CN1312130C - 2－氨基甲基吡啶衍生物的制备方法 - Google Patents
2－氨基甲基吡啶衍生物的制备方法 Download PDFInfo
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- CN1312130C CN1312130C CNB2003801033286A CN200380103328A CN1312130C CN 1312130 C CN1312130 C CN 1312130C CN B2003801033286 A CNB2003801033286 A CN B2003801033286A CN 200380103328 A CN200380103328 A CN 200380103328A CN 1312130 C CN1312130 C CN 1312130C
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical class NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical class N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims description 8
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000007868 Raney catalyst Substances 0.000 claims description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- -1 sulphur compound Chemical class 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/61—Halogen atoms or nitro radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
通式(I)所示的2-氨基甲基吡啶衍生物或其盐的制备方法，式(I)中n表示0、1、2或3，X表示卤原子，各个Y可以相同或不同，且可以为卤原子、卤代烷基、烷氧基羰基或烷基磺酰基。
Description
本发明涉及由2-氰基吡啶衍生物的催化氢化制备2-氨基甲基吡啶衍生物的新方法。该衍生物可用作制备农药的中间体。
现已公开了一些用于制备氨基甲基吡啶的催化氢化反应。如P.N.Rylander所著“Hydrogenation Methods”(Best Synthetic Series，Academic Press出版)，(1985)，第148页中所述，当氰基吡啶被卤原子取代时，由于可能发生的脱卤竞争反应，从而存在额外的困难。
专利申请EP0409716揭示了在碘化物的存在下结合使用阮内镍和催化抑制剂。该方法的缺点是使用了催化抑制剂。在工业生产上应避免使用这种催化抑制剂。
专利申请WO 02/16322揭示了在醇溶剂中用金属催化剂(尤其是钯)进行上述反应。不过，该方法的缺点是高活性钯引起的脱卤反应。另外，钯是非常昂贵的催化剂，而且对催化剂毒物(如在制备2-氰基吡啶的过程中形成的硫化合物)非常敏感。因此，这种氢化方法不能用于工业规模。
现在，我们发现了没有上述缺点且能用于工业规模的2-氨基甲基吡啶衍生物的制备方法。
因此，本发明涉及一种通式(I)所示的2-氨基甲基吡啶衍生物或其盐的制备方法，
式(I)中：n表示0、1、2或3，
X表示卤原子，
各个Y可以相同或不同，且可以是卤原子、卤代烷基、烷氧基羰基和烷基磺酰基，
该方法包括在30～70℃的温度和1～50巴的氢气压力下在乙酸中用阮内镍使通式(II)所示的2-氰基吡啶衍生物或其盐氢化，
式(II)中n、X和Y如上所述。
就本发明的目的而言：
卤代烷基是指用一个或多个卤素原子取代的C1～C6烷基；
烷氧羰基是指C1～C6烷氧羰基。这种基团的合适例子可以是甲氧基羰基、乙氧基羰基、正丙氧基羰基和异丙氧基羰基；
烷基磺酰基是指C1～C6烷基磺酰基；
卤原子可以是溴原子、氯原子、碘原子或氟原子。
在以下说明书中，阮内镍表示为Ni-Ra。
用本发明方法得到的产物是可完全溶解于乙酸中的通式(I)表示的化合物的乙酸盐。催化剂可以通过过滤回收利用，且通式(I)表示的化合物乙酸盐的溶液用本领域中普通技术人员已知的方法进行化验。通式(I)表示的化合物乙酸盐相对于通式(II)表示的2-氰基吡啶衍生物的产率通常超过95％。45℃时，即使使用用水弄湿的Ni-Ra，在没有KI或KBr之类通常与钯催化剂一起使用的脱卤抑制剂存在的情况下一般也观察到不超过0.1％产率的脱卤产物。
本发明涉及通式(I)表示的化合物的制备方法。优选的是，通式(I)表示的化合物的不同特征可以相互独立地选自如下：
-关于X，X是氯；
-关于n，n为1；
-关于Y，Y是卤代烷基，Y优选为三氟甲基；
更优选地，本发明涉及通式(I)表示的化合物的制备方法，其中：
-X是氯；
-n为1；
-Y是三氟甲基。
本发明的方法特别适合于制备2-氨基甲基-3-氯-5-三氟甲基吡啶。
本发明的方法在30～70℃，更好在35～50℃的温度下进行。
本发明的方法在1～50巴，优选在2～30巴，更优选在10～20巴的氢气压力下进行。
本发明的方法在Ni-Ra的存在下进行。相对于通式(II)表示的2-氰基吡啶衍生物，Ni-Ra优选以1～20％的重量比加入。
本发明的方法特别适合于通过在40～50℃的温度和15～20巴的氢气压力下用Ni-Ra在乙酸中氢化3-氯-2-氰基-5-三氟甲基吡啶来制备2-氨基甲基-3-氯-5-三氟甲基吡啶。相对于通式(II)表示的2-氰基吡啶衍生物，Ni-Ra优选以1～20％的重量比加入。
催化剂可以按本领域中普通技术人员众所周知的方法回收利用。具体地说，催化剂可以方便地通过过滤加以回收利用。
现在参照如下实施例，详细说明本发明的方法。
2-氨基甲基-3-氯-5-三氟甲基吡啶的制备实施例
将400克乙酸和6克Ni-Ra(先用水洗涤至洗涤液的pH为7为止)加入到1升不锈钢反应器中。该反应器先用氮气后用氢气进行吹扫。加热反应器，使温度上升至40℃，用氢气将反应器压力升高至18巴。
用泵在2小时内加入120克3-氯-2-氰基-5-三氟甲基吡啶(0.571摩尔)。该反应是放热反应，所以温度升高至45℃。监测氢气消耗量。2小时后，不再消耗氢气，反应已进行完全。将混合物冷却至20℃，排空，然后用氮气吹扫。
