EP0277048A1 - Verfahren zur elektrochemischen Herstellung von Carbonsäuren - Google Patents
Verfahren zur elektrochemischen Herstellung von Carbonsäuren Download PDFInfo
- Publication number
- EP0277048A1 EP0277048A1 EP88400025A EP88400025A EP0277048A1 EP 0277048 A1 EP0277048 A1 EP 0277048A1 EP 88400025 A EP88400025 A EP 88400025A EP 88400025 A EP88400025 A EP 88400025A EP 0277048 A1 EP0277048 A1 EP 0277048A1
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- EP
- European Patent Office
- Prior art keywords
- radical
- heteroatom
- carbon atom
- group
- chosen
- Prior art date
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- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000001735 carboxylic acids Chemical class 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 150000003254 radicals Chemical class 0.000 claims description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- -1 ammonium radical Chemical class 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical group [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- ONDXXAPHPJPFKQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphoryl]-n-methylmethanamine;oxolane Chemical compound C1CCOC1.CN(C)P(=O)(N(C)C)N(C)C ONDXXAPHPJPFKQ-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000005138 alkoxysulfonyl group Chemical group 0.000 claims 1
- 125000004414 alkyl thio group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001721 carbon Chemical group 0.000 description 17
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 238000009396 hybridization Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000021523 carboxylation Effects 0.000 description 3
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960003424 phenylacetic acid Drugs 0.000 description 3
- 239000003279 phenylacetic acid Substances 0.000 description 3
- MOHYOXXOKFQHDC-UHFFFAOYSA-N 1-(chloromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCl)C=C1 MOHYOXXOKFQHDC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 231100001010 corrosive Toxicity 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- SJIPGHSIXKAOIU-UHFFFAOYSA-N n,n-dimethyl-3-phenylpropanamide;hydrochloride Chemical compound [Cl-].C[NH+](C)C(=O)CCC1=CC=CC=C1 SJIPGHSIXKAOIU-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- GEDJSTBRFXDCAM-UHFFFAOYSA-N 2-(1-chloroethyl)thiophene Chemical compound CC(Cl)C1=CC=CS1 GEDJSTBRFXDCAM-UHFFFAOYSA-N 0.000 description 1
- FUOHKPSBGLXIRL-UHFFFAOYSA-N 2-(chloromethyl)thiophene Chemical compound ClCC1=CC=CS1 FUOHKPSBGLXIRL-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NRPFNQUDKRYCNX-UHFFFAOYSA-N 4-methoxyphenylacetic acid Chemical compound COC1=CC=C(CC(O)=O)C=C1 NRPFNQUDKRYCNX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 150000002960 penicillins Chemical class 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003491 tear gas Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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
- C25B3/25—Reduction
Definitions
- the present invention relates to a process for the electrosynthesis of carboxylic acids by electrochemical reduction, in the presence of carbon dioxide, of organic compounds comprising at least one simple carbon-heteroatom covalent bond, process carried out in an electrolysis cell in organic medium .
- Carboxylic acids are products commonly used in the chemical industry, in particular as intermediates for the synthesis of pharmaceutical or phytosanitary products. Mention may in particular be made of their use for the synthesis of penicillins as well as for those of anti-inflammatories and insecticides.
- FR 2,566,434 which the Applicant is the holder of, describes the synthesis of carboxylic acids by electrochemical reduction, in the presence of carbon dioxide, of organic halides.
- the process is carried out in a cell which is preferably not compartmentalized, in an organic medium.
- the anode, made of magnesium, is consumed during electrosynthesis by the electrochemical reaction of which it is the seat.
- benzyl halides are tear gas, irritants and corrosives.
- the most reactive are particularly unstable; paramethoxybenzyl chloride, chloromethyl and chloroethyl thiphenes spontaneously polymerize at room temperature with a significant gassing of hydrochloric acid.
- Alpha arylchloroethanes often undergo dehydrochlorination reactions leading to undesirable styrenic derivatives. All these parasitic reactions are often accelerated due to the operating conditions of electrocarboxylation (polar solvents, presence of metal salts).
- electrocarboxylation of paramethoxybenzyl chloride gives paramethoxyphenylacetic acid only with a yield of 50% while the raw material has completely disappeared.
- BAIZER in JOC 37.12, 1951-60, 1972, obtains benzyl esters or allyl esters, by electrochemical reduction, in the presence of carbon dioxide, halides of corresponding benzyl or allyl, in an organic medium (dimethylformamide-DMF) in the presence of tetraethylammonium chloride as indifferent electrolyte.
