EP2723720A1 - Procédé de préparation de pyrazolyl-carboxanilides - Google Patents

Procédé de préparation de pyrazolyl-carboxanilides

Info

Publication number
EP2723720A1
EP2723720A1 EP12728549.2A EP12728549A EP2723720A1 EP 2723720 A1 EP2723720 A1 EP 2723720A1 EP 12728549 A EP12728549 A EP 12728549A EP 2723720 A1 EP2723720 A1 EP 2723720A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
methyl
tetrahydro
methanonaphthalene
difluoromethyl
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Withdrawn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
EP12728549.2A
Other languages
German (de)
English (en)
Inventor
Wahed Ahmed Moradi
Norbert Lui
Michael Dockner
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.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Intellectual Property GmbH
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
Application filed by Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Priority to EP12728549.2A priority Critical patent/EP2723720A1/fr
Publication of EP2723720A1 publication Critical patent/EP2723720A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/415—1,2-Diazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the present invention relates to a process for the preparation of pyrazolylcarboxanilides by reacting pyrazolylcarboxylic esters with anilines in the presence of a base.
  • pyrazolylcarboxanilides Numerous methods for the synthesis of pyrazolylcarboxanilides are known from the literature (see WO 2006/024388, US 2011/0054183, US 2010/0174094). In the currently most widely practiced processes, corresponding pyrazolylcarboxylic acid derivatives, for example, pyrazolylcarboxylic acid halides (eg, pyrazolylcarboxylic acid chlorides), are reacted with aniline derivatives, for example, 3 ', 4'-dichloro-5-fluorobiphenyl-2-amine, optionally in the presence of a base.
  • pyrazolylcarboxylic acid halides eg, pyrazolylcarboxylic acid chlorides
  • organometallic catalysts are used which, however, do not tolerate highly functionalized substrates and, moreover, are technically impracticable (J.A. Chem. Soc., 1955, 469-472, Tetrahedron Lett., 1971, 321-322, J. Org. Chem., 1963, 2915-2917; J. Org. Chem., 1992, 6101-6103).
  • other catalysts such as cyanides (J. Org. Chem., 1987, 52, 2033-2036), and boron tribromides (Tetrahedron Lett., 1974, 3995), trimethylaluminum has been highlighted.
  • the object of this invention is to provide a process for the synthesis of pyrazolylcarboxanilides starting from pyrazolylcarboxylic acid esters and anilines, which is more economical compared to the processes known from the prior art.
  • the process should be suitable for large-scale implementation and provide pyrazolylcarboxanilides in high yield and high purity.
  • the object is achieved by a process for the preparation of fungicidally active pyrazolylcarboxanilides of the formula (III)
  • ⁇ is hydrogen, fluorine or chlorine, is methyl, difluoromethyl or trifluoromethyl, is hydrogen, fluorine, chlorine, methyl, iso-propyl, methylthio or trifluoromethyl, for 1, 2, 3 or 4, preferably for 1 or 2, especially preferably represents 1, represents optionally mono- to trisubstituted, identically or differently substituted phenyl, where the substituents are selected from halogen, C 1 -C -alkyl, C 1 -C -alkoxy, C 1 -C 2 -haloalkyl or C 2 -C 4 -alkyl.
  • Haloalkoxy having in each case 1 to 6 fluorine, chlorine and / or bromine atoms, hydroxyimino-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxyimino-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxyimino-C 1 -C 4 -alkyl, or in two adjacent substituents of difluoromethylenedioxy or tetrafluoroethylenedioxy; or represents in each case optionally monosubstituted to trisubstituted, identically or differently by C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and / or C 3 -C 10 -cycloalkyl-substituted C 3 -C 10 -cycloalkyl or C 3 -C 10 -cycloalkyl, or unsubstituted (linear or branched) Ci-C2o-al
  • R 1 and R 2 are as defined above and
  • R 5 is C 1 -C 6 -alkyl, C 1 -C 6 -aryl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -thioalkyl, C 1 -C 6 -
  • Ci-C 6 alkylsulphonyl Ci-C 6 alkyl
  • Ci-C 6 cyanoalkyl Ci-C 6 haloalkyl
  • Ci-C 6 - is nitroalkyl, C3-Cg-aryl or C3-Cg-cycloalkyl, with anilines of the formula (II)
  • R, R and n are as defined above, wherein the reaction is carried out in the presence of a base and removing at least one of the products resulting from the reaction and optionally in an inert solvent.
  • the pyrazolylcarboxylic acid esters used as starting materials are generally defined by the formula (I). According to a preferred embodiment of the present invention are used as starting materials Pyrazolylcarbonklareester of formula (I), in which
  • R 5 is methyl, ethyl or benzyl.
  • R 5 is ethyl or methyl.
  • the anilines used as starting materials are generally defined by the formula (II). According to a preferred embodiment of the present invention, the starting materials used are anilines of the formula (II) in which R 3 , R 4 and n are as defined above and the substituent R 3 is in the 5-position.
  • the starting materials used are anilines of the formula (II) in which
  • R 3 is hydrogen, fluorine or chlorine, n is 1 or 2,