过滤催化剂。用液相色谱化验2-氨基甲基-3-氯-5-三氟甲基吡啶乙酸盐的溶液。形成了0.558摩尔2-氨基甲基-3-氯-5-三氟甲基吡啶，相对于3-氯-2-氰基-5-三氟甲基吡啶，2-氨基甲基-3-氯-5-三氟甲基吡啶的产率为97％。仅得到0.05％产率的脱氯类似物。
Claims (12)
1.通式(I)所示的2-氨基甲基吡啶衍生物或其盐的制备方法，
式(I)中：n表示0、1、2或3，
X表示卤原子，
各个Y可以相同或不同，且选自卤原子、卤代烷基、烷氧基羰基和烷基磺酰基，
该方法包括在30～70℃的温度和1～50巴的氢气压力下在乙酸中用阮内镍使通式(II)所示的2-氰基吡啶衍生物或其盐氢化，
式(II)中n、X和Y如上所述。
2.如权利要求1所述的方法，其特征在于X是氯。
3.如权利要求1或2所述的方法，其特征在于n为1。
4.如权利要求1-3中任一项所述的方法，其特征在于Y是卤代烷基。
5.如权利要求4所述的方法，其特征在于Y是三氟甲基。
6.如权利要求1所述的方法，其特征在于X是氯，n为1，且Y为三氟甲基。
7.如权利要求6所述的方法，其特征在于通式(I)所示的化合物是2-氨基甲基-3-氯-5-三氟甲基吡啶。
8.如权利要求1-7中任一项所述的方法，其特征在于所述的温度选自35～50℃。
9.如权利要求1-8中任一项所述的方法，其特征在于所述的氢气压力选自2～30巴。
10.如权利要求9所述的方法，其特征在于所述的氢气压力选自10～20巴。
11.如权利要求1-10中任一项所述的方法，其特征在于相对于通式(II)所示的化合物，加入重量比为1～20重量％的阮内镍。
12.如权利要求7所述的方法，其特征在于所述的温度选自35～50℃，所述的氢气压力选自10～20巴，且相对于通式(II)所示的化合物，加入重量比为1～20重量％的阮内镍。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02356236A EP1422221A1 (en) | 2002-11-20 | 2002-11-20 | Novel process for the preparation of 2-aminomethylpyridine derivative |
| EP02356236.6 | 2002-11-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1711244A CN1711244A (zh) | 2005-12-21 |
| CN1312130C true CN1312130C (zh) | 2007-04-25 |
Family
ID=32187272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801033286A Expired - Lifetime CN1312130C (zh) | 2002-11-20 | 2003-11-18 | 2－氨基甲基吡啶衍生物的制备方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7456290B2 (zh) |
| EP (2) | EP1422221A1 (zh) |
| JP (1) | JP4599165B2 (zh) |
| KR (1) | KR101068069B1 (zh) |
| CN (1) | CN1312130C (zh) |
| AT (1) | ATE348811T1 (zh) |
| AU (1) | AU2003290121A1 (zh) |
| BR (1) | BRPI0314461B1 (zh) |
| DE (1) | DE60310609T2 (zh) |
| DK (1) | DK1565440T3 (zh) |
| ES (1) | ES2274297T3 (zh) |
| IL (1) | IL168416A (zh) |
| WO (1) | WO2004046114A1 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011056806A1 (en) * | 2009-11-03 | 2011-05-12 | Diakron Pharmaceuticals, Inc. | Process for the preparation of pyrazinone thrombin inhibitor and its intermediates |
| CN104557684B (zh) * | 2013-10-09 | 2017-05-10 | 李波 | 制备3‑氯‑2‑氨甲基‑5‑三氟甲基吡啶的方法 |
| EP3088390A1 (en) * | 2015-04-30 | 2016-11-02 | Bayer CropScience AG | Catalytic hydrogenation of substituted cyanopyridines |
| CN106883130B (zh) * | 2017-03-23 | 2018-12-11 | 泰州百力化学股份有限公司 | 一种制备卤代联苯胺的方法 |
| EP3489221A1 (en) | 2017-11-22 | 2019-05-29 | Bayer AG | Process for the preparation of fluopicolide |
| CN108325556A (zh) * | 2018-05-12 | 2018-07-27 | 长乐智高生物科技有限公司 | 一种中间体2,6-二羟基-3-氰基-4-三氟甲基吡啶的合成方法 |
| CN111170934B (zh) * | 2020-01-13 | 2021-07-13 | 大连九信精细化工有限公司 | 2-氨甲基-3-氯-5-三氟甲基吡啶醋酸镍络合物的解离方法 |
| CN111170932A (zh) * | 2020-01-13 | 2020-05-19 | 大连九信精细化工有限公司 | 一种2-氨甲基-5-三氟甲基吡啶盐的制备方法 |
| CN111138351A (zh) * | 2020-01-13 | 2020-05-12 | 大连九信精细化工有限公司 | 一种2-氨甲基-3-氯-5-三氟甲基吡啶醋酸盐的合成方法 |
