EP1362022B1 - Verfahren zur herstellung von orthocarbonsäuretrialkylestern - Google Patents
Verfahren zur herstellung von orthocarbonsäuretrialkylestern Download PDFInfo
- Publication number
- EP1362022B1 EP1362022B1 EP01980340A EP01980340A EP1362022B1 EP 1362022 B1 EP1362022 B1 EP 1362022B1 EP 01980340 A EP01980340 A EP 01980340A EP 01980340 A EP01980340 A EP 01980340A EP 1362022 B1 EP1362022 B1 EP 1362022B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- orthoesters
- ketals
- alkyl
- process according
- radicals
- 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
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 Orthocarbonklatrialkylestern (orthoester O) by electrochemical oxidation of alpha-beta-diketones or alpha-beta-hydroxy ketones, wherein the keto function in the form of a derived from C 1 - to C 4 alkyl alcohols ketal function and the hydroxyl function, if necessary in the form of one derived from C 1 to C 4 alkyl alcohols.
- Etherfunktion is present (Ketals K), in the presence of C 1 to C 4 alcohols (alcohols A), wherein in the electrolyte, the molar ratio of the sum of the orthoester O and the ketals K to the alcohols A 0.2: 1 to 5: 1 amounts to.
- Non-electrochemical processes for the preparation of orthocarboxylic acid trialkyl esters such as trimethyl orthoformate (TMOF) are, for example DE-A-3606472 known, wherein chloroform is reacted together with sodium methylate.
- TMOF trimethyl orthoformate
- EP 212,509 teaches the electrochemical oxidation of benzaldehyde acetals to benzoic acid esters.
- EP 393,668 describes a process in which ethers of Benzylalkohls or derivatives thereof are electrochemically oxidized in the presence of alcohol to the corresponding acetals of benzaldehyde or derivatives thereof.
- the object underlying the invention was therefore to provide an electrochemical process in order to make available orthocarboxylic acid trialkyl ester economically and in particular in high current and product yields and with high selectivity.
- ketals used according to the invention are accessible by generally known preparation processes.
- functional groups these are most easily prepared by starting from a precursor which has a C-C double bond in place of the desired functional group and then functionalized by standard methods (s. Synthesis, (1981) 501-522 ).
- radicals R 5 and R 10 preferably have the same meaning.
- methyl orthoformate (TMOF) or ethyl ester or methyl orthoacetate or ethyl ester can be carried out particularly favorably (Orthoester Id) (these are compounds of formula I, wherein R 1 is hydrogen or methyl and R 2 , R 3 and R 4 are methyl or R 2 , R 3 and R 4 is ethyl), wherein as starting compounds 1,1,2,2-tetramethoxyethane (TME) or 1,1,2,2-tetraethoxyethane (Ketale IId) serve.
- the molar ratio of the sum of the orthoester O 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.
- Conducting salts which are contained in the electrolysis solution are generally alkali metal, tetra (C 1 - to C 6 -alkyl) ammonium or tri (C 1 - to C 6 -alkyl) benzylammonium salts.
- Suitable counterions are sulfate, bisulfate, alkyl sulfates, aryl sulfates, halides, phosphates, carbonates, alkyl phosphates, alkyl carbonates, nitrate, alcoholates, tetrafluoroborate or perchlorate.
- acids derived from the abovementioned anions are suitable as conductive salts.
- MTBS methyltributylammonium methylsulfates
- methyltriethylammonium methylsulfate methyltri-propylmethylammonium methylsulfates.
- the electrolysis solution is added to customary cosolvents.
- these are the inert solvents generally used in organic chemistry with a high oxidation potential. Examples include dimethyl carbonate or propylene carbonate.
- the process according to the invention can be carried out in all customary types of electrolytic cell. Preferably, one works continuously with undivided flow cells.
- the feed rate of the starting materials is generally chosen such that the weight ratio of the ketals K used to the orthoesters I formed in the electrolyte is from 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. 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 include, 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 as the anode and cathode and graphite as the anode and nickel, stainless steel or steel as the cathode.
- the electrolysis solution is worked up by general separation methods.
- the electrolysis solution is generally first distilled and the individual compounds are recovered separately in the form of different fractions. Further purification can be carried out, for example, by crystallization, distillation or by chromatography.
- the electrolyte used was a solution consisting of 2 mol of methanol per mole of TME, which contained 2% by weight of MTBS as the conductive salt.
- the electrolysis was carried out at 300 A / m 2 and an amount of charge of 2 F based on TME was passed through the cell.
- the temperature during the electrolysis was 20 ° C.
- After completion of the electrolysis of the electrolysis products were determined by gas chromatography quantitatively and by GC-MS coupling qualitatively. It was formed with a TME conversion of 69% TMOF with a selectivity of 77%.
- the by-products were mainly methyl formate and methylal.
