WO1997007087A1 - Verfahren zur reduktion von nitroverbindungen - Google Patents
Verfahren zur reduktion von nitroverbindungen Download PDFInfo
- Publication number
- WO1997007087A1 WO1997007087A1 PCT/EP1996/003415 EP9603415W WO9707087A1 WO 1997007087 A1 WO1997007087 A1 WO 1997007087A1 EP 9603415 W EP9603415 W EP 9603415W WO 9707087 A1 WO9707087 A1 WO 9707087A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- catalyst
- soluble
- nitro
- groups
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Definitions
- the invention relates to a process for the reduction of nitro compounds to the corresponding amines using a homogeneous palladium, ruthenium, nickel or rhodium catalyst.
- Oxidation levels which can lead to a complete standstill of the reduction. Due to the nature of a heterogeneous catalyst, troubleshooting in the event of a failure of the reaction is often problematic and sometimes only possible with considerable outlay on equipment.
- EP-A-0 372 313 describes the use of noble metal catalysts with tris (m-sulfophenyl) phosphine as complex ligands.
- Catalysts are used in particular in the water gas reaction
- the invention therefore relates to a method for reducing
- Nitro groups to amino groups characterized in that one Nitro compound with hydrogen in the presence of a water soluble
- M is ruthenium, rhodium, nickel or palladium
- L is the same or different a water-soluble ligand
- Y is the same or different, another ligand or an alkali or
- n 1, 2, 3 or 4;
- n 0, 1 or 2.
- M is preferably rhodium, ruthenium or palladium.
- Catalyst is preferably used in the form of an aqueous solution.
- Water-soluble ligands suitable for the process according to the invention contain, for example, sulfonic acid salt and / or sulfonic acid residues and / or carboxylic acid salt and / or carboxylic acid residues and / or phosphonic acid salt and / or phosphonic acid residues and / or phosphinic acid salt and / or
- Polyether groups with a suitable chain length preferably with more than 10 Alkylene oxide units.
- Carboxylic acid salt carboxylic acid, phosphonic acid salt and
- Preferred classes of water-soluble ligands are phosphines substituted with the above groups, such as trialkylphosphines, tricycloalkylphosphanes, triarylphosphanes, dialkylarylphosphanes, alkyldiarylphosphines and
- Heteroarylphosphanes such as tripyridylphosphine and trifurylphosphine, where the three substituents on the phosphorus can be the same or different, chiral or achiral and where one or more of the substituents can link the phosphorus groups of several phosphines and part of this linkage can also be one or more metal atoms, phosphites ,
- Dibenzophosphole which also includes cyclic or
- water-soluble complex ligands include, for example, bipyridines, phenanthrolines, porphyrins and alizarines, which are modified with the above-mentioned groups.
- Water-soluble phosphines which are preferably used are water-soluble
- Triarylphosphane in addition to those that cause water solubility
- Aryl a phenyl or naphthyl group, also one or more
- Alkyl a straight-chain or branched alkyl group with 1 to 8
- R, R ' F or preferably alkyl, aryl or aralkyl with 1 to 18
- M alkali, alkaline earth metal or NR 4 ;
- n, o, p, q 0, 1 to 8;
- Particularly preferred water-soluble phosphine ligands are:
- Y is preferably H, CO, CN or halogen, preferably Cl, or an alkali or alkaline earth metal ion, preferably Na, K or Li.
- Y particularly preferably denotes Cl ⁇ , CO, Na, K, Li. If M is rhodium, Y particularly preferably denotes Cl ⁇ , CO, Na, K, Li, H.
- the water-soluble complex ligands used according to the invention are largely known from the literature.
- the syntheses of these compounds are described, for example, in WA Herrmann and CW Kohlpainter, Angew. Chem. Int. Ed. Engl. 32 (1993) 1524 and the literature cited therein or can be familiar to the person skilled in the art according to known or analogous literature Methods are done.
- the production of BINAS is described in EP-A-0 571 819 and US-A 5,347,9045.
- the water-soluble metal catalyst of the formula (I) can be synthesized separately or else in situ by combining a ruthenium, nickel, palladium or rhodium salt, such as rhodium chloride hydrate or
- Ruthenium chloride such as rhodium chloride hydrate, ruthenium chloride,
- Nickel halide or palladium (II) salts and a water-soluble ligand can be produced.