  • R 4 is optionally two or three times, identically substituted phenyl, where the substituents are selected from fluorine or chlorine, or for C 2 -C 4 haloalkoxy with in each case 3 to 6 fluorine atoms and 0 to 1 chlorine atoms; or C3-bicycloalkyl optionally substituted once to four times, identically or differently by halogen and / or C 1 -C 4 -alkyl; or unsubstituted (linear or branched) C 2 -C 6 -alkyl; or, together with the phenyl radical, for both syn isomers of N - [(1RS, 4SR, 9RS) - 1, 2,3,4-tetrahydro-9- (isopropyl) -l, 4-methanonaphthalene, or for both anti isomers of N- [(1RS, 4SR, 9SR) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanona
  • R 3 is 5-fluoro, n is 1 and R 4 is 3, 4-dichlorophenyl; or
  • R 3 is hydrogen, n is 1 and
  • R 4 is 3,4,5-trifluorophenyl
  • R 3 is hydrogen, n is 1 and
  • R 4 is 2- (l, l, 2,2-tetrafluoroethoxy), 2- (l, l, 2,3,3,3-hexafluoropropoxy) or 2- (3-Cl-l, l, 2-trifluoroethoxy) ; or
  • R 3 is hydrogen, n is 1 and R 4 is 2- (1, 1'-bicyclopropyl); or
  • R 3 is hydrogen, n is 1 and
  • R 4 is 2- (1,3-dimethylbutyl); or
  • R 3 is hydrogen, n is 1 and
  • R 4 together with the phenyl radical for both syn isomers of N - [(1RS, 4SR, 9RS) - 1, 2,3,4-tetrahydro-9- (isopropyl) -l, 4-methanonaphthalene, or for both anti isomers of N - [(1RS, 4SR, 9SR) -1, 2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalene; or
  • R 3 is hydrogen, n is 1 and R together with the phenyl radical for N- [9- (dichloromethylene) -l, 2,3,4-tetrahydro-1, 4-methanonaphthalen-5-yl], for N - [(1S, 4R) -9- ( Dichloromethylene) -l, 2,3,4-tetrahydro-1, 4-methanonaphthalene-5-yl] - or N - [(1R, 4S) -9- (dichloromethylene) -1,3,3,4-tetrahydro -l, 4-methanonaphthalen-5-yl] -; or R 3 is hydrogen, n is 1, and
  • R 4 together with the phenyl radical is N- (1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl.
  • anilines of the formula (II) to be used as starting materials in carrying out the process according to the invention can also be prepared in situ from the corresponding anilides, for example N-acetanilides.
  • the fungicidally active pyrazolylcarboxanilides of the formula (III) are selected from the group consisting of bixafen, fluxapyroxad, sedaxanes, isopyrazam, N- [9- (dichloromethylene) -1,3,3,4-tetrahydro- l, 4-methanonaphthalene-5-yl] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, N - [(1S, 4R) -9- (dichloromethylene) -1,3,2 , 4-tetrahydro-1,4-methanonaphthalen-5-yl] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-c arb ox amide, N- [(1R, 4S) -9 - (dichloromethylene) - 1, 2,3, 4-tetrahydro-1,
  • Bixafen with the chemical name N- (3 ', 4'-dichloro-5-fluoro-1, -biphenyl-2-yl) -3- (difluoro-methyl) -1-methyl-1H-pyrazole-4-carboxamide and its production process starting from known and commercially available components are described in the document WO 2003/070705 A.
  • F lux ap yrax ad with the same description of 3- (difluoromethyl) -1-methyl-N- (3 ', 4', 5'-trifluorobiphenyl-2-yl) -1H-pyrazole-4 -carboxamide and its production process starting from known and commercially available components is described in the document WO 2006/087343 A.
  • Sedaxane which is a mixture of two cis isomers 2 '- [(lRS, 2RS) -l, 1'-bicycloprop-2-yl] -3- (difluoromethyl) -1-methylpyrazole-4-carboxanilide and two trans isomers are 2'- [(lRS, 2SR) -l, 1'-bicycloprop-2-yl] -3- (difluoromethyl) -1-methylpyrazole-4-carboxanilide and its production process starting from known and commercially available components are described in the publications WO 2003/074491 A, WO 2006/015865 A and WO 2006/015866 A.
  • Isopyrazam which is a mixture of 2 syn isomers of 3- (difluoromethyl) -1-methyl-N - [(IRS, 4SR, 9RS) -1,2,3,4-tetrahydro-9-isopropyl-1 , 4-methanonaphthalene-5-yl] pyrazole-4-carboxamide and 2 anti-isomers of 3- (difluoromethyl) -l-methyl-N - [(lRS, 4SR, 9SR) -l, 2,3,4-tetrahydro- 9-isopropyl-l, 4-methanonaphthalen-5-yl] pyrazole-4-carboxamide and its production process starting from known and commercially available components are described in the document WO 2004/035589 A.
  • Penflufen with the chemical name N- [2- (l, 3-dimethylbutyl) phenyl] -5-fluoro-l, 3-dimethyl-lH-pyrazole-4-carboxamide and its production process starting from known and commercially available components are in the Publication WO 2003/010149 A described.
  • the fungicidally active pyrazolylcarboxanilides of the formula (III) are selected from the group consisting of bixafen, fluxapyroxad and isopyrazam.
  • the fungicidally active pyrazolylcarboxanilide of the formula (III) is bixafen.
  • the at least one reaction product that is removed is at least one alcohol.
  • the at least one alcohol is removed by distillation.
  • the methanol and ethanol formed in the reaction are removed.
  • the general or preferred radical definitions or explanations given above can also be combined as desired between each other, ie between the respective ranges and the preferred ranges. They apply accordingly to the end products as well as to the precursors and intermediates. In addition, individual definitions can be omitted.
  • pyrazolylcarboxylic esters of the formula (I) required as starting materials for carrying out the process according to the invention are known and / or can be prepared by known processes (cf., for example, WO 2009/106230, WO 2008/022777).
  • anilines of the formula (II) furthermore required for carrying out the process according to the invention as starting materials are likewise known and / or can be prepared by known processes, for example by hydrogenation of the corresponding nitroaromatics (R. C. Larock, Comprehensive Organic Transformations, Wiley-VCH, 2 nd edition 1999, 821 ff).
