SI9520102A - New method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde - Google Patents
New method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde Download PDFInfo
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- SI9520102A SI9520102A SI9520102A SI9520102A SI9520102A SI 9520102 A SI9520102 A SI 9520102A SI 9520102 A SI9520102 A SI 9520102A SI 9520102 A SI9520102 A SI 9520102A SI 9520102 A SI9520102 A SI 9520102A
- Authority
- SI
- Slovenia
- Prior art keywords
- nitrobenzaldehyde
- dihydroxy
- zinc chloride
- ranges
- hydrochloric acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- BBFJODMCHICIAA-UHFFFAOYSA-N 3,4-dihydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC(C=O)=CC([N+]([O-])=O)=C1O BBFJODMCHICIAA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 27
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000011592 zinc chloride Substances 0.000 claims abstract description 13
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 13
- MDWLNBVKBMKTKN-UHFFFAOYSA-N 3-ethoxy-4-hydroxy-5-nitrobenzaldehyde Chemical compound CCOC1=CC(C=O)=CC([N+]([O-])=O)=C1O MDWLNBVKBMKTKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- ZEHYRTJBFMZHCY-UHFFFAOYSA-N 5-nitrovanillin Chemical compound COC1=CC(C=O)=CC([N+]([O-])=O)=C1O ZEHYRTJBFMZHCY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000003880 polar aprotic solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006900 dealkylation reaction Methods 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RCCIQDAGHPKBOM-UHFFFAOYSA-N 2-bromo-3,4-dihydroxy-5-nitrobenzaldehyde Chemical compound OC1=C(O)C([N+]([O-])=O)=CC(C=O)=C1Br RCCIQDAGHPKBOM-UHFFFAOYSA-N 0.000 description 1
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- YHKWFDPEASWKFQ-UHFFFAOYSA-N 3-nitrobenzene-1,2-diol Chemical group OC1=CC=CC([N+]([O-])=O)=C1O YHKWFDPEASWKFQ-UHFFFAOYSA-N 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JRURYQJSLYLRLN-BJMVGYQFSA-N entacapone Chemical compound CCN(CC)C(=O)C(\C#N)=C\C1=CC(O)=C(O)C([N+]([O-])=O)=C1 JRURYQJSLYLRLN-BJMVGYQFSA-N 0.000 description 1
- 229960003337 entacapone Drugs 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/44—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
Description
NOVI POSTOPEK ZA PRIPRAVO 3,4-DIHIDROKSI-5-NITROBENZALDEHIDA
Izum se nanaša na novi postopek za pripravo 3,4-dihidroksi-5-nitrobenzaldehida, ki je pomemben intermediat pri sintezi mnogih farmacevtskih spojin, ki imajo 5-substituirano
3-nitrokateholno strukturo, na primer entakapon.
Vsi znani postopki za pripravo 3,4-dihidroksi-5-nitrobenzaldehida temeljijo na demetilaciji 4-hidroksi-3-metoksi-5-nitrobenzaldehida. Naj starejši postopek (Hayduck, F. Chem. Ber. 36 (1903), str. 2930) uporablja klorovodikovo kislino kot reagent. Postopek je neuporaben, ker se izhodni material in/ali proizvod razkrojita med procesom, kar zmanjšuje izkoristek. Proces proizvede tudi nečisti proizvod (tališče 106°C), reakcija pa mora potekati pod pritiskom.
Izboljšani postopek je opisan v EP 237929 in GB 2200109. Ta postopek uporablja bromovodikovo kislino namesto klorovodikove. Specifični problem pri tem postopku je tvorba na obroču bromirane nečistoče (verjetho 2-bromo-3,4-dihidroksi-5nitrobenzaldehid) in neke nespecificirane rjavkasto črne nečistoče. Poleg tega si ta postopek in zgoraj omenjeni postopek na bazi klorovodikove kisline delita skupni problem, da potiskanje reakcije do konca znatno poveča količino nečistoč. Če demetilacija ni izpeljana do konca, proizvedeni 3,4-dihidroksi-5-nitrobenzaldehid vsebuje nekaj 4-hidroksi-3-metoksi-5-nitrobenzaldehida. To nečistočo je zelo težko odstraniti inje zaradi tega 3,4-dihidroksi-5-nitrobenzaldehid slabo primeren za nadaljnje procesiranje.
