EP1362022A1 - Verfahren zur herstellung von orthocarbonsäuretrialkylestern - Google Patents
Verfahren zur herstellung von orthocarbonsäuretrialkylesternInfo
- Publication number
- EP1362022A1 EP1362022A1 EP01980340A EP01980340A EP1362022A1 EP 1362022 A1 EP1362022 A1 EP 1362022A1 EP 01980340 A EP01980340 A EP 01980340A EP 01980340 A EP01980340 A EP 01980340A EP 1362022 A1 EP1362022 A1 EP 1362022A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- same meaning
- alkyl
- ketals
- methyl
- orthoester
- 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.)
- Granted
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
- C25B3/20—Processes
- C25B3/23—Oxidation
Definitions
- the invention relates to a process for the preparation of orthocarboxylic acid trialkyl esters (orthoester 0) by electrochemical oxidation of alpha-beta-diketones or alpha-beta-hydroxyketones, the keto function being in the form of a ketal function derived from C 1 -C 4 -alkyl alcohols and the hydroxyl function is optionally in the form of an ether function derived from Ci to C 4 alkyl alcohols (ketals K), in the presence of Ci to C 4 alcohols (alcohols A), the molar ratio of the sum of the orthoesters in the electrolyte 0 and the ketals K to the alcohols A is 0.2: 1 to 5: 1.
- Non-electrochemical processes for the preparation of orthocarboxylic acid trialkyl esters such as trimethyl orthoforate (TMOF) are e.g. known from DE-A-3606472, wherein chloroform is reacted together with sodium methylate.
- the object on which the invention is based was therefore to provide an electrochemical process for making orthocarboxylic acid trialkyl esters accessible economically and in particular in high current and product yields and with high selectivity.
- R 1 hydrogen, C 1 ⁇ to C 2 n-alkyl, C - to C 0 -alkenyl,
- R 2 , R 3 C 1 -C 20 -alkyl, C 3 - to C 12 -cycloalkyl, and C 4 - to C o-cycloalkyl-alkyl or R 2 and R 3 together form a C 2 - to cio-alkylene
- R 4 Cx to C 4 alkyl.
- R5, RIO the same meaning as R 1
- R 6 , R 7 the same meaning as R 2
- R 8 hydrogen under the condition that R 9 has the same meaning as R 1 or the same meaning as R2
- R 9 the same meaning as R 1 or -0- R 2 .
- R 13 , R 14 the same meaning as R 1
- ketals II which are those in which R 9 has exclusively the same meaning as R 1 .
- R 17 , R 20 the same meaning as R 4 ,
- R 19 the same meaning as R 2 and
- XC 2 - to -C 2 alkylene means (orthoester la)
- R 21 , R 22 the same meaning as R 2
- R 23 the same meaning as R 8
- R 24 the same meaning as R 9 and
- the ketals used according to the invention are accessible by generally known production processes. If these are functional groups, the easiest way to prepare them is to start from a precursor that has a CC double bond at the location of the desired functional group. fertilizer and then functionalized using standard methods (see Synthesis, (1981) 501 - 522).
- the process according to the invention can also be used particularly advantageously for the production of orthoesters Ib, which are compounds in which
- R 1 hydrogen, C ⁇ -C o-alkyl, C 3 -C ⁇ cycloalkyl or
- R 2 , R 3 Ci to C 20 alkyl, C 3 - to -C 2 cycloalkyl, and C 4 - bis
- R 4 Ci to C alkyl (orthoester Ib)
- R 5 , R 10 the same meaning as R 1 in orthoester Ib
- R 6 to R 9 the same meaning as R 2 or R 3 in orthoester Ib (ketals Ilb)
- the process according to the invention can be used in particular for the production of orthoesters Ic in which
- R 1 hydrogen, C 1 -C 5 -alkyl
- R 2 , R 3 , R 4 methyl or ethyl (orthoester Ic)
- R 5 , R 10 the same meaning as R 1 in Orthoester Ic
- R 6 to R 9 the same meaning as R 2 or R 3 in Orthoester Ic (Ketale IIc).
- radicals R 5 and R 10 preferably have the same meaning.
- TMOF orthoformic acid methyl ester
- ethyl ester or orthoacetic acid ethyl ester or ethyl ester orthoester Id
- TAE 1,1,2,2-tetramethoxyethane
- TAE 1, 1, 2, 2-tetraethoxyethane
- the molar ratio of the sum of the orthoesters 0 and the ketals K to the alcohols A is 0.2: 1 to 5: 1, preferably 0.2: 1 - 2: 1 and particularly preferably 0.3: 1 to 1: 1.
- the conductive salts contained in the electrolysis solution are generally alkali, tetra (C ⁇ bis
- C 6 alkyl ammonium or tri (-C ⁇ to C 6 alkyl) benzyl ammonium salts.
- Sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate or perchlorate are suitable as counterions.
- acids derived from the above-mentioned anions can be considered as conductive salts.
- Methyltributylammonium methyl sulfates are preferred,
- customary cosolvents are added to the electrolysis solution. These are the inert solvents with a high oxidation potential that are common in organic chemistry. Examples include dimethyl carbonate or propylene carbonate.
