CN1244564C - 农药化合物的制备方法 - Google Patents
农药化合物的制备方法 Download PDFInfo
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- CN1244564C CN1244564C CNB01810522XA CN01810522A CN1244564C CN 1244564 C CN1244564 C CN 1244564C CN B01810522X A CNB01810522X A CN B01810522XA CN 01810522 A CN01810522 A CN 01810522A CN 1244564 C CN1244564 C CN 1244564C
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000000361 pesticidal effect Effects 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- -1 pyrazole compound Chemical class 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims 2
- 238000005658 halogenation reaction Methods 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 125000001188 haloalkyl group Chemical group 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- HCMJWOGOISXSDL-UHFFFAOYSA-N (2-isothiocyanato-1-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(CN=C=S)C1=CC=CC=C1 HCMJWOGOISXSDL-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 125000004438 haloalkoxy group Chemical group 0.000 abstract 1
- 150000003217 pyrazoles Chemical class 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000005899 Fipronil Substances 0.000 description 5
- 229940013764 fipronil Drugs 0.000 description 5
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NHNUFAASKXPOQA-UHFFFAOYSA-N (3-acetamido-2-hydroxyphenyl)arsonic acid Chemical compound C(C)(=O)NC=1C(=C(C=CC1)[As](O)(=O)O)O NHNUFAASKXPOQA-UHFFFAOYSA-N 0.000 description 1
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical class OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 1
- NOIXNOMHHWGUTG-UHFFFAOYSA-N 2-[[4-[4-pyridin-4-yl-1-(2,2,2-trifluoroethyl)pyrazol-3-yl]phenoxy]methyl]quinoline Chemical class C=1C=C(OCC=2N=C3C=CC=CC3=CC=2)C=CC=1C1=NN(CC(F)(F)F)C=C1C1=CC=NC=C1 NOIXNOMHHWGUTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
一种制备通式(I)所示化合物的方法，其中R1为CN或CSNH2、R2为氢或氯、R3为卤素、卤代烷基、卤代烷氧基或SF5；所述方法包括将通式(II)所示化合物和质子源反应，其中R1、R2和R3如上所述。
Description
技术领域
本发明涉及一种制备取代吡唑化合物的方法。
背景技术
吡唑如5-氨基-1-芳基-3-氰基吡唑化合物及其衍生物，例如Fipronil，可以形成一类重要的杀虫剂。正如WO 00/35884和美国专利5,556,873所揭示的，某些取代5-N-烷基-N-烷氧乙酰氨基-1-芳基-3-氰基吡唑化合物具有有价值的杀虫性。
发明内容
我们已经研制了一种新的生产在制备取代吡唑农药化合物中有用的中间体化合物的合成路线。
因此本发明提供一种制备通式(I)所示化合物的方法，
式中：
n为1，X为碳原子；
R1为CN或CSNH2；
R2为氢或氯；
R3为卤素、卤代烷基、卤代烷氧基或SF5；
所述方法包括将通式(II)所示化合物和质子源反应，
其中n、X、R1、R2和R3如上所述。
用于本发明方法中的质子源宜为酸性水溶液例如盐酸水溶液。
所述反应宜在适当的溶剂或者在能或不能和水部分混溶的溶剂中进行。适当的溶剂包括烃类溶剂如甲苯或二甲苯。
所述反应用的质子源用量宜为0.1～2当量，更好为0.5～1.0当量。
所述反应宜在-50～200℃，更好为50～100℃的温度下进行。
至于R1、R2和R3，R1宜为CN，R2宜为氯，R3宜为卤代烷基，尤其是三氟甲基。
化合物(II)可以通过新颖合成路线制备，根据本发明的另一方面，提供一种制备上述化合物(II)的方法，该方法包括将通式(III)所示化合物和季铵盐反应，
其中n、X、R1、R2和R3如上所述。
所述季铵盐可以是四烷基铵的卤化物如碘化物或溴化物，更好为溴化四烷基铵。适当的溴化四烷基铵包括溴化四丁基铵。所述反应用的卤化物盐用量宜为0.01～2当量，更好为0.1～0.5当量。
所述反应宜在能或不能和水部分混溶的有机溶剂中进行。适当的溶剂包括烃类溶剂如甲苯或二甲苯。所述反应宜在50～100℃的温度下进行。
上述化合物(III)可以由已知包括将具有通式(IV)所示的Fipronil吡唑化合物和原甲酸三甲酯反应的合成路线制备。
此反应可以在酸性催化剂存在下进行。适当的催化剂包括对甲苯磺酸。
