JP2014527032A - 2−アミノ−5−シアノ−n,3−ジメチルベンズアミドを製造する方法 - Google Patents
2−アミノ−5−シアノ−n,3−ジメチルベンズアミドを製造する方法 Download PDFInfo
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- JP2014527032A JP2014527032A JP2014517809A JP2014517809A JP2014527032A JP 2014527032 A JP2014527032 A JP 2014527032A JP 2014517809 A JP2014517809 A JP 2014517809A JP 2014517809 A JP2014517809 A JP 2014517809A JP 2014527032 A JP2014527032 A JP 2014527032A
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- formula
- amino
- cyano
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- UOCPQZOXOQZEGV-UHFFFAOYSA-N 2-amino-5-cyano-n,3-dimethylbenzamide Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1N UOCPQZOXOQZEGV-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 27
- -1 2-amino-5-cyano-3-methylbenzoic acid ester Chemical class 0.000 claims abstract description 54
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 claims description 2
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004001 thioalkyl group Chemical group 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 69
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 10
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000007098 aminolysis reaction Methods 0.000 description 5
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 4
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 4
- 0 C*c1c(C)cccc1S([U]*(OC(C1=CC=CC(C)C1=*)=O)=C)=O Chemical compound C*c1c(C)cccc1S([U]*(OC(C1=CC=CC(C)C1=*)=O)=C)=O 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007333 cyanation reaction Methods 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- NVJKMGDNYCDLGR-UHFFFAOYSA-N methyl 2-amino-5-bromo-3-methylbenzoate Chemical compound COC(=O)C1=CC(Br)=CC(C)=C1N NVJKMGDNYCDLGR-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000010966 qNMR Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 3
- 229950005499 carbon tetrachloride Drugs 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- VURHXMNDXDTGGN-UHFFFAOYSA-N ethyl 2-amino-5-cyano-3-methylbenzoate Chemical compound CCOC(=O)C1=CC(C#N)=CC(C)=C1N VURHXMNDXDTGGN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- HHPMPAYAWGLODN-UHFFFAOYSA-N 2-(cyanoamino)benzoic acid Chemical class OC(=O)C1=CC=CC=C1NC#N HHPMPAYAWGLODN-UHFFFAOYSA-N 0.000 description 2
- UTFWCDLUBLVLCK-UHFFFAOYSA-N 2-ethylhexyl 2-amino-5-bromo-3-methylbenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC(Br)=CC(C)=C1N UTFWCDLUBLVLCK-UHFFFAOYSA-N 0.000 description 2
- VHXBQEKDIKICJH-UHFFFAOYSA-N 2-ethylhexyl 2-amino-5-cyano-3-methylbenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC(C#N)=CC(C)=C1N VHXBQEKDIKICJH-UHFFFAOYSA-N 0.000 description 2
- ZIPVXFKUEKUQHD-UHFFFAOYSA-N 2-methoxyethyl 2-amino-5-cyano-3-methylbenzoate Chemical compound COCCOC(=O)C1=CC(C#N)=CC(C)=C1N ZIPVXFKUEKUQHD-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 2
- HIWXKZCLYZKEDZ-UHFFFAOYSA-N benzyl 2-amino-5-bromo-3-methylbenzoate Chemical compound CC1=CC(Br)=CC(C(=O)OCC=2C=CC=CC=2)=C1N HIWXKZCLYZKEDZ-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- HJJPKQZMXXGRBW-UHFFFAOYSA-N ethyl 2-amino-5-bromo-3-methylbenzoate Chemical compound CCOC(=O)C1=CC(Br)=CC(C)=C1N HJJPKQZMXXGRBW-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- JRTHRJXZTYVWMR-UHFFFAOYSA-N hexyl 2-amino-5-bromo-3-methylbenzoate Chemical compound CCCCCCOC(=O)C1=CC(Br)=CC(C)=C1N JRTHRJXZTYVWMR-UHFFFAOYSA-N 0.000 description 2