Tretji postopek je bil opisan v PCT patentni prijavi WO 93/00323. Temelji na dealkilaciji in uporablja kombinacijo litijevega hidroksida in tiofenola ali 2merkaptobenzotiazola v polarnem aprotičnem topilu. Ta postopek nima problemov v zvezi z razkrojem proizvoda v reakcijskem okolju, tako da reakcijo lahko privedejo do konca. Postopek omogoča pripravo čistega 3,4-dihidroksi-5-nitrobenzaldehida, vendar pa ima še vedno mnogo problemov, ki otežkočajo njegovo široko uporabo na industrijski ravni. Prvič, organski reagent in dragi litijev hidroksid se porabita med reakcijo, tako da ju ni mogoče reciklirati. Drugič, v procesu je potrebno uporabiti polarno aprotično topilo skupaj z drugim organskim topilom in vodo. Med recikliranjem topil je potrebno imeti postopek za medsebojno ločitev organskih topil ter za pridobivanje dovolj suhega polarnega aprotičnega topila za nadaljnjo uporabo.
Izum temelji na presenetljivem opažanju, da 3-etoksi-4-hidroksi -5-nitrobenzaldehid lahko cepimo z reagentom, ki vsebuje cinkov klorid, vodo in vodikov klorid, da se tvori
3,4-dihidroksi-5-nitrobenzaldehid. Presenetljivo je, da je možna uporaba cinkovega klorida kot Lewisova kislina za pospešitev dealkilacijske reakcije, čeprav je znano, da se alkil aril etri lahko cepijo z uporabo Lewisove kisline (Bhatt, M.V. in Kulkarni, S.U., Synthesis (1983), str. 249; Bunvell, R.L. Chem.Rev.(1954), str. 615; K.F. Wedemeyer v Methoden der Organischen Chemie (Houben - Weyl), Vol 6/lc, str. 340-358, Založba Georg Thieme, Stuttgart 1976).
Izjemno je tudi, da lahko reakcijo izvedemo v vodnih pogojih. Tu opisani postopek je specifičen za 3-etoksi-4-hidroksi-5-nitrobenzaldehid in ga ni mogoče uporabiti za 4hidroksi-3-metoksi-5-nitrobenzaldehid, ki je praktično inerten pod uporabljenimi pogoji. Ta ugotovitev je presenetljiva, ker poročajo, da ima etoksi skupina nizko reaktivnost v primerjavi z metoksi skupino pri dealkilaciji katalizirani v navadni kislini (K.-F. Wedemeyer v Methoden der Organischen Chemie, (Houben - Weyl), Vol 6/lc, str. 314, Založba Georg Thieme, Stuttgart 1976).
Predloženi proces je enostaven, reagenti so poceni ter jih z lahkoto recikliramo. Poleg tega pridobimo proizvod visoke čistoče, ker rezidualni izhodni material 3-etoksi-4hidroksi-5 -nitrobenzaldehid lahko odstranimo s kristalizacijo. Reakcija lahko poteka v vodi; organsko topilo ni potrebno. Edini reagent, ki se porabi med procesom, je vodikov klorid. Po reakciji proizvod izoliramo z razredčenjem zmesi z vodo in s filtriranjem proizvoda. Proizvod lahko nadalje očistimo s kristalizacijo z uporabo konvencionalnih organskih topil, prednost ima toluen. Cinkov klorid lahko regeneriramo iz filtrata z izparevanjem do suhega. Pred izparevanjem je koristno ekstrahirati filtrat z organskim topilom kot etilacetat za odstranitev organskih nečistoč. Možno je tudi taljenje cinkovega klorida po izparevanju, ta proces uničuje organske nečistoče.
Proces je uspešen, če ga izvedemo z uporabo naslednjih pogojev: količina cinkovega klorida sega preferencialno od 1,5 kg do 25 kg na 1 kg 3-etoksi-4-hidroksi-5nitrobenzaldehida, najbolje od 2,5 kg do 4 kg. Količina klorovodikove kisline sega preferencialno od 0,17 L do 0,6 L na 1 kg cinkovega klorida, najbolje od 0.22 L do 0,4
L. Koncentracija klorovodikove kisline, ki jo dodamo reakcijski zmesi, sega preferencialno od 10% do 40%, najbolje od 20% do 38%. Temperatura sega preferencialno od 70°C do 130°C, najbolje od 80°C do 110°C.
Priprava izhodnega materiala
3-etoksi-4-hidroksi-5-nitrobenzaldehid: kadečo se dušikovo(V) kislino (22,0 mL) smo dodali (hitrost približno 1,5 mL/min) stresani raztopini 3-etoksi-4-hidroksibenzaldehida (83,0 g) in diklormetana (400 mL) pri 5-10°C. Nato smo stresali 30 minut pri 3°C in filtrirali. Proizvod smo sprali z diklormetanom in vodo in sušili v vakuumu pri 50°C, izkoristek 77,8 g (73,7%).
