EP1348043B1 - Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique - Google Patents

Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique Download PDF

Info

Publication number
EP1348043B1
EP1348043B1 EP01994702A EP01994702A EP1348043B1 EP 1348043 B1 EP1348043 B1 EP 1348043B1 EP 01994702 A EP01994702 A EP 01994702A EP 01994702 A EP01994702 A EP 01994702A EP 1348043 B1 EP1348043 B1 EP 1348043B1
Authority
EP
European Patent Office
Prior art keywords
compounds
alkyl
derivatives
substituted
acid
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.)
Expired - Lifetime
Application number
EP01994702A
Other languages
German (de)
English (en)
Other versions
EP1348043A2 (fr
Inventor
Hermann Pütter
Andreas Fischer
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1348043A2 publication Critical patent/EP1348043A2/fr
Application granted granted Critical
Publication of EP1348043B1 publication Critical patent/EP1348043B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds

Definitions

  • the present invention relates to a process for the preparation of formaldehyde di (C 1 to C 6 alkyl) acetals, ortho-formic acid tri- (C 1 to C 6 alkyl) esters, acetaldehyde di ( C 1 - to C 6 -alkyl) - acetals or ortho-acetic tri- (C 1 - to C 6 -alkyl) esters (compounds 1) by anodic oxidation of 1,2-di- (C 1 - to C 6 - alkoxy) ethane or propane, 1,1,2,2-tetra (C 1 to C 6 alkoxy) ethane or propane, or 2,3-di- (C 1 to C 6 alkoxy) -butane (compounds II) in the presence of a C 1 - to C 6 -alkyl alcohol (compounds III) in which the cathodic depolarizer used is a customary organic compound (compounds IV) which is suitable for electrochemical reduction and in
  • compounds II are 1,2-di (C 1 - to C 6 alkoxy) ethane or propane or 1,1,2,2-tetra (C 1 - to C 6 alkoxy) ethane or -propane used.
  • compounds I the corresponding formaldehyde di (C 1 - to C 6 alkyl) acetals or ortho-antric acid tri (C 1 - to C 6 alkyl) esters are formed and, in the case of the propane derivatives as starting materials also acetaldehyde di- (C 1 - to C 6 alkyl) - acetals or Orthoessigklatri- (C 1 - to C 6 alkyl) ester.
  • the abovementioned acetaldehyde or acetic acid derivatives can likewise be prepared from 2,3-di- (C 1 -C 6 -alkoxy) -butane.
  • cathodic Depolisatoren come usual organic Compounds suitable for anodic reduction, such as aromatic hydrocarbon compounds, activated olefins, Carbonyl compounds, aromatic carboxylic acids and their derivatives and naphthalene or nucleus-substituted naphthalene derivatives.
  • Suitable substituents with which the aromatic nuclei can be substituted in the abovementioned starting compounds are inert, hardly reducible groups, such as C 1 -C 12 -alkyl, C 1 -C 6 -alkoxy or halogen.
  • the molar ratio of the starting compounds for cathode and Anode reaction and the products formed in these reactions in electrolytes to each other is not critical.
  • Conducting salts which are contained in the electrolysis solution are generally alkali, tetra (C 1 - to C 6 -alkyl) -ammonium or tri- (C 1 - to C 6 -alkyl) -benzylammonium salts.
  • Suitable counterions are sulfate, hydrogensulfate, alkyl sulfates, alkyl sulfonates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate or perchlorate.
  • MTBS methyltributylammonium methylsulfate
  • methyltriethylammonium methylsulfate methyltriethylammonium methylsulfate
  • methyl tripropylmethylammonium methyl sulfates Preference is given to methyltributylammonium methylsulfate (MTBS), methyltriethylammonium methylsulfate or methyl tripropylmethylammonium methyl sulfates.
  • the electrolysis solution is subjected to customary cosolvents to. These are those in organic chemistry Commonly used inert solvents with a high oxidation potential. Examples include dimethyl carbonate or Propylene carbonate.
  • the process of the invention can be in all the usual undivided Electrolysis cell types are performed. Preferably works one continuously with undivided flow cells. Especially plate stack cells with serially designed stacking electrodes are suitable, as described for example in DE-A-19533773 are.
  • the current densities at which the process is carried out are generally 1 to 1000, preferably 10 to 100 mA / cm 2 .
  • the temperatures are usually -20 to 60 ° C, preferably 0 to 60 ° C. In general, working at atmospheric pressure. Higher pressures are preferably used when operating at higher temperatures to avoid boiling of the starting compounds or cosolvents.
  • Suitable anode materials are, for example, noble metals such as platinum or metal oxides such as ruthenium or chromium oxide or mixed oxides of the type Ruo x Tio x . Preference is given to graphite or carbon electrodes.
  • cathode materials are, for example, iron, steel, stainless steel, Nickel or precious metals such as platinum and graphite or carbon materials into consideration.
  • the system is graphite Anode and cathode as well as graphite as anode and nickel, stainless steel or steel as a cathode.
  • the electrolyte solution is after worked up general separation methods.
  • the electrolysis solution generally distilled first and the individual Compounds separated in the form of different fractions won. Further purification can be carried out, for example, by crystallization, Distillation or by chromatography.
  • 11 ring disk electrodes each having a surface area of 140 cm 2 and an outer diameter of 14 cm are arranged so as to form a stack. By spacers, the discs are set to a distance of 1 mm, resulting in 10 gaps between the annular discs.
  • the electrode material is graphite. Under electrolysis conditions, the inner 0.5 cm thick disks are bipolar.
  • the top electrode is anodically contacted by means of a graphite punch and a cover plate, the bottom electrode is cathodically contacted, the cathodic contact extends over the bottom plate of the cell.
  • the electrolyte flows through the central bore of the bottom plate into the cell, spreads over the column and leaves the cell above the top electrode.
  • the cell is part of a circulating apparatus in which the electrolyte is circulated, heated or cooled.
  • the electrolysis effluent contained 24.4% butanetetracarboxylic acid methyl ester, 14.2% trimethyl orthoformate, 25.6% tetramethoxyethane and 1.7% maleic dimethyl ester.
  • the selectivity the orthoester formation was 82%.
  • the composition of the electrolysis discharge was determined by gas chromatograph and is in area% (GC area%).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (5)