- the cathode is made of mercury and the anode of platinum.
- allyl or benzyl esters obtained are therefore completely stable with respect to electrocarboxylation since they are isolated with excellent yields.
- the method according to the invention allows, compared to the method described in FR 2 566 434 to retain all the advantages, and in particular those mentioned in the application FR 2 566 434 itself , without having the disadvantages and in particular those mentioned above linked to the use of organic halides.
- the process for the electrosynthesis of carboxylic acids by electrochemical reduction, in the presence of carbon dioxide, of organic compounds comprising at least one simple carbon-heteroatom covalent bond process carried out in an organic medium in a cell.
- electrolysis provided with electrodes is characterized in that the anode is made of a metal chosen from the group consisting of reducing metals and their alloys and in that the heteroatom is chosen from the group consisting of oxygen, nitrogen, sulfur and phosphorus.
- alloys means any alloy containing at least one reducing metal.
- the reducing metal is chosen from the group consisting of magnesium, aluminum, zinc and their alloys.
- the organic compounds comprising at least one simple carbon-heteroatom covalent bond which can be used in the context of the present invention correspond to the general formula RY in which R is an organic radical and Y a heteroatomic radical, the heteroatom chosen from the group consisting of l Oxygen, nitrogen, sulfur and phosphorus being directly linked to a carbon atom of the organic radical R by a simple covalent bond.
- Carboxylic acids of general formula R-COOH are thus obtained by breaking in R-Y of the simple covalent bond connecting the heteroatom of the radical Y to a carbon atom of the radical R and fixing of CO2 on this carbon atom.
- Y is necessarily an ammonium radical
- Y is necessarily a phosphonium radical
- Y is for example a radical
- Y is for example a radical
- radicals R1, R2 and R3 are aliphatic, aromatic or heterocyclic hydrocarbon radicals, substituted or unsubstituted. They can also form rings, with each other or with the radical R.
- unsaturated carboxylic acids are obtained.
- the carbon atom of the organic radical R which is directly linked to the heteroatom of the radical Y is hybridized "sp3" (it is sometimes said that such a carbon atom is a “saturated” carbon atom) and to the at least one of the carbon atoms of the radical R in beta position with respect to the heteroatom of the radical Y is hybridized “sp2". (It is sometimes said that such a carbon atom is an "ethylenically unsaturated” carbon atom).
- “sp3" hybridization is a tetrahedral hybridization
- sp2" hybridization is a plane trigonal hybridization.
- This hybridized "sp2" carbon atom of the radical R in the beta position with respect to the heteroatom is particularly preferably an ethylenic carbon atom or a carbon atom forming part of a substituted or unsubstituted aromatic ring or heterocycle.
- the radical R is preferably an aliphatic radical containing 3 to 10 carbon atoms. This is the case for example when R is an allylic radical.
- the hybridized carbon atom "sp2" of the radical R in the beta position with respect to the heteroatom is part of a substituted or unsubstituted aromatic ring
- the hybridized carbon atom "sp3" of the radical R which is directly linked to the heteroatom preferably bears either 2 hydrogen atoms, or a hydrogen atom and a methyl or ethyl or isopropyl group.
- the radical R is a benzyl radical.
- this aromatic heterocycle is preferably thiophene, N-methyl pyrrole, indole or pyridine.
- This carbon atom of the radical R in the beta position can also be an acetylene carbon (hybridized "sp1") or that of a carbonyl or nitrile group.
- the organic radical R can comprise at least one non-reducible functional group under the conditions of electrosynthesis. Mention may be made, for example, of carbonyl, nitrile, tertiary amines, amides and fluorine groups.
- the anode can have any shape and in particular all the classic forms of metal electrodes (twisted wire, flat bar, cylindrical bar, square section bar, plate, renewable bed, canvas, grid, ribbon, balls, shot, powder, etc).
- a cylindrical bar of diameter adapted to the dimensions of the cell is used.
- the purity of the metal (or alloy) constituting the anode is not an important parameter and the industrial qualities are suitable.
- the cathode is any metal such as stainless steel, nickel, platinum, gold, copper, or graphite. It is preferably formed by a grid or a cylindrical plate arranged concentrically around the anode. For economic reasons, stainless steel is preferably used.