- a reducing agent is added. Usually is
- Hydrogen is the suitable reducing agent to represent the active
- Particularly preferred metal complexes of the formula (I) are Rh (CO) CI (TPPTS) 2 , where TPPTS means triphenylphosphane bisulfonate trisodium salt, Pd (TPPTS) 2 and Ru (TPPTS) 2 Cl 2 .
- the invention further relates to a process for the preparation of Rh (CO) CI (TPPTS) 2 .
- the catalyst mentioned can easily be obtained from an aqueous solution of TPPTS and rhodium trichloride and subsequent addition of formaldehyde with subsequent heating, as described in Example 1 below.
- This process is considerably simpler than that described in EP-O 372 313.
- a Isolation and chromatographic purification of the intermediate stages are eliminated.
- the TPPTS can be used as a technical product, as it occurs in production.
- the carbon monoxide is replaced by the aqueous formaldehyde solution, so that the handling of equipment is also considerably simplified here.
- the process according to the invention is expediently carried out in an autoclave.
- Autoclaves are - according to Römpps Chemie Lexikon - lockable metal containers, tested for high overpressure, with a screwed-on, tightly sealed lid that is secured or pressed in by a bayonet lock.
- Römpps Chemie Lexikon - lockable metal containers tested for high overpressure, with a screwed-on, tightly sealed lid that is secured or pressed in by a bayonet lock.
- Autoclave heads are, for example, connection options for a rupture plate or a safety valve, pressure gauge, thermometer and often also for a gas-tight stirrer.
- stationary autoclaves with internal stirring also magnetic stirring
- the autoclave In the case of laboratory autoclaves (capacity from approx. 100 ml up to several liters), the autoclave is usually heated electrically, larger autoclaves in industrial process engineering (up to several m 3 ) mostly by steam.
- Autoclaves in which reactions take place using gases, for example pressure hydrogenation additionally contain an inlet for the gas-carrying starting material, which is usually conveyed by a compressor.
- the material of the autoclaves is made of high-alloy steel (e.g. V4A), but there are also special autoclaves made of copper, light metal and monel metal.
- the catalyst containing a metal complex of formula (I), is
- the amount of water can vary within a wide range. Since the reaction takes place in the water phase, more nitroaromat will dissolve in the water by providing larger amounts of water, which accelerates the reduction. The amount of water thus has an influence on the Response speed. Since the catalyst itself is extremely soluble in water, the amount of water is not restricted here either.
- Catalyst to water results in a catalyst to water ratio of approximately 1: 500 to 1: 200,000, preferably 1: 2,000 to 1: 190,000, in particular 1: 5,000 to 1: 100,000.
- Rh (CO) CL (TPPTS) 2 Rh (CO) CL (TPPTS) 2 is used as the water-soluble catalyst, the ratio of substrate to catalyst is in particular 1: 2000 to 1: 5000.
- the respective reaction rate depends on many parameters, such as pressure, temperature, the amount of catalyst, the amount of substrate and the amount of water. But it also depends crucially on the solubility of the substrate in water. Nitroaromatics e.g. an ethoxy or
- Containing methoxy group are usually more water-soluble than alkylated compounds.
- the response time is usually depending on the
- the reaction temperature is generally 20 to 150 ° C, preferably 50 to 130 ° C, in particular 60 to 110 ° C.
- the hydrogen pressure can be 1-150 bar, preferably 10-100 bar, particularly preferably 10-20 bar. Frequently chosen reaction conditions are 100 ° C and 20 bar
- Rh (CO) CI (TPPTS) 2 Rh (CO) CI (TPPTS) 2 is used as the water-soluble catalyst, the preferred reaction temperature is 70 to 130 ° C., in particular 90 to 110 ° C.
- the reaction product is separated off from the aqueous catalyst solution.
- the aqueous catalyst solution can be used for further reductions. A loss of activity is not observed on the return. If the catalyst is recycled several times, the aqueous catalyst solution is diluted more and more by the water of reaction added. The original concentration ratios can be restored, for example by membrane filters or by concentration in a vacuum.
