WO2000040550A1 - Procede de preparation de nitroxydes - Google Patents
Procede de preparation de nitroxydesInfo
- Publication number
- WO2000040550A1 WO2000040550A1 PCT/FR1999/003254 FR9903254W WO0040550A1 WO 2000040550 A1 WO2000040550 A1 WO 2000040550A1 FR 9903254 W FR9903254 W FR 9903254W WO 0040550 A1 WO0040550 A1 WO 0040550A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- radical
- formula
- carbon atoms
- branched
- linear
- Prior art date
Links
- 0 *C(C1(CCCCC1)NC12CCCCC1)C2=* Chemical compound *C(C1(CCCCC1)NC12CCCCC1)C2=* 0.000 description 8
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/24—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
Definitions
- the present invention relates to a process for the preparation of N-oxide radicals of secondary amines by oxidation of the corresponding secondary amines.
- nitroxides are free radicals containing a single electron.
- nitroxide radicals can be used as stabilizers for organic polymers, in particular for inhibiting thermal and light degradation of polyolefins (US 3,431, 233) and PVC (US 3,547,874). They are also used as a spin marker for the study of biological compounds and as regulators of radical polymerizations (Georges, M, K et al. Macromoleculules 1993, 26, 2987).
- the main methods for preparing nitroxides are the oxidation of hydroxylamines and the oxidation of secondary amines, this second method being the most frequently used industrially.
- the oxidation reaction takes place in water or a water / alcohol mixture at temperatures between 60 and 100 ° C.
- a process for the oxidation of cyclic secondary amine which consists in reacting said amine in an inert organic solvent, with an organic hydroperoxide such as tert-butyl hydroperoxide, in the presence of catalytic amounts of a carbonyl metal (Mo (CO) 6 ), a metal oxide (M0O3), a metal acetylacetonate or a metal alcoholate (Ti (OiPr) 4 ) whose metal belongs to one of groups IVB, VB, VIB, VIIB and VIII of the periodic table, at a temperature ranging from 0 ° C to 200 ° C.
- an organic hydroperoxide such as tert-butyl hydroperoxide
- reaction times are shorter but the problem of recovering the catalyst still persists.
- the products must be purified and the effluents treated.
- Another method of secondary amine oxidation consists in reacting said secondary amine with dimethyldioxirane (DMD) in the absence of catalysts (US 5,087,752).
- DMD dimethyldioxirane
- DMD is prepared by oxidation of acetone either with OXONE® which is a potassium monoperoxysulfate, or more rarely with Caro acid which is a mixture of H 2 S ⁇ 4 / ⁇ 2 SO 5 .
- Perbenzoic acids such as metachloroperbenzoic acid (Journal of American Chemical Society, 1967, 89 (12) 3055-3056) or paranitroperbenzoic acid (Rassat A. et al. Bulletin de la cios Chimique de France, 1965, 3283- 3290) dissolved in organic solvents such as methylene chloride allow many secondary amines to be oxidized effectively to nitroxides.
- nitroxides can be obtained according to a process which avoids the abovementioned drawbacks, which consists in oxidizing secondary amines by means of aliphatic peracids in two-phase organic solvent / water medium, the aqueous phase of which is maintained at a pH ranging from 4 to 12.
- the present invention therefore relates to a process for the preparation of N-oxide radicals of secondary amines (nitroxide radicals) from the corresponding secondary amines, characterized in that the following steps are carried out: a / the amine is solubilized secondary with an organic solvent, immiscible with water, then water is added, b / a quantity of aliphatic peracid is then added simultaneously and with vigorous stirring to the biphasic medium thus obtained in a molar ratio of peracid / secondary amine ranging from 1.5 to 2.5 and preferably ranging from 1.5 to 2, and a sufficient amount of a basic aqueous solution to obtain a pH of the aqueous phase of the biphasic medium ranging from 4 to 12, at a temperature between -10 ° C and + 40 ° C, until complete conversion of the secondary amine, then c / the organic phase is recovered by simple decantation, and the nitroxide is isolated by evaporation of the organic solvent under pressure r educated.
- aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, decane, cyclohexane, cyclododecane
- aromatic hydrocarbons such as benzene, toluene, xylenes
- aliphatic peracids which can be used according to the present invention, mention will be made of peracetic acid, perpropionic acid, perbutanoic acid.
- peracetic acid or perpropionic acid will be used.
- the process of the present invention therefore consists in dissolving, with stirring, the secondary amine in an organic solvent, immiscible with water and inert with respect to said secondary amine and to the reagents used.