- the process according to the invention can be carried out in all customary electrolysis cell types.
- One preferably works continuously with undivided flow cells.
- the feed rate of the starting materials is generally chosen so that the weight ratio of the ketals K used to the orthoesters I formed in the electrolyte is 10: 1 to 0.05: 1.
- 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.
- normal pressure is used. Higher pressures are preferably used when working at higher temperatures in order 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 RuO x TiO x type .
- Graphite or carbon electrodes are preferred.
- cathode materials are iron, steel, stainless steel, nickel or precious metals such as platinum and graphite or carbon materials.
- the system is preferably graphite as anode and cathode and graphite as anode and nickel, stainless steel or steel as cathode.
- the electrolysis solution is worked up using general separation methods.
- the electrolysis solution is generally first distilled and the individual compounds are obtained separately in the form of different fractions. Further purification can be carried out, for example, by crystallization, distillation or by chromatography.
- Example 3 1, 1, 2-trimethoxyethane, 320 g of methanol and 5.8 g of ammonium tetrafluoroborate are used and subjected to an electrolyte.
- the electrolysis conditions were as described in Example 1. 9.5 GC area% formaldehyde dimethylacetal and 5.9 GC area% trimethyl orthoformate were obtained in the electrolysis discharge.
- Example 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10043789 | 2000-09-06 | ||
DE10043789A DE10043789A1 (de) | 2000-09-06 | 2000-09-06 | Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern |
PCT/EP2001/010216 WO2002020446A1 (de) | 2000-09-06 | 2001-09-05 | Verfahren zur herstellung von orthocarbonsäuretrialkylestern |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1362022A1 true EP1362022A1 (de) | 2003-11-19 |
EP1362022B1 EP1362022B1 (de) | 2007-11-28 |
Family
ID=7655102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01980340A Expired - Lifetime EP1362022B1 (de) | 2000-09-06 | 2001-09-05 | Verfahren zur herstellung von orthocarbonsäuretrialkylestern |
Country Status (10)
Country | Link |
---|---|
US (1) | US7192512B2 (de) |
EP (1) | EP1362022B1 (de) |
JP (1) | JP5015406B2 (de) |
CN (1) | CN1249004C (de) |
AU (1) | AU2002212205A1 (de) |
CA (1) | CA2421353C (de) |
DE (2) | DE10043789A1 (de) |
ES (1) | ES2294037T3 (de) |
NO (1) | NO20031025D0 (de) |
WO (1) | WO2002020446A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10146566A1 (de) * | 2001-09-21 | 2003-07-17 | Basf Ag | Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern |
DE10340737A1 (de) * | 2003-09-04 | 2005-03-31 | Basf Ag | Verfahren zur destillativen Aufarbeitung eines TMOF enthaltenden Elektrolyseaustrages |
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 |
CN107779907A (zh) * | 2017-10-10 | 2018-03-09 | 凯莱英医药集团(天津)股份有限公司 | 电化学合成羰基化合物的方法 |
CN109518211B (zh) * | 2019-01-08 | 2020-11-06 | 合肥工业大学 | 一种芳香偶酰类化合物的电化学合成方法 |
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 (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3435388A1 (de) * | 1984-09-27 | 1986-04-03 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von aromatischen carbonsaeureestern |
DE3529074A1 (de) * | 1985-08-14 | 1987-02-19 | Basf Ag | Verfahren zur herstellung von benzoesaeureorthoestern sowie verbindungen dieser klasse |
DE3913166A1 (de) * | 1989-04-21 | 1990-10-25 | Basf Ag | Verfahren zur herstellung von benzaldehyddialkylacetalen und neue benzaldehyddialkylacetale und benzylester |
-
2000
- 2000-09-06 DE DE10043789A patent/DE10043789A1/de not_active Withdrawn
-
2001
- 2001-09-05 US US10/363,317 patent/US7192512B2/en not_active Expired - Fee Related
- 2001-09-05 CN CNB018152236A patent/CN1249004C/zh not_active Expired - Fee Related
- 2001-09-05 CA CA2421353A patent/CA2421353C/en not_active Expired - Fee Related
- 2001-09-05 WO PCT/EP2001/010216 patent/WO2002020446A1/de active IP Right Grant
- 2001-09-05 EP EP01980340A patent/EP1362022B1/de not_active Expired - Lifetime
- 2001-09-05 AU AU2002212205A patent/AU2002212205A1/en not_active Abandoned
- 2001-09-05 JP JP2002525072A patent/JP5015406B2/ja not_active Expired - Fee Related
- 2001-09-05 ES ES01980340T patent/ES2294037T3/es not_active Expired - Lifetime
- 2001-09-05 DE DE50113334T patent/DE50113334D1/de not_active Expired - Lifetime
-
2003
- 2003-03-05 NO NO20031025A patent/NO20031025D0/no not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0220446A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE50113334D1 (de) | 2008-01-10 |
CA2421353C (en) | 2010-07-13 |
US20030183534A1 (en) | 2003-10-02 |
ES2294037T3 (es) | 2008-04-01 |
JP2004508463A (ja) | 2004-03-18 |
NO20031025L (no) | 2003-03-05 |
CA2421353A1 (en) | 2003-03-05 |
US7192512B2 (en) | 2007-03-20 |
WO2002020446A8 (de) | 2003-04-24 |
CN1249004C (zh) | 2006-04-05 |
NO20031025D0 (no) | 2003-03-05 |
JP5015406B2 (ja) | 2012-08-29 |
EP1362022B1 (de) | 2007-11-28 |
AU2002212205A1 (en) | 2002-03-22 |
DE10043789A1 (de) | 2002-03-14 |
CN1454198A (zh) | 2003-11-05 |
WO2002020446A1 (de) | 2002-03-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0011712B1 (de) | Verfahren zur Herstellung von in 4-Stellung substituierten Benzaldehyddialkylacetalen | |
EP2748353B1 (de) | Verfahren zur elektrochemischen darstellung von gamma-hydroxycarbonsäureestern und gamma-lactonen | |
