EP1966128A2 - Procede pour produire des amides d'acide amino-alcanique - Google Patents

Procede pour produire des amides d'acide amino-alcanique

Info

Publication number
EP1966128A2
EP1966128A2 EP06841384A EP06841384A EP1966128A2 EP 1966128 A2 EP1966128 A2 EP 1966128A2 EP 06841384 A EP06841384 A EP 06841384A EP 06841384 A EP06841384 A EP 06841384A EP 1966128 A2 EP1966128 A2 EP 1966128A2
Authority
EP
European Patent Office
Prior art keywords
component
reaction
catalyst
temperature
separation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06841384A
Other languages
German (de)
English (en)
Inventor
Martin Ernst
Andreas Kusche
Gunnar Heydrich
Horst Grafmans
Holger Evers
Johann-Peter Melder
Harald Meissner
Torsten Freund
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE200510060803 external-priority patent/DE102005060803A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to EP06841384A priority Critical patent/EP1966128A2/fr
Publication of EP1966128A2 publication Critical patent/EP1966128A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for the preparation of AminoalkanTexreamiden by reacting a Cyanalkanchureester with a) ammonia or an amine and b) hydrogen in the presence of a catalyst, optionally occurring intermediates are not isolated and the reaction with component b) simultaneously or not later than a maximum of 100 minutes after the start of the reaction of Cyanalkanchureesters with component a) is started.
  • DE-A 21 10 060 describes a corresponding process for preparing N-substituted carboxamides using primary and secondary aliphatic, cycloaliphatic or mixed aliphatic / cycloaliphatic amines instead of ammonia.
  • US-A 3,235,576 relates to a process for the preparation of ⁇ -aminocaproic acid amides.
  • the starting compound used here is the methyl ester of 7-cyano-2,5-heptadienoic acid, which is first reacted with ammonia to give the corresponding amide.
  • the corresponding 7-cyanoheptanoic acid amide is prepared using a palladium catalyst, for example, and the isolated intermediate is reacted in a second hydrogenation reaction using a cobalt- and nickel-containing catalyst to give ⁇ -aminocaproic acid amide.
  • DE-A 26 01 462 relates to a two-stage process for the preparation of 6-aminocaproic acid amide, wherein in a first reaction stage over a period of 2 to 6 hours, a 5-Cyanvaleriansester reacted with excess ammonia and in a second reaction step in the presence of a cobalt and / or nickel-containing supported catalyst, the resulting intermediate product is hydrogenated to 6-aminocaproic acid amide.
  • DE-A 26 01 461 relates to a process for the preparation of ⁇ -Aminoalkan- carboxylic acid alkyl esters, wherein ⁇ -Cyanalkancarbonklarealkylester be hydrogenated at elevated temperature and elevated pressure using ammonia in the presence of nickel and / or cobalt supported catalysts.
  • ⁇ -Cyanalkancarbonklarealkylester be hydrogenated at elevated temperature and elevated pressure using ammonia in the presence of nickel and / or cobalt supported catalysts.
  • the object underlying the invention is to provide a novel process for the preparation of AminoalkanTexreamiden by reacting Cyanalkan Textreestern with a) ammonia or an amine and b) hydrogen in the presence of a catalyst.
  • this object is achieved by the reaction of a cyanalkanTexreester at elevated pressure with a) at least one mol equivalent of ammonia or one mole equivalent of amine and b) hydrogen in the presence of a catalyst, optionally occurring intermediates are not isolated and the Reaction with component b) is started simultaneously or not later than a maximum of 100 minutes after the beginning of the reaction of the Cyanalkanchureesters with component a).
  • the process according to the invention has the advantage that it can be carried out faster than processes known from the prior art. For example, no catalyst change is required for the amidation and hydrogenation, but the amidation can be carried out without the presence of a catalyst, provided that the amidation and the hydrogenation are not carried out simultaneously and / or spatially separated.
  • the inventive method provides the desired product (Aminoalkanklamid) in high selectivities, preferably of at least 95%, more preferably of at least 98%, particularly preferably of at least 99%.
  • the process according to the invention has the advantage that the unreacted component a) (ammonia or amine) is separated off from the reaction product (aminoalkanoic acid amide) and recovered.
  • the reaction product aminoalkanoic acid amide
  • a further advantage is the fact that using a fixed bed catalyst for the hydrogenation (in particular of a fixed bed supported catalyst), the reaction product contains only very small traces of catalyst metals, so that a final purification by crystallization is possible.
  • the catalyst has to be removed by filtration and the product has to be purified by distillation, since traces of metal present in the end product impair product stability and the product property (possible ligand action).
  • due to the conditions required for the distillation results in a low product yield.
  • Suitable educts are in principle all customary cyanoalkanoic acid esters, if appropriate, it is also possible to use a mixture of two or more cyanoalkanoic acid esters, but preference is given to the use of a cyanoalkanoic acid ester.