- the amount of organic solvent used depends on the solubility of said secondary amine in said solvent.
- organic solvent is not critical and can vary widely. However, for economic reasons and for the sake of respecting the environment, those skilled in the art will endeavor to choose an organic solvent (or a mixture of solvents) so as to use only minimal amounts to dissolve the secondary amine.
- the aliphatic peracid generally in solution in the corresponding aliphatic acid, is added to the biphasic medium obtained, according to a molar peracid / secondary amine ratio. as defined above and a sufficient quantity of a basic aqueous solution of a carbonate or a hydrogen carbonate of an alkali metal or of an alkaline earth metal so that the pH of the aqueous solution of the biphasic medium is maintained at a value ranging from 4 to 12 and preferably ranging from 5 to 9.
- a basic aqueous solution of a carbonate or a hydrogen carbonate of an alkali metal preferably be made of a basic aqueous solution of a carbonate or a hydrogen carbonate of an alkali metal.
- alkali metal carbonates or hydrogen carbonates which can be used according to the present invention, mention will be made of NaHCO 3 , KHCO 3 , K 2 CO 3 , Na 2 CO 3 .
- the reaction is carried out at a temperature ranging from -10 ° C to + 40 ° C and, preferably, ranging from -5 ° C to + 30 ° C until the secondary amine is completely transformed.
- the progress of the reaction can be followed by analytical methods such as the chemical assay of the peracid used according to methods known to those skilled in the art (assay with sulfite and Ce 4 + ) and gas chromatography.
- the organic phase is recovered, generally by simple decantation. This organic phase can optionally be washed with demineralized water and then dried.
- the nitroxide formed is isolated by evaporation of the organic solvent under reduced pressure. If necessary, the purity of the nitroxide can be improved by distillation under reduced pressure or by recrystallization. Nitroxides can be identified by elemental analysis, HPLC, IR, RPE and mass spectrometry (MS).
- the oxidation reaction of secondary amines to nitroxides has the advantage of being carried out with inexpensive oxidants, commercially available, under mild conditions, quickly and with high yields.
- the purification of the nitroxides obtained is simple and the effluents (salts of organic acids) can be optionally recovered.
- the process for the oxidation of secondary amines to nitroxides according to the invention has the advantage of being able to be applied to secondary amines (or secondary polyamines) with steric hindrance or to those having a - CH in ⁇ of the nitrogen atom .
- R a , R b , R c and R d identical or different, represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10, or R a and R b form with l carbon atom which carries them, or R c and R d form with the carbon atom which carries them cycloalkyl having a number of carbon atoms ranging from 3 to 10, a spiranic, cholestanic or androstanic residue.
- the oxidation process of the present invention makes it possible to oxidize the hindered secondary amines to nitroxide comprising at least 1 motif (A) or the secondary amines having at least 1 - CH in ⁇ of the nitrogen atom.
- Rd in which X represents a divalent radical chosen from the following radicals: ⁇ H 2 ; C O; - O - - ⁇ - T c ' ans ' ec l ue ' ⁇ z represents a monovalent residue chosen from - CN, - NHR, - OR, -
- N C (R) 2 in which R represents a hydrogen atom, a linear or branched alkyl radical having a number of carbon atoms ranging from
- Y represents a divalent residue chosen from:
- - S -, - O -, R 2 and R 3 identical or different, represent a hydrogen atom, an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10, n represent an integer ranging from O to 20;
- R 4 represents a hydrogen atom an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10
- R 5 represents a hydrogen atom - CH 3 , - C 2 H 5 , - CH 2 OH, - C (O) NH 2 , —OH, - CHO;
