该步骤是迄今为止的现有技术所必须的又是需要减少的一步操作。
令人惊讶地，本发明方法所得的收率比现有技术方法的收率高得多。
虽然在本发明方法中式(III)化合物与式(II)化合物的反应是在质子溶剂中进行的，但与所预料的相反，未观察到Wlliamson反应(见有机化学教科书)中醚的形成。
在通式I，II和III中，
R1优选代表氢原子或C1-C3烷基，特别优选为氢原子；
A优选代表可以分别被C1-C3烷基取代的亚乙基或三亚甲基，特别优选亚乙基；
X优选代表氧原子或硫原子，特别优选为硫原子；
Z优选代表含有2个选自氧原子，硫原子和氮原子的杂原子的卤代5-或6-元杂环或代表卤代3-或4-吡啶基，特别优选卤代的噻唑基或3-吡啶基，非常优选2-氯-吡啶-5-基；
M优选代表Cl，Br，甲苯磺酰基或OSO2OK，特别优选Cl或Br。
特别优选的式(I)化合物是下列通式(Ia)化合物
该化合物可以通过使下式化合物
与下式化合物
反应而制备。
在与烷基，烷氧基，烷硫基或烷基甲硅烷基相关的术语中，术语“低级”代表C1-C6，优选C1-C4，-烷基，-烷氧基，-烷硫基或-烷基甲硅烷基。
特别适宜的极性质子溶剂是水和醇或水和醇的混合物。如果所用溶剂是醇(并且优选为醇)，通式(I)化合物可以在修饰中直接获得，这对其用作植物保护剂是有利的，并且得到所需纯度。
可以列举醇的实例有：
-一级醇，如甲醇，乙醇，丙醇，丁醇，2-甲基-1-丙醇，1-戊醇，苄醇，
-二级醇，如异丙醇，仲丁醇，2-戊醇，叔醇，如叔丁醇。
特别优选的溶剂是不与或仅部分与水混溶的醇，如异丁醇或正丁醇或戊醇，特别优选正丁醇。
如果适宜，该方法可以在碱存在下进行。可以列举碱的实例有：碱金属氢氧化物和碱土金属氢氧化物，如NaOH，KOH，Ca(OH)2，碱金属碳酸盐或碳酸氢盐，如Na2CO3，Li2CO3，K2CO3，Cs2CO3或NaHCO3和KHCO3。优选K2CO3，NaOH和KHCO3，特别优选K2CO3。
通式(II)化合物可以用碱金属或碱土金属盐的固体或溶解的形式。
如果反应是在水或水/醇混合物中进行，该方法可以在PH为8至13的范围内进行。
所用催化剂可以是相转移催化剂，如果适宜可以是四级铵卤化物，如氯化四丁基铵等。
该方法可以在宽的温度范围内进行，例如在30℃和100℃，优选在50℃和80℃之间进行。该反应优选在大气压下进行；但是，也可以在减压或加压下进行。
在该方法实施时，例如1mol通式(II)化合物与1至1.3mol，优选1至1.1mol式(III)化合物在PH8-9并在极性溶剂，如丁醇中，在0.6至2mol，优选1至1.3mol碱如碳酸钾存在下，并且如果合适在催化剂如氯化四丁基铵存在下反应。
该反应也可以在初始加入通式(II)化合物的碱金属盐或碱土金属盐以溶解或悬浮的形式与相应量的通式(III)化合物在反应温度下进行。
通式(II)和(III)化合物是已知且公开于EP0235725中(该文献在此引用)。
通式(I)化合物适宜，例如用作杀虫剂(EP A2 0235752，EP A2 0259738)。
具体实施方式
下列实施例说明本发明的主题，但不以任何方式限制本发明。
实施例1
将0.3mol 2-氰基亚氨基噻唑烷和0.315mol 2-氯-5-氯-甲基吡啶溶解在240g正丁醇中，将该溶液加热至80℃。在此温度下，计量加入0.36mol碳酸钾，将混合物在80℃搅拌2小时。冷却(至65℃)后，加入250g水并将水相和有机相分离。然后将有机相在50℃搅拌3小时并随后在3小时内将其冷却至3℃。过滤沉淀的产品并干燥；得到62.3g(理论值的83％)。M.P.：135℃。
实施例2
将0.3mol 2-氰基亚氨基噻唑烷和0.315mol 2-氯-5-氯-甲基吡啶和0.015mol溴化四丁基铵悬浮在水中，将悬浮液加热至60℃。将反应混合物的PH值用NaOH持续保持在8至8.5。在60℃反应2小时后，在此温度下分离水相和有机相并将有机相用200ml丁醇稀释再在50℃搅拌3小时。在3小时内，将混合物冷却至3℃，将沉淀的产品用抽吸法过滤；得到55.5g(理论值的72％)。
实施例3
将39.3g浓度为97％的2-氰基亚氨基噻唑烷(＜＝0.3mol)溶解在250g浓度为80％的正丁醇(含有20％的水)中并与26.7g浓度为45％的氢氧化钠水溶液(0.3mol)混合。将所得的浅绿色溶液在65℃与49.5g浓度为95％的2-氯-5-氯甲基吡啶(0.29mol)混合。反应3.5小时后，加入190g水并进行相分离。从有机相中蒸出60g正丁醇/水。然后将有机相冷却至50℃。加入种晶并连续冷却至0℃。在该温度下，将混合物搅拌3小时结晶。过滤并干燥得到61.8g纯度为96％的产品(理论值的87％)。
Claims (4)
1.制备通式(I)化合物的方法
其中
R1代表氢原子或C1-C3烷基，
A代表亚乙基，该亚乙基可以被C1-C3烷基取代，或代表可以被C1-C3烷基取代的三亚甲基，
X代表氧或硫原子，
Z代表卤代5-或6-元杂环，其中含有至少两个选自氧原子，硫原子和氮原子的杂原子，或代表卤代3-或4-吡啶基，
其特征在于使式(II)化合物
其中
A和X定义如上
与式(III)化合物
其中R1和Z各自定义如上且
M1代表Cl、Br、甲苯磺酰基或OSO2-OK，
在选自异丁醇、正丁醇或戊醇的醇的存在下以及在或不在碱存在下反应。