- the electrodes are supplied with direct current via a stabilized power supply.
- the organic solvents used in the context of this invention are all the low-protic solvents usually used in organic electrochemistry. Examples that may be mentioned are hexamethylphosphorotriamide (HMPT), tetrahydrofuran (THF), THF-HMPT mixtures, N-methylpyrrolidone (NMP), tetramethylurea (TMU), dimethylformamide (DMF), acetonitrile.
- HMPT hexamethylphosphorotriamide
- THF tetrahydrofuran
- NMP N-methylpyrrolidone
- TU tetramethylurea
- DMF dimethylformamide
- acetonitrile acetonitrile
- the indifferent electroytes used to make the medium conductive or more conductive can be those usually used in organic electrochemistry. Mention may be made, for example, of tetrabutylammonium tetrafluoroborate (BF4 NBu4), lithium perchlorate (LiClO4), tetrabutylammonium chloride (ClNBu4), tetraethylammonium chloride (ClNEt4, tetrabutylammonium perchlorate (ClO4Nu) and zinc salts magnesium or aluminum.
- BF4 NBu4 tetrabutylammonium tetrafluoroborate
- LiClO4 lithium perchlorate
- ClNBu4 tetrabutylammonium chloride
- ClNEt4 tetraethylammonium chloride
- ClO4Nu zinc salts magnesium or aluminum.
- the indifferent electrolyte is an ammonium salt
- the latter is at least partially carboxylated according to the invention but on the one hand the quantity of indifferent electrolyte can be low compared to the derivative RY and on the other by the acid formed by carboxylation of the electrolyte is easily separated from the desired acid obtained by carboxylation of the derivative RY.
- an indifferent electrolyte is not necessary when the R-Y compound to be reduced is itself ionic, as is the case, for example, for ammonium, sulfonium or phosphonium salts.
- its concentration in the organic solvent is preferably between 5 10 ⁇ 3 M and 5 10 ⁇ 2 M.
- the concentration of the R-Y compound to be reduced in the organic solvent is between 10 ⁇ 1 M and 1 M. This concentration can therefore be relatively high, which is quite unusual in electrosynthesis. This observation is of course very interesting from an economic point of view.
- the carboxylic acid formed, and optionally the unprocessed starting product, are isolated.
- the upper glass part is equipped with 5 tubes allowing the arrival and the exit of carbon dioxide, the electrical passages and the possible samples of solution during electrolysis.
- the lower part consists of a stopper fitted with a seal, screwed onto the upper glass part.
- the total volume of the cell is 150 cm3.
- the anode is a cylindrical bar of magnesium whose diameter is 1 cm. It is introduced into the cell through the central tube and immersed in the solution over a length of approximately 20 cm. The initial working surface of this electrode is 63 cm2.
- the cathode is a cylindrical stainless steel fabric arranged concentrically around the anode.
- DMF dimethylformamide
- CO2 is bubbled through the solution using a tube immersed in this solution.
- the CO2 pressure is atmospheric pressure.
- the solution is stirred via a magnetic bar and the temperature is maintained at around 10 ° C.
- the electrodes are supplied with direct current via a stabilized power supply and a constant current of 2 A is then imposed, ie a current density of 32 mA / cm2 on the magnesium anode.
- reaction medium After electrolysis and evaporation of the DMF, the reaction medium is hydrolyzed with aqueous hydrochloric acid.
- the organic compounds are then extracted with ethyl ether, then the acids are recovered by alkaline extraction.
- the products obtained are identified according to conventional analytical methods, namely in particular NMR, IR, CPG and mass spectrometry.
- Electrolysis chloride paramethoxybenzyl, ethyl, dimethyl ammonium is effected under the same conditions as for Example No. 23, but in a stainless steel cell under a pressure of 5 bar and CO2 at a temperature of 30 ° C .
- a solution of dimethylbenzylacetylammonium chloride is prepared by adding, at 5 ° C, 9 g of acetyl chloride to a solution of 15 g of dimethylbenzylamine in 110 g of DMF.