- R 6 has the same meaning as R 4 and R 7 has the same meaning as R 5 ,
- R 8 and R 9 represent a hydrogen atom, a radical alkyl, linear or branched, having a number of carbon atoms ranging from 1 to 10;
- R 14 , R 15 , R 16 f R 17 f R 18, and R 19, which are identical or different, represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 20, a cycloalkyl radical having at least 3 carbon atoms, a phenyl radical, a benzyl radical, or else R 14 and R 1 5 form with the carbon atom which carries them, or else R 1 6 and R 1 7 form with the carbon atom which carries them, a cycloalkyl having a number of carbon atoms ranging from 3 to 10;
- R 20 and R 21 identical or different, represent a hydrogen atom, a linear alkyl, branched or cyclic alkyl group having a number of carbon atoms ranging from 1 to 10, an aryl radical, an aralkyl radical, or R 20 and R 21 are linked together so as to form a ring including the carbon atom carrying said radicals R 20 and R 21 , said ring having a number of carbon atoms, including carbon carrying the radicals R 20 and R 21 , ranging from 3 to 8;
- R 22 represents a linear or branched, saturated or unsaturated, hydrocarbon-based radical which may comprise at least one ring, said radical having a number of carbon atoms ranging from 1 to 30;
- R 23 and R 24 identical or different, represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 20, a cycloalkyl, aryl, alkoxyl, aryloxyl, aralkyloxyl, perfluor
- W 1 and W 2 are different and represent - C (O) - or - NH -
- R 25 and R 26 identical or different, represent a hydrogen atom, an alkyl radical, linear or branched, having a number carbon atoms ranging from 1 to 1 8, a phenyl radical, a naphthyl radical, a phenylalkyl radical, R 25 and R 26 can also form together and with the carbon atom which carries them a cycloalkyl having a number of carbon atoms ranging from 5 to 1 2 or a 2,2,6,6-tetrapiperidinyl radical;
- R 27 represents an alkylene radical having a number of carbon atoms ranging from 2 to 12 which can be interrupted by an - O - or - NR 28 -, R 28 denoting a hydrogen atom , an alkyl radical having a number of carbon atoms ranging from 1 to 12, a cycloalkyl radical
- the present invention applies very particularly to the following secondary amines:
- the nitroxides obtained are identified by vapor phase chromatography (CPV), by their melting points and by mass spectrometry (MS).
- the magnetic mass spectra were carried out on an AUTOSPEC® mass spectrometer from MICROMASS equipped with an ionization source at atmospheric pressure (API).
- the mass spectra were obtained by accumulation of x spectra (x must correspond to the loop injection time of 20 ⁇ l directly in the API source).
- the amount of aqueous K 2 CO 3 solution is adjusted so that during the addition, the pH of the aqueous phase of the two-phase medium is maintained between 7.2 and 7.5.
- the reaction is stopped and K 2 CO 3 solution is added so as to obtain a pH equal to 9 and then the TEMPO, red in color, is extracted using CH 2 CI 2 .
- the yield of TEMPO relative to the amine used is 88%.
- the biphasic mixture thus obtained is kept under vigorous stirring.
- the mixture is left to settle and the nitroxide is recovered by extraction with CH CI 2 .
- the nitroxide yield relative to the diamine used is 97.3%.
- the solution gradually turns yellow and we check regularly the level of active oxygen in each phase. After 16 hours, the organic phase is orange and the gas evolution has ceased completely. The organic phase is recovered by decantation, the solvent of which is evaporated. The crude nitroxide is in the form of a dark orange oil (4.6 g), the purity of which is 62.5%. The yield of ⁇ -phosphorus nitroxide is 57.5%.
- reaction is exothermic despite the release of CO 2 .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogenated Pyridines (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA01006957A MXPA01006957A (es) | 1999-01-08 | 1999-12-22 | Metodo para preparar nitroxidos. |
