WO2005063389A1 - Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst - Google Patents
Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst Download PDFInfo
- Publication number
- WO2005063389A1 WO2005063389A1 PCT/IN2003/000467 IN0300467W WO2005063389A1 WO 2005063389 A1 WO2005063389 A1 WO 2005063389A1 IN 0300467 W IN0300467 W IN 0300467W WO 2005063389 A1 WO2005063389 A1 WO 2005063389A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- acid
- range
- alumina
- silica
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
- C07D213/10—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from acetaldehyde or cyclic polymers thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the present invention provides a catalyst composite for the synthesis of 2- and 4- picolines.
- the present invention also provides a process for the preparation of a catalyst useful for the synthesis of 2- and 4- Picolines.
- the present invention also provides a process for the preparation of 2- and 4- picolines using said- novel catalyst.
- the present invention finds its usage in preparation of various intermediates for pharmaceuticals and agrochemicals.
- 2-Picoline is one of the main components in manufacture of pesticides.
- Major outlet for 4- Picoline is for the synthesis of 4-NinylPyridine and Iso- ⁇ icotinic Acid Hydrazide (L ⁇ H), an anti-tubercular drug.
- Patent 2,186,392 reveals that ethanolamines may be produced from ammonia or a primary amine and ethylene oxide and a salt of a weak acid, such as ammonium carbonate, in the presence of an aliphatic radical which is positive with respect to hydrogen.
- German Patent 844,449 (CA 48:1429c) informs tertiary amines with hydroxyalkyl radicals may be made from ammonia, primary or secondary amines and an alkylene oxide at a temperature of from 30°C to 60°C, with improved yields being possible if water or a weak acid is also present.
- Alkylpyridines have also been synthesized, as reported in Advances in Catalysis, Volume 18, page 344 (1968) Academic Press, Inc., New York, N.Y., by passing gaseous acetaldehyde and ammonia over crystalline aluminosilicates, NaX and H- mordenite. While initial conversion utilizing these materials as catalysts was high, catalyst 2 deactivation by coking was rapid, providing a commercially unattractive system, characterized by poor catalytic stability.
- US Patent 4,220,783 provides a method for synthesizing pyridine or alkylpyridines by reacting ammonia and a carbonyl reactant which is an aldehyde containing 2 to 4 carbon atoms, a ketone containing 3 to 5 carbon atoms or mixtures of said aldehydes and/or ketones under effective conditions in the presence of a catalyst comprising a crystalline alumino silicate zeolite having a silica to alumina ratio of at least about 12 and a constraint index within the approximate range of 1 to 12 and recovering from the resulting reaction mixture, a product containing at least one compound of pyridine or an alkylpyridine.
- a catalyst comprising a crystalline alumino silicate zeolite having a silica to alumina ratio of at least about 12 and a constraint index within the approximate range of 1 to 12 and recovering from the resulting reaction mixture, a product containing at least one compound of pyridine or an alkyl
- the main object of the invention is to provide a catalyst suitable for the conversion of acetaldehyde and ammonia to 2- and 4-Picolines which obviates the drawbacks as detailed above.
- Another object of the invention is to provide a stable catalyst for the conversion of acetaldehyde and ammonia.
- Still another object of the invention is to provide a catalyst which is highly selective and active.
- the present invention provides a catalyst useful for synthesis of 2- and 4- Picolines which comprises a heteropoly acid selected from the group consisting of silicotungstic acid, phosphotungstic acid, phosphomolybdic acid and vanadotungstic acid provided on a support.
- the support is selected from the group consisting of silica gel, alumina, silica-alumina, clays and montmorillonite.
- the present invention also provides a process for the preparation of a catalyst useful for the synthesis of 2- and 4-picolines, the process comprising dissolving a heteropoly acid in distilled water; mixing the resulting mixture with desired amount of a binder to obtain a slurry; stirring the slurry till uniform impregnation is achieved; drying the slurry in air at 200- 250°C for a time period in the range of 0.5 to 1.5 hours; further heating the slurry at a 3 temperature in the range of 300 to 400°C for time period in the range of 0.5 to 1.5 hours and cooling the resultant product to room temperature in a desiccator to get the desired catalyst.