2.根据权利要求1的方法，其特征在于使A代表亚乙基，X代表硫原子的式(II)化合物与R1代表氢，Z代表2-氯-吡啶-5-基，M1代表Cl或Br的式(III)化合物反应。
3.根据权利要求1制备通式(Ia)化合物的方法，
其特征在于使通式(IIa)化合物与通式(IIIa)化合物反应
4.根据权利要求1-3任一项的方法，其特征在于使用正丁醇。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904310A DE19904310A1 (de) | 1999-01-28 | 1999-01-28 | Verfahren zur Herstellung heterocyclischer Verbindungen |
| DE19904310.8 | 1999-01-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1269363A CN1269363A (zh) | 2000-10-11 |
| CN1161354C true CN1161354C (zh) | 2004-08-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001045075A Expired - Lifetime CN1161354C (zh) | 1999-01-28 | 2000-01-28 | 制备杂环化合物的方法 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US6211379B1 (zh) |
| EP (1) | EP1024140B1 (zh) |
| JP (1) | JP2000219688A (zh) |
| KR (1) | KR100632521B1 (zh) |
| CN (1) | CN1161354C (zh) |
| AT (1) | ATE221530T1 (zh) |
| BR (1) | BR0000184B1 (zh) |
| CZ (1) | CZ297921B6 (zh) |
| DE (2) | DE19904310A1 (zh) |
| DK (1) | DK1024140T3 (zh) |
| ES (1) | ES2179798T3 (zh) |
| HK (1) | HK1031871A1 (zh) |
| HU (1) | HU225245B1 (zh) |
| IL (1) | IL134228A (zh) |
| ZA (1) | ZA200000357B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2369404C (en) * | 1999-06-23 | 2010-06-08 | Syngenta Participations Ag | Method of producing nitroguanidine- and nitroenamine derivatives |
| ES2215120T3 (es) | 2000-01-19 | 2004-10-01 | Bayer Cropscience Ag | Procedimiento para la obtencion de compuestos heterociclicos. |
| US20150005502A1 (en) | 2011-09-02 | 2015-01-01 | Bayer Intellectual Property Gmbh | Process for preparing [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]cyanamide |
| WO2017211594A1 (de) | 2016-06-06 | 2017-12-14 | Bayer Cropscience Aktiengesellschaft | Verfahren zur herstellung heterocyclischer verbindungen |
| CN107629045A (zh) * | 2017-11-10 | 2018-01-26 | 上海生农生化制品股份有限公司 | 一种噻虫啉的水相合成方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5933283A (ja) * | 1982-08-19 | 1984-02-23 | Fujimoto Seiyaku Kk | イソチオウレア誘導体およびその製造法 |
| HU188852B (en) * | 1983-03-16 | 1986-05-28 | Richter Gedeon Vegyeszeti Gyar Rt,Hu | Process for producing thiazolidine derivatives active against gastric ulcer and intestinal ulcer |
| JPH0717621B2 (ja) * | 1986-03-07 | 1995-03-01 | 日本バイエルアグロケム株式会社 | 新規ヘテロ環式化合物 |