  • preferred starting materials have one cyano and one ester group per molecule.
  • the ester group the corresponding molecule having an acid group can also be used.
  • cyanoalkanoic acid esters are the methyl or ethyl esters of cyanoacetic acid, cyanopropionic acid, cyanobutyric acid, cyanovaleric acid or cyancapaproic acid, preferably the cyano group is located at the terminal carbon atom of the underlying alkanoic acid.
  • the alkanoic acid skeleton may have further substituents, preferably one or two C 1 -C 3 -alkyl groups, in particular two methyl substituents.
  • Preferred cyanoalkanoic acid esters including the carbon atoms of the cyano and the ester group, have 4 to 10 carbon atoms, the cyano function being located at the terminal carbon atom of the alkanoic acid skeleton.
  • Particularly preferred is 2-cyano-2,2-dimethylessigklaremethylester or the corresponding ethyl ester.
  • the amidation of the cyanoalkanoic acid ester is carried out with at least one molar equivalent of component a), preferably at a 2 to 30-fold molar excess of component a), more preferably with a 5- to 25-fold molar excess. If several ester functions are amidated in the educt, the amount of component a) must be increased accordingly.
  • component a) are suitable ammonia or an amine, optionally also
  • Mixtures are used. Preferably, however, only one component a) is used, in particular ammonia. If an amine is used, in particular especially monoalkyl or dialkylamines (to give the corresponding monoalkylated or dialkylated amide), in particular methylamine or dimethylamine.
  • 2-cyano-2,2-dimethylacetic acid methyl ester is used as starting material and ammonia is used as component a).
  • the reaction of the educt or in particular of the intermediate product (cyanoalkanoic acid amide) obtained in the amidation with hydrogen (component b); Hydrogenation) takes place in the presence of a catalyst.
  • a catalyst In principle, all hydrogenation catalysts known to those skilled in the art are suitable as catalyst.
  • the catalyst may be, for example, a sponge, carrier, thin film or full catalyst, preferably a supported catalyst.
  • the catalyst is present as a fixed bed catalyst, in particular in the form of a supported catalyst.
  • Preferred catalysts contain at least one noble metal of group VII and VIII, preferably cobalt (Co) and nickel (Ni) and optionally at least one metal from the group copper, manganese, chromium or iron.
  • the support may be selected from the conventional metal oxides, such as aluminum oxide, zirconium oxide, silicon dioxide or mixtures of these metal oxides; preference is given to using aluminum oxide and zirconium oxide, particularly preferably zirconium oxide.
  • preferred catalysts are Raney cobalt (hereinafter also referred to as Ra-Co) or Raney nickel catalysts - this type of catalyst is available as a commercial product in various designs under the name Raney TM cobalt or Raney TM nickel, respectively.
  • Further examples of preferred catalysts are supported hydrogenation catalysts prepared from nickel oxide, cobalt oxide, copper oxide and zirconium oxide, which may optionally contain further metal components.
  • Suitable catalysts and processes for the preparation of these catalysts can be found, for example, in the documents Mozingo et al., Organic Synth. Coli. Vol. 3, pages 181 ff, Fieser and Fieser, Reagents for Org. Synth. Vol. 1, pages 723-731, EP-A 0 963 975 or EP-A 1 106 600 are taken.
  • the reaction of the cyanoalkanoic acid ester to the corresponding aminoalkanoic acid amide is carried out at elevated pressure, preferably at 10 to 250 bar, more preferably 50 to 220 bar, particularly preferably at 80 to 210 bar.
  • the reaction can also be carried out at atmospheric pressure.
  • the temperature may be between 20 and 150 ° C, preferably 60 to 150 ° C, more preferably 80 ° to 120 ° C, particularly preferably 80 to 1 10 ° C.
  • the inventive method is carried out such that the reaction of the educt (Cyanalkanklareester) with the component a) and the component b) either at the same time or the reaction with component b) for a maximum of 100 minutes Beginning of the reaction of the reactant with component a) is started.
  • the process according to the invention is preferably carried out in such a way that the reaction of the starting material with component b) is started at most 100 minutes after the beginning of the reaction of the euct with component a).
  • the reaction with component b) takes place in the second option after a residence time of a maximum of 100 minutes. Preferably, a residence time of 5 to 100 minutes is selected.
  • the intermediates which may be present are not isolated. It is crucial that the addition of component b) to the educt does not take place before the addition or the reaction of component a) with the educt, because the amidation of Aminoalkan yarn proceeds only in minor amounts as a side reaction. If the hydrogenation is not carried out at the same time as the amidation of the cyanoalkanoic ester, it can be assumed that the intermediate formed is mainly the corresponding cyanoalkanoic acid amide.
  • the hydrogenation start is more preferably 5 to 60 minutes later than the beginning of the amidation (residence time of 5 to 60 minutes). Particularly preferred is a residence time of 8 to 20 minutes.