US09/869,798 US6538141B1 (en) | 1999-01-08 | 1999-12-22 | Method for preparing nitroxides |
AT99961146T ATE260247T1 (de) | 1999-01-08 | 1999-12-22 | Verfahren zur herstellung von nitroxiden |
AU17854/00A AU1785400A (en) | 1999-01-08 | 1999-12-22 | Method for preparing nitroxides |
JP2000592259A JP4549537B2 (ja) | 1999-01-08 | 1999-12-22 | ニトロキシドの製造方法 |
EP99961146A EP1140807B1 (fr) | 1999-01-08 | 1999-12-22 | Procede de preparation de nitroxydes |
DE69915111T DE69915111T2 (de) | 1999-01-08 | 1999-12-22 | Verfahren zur herstellung von nitroxiden |
DK99961146T DK1140807T3 (da) | 1999-01-08 | 1999-12-22 | Fremgangsmåde til fremstilling af nitroxider |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR99/00128 | 1999-01-08 | ||
FR9900128A FR2788272B1 (fr) | 1999-01-08 | 1999-01-08 | Procede de preparation de nitroxydes |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000040550A1 true WO2000040550A1 (fr) | 2000-07-13 |
Family
ID=9540704
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/003254 WO2000040550A1 (fr) | 1999-01-08 | 1999-12-22 | Procede de preparation de nitroxydes |
Country Status (12)
Country | Link |
---|---|
US (1) | US6538141B1 (fr) |
EP (1) | EP1140807B1 (fr) |
JP (1) | JP4549537B2 (fr) |
AT (1) | ATE260247T1 (fr) |
AU (1) | AU1785400A (fr) |
DE (1) | DE69915111T2 (fr) |
DK (1) | DK1140807T3 (fr) |
ES (1) | ES2217854T3 (fr) |
FR (1) | FR2788272B1 (fr) |
MX (1) | MXPA01006957A (fr) |
PT (1) | PT1140807E (fr) |
WO (1) | WO2000040550A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2817861A1 (fr) * | 2000-12-11 | 2002-06-14 | Atofina | Procede de preparation de radicaux nitroxyde b-phosphores |
WO2008031733A2 (fr) * | 2006-09-12 | 2008-03-20 | Ciba Holding Inc. | Nitroxydes d'imidazolidinone comme matériaux d'électrode pour des dispositifs de stockage d'énergie |
WO2010089230A1 (fr) | 2009-02-04 | 2010-08-12 | Basf Se | Agents stabilisants |
US8134009B2 (en) | 2003-03-27 | 2012-03-13 | Basf Se | Process for the oxidation of secondary amines into the corresponding nitroxides |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001041640A1 (fr) * | 1999-12-10 | 2001-06-14 | Univ Maryland | Utilisation de dendrimeres polynitroxyles fonctionnalises comme agents de renfort de contraste dans l'imagerie par resonance magnetique d'articulations |
EP1375476A1 (fr) * | 2002-06-25 | 2004-01-02 | Bayer Aktiengesellschaft | Nouveau procédé de synthèse d'alkoxyamines actives dans la polymérisation radicalaire controlée |
FR2870240B1 (fr) * | 2004-05-13 | 2006-07-07 | Arkema Sa | Procede de preparation d'une alcoxyamine ou de ses sels comprenant une etape de photolyse |
US7538130B2 (en) * | 2005-09-26 | 2009-05-26 | Basf Corporation | Hindered amine light stabilizer, methods of making, and compositions |
US7498398B2 (en) * | 2006-03-21 | 2009-03-03 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition, method of making, and articles formed therefrom |
FR2911723A1 (fr) * | 2007-01-19 | 2008-07-25 | Arkema France | Electrode comprenant au moins un polynitroxyde triazinique |
US20100143805A1 (en) * | 2007-03-09 | 2010-06-10 | Ciba Corporation | Nitroxides for lithium-ion batteries |
ES2373255T3 (es) * | 2007-05-04 | 2012-02-01 | Astrazeneca Ab | Proceso para s�?ntesis de �?cidos alquilfosf�?nicos mediante iniciación de una amina y un aminóxido. |
CN106699639A (zh) * | 2016-12-22 | 2017-05-24 | 甘肃省化工研究院 | 一种光稳定剂hs‑112的合成方法 |
WO2023175279A1 (fr) | 2022-03-16 | 2023-09-21 | Melchior Material And Life Science France | Formulations de pheromones encapsulees resistantes aux rayonnements lumineux |
FR3133522A1 (fr) | 2022-03-16 | 2023-09-22 | Melchior Material And Life Science France | Formulations de pheromones encapsulees resistantes aux rayonnements lumineux |
FR3134285A1 (fr) | 2022-04-07 | 2023-10-13 | Melchior Material And Life Science France | Procede biologique de lutte contre les insectes piqueurs |