| JPH07121909B2 (ja) * | 1986-09-10 | 1995-12-25 | 日本バイエルアグロケム株式会社 | 新規複素環式化合物及び殺虫剤 |
-
1999
- 1999-01-28 DE DE19904310A patent/DE19904310A1/de not_active Withdrawn
-
2000
- 2000-01-17 EP EP00100235A patent/EP1024140B1/de not_active Expired - Lifetime
- 2000-01-17 DK DK00100235T patent/DK1024140T3/da active
- 2000-01-17 ES ES00100235T patent/ES2179798T3/es not_active Expired - Lifetime
- 2000-01-17 DE DE50000320T patent/DE50000320D1/de not_active Expired - Lifetime
- 2000-01-17 AT AT00100235T patent/ATE221530T1/de active
- 2000-01-18 JP JP2000009059A patent/JP2000219688A/ja active Pending
- 2000-01-20 US US09/488,436 patent/US6211379B1/en not_active Expired - Lifetime
- 2000-01-20 KR KR1020000002597A patent/KR100632521B1/ko active IP Right Grant
- 2000-01-26 IL IL13422800A patent/IL134228A/en not_active IP Right Cessation
- 2000-01-27 CZ CZ20000322A patent/CZ297921B6/cs not_active IP Right Cessation
- 2000-01-27 ZA ZA200000357A patent/ZA200000357B/xx unknown
- 2000-01-27 BR BRPI0000184-8A patent/BR0000184B1/pt not_active IP Right Cessation
- 2000-01-28 HU HU0000366A patent/HU225245B1/hu not_active IP Right Cessation
- 2000-01-28 CN CNB001045075A patent/CN1161354C/zh not_active Expired - Lifetime
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2001
- 2001-03-30 HK HK01102337A patent/HK1031871A1/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| HU225245B1 (en) | 2006-08-28 |
| HU0000366D0 (en) | 2000-04-28 |
| KR100632521B1 (ko) | 2006-10-09 |
| KR20010006582A (ko) | 2001-01-26 |
| CZ2000322A3 (cs) | 2000-09-13 |
| CZ297921B6 (cs) | 2007-05-02 |
| EP1024140A1 (de) | 2000-08-02 |
| HUP0000366A2 (hu) | 2000-12-28 |
| US6211379B1 (en) | 2001-04-03 |
| CN1269363A (zh) | 2000-10-11 |
| DE50000320D1 (de) | 2002-09-05 |
| ZA200000357B (en) | 2000-08-15 |
| ATE221530T1 (de) | 2002-08-15 |
| BR0000184A (pt) | 2000-09-05 |
| HUP0000366A3 (en) | 2001-12-28 |
| ES2179798T3 (es) | 2003-02-01 |
| JP2000219688A (ja) | 2000-08-08 |
| IL134228A0 (en) | 2001-04-30 |
| BR0000184B1 (pt) | 2010-10-19 |
| EP1024140B1 (de) | 2002-07-31 |
| HK1031871A1 (en) | 2001-06-29 |
| IL134228A (en) | 2002-11-10 |
| DE19904310A1 (de) | 2000-08-03 |
| DK1024140T3 (da) | 2002-11-04 |
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