EP1521745A1 - Procede de production de sels d'imidazolium - Google Patents

Procede de production de sels d'imidazolium

Info

Publication number
EP1521745A1
EP1521745A1 EP03763595A EP03763595A EP1521745A1 EP 1521745 A1 EP1521745 A1 EP 1521745A1 EP 03763595 A EP03763595 A EP 03763595A EP 03763595 A EP03763595 A EP 03763595A EP 1521745 A1 EP1521745 A1 EP 1521745A1
Authority
EP
European Patent Office
Prior art keywords
radicals
imidazolium
substituted
triflate
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03763595A
Other languages
German (de)
English (en)
Inventor
Frank Glorius
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP1521745A1 publication Critical patent/EP1521745A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00

Definitions

  • the invention relates to a process for the preparation of imidazolium salts by reacting bisimines or corresponding heterocycles with a combination of alkylating agent and a metal salt as a promoter of the reaction.
  • This method allows a large number of imidazolium salts to be prepared under mild reaction conditions and in good yields.
  • This synthetic process can be used to prepare novel imidazolium salts of the general formulas II, IV and XI (in particular chiral enantiomerically pure and highly substituted imidazolium salts) and to produce known imidazolium salts of the general formula VI in improved yield.
  • the imidazolium salts can be converted into N-heterocyclic carbenes and their transition metal complexes by deprotonation. These complexes have high thermal and chemical stability, as well as very good catalyst properties in the homogeneous catalysis of various reactions.
  • N-heterocyclic carbenes based on the imidazole backbone as ligands in homogeneous transition metal catalysis has developed into an important area of research. Methods for CC, CO and CN bond formation as well as applications in olefin metathesis have become particularly important.
  • imidazolium salts The deprotonation of imidazolium salts to produce the corresponding N-heterocyclic carbenes and their transition metal complexes has been widely used as the method of choice. Synthetic methods for imidazolium salts that can be used in general are therefore of great interest. Numerous synthetic methods for imidazolium salts already exist. (Review: WA Herrmann, Angew. Chem. (2002) 114, 1342.) Starting from glyoxal, primary amines and formaldehyde, imidazolium salts can be formed under acidic reaction conditions (US Patent No. 5182405).
  • Isolated bisimines obtained from glyoxal can also be reacted with acid and formaldehyde or with chloromethyl ethyl ether to give imidazolium salts (US Patent No. 5077414).
  • Unbalanced 1.3 disubstituie 'rte imidazolium can be obtained by alkylation of mono-substituted imidazoles.
  • the monosubstituted imidazoles required for this can be obtained analogously to the synthesis from glyoxal, formaldehyde and a mixture of a primary amine with ammonium chloride mentioned above.
  • Saturated imidazolium salts can be obtained from substituted 1,2-bisamines by reaction with formaldehyde or trialkyl orthoformate.
  • the invention relates to a process for the preparation of imidazolium salts of the general formulas II, IV and VI, comprising the reaction of the corresponding substrates I, IM and V,
  • X represents O, S, a group NR 9 or CR 9a R 9b in which R 9 , R 9a and R 9 are hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C- o-alkyl-, C 2-5 alkenyl, C 2-5 alkynyl, C 7-19 aralkyl or C 6-14 aryl radicals mean
  • Y is O, S, a group NR 10 or NR 10a R 10b , in which R 10 , R 10a , R 10b are hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1-0 -alkyl-, C 2-5 -alkenyl-, C 2 . 5 -alkynyl, C 7- ⁇ 9 aralkyl or C 6- ⁇ 4 aryl radicals mean, and
  • A represents a mono- or polyvalent, organic or inorganic anion or a metal complex ion, with a combination of an alkylating agent of the general formula VII, VIII or IX
  • MA in which M represents a mono- or polyvalent metal cation, a tetraorganoammonium compound or a triorganosilyl radical, and A has the meaning given above for A " , as a promoter of the reaction.
  • the present invention further provides compounds of the general formulas II, IV and XI,
  • I 1 and I 2 are the same or different imidazolium salts of the formulas II, IV and VI, which are linked to L at the position of the radicals R 1 , R 2 , R 7 , R 8 , R 12 or R 14 , with the proviso that not I 1 and I 2 are both an imidazolium salt of the formula VI, the imidazolium salt of the formula VI, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , X, Y, L and A "have the meaning given above.
