US20080176748A1 - Novel herbicides and methods for preparation thereof - Google Patents

Novel herbicides and methods for preparation thereof Download PDF

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Publication number
US20080176748A1
US20080176748A1 US12/055,384 US5538408A US2008176748A1 US 20080176748 A1 US20080176748 A1 US 20080176748A1 US 5538408 A US5538408 A US 5538408A US 2008176748 A1 US2008176748 A1 US 2008176748A1
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compound
phenyl
weeds
alkyl
independently
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Inventor
Sheng Qiang
Shiguo Chen
Chunlong Yang
Xinbin Dai
Yunfa Dong
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NANTONG JIANGSHANG AGROCHEMICAL & CHEMICAL Ltd LLC
Nantong Jiangshan Agrochemical and Chemical Ltd LLC
Nanjing Agricultural University
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Nantong Jiangshan Agrochemical and Chemical Ltd LLC
Nanjing Agricultural University
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Assigned to NANTONG JIANGSHANG AGROCHEMICAL & CHEMICAL LIMITED LIABILITY CO., LTD., NANJING AGRICULTURAL UNIVERSITY reassignment NANTONG JIANGSHANG AGROCHEMICAL & CHEMICAL LIMITED LIABILITY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DONG, YUNFA, CHEN, SHIGUO, DAI, XINBIN, YANG, CHUNLONG, QIANG, SHENG
Publication of US20080176748A1 publication Critical patent/US20080176748A1/en
Priority to US13/414,711 priority Critical patent/US8921274B2/en
Priority to US14/548,289 priority patent/US9468209B2/en
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/38—2-Pyrrolones