  • suitable bases are, for example, organic bases such.
  • amidine or guanidine bases such as DBU, DBN, pentamethyl or Pentaisopropylguanidin, which must not contain reactive NH groups, and phosphine-imine bases (Schwesinger bases) as the tert-butyliminotris (dimethylamino) -phosphorane and the 1 tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis- [tris (dimethylamino) -phosphoranylideneamino] -2 ⁇ 5 , 4 ⁇ 5 -catenadi (phosphazene).
  • Trialkylamines which may be alicyclic or open-chain; Alkali and alkaline earth salts of aliphatic and / or aromatic carboxylic acids, such as acetates, propionates or benzoates; Alkali and alkaline earth carbonates, bicarbonates, phosphates, hydrogen phosphates and / or hydroxides; and metal alkoxides, in particular alkali metal or alkaline earth metal alkoxides, such as, for example, sodium methoxide, potassium methoxide, sodium ethanolate, magnesium methoxide, calcium ethoxide, sodium tert. Butoxide, potassium tert-butoxide or alkali isoamylate.
  • the base is an alkali alkoxide selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide, sodium tert. butoxide, potassium tert-butoxide and alkali isoamylate.
  • Particularly preferred are sodium methylate and sodium ethylate.
  • the use of sodium methylate and sodium ethylate is particularly preferred for reasons of economy.
  • the necessary amount of base present in the reaction step based on aniline can be determined by the skilled person simply by routine experimentation.
  • the molar ratio of aniline to used base is 0.01 to 10, preferably 0.9 to 2, particularly preferably 1 to 1, 1.
  • the use of larger amounts of base is possible in principle, but is disadvantageous for economic reasons.
  • Suitable solvents for carrying out the process according to the invention are all organic solvents which are inert under the reaction conditions.
  • ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenetole, cyclohexylmethyl ether, dimethyl ether, diethyl ether, dimethyl glycol diphenyl ether, dipropyl ether, diisopropyl ether, D-n-butyl ether , Diisobutyl ether, D ii so amyl ether, ethylene glycol dimethyl ether, diglyme, triglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 2-ethoxyethyl ether, isopropyl ethyl ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, methylcyclopentyl ether, tert-amyl methyl ether (TAME) Dichloroethyl ether and polyether
  • solvents which are selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, dioxane, methylcyclopentyl ether, tert-amyl methyl ether (TAME), diglyme, toluene, xylene, mesitylene, cumene, N, N-dimethylacetamide, ⁇ , ⁇ Dimethylformamide, N-methylpyrrolidone and mixtures of these. Very particular preference is given to mixtures of NMP and toluene, xylene or cumene. Preference is given to a mixing ratio of toluene: NMP of 10: 1, more preferably of 5: 1.
  • Solvents are advantageously used in such an amount that the reaction mixture remains easy to stir throughout the process.
  • the process according to the invention is carried out without a solvent.
  • the reaction is carried out at a temperature of 20 to 200 ° C, preferably from 50 to 100 ° C, more preferably from 50 to 80 ° C, and at a pressure between 1 mbar and 100 bar, preferably at a pressure between 100 mbar and 600 mbar performed.
  • the following examples serve to illustrate the process according to the invention, without limiting it to:
  • reaction mixture was stirred at 500 mbar and 70 ° C for 15 minutes. The vacuum was then reduced to 400 mbar for 15 minutes and to 200 mbar for another hour. The internal temperature dropped to approx. 60 ° C. After completion of the reaction, 200 g of water and 100 g of toluene were added to the still stirrable reaction mixture at 45 ° C. First, a sticky mass formed, from which the product crystallized. The pH of the suspension was adjusted to 7 with an HCl solution, cooled to about 5 ° C, the solid was filtered off, washed with 50 g of water and 50 g of toluene and dried.
  • reaction mixture was stirred at 500 mbar and 70 ° C for 15 minutes. The vacuum was then reduced to 400 mbar for 15 minutes and to 200 mbar for 1.5 hours. After completion of the reaction, 100 g of water and 50 g of toluene were added to the reaction mixture at 45 ° C. After separation of the organic phase, the aqueous phase was extracted three times with 50 g of toluene, the combined organic phases were dried with Na2SÜ4 and then the solvent was removed in vacuo.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Oncology (AREA)
  • Communicable Diseases (AREA)
  • Epidemiology (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé simplifié de préparation de pyrazolyl-carboxanilides par réaction d'esters d'acide pyrazolyl-carbonique avec des anilines en présence d'une base et élimination d'au moins un produit réactionnel.
EP12728549.2A 2011-06-21 2012-06-19 Procédé de préparation de pyrazolyl-carboxanilides Withdrawn EP2723720A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12728549.2A EP2723720A1 (fr) 2011-06-21 2012-06-19 Procédé de préparation de pyrazolyl-carboxanilides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201161499280P 2011-06-21 2011-06-21
EP11170685 2011-06-21
PCT/EP2012/061739 WO2012175511A1 (fr) 2011-06-21 2012-06-19 Procédé de préparation de pyrazolyl-carboxanilides
EP12728549.2A EP2723720A1 (fr) 2011-06-21 2012-06-19 Procédé de préparation de pyrazolyl-carboxanilides