  • the components a) and b) are fed stepwise to the educt.
  • this method is applied in the batch process, by stepwise feeding first component a) and then hydrogen in a solution of Cyanalkanklaresters.
  • This embodiment is particularly preferably used in an autoclave.
  • the hydrogenation is started only after the start of the amidation, and which is likewise preferably used in an autoclave, first the catalyst, a solution of the cyanoalkanoic ester (starting material) and component a) and a part of the hydrogen at a pressure of at most 10 bar presented.
  • a maximum temperature of 60 ° C should not be exceeded, preferably the temperature is 20 to 30 ° C.
  • the temperature is increased to 70 to 150 ° C, preferably to 75 to a maximum of 120 ° C, and the hydrogen pressure by further hydrogen addition to 50 to 210 bar.
  • the increase of the hydrogen pressure and the temperature can take place simultaneously or successively.
  • the temperature is first slowly increased and after the temperature has reached the desired end value (greater than 70 ° C), hydrogen is rapidly injected to the desired final pressure value (greater than 50 bar).
  • the residence time is calculated here starting with the combination of the educt solution and the component a) up to the time at which the temperature is at least 70 ° C and the hydrogen pressure is at least 50 bar.
  • this embodiment can also be carried out by only the solution of the reactant and component a) and the catalyst are presented and the hydrogen is added only at the beginning of the temperature increase.
  • the residence time is also calculated in this case, starting with the time of combining the reactant with the component a) to the time at which the temperature is at least 70 ° C and the hydrogen pressure is at least 50 bar.
  • the amidation and the hydrogenation are spatially separated from each other by pre-switching a residence time.
  • the corresponding starting material and the component a) (preferably ammonia), which are each fed continuously, already react by passing through a residence time before they reach the actual hydrogenation reactor.
  • This residence time section can also consist of a section of the hydrogenation reactor which is filled with catalytically or only slightly active material (such as steel rings, steatite etc.) or in which the temperature is kept below a threshold temperature necessary for the hydrogenation.
  • the temperature in this residence time is 20 to 100 ° C, preferably 30 to 60 ° C.
  • the hydrogenation is carried out after passing through this residence time at a temperature of preferably 60 to 150 ° C, more preferably at 75 to 120 ° C.
  • the amidation and the hydrogenation can also be carried out at the same temperature in a range between 20 and 150 ° C.
  • the process can be carried out in one step in a solvent, for example in an alcohol or N-methylpyrrolidone (NMP), preferably in a monohydric aliphatic alcohol, more preferably in an alcohol of the group MeOH.
  • a solvent for example in an alcohol or N-methylpyrrolidone (NMP), preferably in a monohydric aliphatic alcohol, more preferably in an alcohol of the group MeOH.
  • EtOH ethanol
  • PrOH propanol
  • i-PrOH 1-butanol (1 -BuOH)
  • 2-BuOH 1-pentanol
  • 2-pentanol 2-pentanol
  • 3-pentanol The solvent can be used in a proportion of 5 to 95% [wt .-%] of the reaction mixture, preferably 20 to 70%, particularly preferably 30 to 60%.
  • the process can be carried out in batch, semibatch or continuously, preference being given to continuous reaction.
  • the product can be isolated and purified by distillation or crystallization or a combination of both. Preference is given to crystallization.
  • the crystallization can be carried out in particular if the hydrogenation step has been carried out in the presence of a fixed bed catalyst, because in this case the product has only very small traces of the metals contained in the catalyst as impurity.
  • the methyl cyanoester is hydrogenated as a 50% solution in 2-butanol in the presence of 7 equivalents of liquid ammonia in a batch autoclave at 100 ° C to Raney nickel (5 wt .-%) and simultaneously ins Amide transferred.
  • the catalyst is removed by filtration and the product is isolated by distillation.
  • the methyl cyanoester is combined as a 40% solution in MeOH with 10 to 25 equivalents of ammonia in a displacer-filled tubular reactor (where the ester is converted to the amide) and after a residence time of 8 to 20 minutes 80 to 120 ° C and 150 to 250 bar hydrogenated on a supported hydrogenation catalyst prepared from 28% NiO, 28% CoO, 13% CuO and 31% ZrO 2 .
  • the product is isolated by single-stage crystallization from the crude solution.
  • the unreacted component a) ie the proportions of ammonia or amine which have not been reacted with cyanalkanoic acid ester
  • component b) hydrophilicity
  • the separation of the unreacted component a) preferably takes place at temperatures below 150 ° C., more preferably below 130 ° C., particularly preferably below 110 ° C.
  • the separation of the unreacted component a) is preferably carried out at a lower temperature than the temperature in the reaction with component b) (hydrogenation).