化合物(III)也可以用季铵盐处理，接着酸处理直接制备化合物(I)，而不需要离析化合物(II)。
化合物(I)也可以通过将Fipronil(化合物IV)和甲醛或甲醛三聚体或其化学等价物反应由此形成中间体化合物(V)来制备，
其中n、X、R1、R2和R3如上所述。
然后中间体化合物(V)可以和还原剂反应形成化合物(I)。合适的还原剂包括硼氢化钠。所述还原剂的用量可以是1～5当量。
通式(II)、(III)和(V)的某些化合物是新颖的化合物，根据本发明的另一方面尤其提供如下新颖的化合物：
3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-N-(甲酰基-N-甲氨基)-4-(三氟甲基亚硫酰基)吡唑(化合物II)，
3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-(甲氧基亚甲基氨基)-4-(三氟甲基亚硫酰基)吡唑(化合物III)，
3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-羟甲氨基-4-(三氟甲基亚硫酰基)吡唑(化合物V)。
本发明方法制备的化合物(I)可以用作原料用于形成更重要的已知具有杀虫性的吡唑，如以下通式(VI)所示：
式中：
R1为CN或CSNH2；
X为N或CR4；
R2和R4各自为氢或氯；
R3为卤素、卤代烷基、卤代烷氧基或-SF5；
R5和R6各自为烷基；
n为0，1或2。
已知在本文所参考的国际专利申请号WO 00/35884中记述了由化合物(I)制备此化合物的方法。更具体的说是化合物(I)在三乙胺存在下和乙氧乙酰氯反应制备化合物(VI)。
具体实施方式
现在，将参考以下非限制性实施例说明本发明。
实施例1
在回流下，在0.5当量对甲苯磺酸存在下使摩尔过量的原甲酸三甲酯和Fipronil(化合物IV)反应，制备3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-(甲氧基亚甲基氨基)-4-(三氟甲基亚硫酰基)吡唑(化合物III)。
此产物立即在100℃的二甲苯中用0.1当量碘化四丁基铵处理5小时，形成3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-(N-甲酰基-N-甲氨基)-4-(三氟甲基亚硫酰基)吡唑(化合物II)。将此介质立即和盐酸水溶液反应形成最终产物3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-甲氨基-4-(三氟甲基亚硫酰基)吡唑(化合物I)。
实施例2
将5当量甲醇钠(30％甲醇溶液)迅速加入0.437克Fipronil和1.4当量低聚甲醛在3毫升甲醇的悬浮液中，在20℃反应3小时和60℃反应1小时后形成3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-羟甲氨基-4-(三氟甲基亚硫酰基)吡唑(化合物V)。然后往此介质中加入1当量硼氢化钠，经过常规提取和色谱分离后形成3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-甲氨基-4-(三氟甲基亚硫酰基)吡唑(化合物I)。
Claims (5)
1.一种制备通式(I)所示化合物的方法，
式中：R1为CN；R2为氯；R3为三氟甲基；n为1，X为CR4，R4是氯；所述方法包括将通式(II)所示化合物和盐酸水溶液反应，
其中R1、R2、R3、n和X如上所述。
2.一种制备权利要求1中所述化合物(II)的方法，该方法包括将通式(III)
所示化合物和季铵盐反应，其中n、X、R1、R2和R3如权利要求1中所述。
3.权利要求2所述的方法，其特征在于所述季铵盐为卤化四烷基铵。
4.权利要求3所述的方法，其特征在于所述卤化四烷基铵是溴化四烷基铵。
5.一种3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-5-(N-甲酰基-N-甲氨基)-4-(三氟甲基亚硫酰基)吡唑化合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21080300P | 2000-06-09 | 2000-06-09 | |
| US60/210,803 | 2000-06-09 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510104171XA Division CN100400516C (zh) | 2000-06-09 | 2001-06-07 | 农药化合物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1432002A CN1432002A (zh) | 2003-07-23 |
| CN1244564C true CN1244564C (zh) | 2006-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510104171XA Expired - Fee Related CN100400516C (zh) | 2000-06-09 | 2001-06-07 | 农药化合物的制备方法 |
| CNA2007100893143A Pending CN101062920A (zh) | 2000-06-09 | 2001-06-07 | 除虫化合物的制备方法及其新的中间体 |
| CNB01810522XA Expired - Fee Related CN1244564C (zh) | 2000-06-09 | 2001-06-07 | 农药化合物的制备方法 |
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| CNB200510104171XA Expired - Fee Related CN100400516C (zh) | 2000-06-09 | 2001-06-07 | 农药化合物的制备方法 |
| CNA2007100893143A Pending CN101062920A (zh) | 2000-06-09 | 2001-06-07 | 除虫化合物的制备方法及其新的中间体 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US7199246B2 (zh) |
| EP (1) | EP1286969B1 (zh) |