Definitions

  • This invention relates to the application of chemicals and biochemicals to weed control in agriculture and, more specifically to pyrrolidineone derivatives of herbicidal tenuazonic acid (3-acetyl-4-hydroxy-5-tert-butylpyrroline-2-ketone), and to their use as herbicides.
  • Tenuazonic acid (formula name: 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone) is a strong phytotoxin, isolated, purified and identified from metabolites of Alternaria Alternata by Qiang Sheng et al. It is isolated from the crude mixture of metabolites by the extraction of the fermentation fluid. Due to the low yield (0.0005%) and high cost of fermentation, it is very important to develop a synthetic process. Through a rational design, more potent compounds can be made that are also easy to manufacture. Environmentally safe herbicides can be developed with low toxicity. This is the main direction of the current herbicide development.
  • 3-Acetyl-4-hydroxy-5-tert-butylpyrroline-2-ketone is a heterocyclic compound containing carbonyl and hydroxyl functional groups.
  • the lactam that is part of the heterocyclic ring is the most important functional group.
  • the hydrophobic side chain also plays an important role in its herbicidal activity.
  • the compound is very effective at killing monocotyledon weeds (such as common crabgrass and barnyardgrass) and dicotyledonous weeds including Crofton weeds at a concentration of 50 ⁇ g/mL. It has the potential to become a biological herbicide (CN Pat. Appl. No. 200510038263.2; CN Pat. No. 1644046. However, the low yield and high cost associated with the fermentation process prevents large-scale production of this compound.
  • A1994 patent (WO1994/01401) discloses 3-benzoylpyrrolidine-2,4-dione derivatives and their herbicidal activity.
  • toxin interacts with D1 protein by competing with Q B for the binding site and thus inhibits the electron transfer. Therefore, it is an inhibitory phytotoxin of photosystem II. Based on the discovery of this mechanism, the molecular structure of tenuazonic acid has heretofore been and new herbicidal molecules discovered.
  • CN Appl. Nos. 200510094521.9 and 200610038765.X, and CN Pat Pub No CN1752075 disclose certain compounds and methods of their synthesis.
  • photosystem II inhibitors have successfully become commercial herbicides, such as s-triazines, triazinones and phenols, etc., and have become major players in the field of herbicides.
  • photosystem II inhibitors There are two advantages associated with photosystem II inhibitors: first, since photosynthesis is a common phenomenon among plants, and inhibition is specific to the plants, the toxicity to animals is low, thus this type of herbicides possesses the characteristics of high efficacy and low toxicity.
  • transgenic technology there are 67,700,000 hectares of farm land that grow transgenic crops globally and greater than 80% of these crops are herbicide-resistant transgenic (based on Monsanto's 2003 data).
  • the photosynthetic inhibitors herbicides have a growing share of the herbicides market. With combination of new herbicides and transgenic agricultural products, the chemical pollution to the environment has been greatly reduced. Since the photosynthetic inhibition is the only effect for 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone on the plant cells, this type of herbicide with high potency, quick action, broad-spectrum, simple structure and easy synthesis will have a bright future.
  • photosystem II inhibitors There are many types of photosystem II inhibitors according to their chemical structures such as ureas, pyridines, triazinones, pyridazinones, dinitrophenols and cyanophenols, etc. They can be divided into two main groups such as ureas/triazine and phenol.
  • the first type (classical photosystem II inhibitors) can be represented as N—C ⁇ X (X stands for O or N atom, not sulfur atom), i.e. atrazine, metribuzin, phemedipham, terbutryand, N-(3,4-dichlorophenyl)-N′-methylurea (DCMU) et al.
  • the second type is phenolic herbicide, including ioxynil, dinoseb and 2-iodo-4-nitro-6-isobutylphenol, etc.
  • the common feature of the second type of herbicide is that the molecules contain at least one carbonyl oxygen, or a hydroxy oxygen and a long hydrophobic hydrocarbon side-chain. Most of these herbicides form a hydrogen bond between the carbonyl hydrogen and the D1 protein of photosystem II, which enables them to successfully compete with plastoquinone Q B (secondary electron acceptor), thus block electron transfer from Q A to Q B , and lead to the inhibition of photosynthetic process of the plant.
  • Q B secondary electron acceptor
  • 3-Acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone has moderate toxicity of 200 mg/kg to rat and moderate level phytotoxicity, which is acceptable in light of its high biological activity. However, its toxicity level may be reduced through modification of its chemical structure.
  • the invention is directed to compounds represented by the general formula (I), or (II), or a salt thereof
  • R 1 independently and at each occurrence represents H; or —C k H 2k+1 , —OC k H 2k+1 , —(C ⁇ O)C k H 2k+1 , —COOC k H 2+1 , —C k H 2k ⁇ 1 , —OC k H 2k ⁇ 1 , —(C ⁇ O)C k H 2k ⁇ 1 , or —COOC k H 2k ⁇ 1 , each unsubstituted or substituted by one or more substituents selected from a heterocycle, an aryl, a phenylalkyl, a heterocycloalkyl phenyl, a heterocycloalkyl, a heterocycloalkoxyl, a phenoxyl; a phenoxy phenyl; a halogen, a cyano, a nitro, an alkoxyalkyl, an alkoxycarbonyl, and/or an amido.
  • R 2 , and R 3 each independently and at each occurrence represent H, C n H 2n+1 , C n H 2n ⁇ 1 , a halogen, —CN, a phenyl, a halogenated alkyl, a cyano-alkyl, a phenylalkyl, a halogenoalkenyl, a cyanoalkenyl, or a phenylalkenyl.
  • R 2 and R 3 each independently and at each occurrence represent H, —CH 3 , —C 2 H 5 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , —(CH 2 ) 3 CH 3 , —C(CH 3 ) 3 , —CH 2 CH(CH 3 )CH 3 , —CH(CH 3 )CH 2 CH 3 , —(CH 2 ) 4 CH 3 , —CH(CH 3 )CH 2 CH 2 CH 3 , —CH 2 CH(CH 3 )CH 2 CH 3 , —CH 2 CH 2 CH(CH 3 ) 2 , —CH(CH 2 CH 3 ) 2 , —C(CH 2 ) 2 C 2 H 5 , —(CH 2 ) 5 CH 3 , —CH(CH 3 )(CH 2 ) 3 CH 3 , —CH 2 CH(CH 3 )(CH 2 ) 2 CH 3 , —CH 2 CH 2 CH(CH 3 ) 3 ,