- the heteropoly acid is selected from the group consisting of silicotungstic acid, phosphotungstic acid, phosphomolybdic acid and vanadotungstic acid.
- the binder is selected from the group consisting of silica, alumina, silica-alumina, clays and montmorillonite.
- the heteropoly acid is dissolved in distilled water in a ratio of 0.5:4.5 (w/w).
- the binder comprises silica gel of mesh size
- the slurry is stirred for a time period in the range of 30-40 minutes.
- the present invention also provides for a process for the preparation of 2- and 4- picolines which comprises reacting acetaldehyde and ammonia under heat in the presence of a catalyst comprising a composite of a heteropolyacid impregnated on a support, the catalyst being present in an amount in the range of 5 to 15 wt %, and separating the 2- and 4- picoline formed.
- the acetaldehyde and ammonia are taken in a ratio of 0.8 to 1.2 (w/w) and are reacted at a temperature in the range of 300 to 500°C.
- the reaction is carried out in a glass reactor.
- the weight hourly space velocity of the acetaldehyde and ammonia is maintained in the range of 0.1 to 10 g/g of catalyst (preferably 1 to 3).
- the 2- and 4-picolines are separated by fractional distillation. Detailed description of the invention The present invention provides a catalyst useful for synthesis of 2- and 4- Picolines which is prepared by dissolution of a heteropoly acid in distilled water in a suitable proportion in the range of 0.5:4.5 (w/w).
- the resulting mixture is then mixed with desired amount of a binder such as silica gel (having mesh size 6-14) and the slurry obtained stirred for a time period in the range of 30-40 minutes to get a uniform impregnation.
- a binder such as silica gel (having mesh size 6-14)
- the slurry obtained stirred for a time period in the range of 30-40 minutes to get a uniform impregnation.
- the slurry is first dried in air at a temperature in the range of 200- 250°C for a time period in the range of 0.5 to 1.5 hours and then further heated at temperature 4 in the range of 300 to 400°C for time period in the range of 0.5 to 1.5 hours.
- the resulting product is then cooled to room temperature in a desiccator to get the desired catalyst.
- the heteropoly acid is selected from silicotungstic acid, phosphotungstic acid, phosphomolybdic acid and vanadotungstic acid and the binder is from silica, alumina, silica- alumina, clays, montmorilonite.
- the catalyst obtained is useful for the synthesis of 2- and 4- picolines by heating acetaldehyde and ammonia in a ratio of 0.8 to 1.2 (w/w) at a temperature in the range of 300 to 500°C.
- the amount of the catalyst is in the range of 5 to 15 wt % and the reaction is carried out preferably in a glass reactor.
- the reaction is carried out by maintaining weight hourly space velocity of the feed, comprising of acetaldehyde and ammonia, between 0.1 to 10 g/g of catalyst (preferably 1 to 3).
- the pyridine bases and product obtained are analyzed by by known spectrochromatographic methods and the pyridine bases separated from the desired products by conventional fractional distillation.
- the novelty of the present invention lies in preparing the catalyst for the conversion of acetaldehyde and ammonia to 2- and 4-picohnes in an ecofriendly manner. This process avoids environmental pollution in comparison to prior art processes.
- the following examples are given by way of illustration of the present invention and should not be construed to limit the scope of the present invention.
- Example-1 Preparation of the Catalyst: Silica gel, mesh size 6-14, was used as the silica support. Phosphotungstic acid (10 g) was dissolved in water (25 ml) and the solution was mixed with silica gel (100 g). The slurry was stirred to get a uniform impregnation, dried in air at 200-250°C for one hr., then at 400°C for one hour, and finally cooled to room temperature in a desiccator. This catalyst was used for the reaction between acetaldehyde and ammonia. The experiment was carried out in a downward flow glass reactor of internal diameter of 2 cm and of sufficient length which was kept in a furnace of length 32 cm.