- the catalyst system is relatively insensitive to air, but the aqueous solution should be treated inertly in order to ensure the longest possible service life and traceability of the catalyst.
- the reduction of an organic solvent for the nitroaromatic can be dispensed with. This also eliminates the time-consuming and costly preparation of solvents. The filtration from the catalyst required for heterogeneous catalytic reduction is also eliminated.
- the nitro compound it is also possible for the nitro compound to be mixed with an organic solvent, for example with toluene, o-xylene, m-xylene, p-xylene, mixtures of isomeric xylenes, ethylbenzene, mesitylene, chlorobenzene, dichlorobenzene, chlorotoluene, cyclohexane, cumene, decalin , Ethyl acetate, butyl acetate or a mixture of two or more of these solvents.
- Preferred educts of the process according to the invention are aromatic
- -S- may contain from 4 to 20 carbon atoms, preferably phenyl or naphthyl;
- n depending on the aromatic base, it is 0, 1, 2, 3, 4 or 0, 1, 2, 3,
- R is the same or different -H, -F, -Cl, -Br, -I, CN, -SCN, -OCN,
- R ' is the same or different H, a branched or unbranched
- R is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl -, 2-ethylhexyl, 2-ethyldecyl, n-decyl, n-dodecyl, and also methoxy, ethoxy, propoxy,
- 2-ethylhexyloxy, decyloxy, dodecyloxy also a carboxylic acid, carboxylic acid methyl ester, carboxylic acid ethyl ester, Carboxylic acid propyl ester, carboxylic acid butyl ester,
- Carboxylic acid pentyl ester carboxylic acid hexyl ester, carboxylic acid 2-ethylhexyl ester, carboxylic acid phenyl ester, formyl, carboxamide, carboxylic acid dimethylamide, carboxylic acid diethylamide,
- Very particularly preferred starting compounds are those of the formula (X)
- R 1 and R 2 may be the same or different and are hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, C 1 -C 4 alkylphenyl, nitro, amino, cyano, -COOR 3 , -SO 2 OR 3 or sulfamoyl and R 3 is hydrogen or the equivalent of a cation.
- the compounds produced according to the invention are used in many different ways, for example as intermediates for the production of active ingredients, polymers and dyes.
- the compounds prepared according to the invention preferably serve as
- Diazonium salts serve, for example, as intermediates for the production of active ingredients, polymers and dyes and in particular as
- RhCI 3 ⁇ H 2 O (0.26 g, 1 mmol) was added to a boiling solution of TPPTS (29.2%, 19.5 g, 10 mmol). After about 15-20 seconds, a formaldehyde solution (35%, 15 g, 175 mmol) was added. The solution turned from dark red to yellow. The mixture was then heated to about 80 ° C. for 10 minutes and ethanol was added dropwise until a slight turbidity occurred. Upon cooling, TPPTS and the Rh-TPPTS complex crystallized out of the solution. The crystals of the complex were washed with
- a two-phase system consisting of 200 g (1.62 mol) nitrobenzene, 200 g water and 0.31 g was placed in a 2 l autoclave with a gassing stirrer
- Example 2 Under the same reaction conditions as in Example 2, 200 g (1.31 mol) of 4-ethoxynitrobenzene in 400 g of toluene were reacted with fresh rhodium catalyst from Example 1 (0.23 mol in 200 ml of water). The reaction was complete after an hour. According to GC, the solution contained 95.5% 4-ethoxyaniline and 1.4% 4-ethoxynitrobenzene after phase separation.
- Catalyst solution from Example 10 After 9.5 hours, the conversion was 99.9% and the solution had a 95.6% content of 5-chloro-2-aminophenol.
- the catalyst phase was separated off by filtration of the product.