EP0012240B1 (de) | Verfahren zur Herstellung von gegebenenfalls substituierten Benzaldehyd-dialkylacetalen | |
EP1619273B1 (de) | Verfahren zur Herstellung von 2-Alkin-1-acetalen | |
EP2616424B1 (de) | Verfahren zur herstellung von 2-methyl-3-(4-tert-butylphenyl)-propanal mit hoher para-isomerenreinheit | |
EP1362022B1 (de) | Verfahren zur herstellung von orthocarbonsäuretrialkylestern | |
EP2411564B1 (de) | Elektrochemisches verfahern zur herstellung von 3-tert.-butylbenzaldehyd-dimethylacetal | |
EP1430165B1 (de) | Verfahren zur herstellung von orthocarbonsäuretrialkylestern | |
EP2534281B1 (de) | Verfahren zur herstellung von 4-isopropylcyclohexylmethanol | |
EP0502372B1 (de) | 4-tert-Alkyl-2-Methylbenzaldehyddialkylacetale | |
EP1769103A1 (de) | Verfahren zur herstellung von prim[ren aminen mit einer an ein aliphatisches oder cycloaliphatisches c-atom gebunden prim[ren aminogruppe und einer cyclopropyl-einheit | |
DE102005007285A1 (de) | Elektrochemisches Verfahren zur Herstellung von Trimethylorthoformiat oder Orthokohlensäuremethylester | |
EP1206590B1 (de) | Verfahren zur herstellung von in alpha-stellung oxidierten carbonylverbindungen | |
WO2007014932A1 (de) | Verfahren zur herstellung von 1,1,4,4-tetraalkoxy-but-2-enderivaten | |
EP0554564A1 (de) | Verfahren zur Herstellung von Benzaldehydacetalen | |
EP0339521B1 (de) | Verfahren zur Herstellung von Tetralinderivaten und neue Tetralinderivate | |
DE10209195A1 (de) | Elektrosynthese von Trialkylameisensäureorthoestern aufbauend auf der Acetalisierung Glyoxal zu Diacetalen | |
DE102005007286A1 (de) | Elektrochemisches Verfahren zur Herstellung eines aliphatischen Orthocarbonsäureesters oder eines Orthokohlensäureesters | |
DE2923531A1 (de) | Verfahren zur herstellung von gegebenenfalls substituierten benzaldehyd- dialkylacetalen | |
EP1637628A2 (de) | Verfahren zur Herstellung von Glyoxalsäurealkylesterdialkylacetal | |
DE3615472A1 (de) | Verfahren zur herstellung von (omega)-hydroxyaldehyden oder deren zyklischer halbacetale | |
DE2930480A1 (de) | Verfahren zur herstellung von substituierten benzaldehyd-dialkylacetalen | |
DE10215899A1 (de) | Verfahren zur elektroorganischen Synthese an Kohlenstoffanoden |
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: A1 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 |
|
17P | Request for examination filed |
Effective date: 20030407 |
|
17Q | First examination report despatched |
Effective date: 20060614 |
|
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 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 50113334 Country of ref document: DE Date of ref document: 20080110 Kind code of ref document: P |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20080213 |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: BASF SE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2294037 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: 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: 20080228 |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: BASF SE Effective date: 20080305 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20071128 |
|
ET | Fr: translation filed | ||
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: 20071128 |
|
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: 20080428 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
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 |
|
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: 20071128 |
|
26N | No opposition filed |
Effective date: 20080829 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20080229 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080930 |
|
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: 20071128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080905 |
|
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: 20080905 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20071128 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20130925 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20130930 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20130923 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20131129 Year of fee payment: 13 Ref country code: BE Payment date: 20131030 Year of fee payment: 13 Ref country code: FR Payment date: 20130930 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20131025 Year of fee payment: 13 Ref country code: NL Payment date: 20131003 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50113334 Country of ref document: DE |
|
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: 20140905 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50113334 Country of ref document: DE Effective date: 20150401 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150529 |
|
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: 20140930 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150401 |
|
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: 20140930 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140930 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150401 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140905 |
|
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: 20140930 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140905 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20151027 |
|
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: 20140906 |