CN116836483B (zh) * | 2023-07-05 | 2024-02-06 | 深圳市富恒新材料股份有限公司 | 一种高韧性电池外盖用阻燃复合材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2036557A5 (fr) * | 1969-03-25 | 1970-12-24 | Logeais Laboratoires | |
US4845090A (en) * | 1983-08-03 | 1989-07-04 | Schering Aktiengesellschaft | Nitroxyl compound and diagnostic media based thereon useful for enhancing NMR imaging |
WO1996024620A1 (fr) * | 1995-02-07 | 1996-08-15 | Elf Atochem S.A. | POLYMERISATION EN PRESENCE D'UN RADICAL NITROXYDE β-SUBSTITUE |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1199351A (en) * | 1968-03-06 | 1970-07-22 | Bp Chem Int Ltd | Improvements in the Preparation of Nitroxides |
US4665185A (en) * | 1984-03-22 | 1987-05-12 | Ciba-Geigy Corporation | Process for preparing nitroxyls of sterically hindered amines |
US5087752A (en) * | 1989-09-14 | 1992-02-11 | Curators Of The University Of Missouri | Synthesis of nitroxides using dioxiranes |
IT1243402B (it) * | 1990-11-30 | 1994-06-10 | Enichem Sintesi | Procedimento per la preparazione dei radicali nitrosilici delle amminestericamente impedite. |
CN1198750A (zh) * | 1996-06-04 | 1998-11-11 | 埃勒夫阿托化学有限公司 | 通过在稳定的自由基存在下进行1,3-二烯的控制的自由基聚合制备1,3-二烯的遥爪低聚物的方法 |
-
1999
- 1999-01-08 FR FR9900128A patent/FR2788272B1/fr not_active Expired - Fee Related
- 1999-12-22 AT AT99961146T patent/ATE260247T1/de not_active IP Right Cessation
- 1999-12-22 DK DK99961146T patent/DK1140807T3/da active
- 1999-12-22 WO PCT/FR1999/003254 patent/WO2000040550A1/fr active IP Right Grant
- 1999-12-22 AU AU17854/00A patent/AU1785400A/en not_active Abandoned
- 1999-12-22 PT PT99961146T patent/PT1140807E/pt unknown
- 1999-12-22 DE DE69915111T patent/DE69915111T2/de not_active Expired - Lifetime
- 1999-12-22 ES ES99961146T patent/ES2217854T3/es not_active Expired - Lifetime
- 1999-12-22 MX MXPA01006957A patent/MXPA01006957A/es unknown
- 1999-12-22 EP EP99961146A patent/EP1140807B1/fr not_active Expired - Lifetime
- 1999-12-22 US US09/869,798 patent/US6538141B1/en not_active Expired - Lifetime
- 1999-12-22 JP JP2000592259A patent/JP4549537B2/ja not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2036557A5 (fr) * | 1969-03-25 | 1970-12-24 | Logeais Laboratoires | |
US4845090A (en) * | 1983-08-03 | 1989-07-04 | Schering Aktiengesellschaft | Nitroxyl compound and diagnostic media based thereon useful for enhancing NMR imaging |
WO1996024620A1 (fr) * | 1995-02-07 | 1996-08-15 | Elf Atochem S.A. | POLYMERISATION EN PRESENCE D'UN RADICAL NITROXYDE β-SUBSTITUE |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2817861A1 (fr) * | 2000-12-11 | 2002-06-14 | Atofina | Procede de preparation de radicaux nitroxyde b-phosphores |
WO2002048159A1 (fr) * | 2000-12-11 | 2002-06-20 | Atofina | PROCEDE DE PREPARATION DE RADICAUX NITROXYDE ss-PHOSPHORES |
US7126021B2 (en) | 2000-12-11 | 2006-10-24 | Arkema (Formerly Atofina) | Method for preparing β-phosphorus nitroxide radicals |
US8134009B2 (en) | 2003-03-27 | 2012-03-13 | Basf Se | Process for the oxidation of secondary amines into the corresponding nitroxides |
WO2008031733A2 (fr) * | 2006-09-12 | 2008-03-20 | Ciba Holding Inc. | Nitroxydes d'imidazolidinone comme matériaux d'électrode pour des dispositifs de stockage d'énergie |
WO2008031733A3 (fr) * | 2006-09-12 | 2008-07-17 | Ciba Holding Inc | Nitroxydes d'imidazolidinone comme matériaux d'électrode pour des dispositifs de stockage d'énergie |
WO2010089230A1 (fr) | 2009-02-04 | 2010-08-12 | Basf Se | Agents stabilisants |
Also Published As
Publication number | Publication date |
---|---|
MXPA01006957A (es) | 2002-04-10 |
DE69915111D1 (de) | 2004-04-01 |
US6538141B1 (en) | 2003-03-25 |
DK1140807T3 (da) | 2004-06-28 |
ATE260247T1 (de) | 2004-03-15 |
EP1140807A1 (fr) | 2001-10-10 |
EP1140807B1 (fr) | 2004-02-25 |
JP2002534409A (ja) | 2002-10-15 |
PT1140807E (pt) | 2004-07-30 |
FR2788272A1 (fr) | 2000-07-13 |
DE69915111T2 (de) | 2004-10-21 |
JP4549537B2 (ja) | 2010-09-22 |
AU1785400A (en) | 2000-07-24 |
ES2217854T3 (es) | 2004-11-01 |
FR2788272B1 (fr) | 2001-03-16 |
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