  • R 11 and R 12 are linked to one another to form a substituted or unsubstituted cycle, preferably to form a pyridyl ring.
  • Preferred substituents are C 1-6 alkyl and C 6- ⁇ aryl. The substituents are preferably bonded to the carbon adjacent to the ring nitrogen.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 9a , R 9b , R 10a , R 10 , R 11 , R 2 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 are the same or different and are saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1- 6 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 7-10 aralkyl or phenyl radicals.
  • the C 1-6 alkyl radicals can be selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, n-hexyl , i-hexyl, t-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • the C 2-4 alkenyl radicals can be selected from ethenyl, propenyl or butenyl, the C 2 .
  • the C 7-10 aralkyl radicals can be selected from benzyl, phenylethyl, phenylpropyl and phenylbutyl.
  • the radicals R 1 to R 19 can be halogenated, in particular by one or more, identical or different amine, nitro, nitrile, isonitrile, ether, alcohol, aldehyde or ketone groups, carboxylic acid derivatives, in particular esters or amides fluorinated or perfluorinated hydrocarbon residues, carbohydrate, phosphane, phosphine oxide, phosphine sulfide, phosphole residues, phosphite derivatives, aliphatic or aromatic sulfonic acid derivatives, their salts, esters or amides, silyl functions, boryl groups or heterocyclic substituents.
  • radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 4 are CC 6 - alkyl, C 2 -C 4 alkenyl, or C 2 . 4 - alkynyl residues.
  • one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 4 is substituted by an azolium salt or a pyridine ring.
  • one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 14 is a linker L to a further imidazolium salt of the formula II, IV or VI.
  • L can in particular be a C 1-4 - Alkylene radical (such as a methylene, ethylene, propylene or butylene radical), a C 5-12 cycloalkylene radical (such as a 1, 2- or 1, 4-cyclohexylene radical), a C 6 . 12 arylene residue (such as a 1,2-, 1,3- or 1,4-phenylene residue) or a C 6-12 heteroarylene residue (such as a 2,3-, 2,4- or 2,6-pyridinylene residue) his.
  • a C 1-4 - Alkylene radical such as a methylene, ethylene, propylene or butylene radical
  • a C 5-12 cycloalkylene radical such as a 1, 2- or 1, 4-cyclohexylene radical
  • a C 6 . 12 arylene residue such as a 1,2-, 1,3- or 1,4-phenylene residue
  • a C 6-12 heteroarylene residue such as a 2,3-, 2,4- or 2,6-pyri
  • radicals can optionally be substituted (for example with C 1-4 -alkyl radicals, d ⁇ -alkoxy radicals, halogen atoms, hydroxyl groups etc.) or by a hetero atom (for example O or NH) or a cyclic radical (for example a phenyl or cyclohexyl radical) be interrupted.
  • An imidazolium salt which has the general formula X is particularly preferred
  • the mono- or polyvalent organic anion A " in the general formulas II, IV, VI and XI is a sulfate, halide, pseudohalide, borate, phosphate or metal complex ion or an optionally halogenated sulfonate -, carboxylate or acetylacetonate ion and in particular A " for a triflate, mesylate, tosylate, nonaflate, tresylate, benzenesulfonate, brosylate, nosylate, fluorosulfonate, tetraphenylborate, tetrakis [3 , 5-bis (trifluoromethyl) phenyl] borate (BARF) -, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, acetate, trifluoroacetate, perchlorate, tetracarbonyl cobaltate or hexa
  • Process (1) comprises the use of an alkylating agent of the general formula VII, VIII or IX defined above.
  • the leaving group Z in this alkylating agent preferably represents a halide, pseudohalide or (optionally halogenated) carboxylate, particularly preferably a halide, particularly preferably chloride.
  • Preferred alkylating agents are those in which R 15 represents an unsubstituted or substituted phenyl, benzyl or C 1-4 alkyl radical, which can each contain one or more substituents, in particular ether, ester or silyl substituents.
  • Preferred metal salts of the general formula MA which can be used in process (1) are those in which the mono- or polyvalent metal cation M is a silver (I), alkali and alkaline earth metal, lanthanide, lead (II) , Mercury (II), cadmium (II), thallium (I), copper (II), zinc (II) or aluminum (III) ion, and those in which the tetraorganoammonium compound is a tetraalkylammonium compound and finally those in which the triorganosilyl radical is a trialkylsilyl radical.