  1. Procédé de préparation de formaldéhyde-di-(C1-C6-alkyl)-acétals, d'esters tri-(C1-C6-alkyliques) d'acide ortho-formique, d'acétaldéhyde-di-(C1-C6-alkyl)-acétals ou d'esters tri-(C1-C6-alkyliques) d'acide ortho-acétique (composés I)
    par oxydation anodique
    de 1,2-di-(C1-C6-alcoxy)-éthane ou -propane, de 1,1,2,2-tétra(C1-C6-alcoxy)-éthane ou -propane, ou de 2,3-di(C1-C6-alcoxy)-butane (composés II)
    en présence d'un alcool alkylique en C1-C6 (composés III), dans lequel on met en oeuvre, comme dépolarisant cathodique, un composé organique usuel (composé IV) qui est approprié pour la réduction électrochimique, et dans lequel on effectue l'oxydation anodique et la réduction cathodique dans une cellule d'électrolyse non divisée, en présence d'alcools alkyliques en C1-C6.
  2. Procédé suivant la revendication 1, dans lequel les composés I sont de l'ester triméthylique d'acide ortho-formique ou du formaldéhydediméthylacétal, ces composés pouvant être également formés sous la forme d'un mélange.
  3. Procédé suivant l'une des revendications 1 et 2, dans lequel, en ce qui concerne le composé IV, il s'agit de composés d'hydrocarbures aromatiques, d'oléfines activées, d'acides carboxyliques aromatiques et de leurs dérivés, de composés carbonyle, d'imines, d'hétérocycles, de naphtalène ou de dérivés de naphtalène substitués sur le noyau.
  4. Procédé suivant la revendication 3, dans lequel, en ce qui concerne la dépolarisation cathodique, il s'agit d'une des réactions suivantes :
    a) de l'acide maléique ou des dérivés de l'acide maléique, où la fonction acide se présente sous la forme d'esters alkyliques, pour former un ester tétraalkylique d'acide butanetétracarboxylique avec hydrodimérisation,
    b) des acides benzènemono-, di-, ou tri- carboxyliques, différents de l'acide phtalique ou des dérivés de l'acide phtalique, ou respectivement des dérivés de ces composés où la fonction acide se présente sous la forme d'esters alkyliques, ou des dérivés substitués sur le noyau aromatique, pour former les composés correspondants de mono-, di- et tri-formylbenzène, dans lesquels les groupes formyle se présentent sous la forme d'un acétal,
    c) de l'acide acrylique, de l'acrylate d'alkyle, de l'acrylamide ou de l'acrylonitrile ou des homologues de ces composés pour former les produits d'hydrodimérisation correspondants,
    d) de l'acide phtalique, du phtalate d'alkyle ou des dérivés substitués sur le noyau aromatique de ces composés, pour former du phtalide ou des dérivés de phtalide substitués sur le noyau, de l'acide cyclohexane- ou cyclohexène-1,2-dicarboxylique, des esters dialkyliques d'acide cyclohexane- ou cyclohexène-1,2-dicarboxylique ou, conformément au modèle de substitution des dérivés d'acide phtalique substitués sur le noyau aromatique, des dérivés substitués sur le noyau de cyclohexane ou de cyclohexène,
    e) du naphtalène ou des dérivés de naphtalène substitués sur le noyau, pour former du 1,2,3,4-tétrahydronaphtalène ou les dérivés correspondants de 1,2,3,4-tétrahydronaphtalène,
    f) de la pyridine ou des dérivés de pyridine substitués sur le noyau pour former de la 1,4-dihydropyridine ou les dérivés correspondants de 1,4-dihydropyridine.
  5. Procédé suivant les revendications 1 à 4, dans lequel on effectue le procédé dans une cellule à pile de plateaux présentant des électrodes empilées, montées en série.
EP01994702A 2000-11-24 2001-11-22 Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique Expired - Lifetime EP1348043B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10058304 2000-11-24
DE10058304A DE10058304A1 (de) 2000-11-24 2000-11-24 Verfahren zur Herstellung von alkoxylierten Carbonylverbindungen durch ein anodisches Oxidationsverfahren unter Nutzung der kathodischen Koppelreaktion zur organischen Synthese
PCT/EP2001/013587 WO2002042524A2 (fr) 2000-11-24 2001-11-22 Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique

Publications (2)

Publication Number Publication Date
EP1348043A2 EP1348043A2 (fr) 2003-10-01
EP1348043B1 true EP1348043B1 (fr) 2005-03-09

Family

ID=7664478

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01994702A Expired - Lifetime EP1348043B1 (fr) 2000-11-24 2001-11-22 Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique

Country Status (11)

Country Link
US (1) US6822124B2 (fr)
EP (1) EP1348043B1 (fr)
JP (1) JP3906153B2 (fr)
CN (1) CN1329556C (fr)
AT (1) ATE290616T1 (fr)
AU (1) AU2002224874A1 (fr)
CA (1) CA2429450A1 (fr)
DE (2) DE10058304A1 (fr)
ES (1) ES2238501T3 (fr)
NO (1) NO20032335L (fr)
WO (1) WO2002042524A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013186094A2 (fr) 2012-06-15 2013-12-19 Basf Se Oxydation anodique de substrats organique en présence de nucléophiles

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10146566A1 (de) * 2001-09-21 2003-07-17 Basf Ag Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern
DE10355087A1 (de) * 2003-11-24 2005-06-09 Basf Ag Verfahren zur elektrochemischen Herstellung eines kristallinen porösen metallorganischen Gerüstmaterials
FR2910784B1 (fr) 2006-12-27 2009-02-20 Arkema France Utilisation de composes pour la conservation du corps humain ou animal et compositions les comprenant
DE102007008668A1 (de) * 2007-02-20 2008-08-21 Tesa Ag Verfahren zum Beschriften oder Markieren von Oberflächen
US8889920B2 (en) * 2010-02-12 2014-11-18 Basf Se Process for preparing 4-isopropylcyclohexylmethanol
WO2011098432A2 (fr) * 2010-02-12 2011-08-18 Basf Se Procédé de préparation de 4-isopropylcyclohexylméthanol
CN107473945B (zh) * 2016-06-08 2020-09-01 中国科学院大连化学物理研究所 一种催化甲醇直接氧化酯化制四甲氧基甲烷的方法
CN106591877A (zh) * 2016-11-14 2017-04-26 江苏科技大学 一种中心原子可变换的偶联剂及其制备方法
US11060197B2 (en) * 2016-11-24 2021-07-13 Avantium Knowledge Centre B.V. Process for treating a dicarboxylic acid composition
DE102017113141A1 (de) * 2017-06-14 2018-12-20 Westfälische Wilhelms-Universität Münster Elektrolyt für Lithium-Ionen-Batterien
DE102017012021A1 (de) 2017-12-22 2019-06-27 Friedrich-Schiller-Universität Jena Acetalischer Elektrolyt
JP7105418B2 (ja) * 2018-02-08 2022-07-25 Ｅｎｅｏｓ株式会社 シス－二置換非芳香族化合物の製造装置および製造方法
CN108677210B (zh) * 2018-04-17 2019-10-29 大连理工大学 一种酮与羧酸在电化学氢泵反应器中一步加氢酯化的方法
CN112195481B (zh) * 2020-11-02 2021-12-10 上海漫关越水处理有限公司 膜电解合成四甲氧基乙烷的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3000243A1 (de) * 1980-01-05 1981-07-09 Hoechst Ag, 6230 Frankfurt Verfahren zur elektrochemischen alkoxylierung von aliphatischen ethern
US4450055A (en) * 1983-03-30 1984-05-22 Celanese Corporation Electrogenerative partial oxidation of organic compounds
US4648948A (en) * 1985-05-23 1987-03-10 Meshbesher Thomas M Electrogenerative oxidation of lower alcohols to useful products
US5223102A (en) * 1992-03-03 1993-06-29 E. I. Du Pont De Nemours And Company Process for the electrooxidation of methanol to formaldehyde and methylal
DE19618854A1 (de) * 1996-05-10 1997-11-13 Basf Ag Verfahren zur Herstellung von Phthaliden
DE19741423A1 (de) * 1997-09-19 1999-03-25 Basf Ag Verfahren zur Herstellung von Phthaliden