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- 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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8700134 | 1987-01-09 | ||
FR8700134A FR2609474B1 (fr) | 1987-01-09 | 1987-01-09 | Procede de synthese electrochimique d'acides carboxyliques |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0277048A1 true EP0277048A1 (de) | 1988-08-03 |
EP0277048B1 EP0277048B1 (de) | 1991-04-10 |
Family
ID=9346756
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88400025A Expired - Lifetime EP0277048B1 (de) | 1987-01-09 | 1988-01-07 | Verfahren zur elektrochemischen Herstellung von Carbonsäuren |
Country Status (5)
Country | Link |
---|---|
US (1) | US4824532A (de) |
EP (1) | EP0277048B1 (de) |
JP (1) | JP2688416B2 (de) |
DE (1) | DE3862306D1 (de) |
FR (1) | FR2609474B1 (de) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE9703314D0 (sv) * | 1997-09-15 | 1997-09-15 | Sangtec Medical Ab | Capacity affinity sensor |
JP4613066B2 (ja) * | 2002-09-10 | 2011-01-12 | ソルヴェイ(ソシエテ アノニム) | 有機塩及び電気化学反応における試薬としてのその使用 |
DE10326047A1 (de) * | 2003-06-10 | 2004-12-30 | Degussa Ag | Verfahren zur Herstellung alpha-substituierter Carbonsäuren aus der Reihe der alpha-Hydroxycarbonsäuren und N-substituierten-alpha-Aminocarbonsäuren |
US8313634B2 (en) | 2009-01-29 | 2012-11-20 | Princeton University | Conversion of carbon dioxide to organic products |
US20110114502A1 (en) * | 2009-12-21 | 2011-05-19 | Emily Barton Cole | Reducing carbon dioxide to products |
US8500987B2 (en) | 2010-03-19 | 2013-08-06 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
US8845877B2 (en) | 2010-03-19 | 2014-09-30 | Liquid Light, Inc. | Heterocycle catalyzed electrochemical process |
US8721866B2 (en) | 2010-03-19 | 2014-05-13 | Liquid Light, Inc. | Electrochemical production of synthesis gas from carbon dioxide |
US8524066B2 (en) | 2010-07-29 | 2013-09-03 | Liquid Light, Inc. | Electrochemical production of urea from NOx and carbon dioxide |
US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
US8562811B2 (en) | 2011-03-09 | 2013-10-22 | Liquid Light, Inc. | Process for making formic acid |
CA2841062A1 (en) | 2011-07-06 | 2013-01-10 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
CA2839004A1 (en) | 2011-07-06 | 2013-01-10 | Liquid Light, Inc. | Carbon dioxide capture and conversion to organic products |
CN114381749B (zh) * | 2022-01-10 | 2023-05-30 | 万华化学集团股份有限公司 | 一种合成薄荷甲酸的方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0189120A1 (de) * | 1985-01-21 | 1986-07-30 | Consiglio Nazionale Delle Ricerche | Verfahren für die Elektrocarboxylierung von Carbonylverbindungen zur Herstellung von alpha-Hydroxycarbonylsäuren |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4028201A (en) * | 1972-11-13 | 1977-06-07 | Monsanto Company | Electrolytic monocarboxylation of activated olefins |
US4072583A (en) * | 1976-10-07 | 1978-02-07 | Monsanto Company | Electrolytic carboxylation of carbon acids via electrogenerated bases |
FR2566434B1 (fr) * | 1984-06-21 | 1986-09-26 | Poudres & Explosifs Ste Nale | Procede d'electrosynthese d'acides carboxyliques |
-
1987
- 1987-01-09 FR FR8700134A patent/FR2609474B1/fr not_active Expired - Lifetime
-
1988
- 1988-01-07 US US07/141,492 patent/US4824532A/en not_active Expired - Lifetime
- 1988-01-07 DE DE8888400025T patent/DE3862306D1/de not_active Expired - Lifetime
- 1988-01-07 EP EP88400025A patent/EP0277048B1/de not_active Expired - Lifetime
- 1988-01-08 JP JP63001400A patent/JP2688416B2/ja not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0189120A1 (de) * | 1985-01-21 | 1986-07-30 | Consiglio Nazionale Delle Ricerche | Verfahren für die Elektrocarboxylierung von Carbonylverbindungen zur Herstellung von alpha-Hydroxycarbonylsäuren |
Also Published As
Publication number | Publication date |
---|---|
DE3862306D1 (de) | 1991-05-16 |
JP2688416B2 (ja) | 1997-12-10 |
FR2609474B1 (fr) | 1991-04-26 |
JPS63190186A (ja) | 1988-08-05 |
EP0277048B1 (de) | 1991-04-10 |
FR2609474A1 (fr) | 1988-07-15 |
US4824532A (en) | 1989-04-25 |
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