  • Particularly preferred metal salts are those in which M is silver (I) and A is a sulfonate, sulfate, halide, pseudohalide, oxide, borate, phosphate, carboxylate, acetylacetonate or metal complex ion , preferably for a trifluoromethanesulfonate (triflate) -, methanesulfonate (mesylate), p-toluenesulfonate (tosylate) -, nonafluorobutanesulfonate (nonaflate) -, 2,2,2-trifluoroethanesulfonate (tresylate) -, benzenesulfonate, p-bromobenzenesulfonate Brosylate), p-nitrobenzenesulfonate (nosylate), fluorosulfonate, tetraphenyl borate, tetrakis [3,5-bis (triflu
  • alkylating agents and metal salts are used in at least a stoichiometric amount, preferably in a 5 to 100% excess with respect to the substrate.
  • the ratio of alkylating agent to metal salt can be varied within a wide range and is preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1: 1.2.
  • the imidazolium salts of the general formulas II, IV and VI are preferably synthesized with the exclusion of air and moisture. It has proven to be particularly advantageous to add the alkylating agent to a solution of the corresponding starting material of the general formula I, III or V and the metal salt in an organic solvent.
  • Suitable solvents can be acetone, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1, 2-dimethoxyethane, 1, 4-dioxane, petroleum ether, dimethyl sulfoxide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 1, 3- Dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidone, acetonitrile, propionitrile, ethyl acetate, benzene, toluene, xylene, gasoline, chloroform, 1, 2-dichloroethane and methylene chloride, preferably methylene chloride.
  • the reaction solution is purified in a conventional manner according to the physical properties of the products, e.g. B. by column chromatography or crystallization.
  • the imidazolium salts of the present invention are in particular those compounds in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , RR 18 , X, Y, L and A "have the preferred meaning given above.
  • OTf means trifluoromethanesulfonate (triflate), Ph phenyl, TMS trimethylsilyl, TES triethylsilyl and Bn benzyl.
  • OTf means trifluoromethanesulfonate (triflate), Ph phenyl, and Bn benzyl.
  • the compounds specifically mentioned above may also have tetrafluoroborate, mesylate, tosylate, nonaflate or hexafluoroantimonate instead of triflate as the counter anion.
  • the method according to the invention enables a large number of previously unknown, achiral and chiral imidazolium salts to be prepared in surprisingly good yield, high purity and, if appropriate, high optical purity. This is due, on the one hand, to the large constitutional diversity of the starting materials of the general formulas I, III and V and, on the other hand, to the mild alkylation conditions, which surprisingly become possible through the combined use of an alkylating agent and a metal salt as a promoter.
  • the method according to the invention has proven particularly useful therefore for the production of imidazolium salts from acid-sensitive substrates and for the production of chiral imidazolium salts. Furthermore, the method can be used for the synthesis of milligram and multigram amounts of imidazolium salts. Because of the simple reaction procedure, the process is also suitable for industrial use.
  • the imidazolium salts of the general formulas II, IV and VI which can be prepared by this process can be deprotonated in accordance with the literature and thus converted into N-heterocyclic carbenes or their transition metal complexes.
  • These transition metal-carbene complexes can be used as catalysts in homogeneous catalysis , wherein chiral, enantiomerically pure imidazolium salts of the general formulas II, IV and VI lead to chiral transition metal complexes which can be used in particular in asymmetric catalysis.
  • novel imidazolium salts of the general formulas II and IV in which the imidazolium nucleus is bridged by one (IV) or two (II) rings, are particularly promising.
  • suitable substitution of these bridges with the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 chiral, enantiomerically pure imidazolium salts with rigid geometry can be obtained, the transition metal-carbene complexes of which asymmetric catalysis can be used.
  • CDCI 3 ⁇ 141.5 (C), 137.9 (NCHN), 134.0 (C), 130.4 (C), 129.9 (CH ar ), 124.9 (NCHCHN),

