JP4588989B2 - 5−ホルミル−2−フリルホウ酸の製法 - Google Patents
5−ホルミル−2−フリルホウ酸の製法 Download PDFInfo
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- JP4588989B2 JP4588989B2 JP2003331956A JP2003331956A JP4588989B2 JP 4588989 B2 JP4588989 B2 JP 4588989B2 JP 2003331956 A JP2003331956 A JP 2003331956A JP 2003331956 A JP2003331956 A JP 2003331956A JP 4588989 B2 JP4588989 B2 JP 4588989B2
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- Prior art keywords
- acid
- formyl
- furylboric
- process according
- solvent
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- BVDYCMMQBBNFSG-UHFFFAOYSA-N (5-formylfuran-2-yl)oxyboronic acid Chemical compound OB(O)OC1=CC=C(C=O)O1 BVDYCMMQBBNFSG-UHFFFAOYSA-N 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002955 isolation Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011260 aqueous acid Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- SEILDMUKBMYIEZ-UHFFFAOYSA-N Furfural diethyl acetal Chemical compound CCOC(OCC)C1=CC=CO1 SEILDMUKBMYIEZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 4
- BCFKMVCTVAXNDB-UHFFFAOYSA-N boric acid furan-2-carbaldehyde Chemical compound B(O)(O)O.C(C1=CC=CO1)=O BCFKMVCTVAXNDB-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 abstract description 30
- -1 boric acid ester Chemical class 0.000 abstract description 19
- 239000004327 boric acid Substances 0.000 abstract description 9
- 125000006239 protecting group Chemical group 0.000 abstract description 6
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract description 5
- JUWYQISLQJRRNT-UHFFFAOYSA-N (5-formylfuran-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)O1 JUWYQISLQJRRNT-UHFFFAOYSA-N 0.000 abstract 1
- 238000010626 work up procedure Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000010306 acid treatment Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UQQJPTWUHRGTLU-UHFFFAOYSA-N C(C)OC(C1=CC=C(O1)OB(O)O)OCC Chemical compound C(C)OC(C1=CC=C(O1)OB(O)O)OCC UQQJPTWUHRGTLU-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical group C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Chemical group OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- WJTFHWXMITZNHS-UHFFFAOYSA-N 5-bromofuran-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)O1 WJTFHWXMITZNHS-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- QQIRAVWVGBTHMJ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;lithium Chemical compound [Li].C[Si](C)(C)N[Si](C)(C)C QQIRAVWVGBTHMJ-UHFFFAOYSA-N 0.000 description 1
- FYJKEHKQUPSJDH-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane;potassium Chemical compound [K].C[Si](C)(C)N[Si](C)(C)C FYJKEHKQUPSJDH-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
a)ホウ酸エステルおよび2−フルアルデヒドからなる組成物に塩基を添加する工程、ここで2−フルアルデヒドのホルミル官能基は保護基で保護されている、および
b)工程a)の反応混合物の酸性処理の工程、および
c)5−ホルミル−2−フリルホウ酸の単離の工程。
a)トリイソプロピルボレートおよびフルフラールジエチルアセタール、および場合により溶剤からなる組成物にリチウムジイソプロピルアミドを添加する工程、
b)工程a)の反応混合物の酸性処理の工程、および
c)5−ホルミル−2−フリルホウ酸の単離の工程からなる。
機械的撹拌機、内部温度計および添加ロートを有する乾燥させた500ml三頸フラスコ中に窒素雰囲気下にフルフラールジエチルアセタール20.16g(0.118モル)、トリイソプロピルボレート33.4g(0.177モル)および無水THF40mlを装入する。反応混合物の水分含量はカール・フィッシャー滴定法により測定し、かつ800μg/mlより少量の水が測定された。この溶液を−10℃の開始温度に冷却した。温度を−10℃〜0℃に保持しつつ、LDA84ml(25質量%、ChemmetalからのTHF、ヘプタン、エチルベンゼン1.84M溶液、濃度は滴定により測定、1.3当量)を反応混合物中に添加ロートを介して1時間にわたって添加した。その後、カニューレを用いて反応混合物を、濃塩酸33mlと水55mlとを混合することにより得られた前冷却した水性酸に移した。反応温度を30℃未満の温度に保持した。生じた5−ホルミル−2−フリルホウ酸の淡褐色スラリーを0℃に冷やし、濾過した。このフィルターケーキを冷水20mlで2回洗浄すると、湿潤ケーキ17.6gが得られた。乾燥(40℃、真空オーブン)によりオフホワイトの生成物12.41gが得られた。5−ホルミル−2−フリルホウ酸の全収率は75%であった。粗生成物中の未反応のフルフラールの含量は0.1質量未満であることが測定された。
機械的撹拌機を備える2 l頸付きフラスコに5−ホルミル−2−フリルホウ酸130g、アセトニトリル900mlおよび水400mlを装入する。生じたスラリーを、固体が溶液中に行く点で、加熱環流させた。暗色溶液を0℃に一夜冷却した。生じたスラリーを濾過し、アセトニトリル100mlで洗浄した。乾燥により、5−ホルミル−2−フリルホウ酸116.7gが白色結晶固体として得られる(収率90%)。
Claims (7)
- 以下の工程:
a)トリイソプロピルボレートおよびフルフラールジエチルアセタールからなる組成物にリチウムジイソプロピルアミドを添加する工程、
b)工程a)の反応混合物の酸性処理の工程、および
c)5−ホルミル−2−フリルホウ酸の単離の工程
からなる、5−ホルミル−2−フリルホウ酸の製法。 - 溶剤が工程a)中に存在する、請求項1記載の製法。
- 溶剤がテトラヒドロフラン、1,2−ジメトキシエタン、1,4−ジオキサンおよびこれらの混合物からなる群から選択される、請求項2記載の製法。