| JP (2) | JP4954425B2 (zh) |
| KR (1) | KR100784935B1 (zh) |
| CN (3) | CN100400516C (zh) |
| AT (1) | ATE479661T1 (zh) |
| AU (2) | AU7637001A (zh) |
| BR (1) | BR0111654A (zh) |
| CA (1) | CA2407839C (zh) |
| DE (1) | DE60142962D1 (zh) |
| ES (1) | ES2347317T3 (zh) |
| HU (1) | HUP0301672A3 (zh) |
| IL (2) | IL152696A0 (zh) |
| MX (1) | MXPA02012113A (zh) |
| RU (2) | RU2291863C2 (zh) |
| WO (1) | WO2001094315A2 (zh) |
| ZA (2) | ZA200208986B (zh) |
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| IL163790A0 (en) * | 2002-03-05 | 2005-12-18 | Bayer Cropscience Sa | 5-Substituted-alkylaminopyrazole derivatives as pesticides |
| AU2003211629B8 (en) * | 2002-03-05 | 2009-01-22 | Boehringer Ingelheim Animal Health USA Inc. | 5-substituted-alkylaminopyrazole derivatives as pesticides |
| US8993613B2 (en) | 2013-04-17 | 2015-03-31 | The Hartz Mountain Corporation | Ectoparasiticidal formulations |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2422400A (en) * | 1944-04-07 | 1947-06-17 | Du Pont | Production of n-methylamides |
| ATE10272T1 (de) * | 1979-08-22 | 1984-11-15 | Sandoz Ag | Propenylamine, verfahren zu ihrer herstellung, sie enthaltende pharmazeutische zusammensetzungen und ihre verwendung als arzneimittel. |
| EP0215964B1 (en) * | 1985-09-10 | 1991-01-23 | Kawaken Fine Chemicals Co., Ltd. | Process for preparing cyclic urea derivatives |
| GB8713768D0 (en) * | 1987-06-12 | 1987-07-15 | May & Baker Ltd | Compositions of matter |
| US5232940A (en) | 1985-12-20 | 1993-08-03 | Hatton Leslie R | Derivatives of N-phenylpyrazoles |
| DE3719732A1 (de) * | 1987-06-12 | 1989-01-05 | Bayer Ag | Substituierte 5-methylamino-1-arylpyrazole |
| JPH0283376A (ja) * | 1988-09-19 | 1990-03-23 | Pfizer Pharmaceut Co Ltd | ベンゾオキサゾロン誘導体および抗アレルギー又は抗炎症組成物 |
| US4966898A (en) * | 1989-08-15 | 1990-10-30 | Merrell Dow Pharmaceuticals Inc. | 4-substituted 17β-(cyclopropylamino)androst-5-en-3β-ol and related compounds useful as C17-20 lyase inhibitors |
| NO179282C (no) * | 1991-01-18 | 1996-09-11 | Rhone Poulenc Agrochimie | Nye 1-(2-pyridyl)pyrazolforbindelser til kontroll av skadeinsekter |
| US5556873A (en) | 1993-02-24 | 1996-09-17 | Rhone-Poulenc Inc. | Pesticidal 1-aryl-5-(substituted alkyl (thio) amido)pyrazoles |
| AU746514B2 (en) * | 1996-12-24 | 2002-05-02 | Merial, Inc. | Pesticidal 1-arylpyrazoles |
| AR021608A1 (es) | 1998-12-11 | 2002-07-31 | Merial Ltd | Represion de artropodos en animales |
-
2001
- 2001-06-07 RU RU2002135674/04A patent/RU2291863C2/ru not_active IP Right Cessation
- 2001-06-07 MX MXPA02012113A patent/MXPA02012113A/es active IP Right Grant
- 2001-06-07 CN CNB200510104171XA patent/CN100400516C/zh not_active Expired - Fee Related
- 2001-06-07 ES ES01953994T patent/ES2347317T3/es not_active Expired - Lifetime
- 2001-06-07 HU HU0301672A patent/HUP0301672A3/hu unknown