Publications (1)

Publication Number Publication Date
EP2723720A1 true EP2723720A1 (fr) 2014-04-30

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ID=44315246

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12728549.2A Withdrawn EP2723720A1 (fr) 2011-06-21 2012-06-19 Procédé de préparation de pyrazolyl-carboxanilides

Country Status (8)

Country Link
US (1) US20140128617A1 (fr)
EP (1) EP2723720A1 (fr)
JP (1) JP2014523425A (fr)
KR (1) KR20140036240A (fr)
CN (1) CN103619822A (fr)
BR (1) BR112013032988A2 (fr)
MX (1) MX2013014312A (fr)
WO (1) WO2012175511A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP2980078A1 (fr) * 2014-07-29 2016-02-03 Solvay SA Procédé pour la préparation de pyrazole-4-carboxamides
WO2019044266A1 (fr) 2017-08-28 2019-03-07 株式会社日本ファインケム Procédé de production d'un dérivé de pyrazole-4-carboxamide

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US4877441A (en) 1987-11-06 1989-10-31 Sumitomo Chemical Company Ltd. Fungicidal substituted carboxylic acid derivatives
JPH09255675A (ja) * 1996-03-28 1997-09-30 Daicel Chem Ind Ltd フラン−３−カルボキシアミド誘導体の製造法
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Also Published As

Publication number Publication date
MX2013014312A (es) 2014-01-31
JP2014523425A (ja) 2014-09-11
US20140128617A1 (en) 2014-05-08
WO2012175511A1 (fr) 2012-12-27
CN103619822A (zh) 2014-03-05
KR20140036240A (ko) 2014-03-25
BR112013032988A2 (pt) 2016-08-16

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