- the catalyst phase was separated off by filtration of the product and reused.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96927664A EP0854856B1 (de) | 1995-08-14 | 1996-08-02 | Verfahren zur reduktion von nitroverbindungen |
DE59604907T DE59604907D1 (de) | 1995-08-14 | 1996-08-02 | Verfahren zur reduktion von nitroverbindungen |
JP50871297A JP3827328B2 (ja) | 1995-08-14 | 1996-08-02 | ニトロ化合物の還元方法 |
US09/011,677 US6054617A (en) | 1995-08-14 | 1996-08-02 | Nitro compound-reducing process |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19529874.8 | 1995-08-14 | ||
DE1995129874 DE19529874A1 (de) | 1995-08-14 | 1995-08-14 | Verfahren zur Reduktion von Nitroverbindungen |
DE19619359.1 | 1996-05-14 | ||
DE1996119359 DE19619359A1 (de) | 1996-05-14 | 1996-05-14 | Verfahren zur Reduktion von Nitroverbindungen |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997007087A1 true WO1997007087A1 (de) | 1997-02-27 |
Family
ID=26017686
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/003415 WO1997007087A1 (de) | 1995-08-14 | 1996-08-02 | Verfahren zur reduktion von nitroverbindungen |
Country Status (6)
Country | Link |
---|---|
US (1) | US6054617A (de) |
EP (1) | EP0854856B1 (de) |
JP (1) | JP3827328B2 (de) |
CA (1) | CA2229481A1 (de) |
DE (1) | DE59604907D1 (de) |
WO (1) | WO1997007087A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003298465A1 (en) * | 2003-12-24 | 2005-08-11 | Council Of Scientific And Industrial Research | Selective hydrogenation of nitrogen containing aromatics |
EP1847029B1 (de) * | 2005-01-31 | 2014-03-12 | ST-Ericsson SA | Verfahren und vorrichtung zum verbreiten von daten in einem drahtlosen kommunikationssystem |
US7623643B2 (en) * | 2005-07-26 | 2009-11-24 | Microsoft Corporation | Augmenting a call with context |
CN100593535C (zh) * | 2007-04-30 | 2010-03-10 | 浙江工业大学 | 一种2-烷氧基-5-乙酰氨基苯胺的绿色合成工艺 |
CN114369240B (zh) * | 2021-11-10 | 2023-07-14 | 贵研铂业股份有限公司 | 卟啉基多孔有机聚合物、制备方法及其负载钯催化剂的制备方法与用途 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0372313A2 (de) * | 1988-12-02 | 1990-06-13 | Hoechst Aktiengesellschaft | Sulfonierte Phenylphosphane enthaltende Komplexverbindungen |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3504035A (en) * | 1966-07-01 | 1970-03-31 | American Cyanamid Co | Process for preparing aromatic amines from aromatic nitro compounds |
US3944615A (en) * | 1971-04-30 | 1976-03-16 | Monsanto Company | Process for the production of aromatic primary amines |
JPS539403A (en) * | 1976-07-14 | 1978-01-27 | Pioneer Electronic Corp | Fm stereophonic receiver |
IT1151804B (it) * | 1982-06-21 | 1986-12-24 | Montedison Spa | Processo per la riduzione catalitica di composti nitroaromatici |
DE68913661T2 (de) * | 1988-11-18 | 1994-06-09 | Sumitomo Chemical Co | Verfahren zur Herstellung von aromatischen Aminen. |
EP0426536B1 (de) * | 1989-10-31 | 1994-12-14 | Sumitomo Chemical Company Limited | Herstellung aromatischer Amine |
-
1996
- 1996-08-02 US US09/011,677 patent/US6054617A/en not_active Expired - Fee Related
- 1996-08-02 CA CA002229481A patent/CA2229481A1/en not_active Abandoned
- 1996-08-02 WO PCT/EP1996/003415 patent/WO1997007087A1/de active IP Right Grant
- 1996-08-02 EP EP96927664A patent/EP0854856B1/de not_active Expired - Lifetime
- 1996-08-02 DE DE59604907T patent/DE59604907D1/de not_active Expired - Fee Related
- 1996-08-02 JP JP50871297A patent/JP3827328B2/ja not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0372313A2 (de) * | 1988-12-02 | 1990-06-13 | Hoechst Aktiengesellschaft | Sulfonierte Phenylphosphane enthaltende Komplexverbindungen |
Non-Patent Citations (2)
Title |
---|