Vzorec
3,4-dihidroksi-5-nitrobenzaldehid: zmes 3-etoksi-4-hidroksi-5 -nitrobenzaldehida (20,0
g), cinkovega klorida (60,0 g) in klorovodikove kisline (37%, 15 mL) smo stresali pri
90°C 17 ur. Zmes smo razredčili z vodo (100 mL) in nato ohladili na 3°C. Po eni uri smo proizvod filtrirali in sprali z mrzlo vodo. Proizvod smo sušili v vakuumu pri 100°C, kar daje 16,5 g (95,1%) surovega proizvoda. Surovi proizvod smo zmešali s toluenom (275 mL) in aktivnim ogljem (2,0 g) in nastalo zmes refluksirali 45 min. Vročo raztopino smo filtrirali in nato ohladili na 3°C. Po eni uri smo proizvod filtrirali in sprali z mrzlim toluenom. Sušili smo ga v vakuumu pri 50°C in dobili 12,6 g (72,6%) čistega
3,4-dihidroksi-5-nitrobenzaldehida (tališče 146-8°C).
Claims (10)
- PATENTNI ZAHTEVKI1. Postopek za pripravo 3,4-dihidroksi-5-nitrobenzaldehida, označen s tem, da 3etoksi-4-hidroksi-5-nitrobenzaldehid reagira z reagentom, ki vsebuje cinkov klorid, vodo in klorovodikovo kislino.
- 2. Postopek v skladu z zahtevkom 1, označen s tem, da količina cinkovega klorida sega od 1,5 kg do 25 kg na 1 kg 3-etoksi-4-hidroksi-5-nitrobenzaldehida.
- 3. Postopek v skladu z zahtevkom 2, označen s tem, da količina cinkovega klorida sega od 2,5 kg do 4 kg na 1 kg 3-etoksi-4-hidroksi-5-nitrobenzaldehida.
- 4. Postopek v skladu z zahtevkom 1, označen s tem, da količina klorovodikove kisline sega od 0,17 L do 0,6 L na 1 kg cinkovega klorida.
- 5. Postopek v skladu z zahtevkom 4, označen s tem, da količina klorovodikove kisline sega od 0,22 L do 0,4 L na 1 kg cinkovega klorida.
- 6. Postopek v skladu z zahtevkom 1, označen s tem, da sega koncentracija klorovodikove kisline od 10% do 40%.
- 7. Postopek v skladu z zahtevkom 6, označen s tem, da sega koncentracija klorovodikove kisline od 20% do 38%.
- 8. Postopek v skladu z zahtevkom 1, označen s tem, da sega temperatura od 70°C do 130°C.
- 9. Postopek v skladu z zahtevkom 8, označen s tem, da sega temperatura od 80°C doll0°C.
- 10. Postopek v skladu z zahtevkom 1, označen s tem, da surov proizvod nadalje kristaliziramo iz toluena. ,
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9419274A GB9419274D0 (en) | 1994-09-23 | 1994-09-23 | New method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SI9520102A true SI9520102A (en) | 1997-08-31 |
Family
ID=10761838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SI9520102A SI9520102A (en) | 1994-09-23 | 1995-09-20 | New method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde |
Country Status (28)
| Country | Link |
|---|---|
| US (1) | US5710343A (sl) |
| EP (1) | EP0782559B1 (sl) |
| JP (1) | JP3717933B2 (sl) |
| KR (1) | KR100368163B1 (sl) |
| CN (1) | CN1064673C (sl) |
| AT (1) | ATE175660T1 (sl) |
| AU (1) | AU684672B2 (sl) |
| BG (1) | BG61912B1 (sl) |
| BR (1) | BR9508852A (sl) |
| CA (1) | CA2200227C (sl) |
| CZ (1) | CZ288684B6 (sl) |
| DE (1) | DE69507309T2 (sl) |
| DK (1) | DK0782559T3 (sl) |
| ES (1) | ES2127552T3 (sl) |
| GB (1) | GB9419274D0 (sl) |
| GR (1) | GR3029815T3 (sl) |
| HU (1) | HU224821B1 (sl) |
| IL (1) | IL115122A (sl) |
| LV (1) | LV11831B (sl) |
| MX (1) | MX9702064A (sl) |
| NO (1) | NO306670B1 (sl) |
| NZ (1) | NZ292187A (sl) |
| PL (1) | PL180016B1 (sl) |
| RO (1) | RO119540B1 (sl) |
| RU (1) | RU2130449C1 (sl) |
| SI (1) | SI9520102A (sl) |
| SK (1) | SK281789B6 (sl) |
| WO (1) | WO1996009274A1 (sl) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9419274D0 (en) * | 1994-09-23 | 1994-11-09 | Orion Yhtymae Oy | New method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde |
| AU2007346018A1 (en) * | 2007-01-31 | 2008-08-07 | Bial - Portela & Ca, S.A. | Dosage regimen for COMT inhibitors |
| EP2251323B1 (en) | 2009-05-14 | 2014-04-23 | F.I.S.- Fabbrica Italiana Sintetici S.p.A. | Method for the purification of entacapone |