- Example 2 In an electrolytic cell with an electrode area of 316.4 cm 2 , otherwise described in Example 1, 240.3 g of 1,1,2-trimethoxyethane, 320 g of methanol and 5.8 g of ammonium tetrafluoroborate were used and subjected to an electrolyte. The electrolysis conditions were as described in Example 1. 9.5 GC area% formaldehyde dimethyl acetal and 5.9 GC area% trimethyl orthoformate were obtained in the electrolysis discharge.
- Example 2 In an electrolytic cell with an electrode area of 298.8 cm 2 , otherwise described in Example 1, 89, g were 2,2,3,3-tetramethoxybutene (80%, prepared from diacetyl and trimethyl orthoformate), 64 g of methanol and 1 , 7 g of ammonium tetrafluoroborate reacted.
- the electrolysis conditions were as described in Example 1. After electrothermal feed of 2. Faraday, 1.7 GC area% trimethyl orthoacetate was obtained in the electrolysis discharge and 18 GC area% after 8 F power input.
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)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10043789A DE10043789A1 (de) | 2000-09-06 | 2000-09-06 | Verfahren zur Herstellung von Orthocarbonsäuretrialkylestern |
DE10043789 | 2000-09-06 | ||
PCT/EP2001/010216 WO2002020446A1 (de) | 2000-09-06 | 2001-09-05 | Verfahren zur herstellung von orthocarbonsäuretrialkylestern |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1362022A1 EP1362022A1 (de) | 2003-11-19 |
EP1362022B1 true 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 (ja) |
EP (1) | EP1362022B1 (ja) |
JP (1) | JP5015406B2 (ja) |
CN (1) | CN1249004C (ja) |
AU (1) | AU2002212205A1 (ja) |
CA (1) | CA2421353C (ja) |
DE (2) | DE10043789A1 (ja) |
ES (1) | ES2294037T3 (ja) |
NO (1) | NO20031025D0 (ja) |
WO (1) | WO2002020446A1 (ja) |
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 DE DE50113334T patent/DE50113334D1/de not_active Expired - Lifetime
- 2001-09-05 AU AU2002212205A patent/AU2002212205A1/en not_active Abandoned
- 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 EP EP01980340A patent/EP1362022B1/de not_active Expired - Lifetime
- 2001-09-05 ES ES01980340T patent/ES2294037T3/es not_active Expired - Lifetime
- 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 JP JP2002525072A patent/JP5015406B2/ja not_active Expired - Fee Related
-
2003
- 2003-03-05 NO NO20031025A patent/NO20031025D0/no not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
CN1249004C (zh) | 2006-04-05 |
WO2002020446A8 (de) | 2003-04-24 |
CA2421353C (en) | 2010-07-13 |
NO20031025L (no) | 2003-03-05 |
US20030183534A1 (en) | 2003-10-02 |
AU2002212205A1 (en) | 2002-03-22 |
CN1454198A (zh) | 2003-11-05 |
NO20031025D0 (no) | 2003-03-05 |
US7192512B2 (en) | 2007-03-20 |
EP1362022A1 (de) | 2003-11-19 |
CA2421353A1 (en) | 2003-03-05 |
DE10043789A1 (de) | 2002-03-14 |
JP5015406B2 (ja) | 2012-08-29 |
JP2004508463A (ja) | 2004-03-18 |
DE50113334D1 (de) | 2008-01-10 |
WO2002020446A1 (de) | 2002-03-14 |
ES2294037T3 (es) | 2008-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0011712B1 (de) | Verfahren zur Herstellung von in 4-Stellung substituierten Benzaldehyddialkylacetalen | |
EP0012240B1 (de) | Verfahren zur Herstellung von gegebenenfalls substituierten Benzaldehyd-dialkylacetalen | |
EP1619273B1 (de) | Verfahren zur Herstellung von 2-Alkin-1-acetalen | |
EP1362022B1 (de) | Verfahren zur herstellung von orthocarbonsäuretrialkylestern | |
EP1348043A2 (de) | Verfahren zur herstellung von alkoxylierten carbonylverbindungen durch ein anodisches oxidationsverfahren unter nutzung der kathodischen koppelreaktion zur organischen synthese | |
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 | |
DE4327361A1 (de) | Verfahren zur Herstellung von Benzaldehyddialkylacetalen | |
DE102005007285A1 (de) | Elektrochemisches Verfahren zur Herstellung von Trimethylorthoformiat oder Orthokohlensäuremethylester | |
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 | |
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 | |
DE102005007286A1 (de) | Elektrochemisches Verfahren zur Herstellung eines aliphatischen Orthocarbonsäureesters oder eines Orthokohlensäureesters | |
DE2851732A1 (de) | Verfahren zur herstellung von substituierten benzaldehyd-dialkylacetalen | |
DE2923531A1 (de) | Verfahren zur herstellung von gegebenenfalls substituierten benzaldehyd- dialkylacetalen | |
DE10207238A1 (de) | Verfahren zur elektroorganischen Synthese an Kohlenstoffelektroden | |
EP1637628A2 (de) | Verfahren zur Herstellung von Glyoxalsäurealkylesterdialkylacetal | |
DE2930480A1 (de) | Verfahren zur herstellung von substituierten benzaldehyd-dialkylacetalen |
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 |