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

L'invention concerne un procédé de production de sels d'imidazolium par réaction de bisimines ou d'hétérocycles correspondants avec une association d'un agent d'alkylation et d'un sel métallique servant de promoteurs de la réaction. Ce procédé permet d'obtenir divers sels d'imidazolium dans des conditions de réaction douces et avec de bons rendements. Les sels d'imidazolium produits selon ce procédé à partir d'hétérocycles constituent de nouveaux composés.
EP03763595A 2002-07-11 2003-07-08 Procede de production de sels d'imidazolium Withdrawn EP1521745A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10231368A DE10231368A1 (de) 2002-07-11 2002-07-11 Verfahren zur Herstellung von Imidazoliumsalzen
DE10231368 2002-07-11
PCT/DE2003/002285 WO2004007465A1 (fr) 2002-07-11 2003-07-08 Procede de production de sels d'imidazolium

Publications (1)

Publication Number Publication Date
EP1521745A1 true EP1521745A1 (fr) 2005-04-13

Family

ID=30009904

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03763595A Withdrawn EP1521745A1 (fr) 2002-07-11 2003-07-08 Procede de production de sels d'imidazolium

Country Status (6)

Country Link
US (1) US20050240025A1 (fr)
EP (1) EP1521745A1 (fr)
JP (1) JP2005538071A (fr)
AU (1) AU2003247251A1 (fr)
DE (1) DE10231368A1 (fr)
WO (1) WO2004007465A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008014028A1 (de) 2008-03-13 2009-09-17 Doris Dr. Kunz Verfahren zur Herstellung 1,3-disubstituierter Imidazoliumsalze
JP5575913B2 (ja) 2009-11-30 2014-08-20 ノバルティス アーゲー アルドステロン合成酵素阻害剤としてのイミダゾール誘導体
JP2011178709A (ja) * 2010-02-28 2011-09-15 Chiba Univ イミダゾリウム塩及びそれを用いた不斉合成触媒並びにイミダゾリウム塩の製造方法
DE102010040822B4 (de) * 2010-09-15 2013-09-12 Ernst-Moritz-Arndt-Universität Neue Imidazoliumsalze und darauf basierende Carben-Metallkomplexe zur Verwendung als bioanalytische Marker für Biomoleküle
DE102011106849A1 (de) 2010-12-15 2012-06-21 Merck Patent Gmbh Verfahren zur Synthese N-N verknüpfter und um die N-N Bindung rotationsgehinderter bis-N-heterocyclische Carbene und deren Einsatz als Liganden für Metallkomplexe
EP2701511A4 (fr) 2011-04-29 2015-06-10 Univ Akron Antimicrobiens et antinéoplasiques de sels d'azolium et de purinium
DE102011054477A1 (de) * 2011-10-13 2013-04-18 Westfälische Wilhelms-Universität Münster Verfahren zur katalytischen Heteroaromatenhydrierung
JP2015061834A (ja) * 2014-09-22 2015-04-02 国立大学法人 千葉大学 イミダゾリウム塩及びそれを用いた不斉合成触媒並びにイミダゾリウム塩の製造方法
CN105503763B (zh) 2014-10-17 2020-11-03 上海中科康润新材料科技有限公司 聚烯烃油催化剂及其应用
JP2016074729A (ja) * 2015-12-31 2016-05-12 国立大学法人 千葉大学 イミダゾリウム塩及びそれを用いた不斉合成触媒並びにイミダゾリウム塩の製造方法
CN110407753B (zh) * 2019-07-21 2022-08-09 桂林理工大学 一种由二芳基碘鎓盐与咪唑合成五芳基咪唑鎓盐的方法
CN110305171B (zh) * 2019-07-28 2021-09-28 苏州大学 含双噁唑啉衍生的氮杂环卡宾配体和亚磷酸酯配体的混配型镍(ii)配合物的制备及应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5077414A (en) * 1990-03-29 1991-12-31 E. I. Du Pont De Nemours And Company Preparation of 1,3-disubstituted imidazolium salts
US5182405A (en) * 1990-03-29 1993-01-26 E. I. Du Pont De Nemours And Company Preparation of 1,3-disubstituted imidazolium salts
DE4447067A1 (de) * 1994-12-29 1996-07-04 Hoechst Ag Verfahren zur Herstellung von Aldehyden
DE19815275B4 (de) * 1998-04-06 2009-06-25 Evonik Degussa Gmbh Alkylidenkomplexe des Rutheniums mit N-heterozyklischen Carbenliganden und deren Verwendung als hochaktive, selektive Katalysatoren für die Olefin-Metathese