AHMED M. TAFESH ET AL.: "First Selective Reduction of Aromatic Nitro Compounds Using Water Soluble Catalysts", TETRAHEDRON LETTERS, vol. 36, no. 51, 18 December 1995 (1995-12-18), OXFORD GB, pages 9305 - 9308, XP002018367 * |
J. F. KNIFTON: "Homogenous Catalyzed Reduction of Nitro Compounds. IV. Selective and Sequential Hydrogenation of Nitroaromatics", JOURNAL OF ORGANIC CHEMISTRY, vol. 41, no. 7, 2 April 1976 (1976-04-02), EASTON US, pages 1200 - 1205, XP002018366 * |
Also Published As
Publication number | Publication date |
---|---|
US6054617A (en) | 2000-04-25 |
DE59604907D1 (de) | 2000-05-11 |
EP0854856A1 (de) | 1998-07-29 |
JPH11510512A (ja) | 1999-09-14 |
CA2229481A1 (en) | 1997-02-27 |
EP0854856B1 (de) | 2000-04-05 |
JP3827328B2 (ja) | 2006-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69222417T3 (de) | Verfahren zur herstellung von 4-aminodiphenylamin | |
EP0595124B1 (de) | Verfahren zur Herstellung von chlorsubstituierten aromatischen Aminen und von Katalysatoren | |
EP0854856B1 (de) | Verfahren zur reduktion von nitroverbindungen | |
EP0347796B1 (de) | Verfahren zur Herstellung von 4-Chlor-2,5-dimethoxyanilin | |
EP0924218B1 (de) | Nichtwässrige ionogene Ligandflüssigkeiten, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatorbestandteil | |
EP2705902B1 (de) | Verfahren zur Hydrierung von Nitroaromaten mit ausgewählten Platinkatalysatoren | |
DE19911865A1 (de) | Verfahren zur katalytischen Hydrierung von Dinitrotoluol sowie Katalysator | |
EP1324964A2 (de) | Verfahren zur herstellung von arylverbindungen | |
DE19619359A1 (de) | Verfahren zur Reduktion von Nitroverbindungen | |
EP1437340A1 (de) | Verfahren zur Herstellung von Aminodiphenylaminen | |
EP1081128B1 (de) | Verfahren zur Herstellung von Nitrodiphenylaminen | |
EP0825181B1 (de) | Verfahren zur Herstellung von Carbazol | |
DE2455238A1 (de) | Verfahren zur herstellung aromatischer hydroxylamine durch hydrierung aromatischer nitroderivate | |
JPS6247A (ja) | N−モノアルキルアニリン誘導体の製造方法 | |
CH639937A5 (de) | Verfahren zur herstellung von p-amino-diphenylamin. | |
EP0816308A1 (de) | Komplexe, die Tris-(hydroxyalkyl)phosphane als Liganden enthalten, für Telomerisationen, als Katalysatoren und neue Tris-(hydroxyalkyl)-phosphane enthaltende Komplexe | |
EP1174435B1 (de) | Verfahren zur Herstellung von Platin-Alkenylpolysiloxan-Komplexen, insbesondere von Platin-Divinyltetramethyldisiloxan | |
EP3166953A1 (de) | Verfahren zur herstellung von hydridocarbonyltris(triphenylphosphin)rhodium(i) | |
EP1180093B1 (de) | Phosphorsäuresalz eines aromatischen diamins | |
EP0066103B1 (de) | Verfahren zur Reduktion von reduzierbaren Gruppen und dessen Anwendung | |
DE1493746B2 (de) | 2- (p-Aminobenzoyloxy)-3-methylnaphtho-l,4-hydrochinon und Verfahren zu seiner Herstellung | |
DE19529874A1 (de) | Verfahren zur Reduktion von Nitroverbindungen | |
EP1099683B1 (de) | Verfahren zur Herstellung von Nitrosobenzolen | |
DE69916029T2 (de) | Verfahren zur herstellung von 4,6-diaminoresorcinol oder salzen davon | |
WO2023161204A1 (de) | Verfahren zur herstellung von cis-4-aminotetrahydrofuran-2-carbonsäureestern |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2229481 Country of ref document: CA Ref country code: CA Ref document number: 2229481 Kind code of ref document: A Format of ref document f/p: F |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1997 508712 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1996927664 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09011677 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1996927664 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1996927664 Country of ref document: EP |