  • R 2 and R 3 each independently and at each occurrence represent —CN or a phenyl group substituted at positions 1-3 by a substituent selected from: —CHClCH 3 , —CHClCH 2 CH 3 , —CHClC 3 H 7 , —CHClC 4 H 9 , —CHClC 5 H 11 , —CHClC 6 H 13 , —CHClC 7 H 15 , —CHFCH 3 , —CHFCH 2 CH 3 , —CHFC 3 H 7 , —CHFC 4 H 9 , —CHFC 5 H 11 , —CHFC 6 H 13 , —CHFC 7 H 15 , —CHCNCH 3 , —CHCNCH 2 CH 3 , —CHCNC 3 H 7 , —CHCNC 4 H 9 , —CHCNC 5 H 11 , —CHCNC 6 H 13 , —CHCNC 7 H 15 , —CH(
  • X is CN, a C 1 to C 5 amido, a benzyl, a naphthalenyl, a phenyl, a pyrrolyl, a furyl, a thiazolyl, a heterocyclic alkyl phenyl; each phenyl or heterocycle being unsubstituted or substituted by a substituent selected from a C 1 to C 6 alkyl, a C 1 to C 4 alkoxy, a halogenated C 1 to C 5 alkyl, a halogen, a C 1 to C 5 amido, a nitro, a cyano, an alkoxycarbonyl, and/or a C 1 to C 5 sulfonyl group.
  • the compounds are calcium, magnesium, copper, iron, nickel, sodium, potassium, magnesium, zinc or ammonium salts.
  • k represents an integer from 1 to 8.
  • n represent an integer from 1 to 15.
  • the invention is directed to compounds represented by the general formula (III), (IV) or (V)
  • X independently and at each occurrence represents H; or —C m H 2m+1 , or —OC m H 2m+ , each unsubstituted or substituted by one or more substituents selected from a heterocyclic alkyl, a heterocyclic aryl, an aryl, a phenylalkyl, a heterocycloalkyl phenyl, a heterocycloalkyl, a heterocycloalkoxyl, a phenoxyl; a phenoxy phenyl; a halogen, a cyano, a nitro, an alkoxyalkyl, an alkoxycarbonyl, and/or an amido.
  • R 2 and R 3 each independently and at each occurrence represents H, C n H 2n+1 , C n H 2n ⁇ 1 , a halogen, —CN, a phenyl, a halogenated alkyl, a cyano-alkyl, a phenylalkyl, a halogenoalkenyl, a cyanoalkenyl, or a phenylalkenyl.
  • n represents an integer from 1 to 7.
  • the invention is directed to a method for preparation of a compound of claim 1 comprising the following steps:
  • X independently and at each occurrence represents H; or —C m H 2m+1 , or —OC m H 2m+1 , each unsubstituted or substituted by one or more substituents selected from a heterocyclic alkyl, a heterocyclic aryl, an aryl, a phenylalkyl, a heterocycloalkyl phenyl, a heterocycloalkyl, a heterocycloalkoxyl, a phenoxyl; a phenoxy phenyl; a halogen, a cyano, a nitro, an alkoxyalkyl, an alkoxycarbonyl, and/or an amido.
  • n represents an integer from 1 to 7.
  • Y is Cl or Br.
  • the steps are carried out in situ without purification of intermediates.
  • the invention is directed to a method of eradicating weeds, comprising applying to the weeds compounds described herein.
  • the compound is applied in a solution having a concentration of between 10 and 800 ⁇ g of the compound per 1 g of the solution.
  • the weeds are broadleaf plants, grassy weeds, or sedge weeds.
  • the compound is applied under exposure to sun light.
  • the compound inhibits photosynthesis and metabolism of the plant cell, which causes a rapid accumulation of large amounts of reactive oxygen species in cells of the weeds and subsequent death of the cells.
  • This invention provides a pyrrolidineone-type herbicide, which was developed through a modification of tenuazonic acid, a patented herbicidal compound (chemical name: 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone).
  • the modification provided us a quick and effective way of developing the new herbicides.
  • the synthetic pathway is as follows:
  • n represents from 1 to 7 carbon atoms
  • R 2 , and R 3 each independently and at each occurrence represent H, —CH 3 , —C 2 H 5 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , —(CH 2 ) 3 CH 3 , —C(CH 3 ) 3 , —CH 2 CH(CH 3 )CH 3 , —CH(CH 3 )CH 2 CH 3 , —(CH 2 ) 4 CH 3 , —CH(CH 3 )CH 2 CH 2 CH 3 , —CH 2 CH(CH 3 )CH 2 CH 3 , —CH 2 CH 2 CH(CH 3 ) 2 , —CH(CH 2 CH 3 ) 2 , —C(CH 2 ) 2 C 2 H 5 , —(CH 2 ) 5 CH 3 , —CH(CH 3 )(CH 2 ) 3 CH 3 , —CH 2 CH(CH 3 )(CH 2 ) 2 CH 3 , —CH 2 CH 2 CH(CH 3 )CH 2
  • 3-Acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone analogs were dissolved in a small amount of methanol and diluted with water to a concentration of 5-100 ⁇ g/g.
  • a pathogenic test was conducted by placing the toxic liquid on the slightly wounded leaf of Crofton weed with a needle. The test has shown that the pathogenic capability of 3-Acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone analogs with respect to Crofton weed increases with the increase of concentration.
  • the spot diameter caused on the leaf of Crofton weed after 24 hours was 2 mm at 50 ⁇ g/g.
  • the mechanism of action of 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone analogs on weeds is the effect on plant photosynthesis; significantly reducing the photosynthetic oxygen evolution rate and the apparent quantum efficiency.
  • the main action site of the compounds is the thylakoid membrane, inhibiting the electron transfer reaction of two photosystems, especially photosystem II, but no effect has been observed on the structure and synthesis of the membrane protein.
  • the active oxygen content significantly increased 3 hours after the leaf was treated with 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone analogs. This may be the cause of cell death and appearance of the brown spots on the leaf. Moreover, it may also block the synthesis of protein in the ribosome.
  • the main advantages and positive effects of the invention include: modification of 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone was carried out, based on (1): its inhibitory activity to photosystem II and its binding mode to D1 protein; and (2): its inhibitory activity and its action sites, combined with chemical synthetic route of 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone. Focus was placed on the carbonyl oxygen (a few hydroxyl oxygens), which played essential role in the protein binding. The structure of D1 protein from algae was carefully analyzed and of various factors including hydrophobicity, electronegativity and stereo hindrance were considered when designing and selecting the target molecules. It is obvious that such rational design has advantage over the traditional chemical herbicide screening.