- 2001-06-07 CN CNA2007100893143A patent/CN101062920A/zh active Pending
- 2001-06-07 JP JP2002501865A patent/JP4954425B2/ja not_active Expired - Lifetime
- 2001-06-07 WO PCT/EP2001/007398 patent/WO2001094315A2/en active Application Filing
- 2001-06-07 KR KR1020027016788A patent/KR100784935B1/ko not_active IP Right Cessation
- 2001-06-07 CN CNB01810522XA patent/CN1244564C/zh not_active Expired - Fee Related
- 2001-06-07 RU RU2006129645/04A patent/RU2439061C2/ru not_active IP Right Cessation
- 2001-06-07 DE DE60142962T patent/DE60142962D1/de not_active Expired - Lifetime
- 2001-06-07 EP EP01953994A patent/EP1286969B1/en not_active Expired - Lifetime
- 2001-06-07 BR BR0111654-1A patent/BR0111654A/pt not_active IP Right Cessation
- 2001-06-07 AT AT01953994T patent/ATE479661T1/de not_active IP Right Cessation
- 2001-06-07 AU AU7637001A patent/AU7637001A/xx active Pending
- 2001-06-07 AU AU2001276370A patent/AU2001276370B2/en not_active Ceased
- 2001-06-07 CA CA002407839A patent/CA2407839C/en not_active Expired - Fee Related
- 2001-06-07 US US10/297,676 patent/US7199246B2/en not_active Expired - Lifetime
- 2001-06-07 IL IL15269601A patent/IL152696A0/xx active IP Right Grant
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2002
- 2002-11-05 ZA ZA200208986A patent/ZA200208986B/xx unknown
- 2002-11-07 IL IL152696A patent/IL152696A/en not_active IP Right Cessation
- 2002-11-27 ZA ZA200209653A patent/ZA200209653B/en unknown
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2012
- 2012-02-09 JP JP2012025809A patent/JP2012136525A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE479661T1 (de) | 2010-09-15 |
| US7199246B2 (en) | 2007-04-03 |
| KR100784935B1 (ko) | 2007-12-17 |
| BR0111654A (pt) | 2003-05-20 |
| WO2001094315A3 (en) | 2002-04-18 |
| CA2407839A1 (en) | 2001-12-13 |
| MXPA02012113A (es) | 2003-04-25 |
| EP1286969A2 (en) | 2003-03-05 |
| US20040058819A1 (en) | 2004-03-25 |
| ES2347317T3 (es) | 2010-10-28 |
| CN1432002A (zh) | 2003-07-23 |
| JP4954425B2 (ja) | 2012-06-13 |
| CN100400516C (zh) | 2008-07-09 |
| HUP0301672A3 (en) | 2005-01-28 |
| DE60142962D1 (de) | 2010-10-14 |
| AU7637001A (en) | 2001-12-17 |
| RU2291863C2 (ru) | 2007-01-20 |
| EP1286969B1 (en) | 2010-09-01 |
| HUP0301672A2 (hu) | 2003-08-28 |
| IL152696A0 (en) | 2003-06-24 |
| RU2006129645A (ru) | 2008-02-27 |
| CA2407839C (en) | 2009-09-08 |
| CN101062920A (zh) | 2007-10-31 |
| JP2003535848A (ja) | 2003-12-02 |
| AU2001276370B2 (en) | 2006-08-03 |
| JP2012136525A (ja) | 2012-07-19 |
| WO2001094315A2 (en) | 2001-12-13 |
| IL152696A (en) | 2008-08-07 |
| KR20030007931A (ko) | 2003-01-23 |
| RU2439061C2 (ru) | 2012-01-10 |
| ZA200208986B (en) | 2003-11-04 |
| ZA200209653B (en) | 2004-02-27 |
| CN1740162A (zh) | 2006-03-01 |
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