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013186094A2 (fr) 2012-06-15 2013-12-19 Basf Se Oxydation anodique de substrats organique en présence de nucléophiles

Also Published As

Publication number Publication date
EP1348043A2 (fr) 2003-10-01
NO20032335D0 (no) 2003-05-23
US20040026263A1 (en) 2004-02-12
CN1476491A (zh) 2004-02-18
DE50105570D1 (de) 2005-04-14
AU2002224874A1 (en) 2002-06-03
ES2238501T3 (es) 2005-09-01
CN1329556C (zh) 2007-08-01
CA2429450A1 (fr) 2002-05-30
WO2002042524A2 (fr) 2002-05-30
JP2004514791A (ja) 2004-05-20
JP3906153B2 (ja) 2007-04-18
ATE290616T1 (de) 2005-03-15
WO2002042524A3 (fr) 2003-03-13
US6822124B2 (en) 2004-11-23
DE10058304A1 (de) 2002-05-29
NO20032335L (no) 2003-07-14

Similar Documents

Publication Publication Date Title
EP1348043B1 (fr) Procede de production de liaisons carbonyle alcoxylees par oxydation anodique et reaction de couplage cathodique pour realiser une synthese organique
EP0012240B1 (fr) Procédé de préparation de dialcoylacétals de benzaldéhyde éventuellement substitués
EP2748353B1 (fr) Procédé de préparation électrochimique d'esters d'acide gamma-hydroxycarboxylique et de gamma-lactones
DE69319342T2 (de) Elektrokatalytische asymmetrische dihydroxylierung von olefinen
EP2411564B1 (fr) Procédé électrochimique de production de 3-tert-butylbenzaldehyde-dimetylacetals
DE10057888A1 (de) Herstellung von Butantetracarbonsäurederivaten mittels gekoppelter Elektrosynthese
WO2023186658A1 (fr) Oxydation électrochimique de cycloalcènes pour former des acides alpha, oméga-dicarboxyliques et des acides cétocarboxyliques
EP0129795B1 (fr) Procédé de production de dialkylacétals de benzaldéhyde
EP0638665B1 (fr) Procédé pour la préparation d'acetals dialkyls de benzaldehyde
WO2008145627A1 (fr) Oxydation électrochimique sur des groupes allyle
EP0179289B1 (fr) Procédé pour la préparation d'esters carboxyliques aromatiques
EP2534281B1 (fr) Procédé de préparation de 4-isopropylcyclohexylméthanol
EP1619273B1 (fr) Procédé de production de 2-alcyne-1-acetals
EP0502372B1 (fr) Dialkylacétals de 4-tert-alkyl-2-méthylbenzaldéhydes
EP0078004B1 (fr) Procédé électrochimique de fabrication des 2,5-dialcoxy-2,5-dihydrofurannes
EP1430165B1 (fr) Procede pour produire des orthotrialkylesters d'acide carboxylique
EP0513577B1 (fr) Procédé pour la préparation de 1-alkoxyisochromanes
EP0393668A2 (fr) Procédé de préparation d'acétals dialkyls de benzaldéhyde et acétals dialkyls de benzaldéhyde
WO2007014932A1 (fr) Procede pour produire des derives de 1,1,4,4-tetraalcoxy-but-2-ene
DE4308846A1 (de) Verfahren zur Herstellung von Terephthalaldehydtetraalkylacetalen
DE2923531A1 (de) Verfahren zur herstellung von gegebenenfalls substituierten benzaldehyd- dialkylacetalen
DE10207238A1 (de) Verfahren zur elektroorganischen Synthese an Kohlenstoffelektroden

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

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PUETTER, HERMANN

Inventor name: FISCHER, ANDREAS

17P Request for examination filed

Effective date: 20030915

17Q First examination report despatched

Effective date: 20040630

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050309

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050309

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050309

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 50105570

Country of ref document: DE

Date of ref document: 20050414

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050609

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050609

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20050519

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2238501

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050907

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051122

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051130

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051130

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

ET Fr: translation filed
26N No opposition filed

Effective date: 20051212

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050609

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20071115

Year of fee payment: 7

Ref country code: ES

Payment date: 20071219

Year of fee payment: 7

Ref country code: NL

Payment date: 20071104

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20071126

Year of fee payment: 7

Ref country code: CH

Payment date: 20071114

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20071108

Year of fee payment: 7

Ref country code: GB

Payment date: 20071121

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20071130

Year of fee payment: 7

BERE Be: lapsed

Owner name: *BASF A.G.

Effective date: 20081130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20081122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20090601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081122

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090603

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081122

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20081124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081130