- Example-2 Preparation of the Catalyst: Silica gel, mesh size 6-14, was used as the silica support. Silicotungstic acid (10 g) was dissolved in water (25 ml) and the solution was mixed with silica gel (100 g). The slurry was stirred to get a uniform impregnation, dried in air at 225°C for one hr., then at 400°C for one hour, and finally cooled to room temperature in a desiccator. This catalyst was used for the reaction between acetaldehyde and ammonia. The experiment was carried out in a downward flow glass reactor of internal diameter of 2 cm and of sufficient length which was kept in a furnace of length 32 cm.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03819218A EP1708811A1 (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
PCT/IN2003/000467 WO2005063389A1 (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
CA2552158A CA2552158C (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2- and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
NZ548652A NZ548652A (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
CNB2003801109444A CN100448534C (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
AU2003300723A AU2003300723B2 (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IN2003/000467 WO2005063389A1 (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005063389A1 true WO2005063389A1 (en) | 2005-07-14 |
Family
ID=34717583
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IN2003/000467 WO2005063389A1 (en) | 2003-12-31 | 2003-12-31 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1708811A1 (en) |
CN (1) | CN100448534C (en) |
AU (1) | AU2003300723B2 (en) |
CA (1) | CA2552158C (en) |
WO (1) | WO2005063389A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100446857C (en) * | 2006-11-02 | 2008-12-31 | 武汉理工大学 | Method for preparing heteropoly acid/ordered mesic porous silicon oxide catalyst, and its application |
CN110586187A (en) * | 2019-10-11 | 2019-12-20 | 沧州那瑞化学科技有限公司 | Supported phosphotungstic acid catalyst, and preparation method and application thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107983398B (en) * | 2017-10-27 | 2020-07-17 | 苏州盖德精细材料有限公司 | Production method of nano-attapulgite composite catalyst for preparing 3-methylpyridine |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2463466A (en) * | 1948-09-29 | 1949-03-01 | Socony Vacuum Oil Co Inc | Production of nitriles |
WO1990003366A1 (en) * | 1988-09-30 | 1990-04-05 | Reilly Industries, Inc. | Pyridine base synthesis process and catalyst for same |
US5856575A (en) * | 1997-01-22 | 1999-01-05 | Council Of Scientific Industrial Research | Process for the preparation of N-acetyl aminophenols |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9419387D0 (en) * | 1994-09-26 | 1994-11-09 | Bp Chem Int Ltd | Olefin hydration process |
CN1093000C (en) * | 1996-12-27 | 2002-10-23 | 吉林化学工业公司研究院 | Catalyst for ether pyrolysis isobutylene and applications |
US5994550A (en) * | 1998-12-30 | 1999-11-30 | Mobil Oil Corporation | Pyridine/picoline production process |
-
2003
- 2003-12-31 CN CNB2003801109444A patent/CN100448534C/en not_active Expired - Fee Related
- 2003-12-31 CA CA2552158A patent/CA2552158C/en not_active Expired - Fee Related
- 2003-12-31 EP EP03819218A patent/EP1708811A1/en not_active Withdrawn
- 2003-12-31 AU AU2003300723A patent/AU2003300723B2/en not_active Ceased
- 2003-12-31 WO PCT/IN2003/000467 patent/WO2005063389A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2463466A (en) * | 1948-09-29 | 1949-03-01 | Socony Vacuum Oil Co Inc | Production of nitriles |
WO1990003366A1 (en) * | 1988-09-30 | 1990-04-05 | Reilly Industries, Inc. | Pyridine base synthesis process and catalyst for same |
US5856575A (en) * | 1997-01-22 | 1999-01-05 | Council Of Scientific Industrial Research | Process for the preparation of N-acetyl aminophenols |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100446857C (en) * | 2006-11-02 | 2008-12-31 | 武汉理工大学 | Method for preparing heteropoly acid/ordered mesic porous silicon oxide catalyst, and its application |
CN110586187A (en) * | 2019-10-11 | 2019-12-20 | 沧州那瑞化学科技有限公司 | Supported phosphotungstic acid catalyst, and preparation method and application thereof |
CN110586187B (en) * | 2019-10-11 | 2022-05-13 | 沧州那瑞化学科技有限公司 | Supported phosphotungstic acid catalyst, and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
EP1708811A1 (en) | 2006-10-11 |
CA2552158C (en) | 2010-06-22 |
CA2552158A1 (en) | 2005-07-14 |
AU2003300723A1 (en) | 2005-07-21 |
CN100448534C (en) | 2009-01-07 |
CN1886195A (en) | 2006-12-27 |
AU2003300723B2 (en) | 2010-01-14 |
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