  • the removal of the unreacted component a) takes place at temperatures below 150 ° C., more preferably below 130 ° C., particularly preferably below 110 ° C.
  • the separation step as such (the separation of unreacted component a) from the reaction mixture) is carried out as quickly as possible in terms of time.
  • the term "as fast as possible in terms of time” is to be understood as meaning that the separation step as such lasts for a maximum of 300 minutes, more preferably not more than 200 minutes, particularly preferably not more than 120 minutes.
  • the separation preferably takes place on unreacted component a) both at a lower temperature and as quickly as possible over time.
  • the separation of unreacted component a) takes place in a separate apparatus.
  • a separate apparatus is to be understood as meaning all separation units known to the person skilled in the art, in particular a compressed gas column or a distillation column.
  • the separation of the unreacted component a) from the separation unit is preferably carried out at temperatures below 150 ° C, more preferably below 130 ° C, more preferably below 1 10 ° C.
  • the residence time of Aminoalkanklamids (product) in the separation of the unreacted component a) in the separation unit is preferably 1 to 300 minutes, more preferably 1 to 200 minutes, more preferably 1 to 120 minutes.
  • the temporally as fast as possible separation of unreacted component a) from the reaction mixture has proved particularly advantageous because the amidation is an equilibrium reaction that can be shifted in the direction of the ester when the amine or ammonia continuously at elevated temperature from the Reaction mixture are removed and the relatively slow reaction is given sufficient time.
  • the educt and the catalyst are introduced into the autoclave and the contents are rendered inert by flushing with nitrogen. Subsequently, 5 bar hydrogen is injected. The desired amount of ammonia is metered in and then heated slowly with stirring to the reaction temperature (80 ° C). This step lasts on average 90 min. the residence time of the educt solution in contact with ammonia is about 90 min.
  • hydrogen is rapidly injected onto the pressure indicated in the following Table 1, and hydrogen consumed in a pressure-controlled manner is metered in over the test period until there is no more hydrogen uptake.
  • the autoclave experiments are carried out in a 2.5 l autoclave with a hollow shaft disk stirrer (rotational speed about 600 rpm), electric heating and jacket air cooling, 2 breakwaters, gassing via the autoclave cover and introduction of the hydrogen via the hollow shaft stirrer.
  • the weights for Raney catalysts are corrected for 10% water moisture, i. in reality, 10% more water-moist catalyst is weighed than indicated.
  • Reaction discharges are analyzed by gas chromatography (GC) (conditions: 60 m DB1701, inside diameter 0.32 mm, film thickness 0.25 ⁇ m, detector: FID, temperature program: 80 ° C ⁇ 10 K / min ⁇ 280 ° C, 40 min.
  • Split ratio 100 1, carrier gas helium
  • the reactor yield is determined by means of gas chromatography with internal standard (LS) (LS piperidine, the concentration thus obtained in the crude feed is multiplied by the total mass of the crude feed and the calculated thus compared with the theoretical yield).
  • the batches are all carried out with 2-cyano-2,2-dimethylacetic acid methyl ester with a purity of> 99.8%.
  • aminopivalic acid amide (3-amino-2,2-dimethylpropionic acid amide) is obtained. Table 1
  • Example 8 shows that with Raney nickel and Raney cobalt very good selectivities of at least 90% can be achieved.
  • a metal determination is performed; it is found 430 ppm Co in the reaction.
  • the experimental examples are in a 1 I reactor (10 x 2000 mm), equipped with feed pumps for solvent, ammonia and nitrile ester, filled with 250 ml steel rings in the lower and upper part of the reactor, centered with 500 ml tablets (5 x 3 mm) of a hydrogenation catalyst of the following composition: 28% NiO, 28% CoO, 13% CuO and 31% ZrO 2 , carried out in the upflow mode.
  • the reduction procedure of the catalyst is as follows: The reactor is heated to 180 ° C. in 5 hours with a hydrogen feed of 50 l / h, then maintained at 180 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé servant à produire des amides d'acide amino-alcanique par réaction d'esters d'acide cyano-alcanique avec a) de l'ammoniac ou une amine et b) de l'hydrogène, en présence d'un catalyseur. Selon l'invention, la réaction avec le constituant b) est démarrée en même temps ou au plus tard 100 minutes après le début de la réaction de l'ester d'acide cyano-alcanique avec le constituant a).
EP06841384A 2005-12-20 2006-12-15 Procede pour produire des amides d'acide amino-alcanique Withdrawn EP1966128A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06841384A EP1966128A2 (fr) 2005-12-20 2006-12-15 Procede pour produire des amides d'acide amino-alcanique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE200510060803 DE102005060803A1 (de) 2005-12-20 2005-12-20 Verfahren zur Herstellung von Aminoalkansäureamiden
EP06115783 2006-06-21
PCT/EP2006/069777 WO2007071626A2 (fr) 2005-12-20 2006-12-15 Procede pour produire des amides d'acide amino-alcanique
EP06841384A EP1966128A2 (fr) 2005-12-20 2006-12-15 Procede pour produire des amides d'acide amino-alcanique