- 工程b)の酸性処理を水性酸を使用して実施する、請求項1記載の製法。
- 酸が塩酸、硫酸、クエン酸、酢酸、ギ酸およびこれらの混合物からなる群から選択される、請求項4記載の製法。
- 工程c)の5−ホルミル−フラン−ホウ酸の単離を濾過、遠心分離および/または結晶化により実施する、請求項4記載の製法。
- 工程c)の後に5−ホルミル−フラン−ホウ酸を更に再結晶を用いて精製する、請求項1から6までのいずれか1項記載の製法。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02021439 | 2002-09-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2004115520A JP2004115520A (ja) | 2004-04-15 |
JP4588989B2 true JP4588989B2 (ja) | 2010-12-01 |
Family
ID=32187153
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003331956A Expired - Fee Related JP4588989B2 (ja) | 2002-09-25 | 2003-09-24 | 5−ホルミル−2−フリルホウ酸の製法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US7045640B2 (ja) |
EP (1) | EP1403271B1 (ja) |
JP (1) | JP4588989B2 (ja) |
AT (1) | ATE310006T1 (ja) |
CA (1) | CA2442252A1 (ja) |
DE (1) | DE60302309T2 (ja) |
DK (1) | DK1403271T3 (ja) |
ES (1) | ES2252600T3 (ja) |
SI (1) | SI1403271T1 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005023989A1 (de) * | 2005-05-20 | 2006-11-23 | Clariant Lsm (Deutschland) Gmbh | Verfahren zur Herstellung von 2-Formylfuran-4-boronsäure durch Metallierung von 4-Halogenfurfuralacetalen in Gegenwart geeigneter Boronsäureester oder -anhydride |
ATE482962T1 (de) | 2005-10-24 | 2010-10-15 | Chemetall Gmbh | Verfahren zur herstellung funktionalisierter fünfringheterocyclen und deren verwendung |
US7842355B2 (en) * | 2005-11-01 | 2010-11-30 | Applied Materials, Inc. | System and method for modulation of power and power related functions of PECVD discharge sources to achieve new film properties |
CZ2012712A3 (cs) | 2012-10-17 | 2014-04-30 | Zentiva, K.S. | Nový způsob výroby klíčového intermediátu výroby lapatinibu |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3262270D1 (en) * | 1981-03-20 | 1985-03-28 | Ciba Geigy Ag | Process for colouring highly molecular organic material and polycyclic pigments |
AU568298B2 (en) * | 1982-05-17 | 1987-12-24 | Ciba Specialty Chemicals Holding Inc. | Synthesis of pyrrol0 (3,4-c) pyrrole pigments |
DE3584138D1 (de) * | 1984-11-07 | 1991-10-24 | Ciba Geigy Ag | Pigmentmischungen. |
TW372244B (en) * | 1993-07-29 | 1999-10-21 | Ciba Sc Holding Ag | Process for producing novel finely divided highly transparent diketopyrrolopyrrole pigments |
EP0704497B1 (de) * | 1994-09-28 | 1999-12-15 | Ciba SC Holding AG | Mischkristalle und feste Lösungen von 1,4-Diketopyrrolopyrrolen |
MX9703687A (es) * | 1994-11-24 | 1997-08-30 | Hoffmann La Roche | Nuevas bencil pirimidinas. |
TW370546B (en) * | 1995-09-18 | 1999-09-21 | Ciba Sc Holding Ag | Solid solutions of 1,4-diketopyrrolopyrroles |
DE69701232T2 (de) * | 1996-03-06 | 2000-08-10 | Ciba Specialty Chemicals Holding Inc., Basel | Ternäre feste Lösungen von 1,4-Diketopyrrolopyrrolen und Chinacridonen |
US20010015154A1 (en) * | 2000-01-27 | 2001-08-23 | Roman Lenz | Ternary pigment compositions |
-
2003
- 2003-08-21 DE DE60302309T patent/DE60302309T2/de not_active Expired - Lifetime
- 2003-08-21 AT AT03018657T patent/ATE310006T1/de active
- 2003-08-21 ES ES03018657T patent/ES2252600T3/es not_active Expired - Lifetime
- 2003-08-21 DK DK03018657T patent/DK1403271T3/da active
- 2003-08-21 EP EP03018657A patent/EP1403271B1/en not_active Expired - Lifetime
- 2003-08-21 SI SI200330161T patent/SI1403271T1/sl unknown
- 2003-09-17 US US10/663,798 patent/US7045640B2/en not_active Expired - Fee Related
- 2003-09-23 CA CA002442252A patent/CA2442252A1/en not_active Abandoned
- 2003-09-24 JP JP2003331956A patent/JP4588989B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE60302309D1 (de) | 2005-12-22 |
JP2004115520A (ja) | 2004-04-15 |
SI1403271T1 (sl) | 2006-04-30 |
EP1403271A1 (en) | 2004-03-31 |
ES2252600T3 (es) | 2006-05-16 |
ATE310006T1 (de) | 2005-12-15 |
EP1403271B1 (en) | 2005-11-16 |
DK1403271T3 (da) | 2006-03-20 |
US20040127725A1 (en) | 2004-07-01 |
CA2442252A1 (en) | 2004-03-25 |
DE60302309T2 (de) | 2006-07-20 |
US7045640B2 (en) | 2006-05-16 |
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