| CN102633646B (zh) * | 2012-04-10 | 2014-06-04 | 中国海洋大学 | 一种新的5-硝基水杨醛制备方法 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO107714C (sl) * | 1961-06-21 | |||
| FR1330382A (fr) * | 1961-06-21 | 1963-06-21 | Monsanto Chemicals | Procédé de clivage des éthers d'alcoyle o-hydroxyphényle et de préparation simultanée de composés 1-alkyl-2,3-dihydroxyphényliques |
| US4213920A (en) * | 1977-07-06 | 1980-07-22 | Ciba-Geigy Corporation | Process for the production of substituted benzaldehydes |
| DK175069B1 (da) * | 1986-03-11 | 2004-05-24 | Hoffmann La Roche | Pyrocatecholderivater |
| YU213587A (en) * | 1986-11-28 | 1989-06-30 | Orion Yhtymae Oy | Process for obtaining new pharmacologic active cateholic derivatives |
| DE4012008A1 (de) * | 1990-04-13 | 1991-10-17 | Bayer Ag | Verfahren zur herstellung von o-hydroxy-benzaldehyden |
| GB9113431D0 (en) * | 1991-06-20 | 1991-08-07 | Orion Yhytma Oy | Method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde |
| CA2085137A1 (fr) * | 1991-12-12 | 1993-06-13 | Hoechst Marion Roussel | Nouvelles cephalosporines comportant en position 7 un radical benzyloxyimino substitue, leur procede de preparation, leur application comme medicaments |
| GB9419274D0 (en) * | 1994-09-23 | 1994-11-09 | Orion Yhtymae Oy | New method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde |
-
1994
- 1994-09-23 GB GB9419274A patent/GB9419274D0/en active Pending
-
1995
- 1995-05-22 KR KR1019970701878A patent/KR100368163B1/ko not_active Expired - Fee Related
- 1995-08-31 IL IL11512295A patent/IL115122A/xx not_active IP Right Cessation
- 1995-09-20 CA CA002200227A patent/CA2200227C/en not_active Expired - Fee Related
- 1995-09-20 HU HU9702258A patent/HU224821B1/hu unknown
- 1995-09-20 US US08/809,405 patent/US5710343A/en not_active Expired - Fee Related
- 1995-09-20 WO PCT/FI1995/000513 patent/WO1996009274A1/en not_active Ceased
- 1995-09-20 DK DK95930558T patent/DK0782559T3/da active
- 1995-09-20 SK SK378-97A patent/SK281789B6/sk unknown
- 1995-09-20 RO RO97-00574A patent/RO119540B1/ro unknown
- 1995-09-20 RU RU97106330A patent/RU2130449C1/ru not_active IP Right Cessation
- 1995-09-20 ES ES95930558T patent/ES2127552T3/es not_active Expired - Lifetime
- 1995-09-20 JP JP51063396A patent/JP3717933B2/ja not_active Expired - Fee Related
- 1995-09-20 NZ NZ292187A patent/NZ292187A/en unknown
- 1995-09-20 CN CN95195222A patent/CN1064673C/zh not_active Expired - Fee Related
- 1995-09-20 PL PL95319348A patent/PL180016B1/pl not_active IP Right Cessation
- 1995-09-20 CZ CZ1997800A patent/CZ288684B6/cs not_active IP Right Cessation
- 1995-09-20 SI SI9520102A patent/SI9520102A/sl not_active IP Right Cessation
- 1995-09-20 BR BR9508852A patent/BR9508852A/pt not_active IP Right Cessation
- 1995-09-20 DE DE69507309T patent/DE69507309T2/de not_active Expired - Fee Related
- 1995-09-20 AU AU33901/95A patent/AU684672B2/en not_active Ceased
- 1995-09-20 EP EP95930558A patent/EP0782559B1/en not_active Expired - Lifetime
- 1995-09-20 AT AT95930558T patent/ATE175660T1/de not_active IP Right Cessation
- 1995-09-20 MX MX9702064A patent/MX9702064A/es not_active IP Right Cessation
-
1997
- 1997-03-11 BG BG101309A patent/BG61912B1/bg unknown
- 1997-03-21 NO NO971325A patent/NO306670B1/no unknown
- 1997-04-03 LV LVP-97-54A patent/LV11831B/en unknown
-
1999
- 1999-03-30 GR GR990400905T patent/GR3029815T3/el unknown
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| IF | Valid on the event date | ||
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Owner name: ORION OYJ (ORION CORPORATION); FI Effective date: 20071108 |
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Effective date: 20090424 |