  • a series of herbicidal molecules was prepared through the modification of 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone, a metabolic phytotoxin of Alternaria alternata . These compounds kill weeds quickly; the weeds treated with the herbicidal agents clearly show symptoms after 24 hours, and the weeds can be killed in about 3 to 5 days.
  • the method of biocontrolling weeds using the analogues of tenuazonic acid and their salts effectively controls and eradicates the main gramineous weeds in the farmland, such as common crabgrass, barnyardgrass, goosegrass, green foxtail, equal alopecurus, Japanese alopecurus, Beckmannia syzigachne Fern, wild oat, annual bluegrass, keng stiffgrass, common polypogon, and rabbitfoot polypogon; broad leaf weeds, such as Crofton weed, Copperleaf, Yerbadetajo, Redroot pigweed, Tender catchweed bedstraw, Narrowleaf vetch, Sheathed monochoria, Indian rotala, Water ammannia, Purslane, Flixweed tansymustard, Shepherdspurse, Common dayflower, Wild cress, Wormseed mustard, Pennsylvania bittercress, Geminate speedwell, Mouse-ear chickweed; and sedges, such as Needle spike
  • the compounds of the invention have high activity at concentration as low as from 5 to 50 ⁇ g/g. At a concentration of 10 to 800 ⁇ g/g (close to 45-360 g/hectare), the compounds can kill a variety of broad-leaf weeds, grassy weeds and sedge weeds. They are highly potential herbicides.
  • the analogues disclosed herein have comparable herbicidal activity to the original tenuazonic acid. These molecules are easy to make, thus reducing the manufacturing cost. Because these compounds were obtained through modification of the metabolite of a fungus, a natural product, these analogs have some desirable characteristics of bio-based herbicides: low pollution, few byproducts, high rate of decomposition and high environmental safety.
  • the new synthetic process can be carried out in one pot without isolation and purification of the intermediates. This process can reduce the manufacturing cost.
  • the study results showed different herbicidal activities of the above compounds.
  • the different compounds also effect the Hill reaction rate and fluorescence of the chlorophyll.
  • 3-Acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone analogue (Table 3, compounds 10-57) was dissolved in small amount of methanol. The solution was then diluted with distilled water to a concentration of 50 ⁇ g/mL. Methanol solution with same concentration and pure distilled water were used as control of the experiment. A pathogenic test was conducted by placing the toxic liquid on the slightly wounded leaf of Crofton weed with a needle. The experiment was carried out at 25° C. under the natural light and each test was repeated 6 times. It was measure the diameter of the spot after 24 h. The experimental results are listed in Table 4. The data indicated that most of the 3-acetyl-4-hydroxy-5-sec-butylpyrroline-2-ketone analogs have high herbicidal activity. The size of the side chain also has an effect on their activity.
  • Compound 10-57 were dissolved in small amount of methanol. The solutions were then diluted with distilled water to a concentration of 50 ⁇ g/mL. A mixture of methanol and water in the same ratio as the sample solution was also prepared and used as control in the experiment. The healthy leaves of Crofton weed were washed in water for 30 minutes and then rinsed with distilled water. The clean and tissue dried leaves were placed in petri dish with the back-side of the leaves facing up. Wet filter paper was also placed in the in petri dish for moisture control. Water, methanol and chemical solutions of the analogues were applied to the back-side of each leaf. Test sample was then placed in vacuum chamber at 25° C.
  • the salt form of these compounds is much more herbicidal.
  • the ammonium salt, the sodium salt, the potassium salt, the magnesium salt and the zinc salt have higher activity than the calcium, magnesium and copper salts.
  • results listed in the table 10 suggest that eight compounds (7, 14, 15, 16, 40, 44, 48, and 53) have potential to be used to control or kill grassy weed such as Common crabgrass, Bbarnyardgrass, Difformed galingale, broadleaf weeds, Yerbadetajo, Copperleaf, Chenopodium serotinum, Commelina communis, Alligator weed, Redroot pigweed, Japanese false bindweed, Sonchus oleraceus etc.
  • grassy weed such as Common crabgrass, Bbarnyardgrass, Difformed galingale, broadleaf weeds, Yerbadetajo, Copperleaf, Chenopodium serotinum, Commelina communis, Alligator weed, Redroot pigweed, Japanese false bindweed, Sonchus oleraceus etc.
  • Compound 1, 2, 3 and 40 were dissolved in small amount of methanol and diluted with distilled water to concentration of 50 ⁇ g/mL. The solution was sprayed to the soil sample until the soil was wet but not overflows. After standing at room temperature for 3 hours, the soil sample was washed with water and methanol. The wash solution was collected and concentrated. Such process was repeated three times. The concentrated solutions were used for herbicidal activity test using the method of needle puncture on Crofton weed. Methanol water solution and pure water were used as control. The experiment for every sample was repeated six times. The spot diameters were measured with vernier caliper after the plant was kept under natural light at 25° C. for 24 hours (Table 11).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pyrrole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US12/055,384 2005-09-26 2008-03-26 Novel herbicides and methods for preparation thereof Abandoned US20080176748A1 (en)