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004007465A1 *

Also Published As

Publication number Publication date
WO2004007465A1 (fr) 2004-01-22
DE10231368A1 (de) 2004-02-05
AU2003247251A1 (en) 2004-02-02
JP2005538071A (ja) 2005-12-15
US20050240025A1 (en) 2005-10-27

Similar Documents

Publication Publication Date Title
DE60306795T2 (de) Ruthenium-komplexe als (pre)katalysatoren für metathesereaktionen
EP0842145B1 (fr) Procede de mise en uvre de reactions de couplages croises
EP2260047B1 (fr) Procédé de production de complexes ruthénium-carbène
WO2004007465A1 (fr) Procede de production de sels d'imidazolium
EP1177199B1 (fr) Liquides ioniques, leur production et leur utilisation
WO2021001240A1 (fr) Hydrogénation d'esters en vue d'obtenir des alcools en présence d'un complexe de ru-pnn
EP1300410A2 (fr) Complexes des métaux de transition comprenant un ligand de type diaminocarben et leur utilisation dans des réactions catalysées par des métaux de transition
DE10300097A1 (de) Kupfer-Komplexe und ihre Verwendung
DE10137051A1 (de) Neue Übergangsmetall-Komplexe und deren Einsatz in Übergangsmetall-katalysierten Reaktionen
EP1308157B1 (fr) Complexes de carbènes N-heterocycliques et leur utilisation
EP1394168B1 (fr) Procédé de préparation de phosphites et de complexes avec des métaux de transition
EP2678344B1 (fr) Cations de phosphénium stabilisés au cyclopropénylidène
DE10222033A1 (de) Verfahren zur Herstellung tertiärer Phosphane
DE10051316A1 (de) Verfahren zur Herstellung von mono-, bi- oder polyfunktionellen Biarylen
EP2303902B1 (fr) Acides bis(perfluoroalkyl)phosphineux et dérivés ainsi que leur utilisation
EP0806415B1 (fr) Procédé pour la préparation d'arylamides d'acides carboxyliques hétéroaromatiques
DE60219299T2 (de) Verfahren zur herstellung von multidentaten phosphin-verbindungen
WO2009153272A2 (fr) Procédé d'iodation de composés aromatiques et/ou hétéroaromatiques
DE10225283A1 (de) Neue Phosphine und Verfahren zu ihrer Herstellung
DE10157184A1 (de) Verfahren zur Herstellung von Vinylarenen, -heteroarenen und 1,3-Dienen aus Aryl-, bzw. Heteroaryl-bzw. Vinylcarbonsäurederivaten
EP4180440A1 (fr) Biarylphosphines cycliques comme ligands pour catalyseurs contenant du palladium dans les réactions de couplage croisé
DE19711154A1 (de) Verfahren zur Herstellung von Silaheterocyclen, neuartige Silaheterocyclen, deren Verwendung zur Herstellung von Silylenverbindungen sowie daraus erhaltene Silylenverbindungen
DE10108473A1 (de) Neue Diphosphine und Verfahren zu ihrer Herstellung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041223

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070201