| WO2024013736A1 (en) | 2022-07-12 | 2024-01-18 | Adama Makhteshim Ltd. | Process for preparing substituted benzamides |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042705A (zh) * | 1988-11-15 | 1990-06-06 | Cl药物股份公司 | 3，5-二甲基-4-甲氧基吡啶衍生法及用于该制法的新型中间产物 |
| WO2002016322A2 (en) * | 2000-08-25 | 2002-02-28 | Bayer Cropscience Sa | Process for the preparation of 2-aminoethylpyridines |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2649978B1 (fr) * | 1989-07-20 | 1991-10-25 | Rhone Poulenc Chimie | Procede d'hydrogenation de derives halogeno nitroaromatiques en presence d'iodures |
| JP3890452B2 (ja) * | 1996-10-02 | 2007-03-07 | 日本精化株式会社 | アミノメチルピリジン化合物の製造法 |
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2002
- 2002-11-20 EP EP02356236A patent/EP1422221A1/en not_active Withdrawn
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2003
- 2003-11-18 CN CNB2003801033286A patent/CN1312130C/zh not_active Expired - Lifetime
- 2003-11-18 DK DK03782483T patent/DK1565440T3/da active
- 2003-11-18 KR KR1020057009056A patent/KR101068069B1/ko active IP Right Grant
- 2003-11-18 US US10/535,723 patent/US7456290B2/en not_active Expired - Fee Related
- 2003-11-18 EP EP03782483A patent/EP1565440B1/en not_active Expired - Lifetime
- 2003-11-18 AU AU2003290121A patent/AU2003290121A1/en not_active Abandoned
- 2003-11-18 AT AT03782483T patent/ATE348811T1/de not_active IP Right Cessation
- 2003-11-18 DE DE60310609T patent/DE60310609T2/de not_active Expired - Lifetime
- 2003-11-18 ES ES03782483T patent/ES2274297T3/es not_active Expired - Lifetime
- 2003-11-18 BR BRPI0314461A patent/BRPI0314461B1/pt not_active IP Right Cessation
- 2003-11-18 WO PCT/EP2003/014892 patent/WO2004046114A1/en active IP Right Grant
- 2003-11-18 JP JP2004552709A patent/JP4599165B2/ja not_active Expired - Fee Related
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042705A (zh) * | 1988-11-15 | 1990-06-06 | Cl药物股份公司 | 3，5-二甲基-4-甲氧基吡啶衍生法及用于该制法的新型中间产物 |
| WO2002016322A2 (en) * | 2000-08-25 | 2002-02-28 | Bayer Cropscience Sa | Process for the preparation of 2-aminoethylpyridines |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0314461B1 (pt) | 2016-03-29 |
| DE60310609T2 (de) | 2007-11-08 |
| JP4599165B2 (ja) | 2010-12-15 |
| BR0314461A (pt) | 2005-07-26 |
| AU2003290121A1 (en) | 2004-06-15 |
| JP2006508143A (ja) | 2006-03-09 |
| KR20050102077A (ko) | 2005-10-25 |
| WO2004046114A1 (en) | 2004-06-03 |
| DK1565440T3 (da) | 2007-03-12 |
| US20060004206A1 (en) | 2006-01-05 |
| ATE348811T1 (de) | 2007-01-15 |
| DE60310609D1 (de) | 2007-02-01 |
| US7456290B2 (en) | 2008-11-25 |
| EP1565440B1 (en) | 2006-12-20 |
| EP1565440A1 (en) | 2005-08-24 |
| CN1711244A (zh) | 2005-12-21 |
| EP1422221A1 (en) | 2004-05-26 |
| IL168416A (en) | 2010-12-30 |
| ES2274297T3 (es) | 2007-05-16 |
| KR101068069B1 (ko) | 2011-09-28 |
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