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US13/414,711 US8921274B2 (en) 2005-09-26 2012-03-07 Method for eradicating weeds with derivatives of 3-acetyl-5-sec-butyl-4-hydroxy-3-pyrrolin-2-one
US14/548,289 US9468209B2 (en) 2005-09-26 2014-11-20 Method for eradicating weeds with derivatives of 3-acetyl-5-sec-butyl-4-hydroxy-3-pyrrolin-2-one

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CNA2005100945219A CN1752075A (zh) 2005-09-26 2005-09-26 一种生物源化合物的结构修饰产品及其用于除草
CN200510094521.9 2005-09-26
PCT/CN2006/001315 WO2007033544A1 (fr) 2005-09-26 2006-06-13 Technique de modification de la molécule d'un bio-produit et application pour la lutte contre les mauvaises herbes

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US14/548,289 Active US9468209B2 (en) 2005-09-26 2014-11-20 Method for eradicating weeds with derivatives of 3-acetyl-5-sec-butyl-4-hydroxy-3-pyrrolin-2-one

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CN101715785B (zh) * 2009-11-26 2012-04-25 李翠兰 紫茎泽兰专用生长抑制剂
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WO2016000230A1 (zh) * 2014-07-03 2016-01-07 上海医药工业研究院 一种达比加群酯中间体的制备方法及中间体化合物
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US9468209B2 (en) 2016-10-18
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CN101228124A (zh) 2008-07-23
CN1752075A (zh) 2006-03-29
US8921274B2 (en) 2014-12-30
EP1997803B1 (en) 2018-02-14
US20150141254A1 (en) 2015-05-21
US20120172226A1 (en) 2012-07-05
CN103922990A (zh) 2014-07-16
EP1997803A4 (en) 2010-11-24
WO2007033544A1 (fr) 2007-03-29
JP2009509944A (ja) 2009-03-12

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