Publications (1)

Publication Number Publication Date
EP1966128A2 true EP1966128A2 (fr) 2008-09-10

Family

ID=38006583

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06841384A Withdrawn EP1966128A2 (fr) 2005-12-20 2006-12-15 Procede pour produire des amides d'acide amino-alcanique

Country Status (4)

Country Link
US (1) US8759580B2 (fr)
EP (1) EP1966128A2 (fr)
JP (1) JP5215870B2 (fr)
WO (1) WO2007071626A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102574776A (zh) 2009-07-31 2012-07-11 桑多斯股份公司 ω-氨基-烷酰胺和ω-氨基-烷硫酰胺的制备方法及该方法的中间体
WO2012010651A2 (fr) 2010-07-23 2012-01-26 Sandoz Ag Procédé de préparation d'oméga-amino-alcaneamides et d'oméga-amino-alcanethioamides et intermédiaires de ce procédé

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DE597305C (de) 1931-07-24 1934-05-22 Merck Ag E Verfahren zur Herstellung von aliphatischen primaeren Aminosaeuren oder deren Derivaten
CH378868A (de) * 1958-07-29 1964-06-30 Montedison Spa Verfahren zur Herstellung des w-Amino-caprylsäureamids
DE2110060C3 (de) * 1971-03-03 1980-06-26 Henkel Kgaa, 4000 Duesseldorf Verfahren zur Herstellung von Nsubstituierten Carbonsäureamiden
US3816483A (en) * 1970-06-02 1974-06-11 Henkel & Cie Gmbh Carboxylic acid amide preparation
DE2601461A1 (de) * 1976-01-16 1977-07-28 Basf Ag Verfahren zur herstellung von omega-aminoalkancarbonsaeurealkylestern
DE2601462C3 (de) * 1976-01-16 1979-11-22 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von 6-Aminocapronsäureamid
DE2947825C2 (de) 1979-11-28 1982-02-04 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von 4-Aminobuttersäureamid-hydrochlorid
US4780542A (en) * 1983-09-26 1988-10-25 Montefiore Medical Center Process for the synthesis of esters and amides of carboxylic acids
US4590292A (en) * 1985-06-10 1986-05-20 Ciba-Geigy Corporation Process for the manufacture of cyclopropylamine
DE4010254A1 (de) * 1990-03-30 1991-10-02 Basf Ag Verfahren zur herstellung von 2-(3-aminopropyl)-cycloalkylaminen
JPH1059801A (ja) * 1996-06-05 1998-03-03 Otsuka Chem Co Ltd シクロアルカン誘導体、カルボン酸誘導体及び該誘導体を用いた切り花用鮮度保持剤
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DE50007278D1 (de) * 1999-12-06 2004-09-09 Basf Ag Verfahren zur Herstellung von Aminen
US6331624B1 (en) * 2000-04-05 2001-12-18 E.I. Du Pont De Nemours And Company Process for preparing 6-aminocaproamide
DE10028950A1 (de) * 2000-06-16 2001-12-20 Basf Ag Verfahren zur Herstellung von Caprolactam
DE10357978A1 (de) * 2003-12-11 2005-07-21 Langhals, Heinz, Prof. Dr. Perylen-Pigmente mit Metallic-Effekten

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Also Published As

Publication number Publication date
US20080306299A1 (en) 2008-12-11
JP2009519994A (ja) 2009-05-21
WO2007071626A2 (fr) 2007-06-28
JP5215870B2 (ja) 2013-06-19
US8759580B2 (en) 2014-06-24
WO2007071626A3 (fr) 2007-08-09

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