- WZSFIFBAKLLVAE-UHFFFAOYSA-N hexyl 2-amino-5-cyano-3-methylbenzoate Chemical compound CCCCCCOC(=O)C1=CC(C#N)=CC(C)=C1N WZSFIFBAKLLVAE-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VTNGSRHTTZVQSV-UHFFFAOYSA-N pentyl 2-amino-5-bromo-3-methylbenzoate Chemical compound CCCCCOC(=O)C1=CC(Br)=CC(C)=C1N VTNGSRHTTZVQSV-UHFFFAOYSA-N 0.000 description 2
- IWHZTBBLHBHIQC-UHFFFAOYSA-N pentyl 2-amino-5-cyano-3-methylbenzoate Chemical compound CCCCCOC(=O)C1=CC(C#N)=CC(C)=C1N IWHZTBBLHBHIQC-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WNAJXPYVTFYEST-UHFFFAOYSA-N 2-Amino-3-methylbenzoate Chemical compound CC1=CC=CC(C(O)=O)=C1N WNAJXPYVTFYEST-UHFFFAOYSA-N 0.000 description 1
- RWLPKYJTGUCBQH-UHFFFAOYSA-N 2-amino-5-bromo-3-methylbenzoic acid Chemical compound CC1=CC(Br)=CC(C(O)=O)=C1N RWLPKYJTGUCBQH-UHFFFAOYSA-N 0.000 description 1
- FYPIIMYXBCWBPQ-UHFFFAOYSA-N 2-amino-5-cyano-3-methylbenzoic acid Chemical compound CC1=CC(C#N)=CC(C(O)=O)=C1N FYPIIMYXBCWBPQ-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- QZCUFWWEWHSKFF-UHFFFAOYSA-N 2-ethylhexyl 2-amino-3-methylbenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC(C)=C1N QZCUFWWEWHSKFF-UHFFFAOYSA-N 0.000 description 1
- SEURHXCZPPGZGX-UHFFFAOYSA-N 2-methoxyethyl 2-amino-3-methylbenzoate Chemical compound COCCOC(=O)C1=CC=CC(C)=C1N SEURHXCZPPGZGX-UHFFFAOYSA-N 0.000 description 1
- KBVVPLPLGGTYAL-UHFFFAOYSA-N 2-methoxyethyl 2-amino-5-bromo-3-methylbenzoate Chemical compound COCCOC(=O)C1=CC(Br)=CC(C)=C1N KBVVPLPLGGTYAL-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- MXSONIWDPQQCBO-UHFFFAOYSA-N CC1=CC(=CC(=C1CC2=CC=CC=C2)C(=O)O)C#N Chemical compound CC1=CC(=CC(=C1CC2=CC=CC=C2)C(=O)O)C#N MXSONIWDPQQCBO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ZXYMHLVAEFGNLJ-UHFFFAOYSA-N benzyl 2-amino-5-cyano-3-methylbenzoate Chemical compound CC1=CC(C#N)=CC(C(=O)OCC=2C=CC=CC=2)=C1N ZXYMHLVAEFGNLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- QQMPSVJJDHTORK-UHFFFAOYSA-N cyano 2-aminobenzoate Chemical compound NC1=CC=CC=C1C(=O)OC#N QQMPSVJJDHTORK-UHFFFAOYSA-N 0.000 description 1
- 238000007257 deesterification reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- SAFXLTVQYJESOM-UHFFFAOYSA-N ethyl 2-amino-5-bromo-3-ethylbenzoate Chemical compound CCOC(=O)C1=CC(Br)=CC(CC)=C1N SAFXLTVQYJESOM-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- ITOQPZFEKLBSIO-UHFFFAOYSA-N hexyl 2-amino-3-methylbenzoate Chemical compound CCCCCCOC(=O)C1=CC=CC(C)=C1N ITOQPZFEKLBSIO-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- VSFYTPXXMLJNAU-UHFFFAOYSA-N methyl 2-amino-3-methylbenzoate Chemical compound COC(=O)C1=CC=CC(C)=C1N VSFYTPXXMLJNAU-UHFFFAOYSA-N 0.000 description 1
- UHFVZQIOQVEYQM-UHFFFAOYSA-N methyl 2-amino-5-cyano-3-methylbenzoate Chemical compound COC(=O)C1=CC(C#N)=CC(C)=C1N UHFVZQIOQVEYQM-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RJLFOJRFYXZPME-UHFFFAOYSA-N pentyl 2-amino-3-methylbenzoate Chemical compound CCCCCOC(=O)C1=CC=CC(C)=C1N RJLFOJRFYXZPME-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
R1は、アルキル、シクロアルキル、アルコキシアルキル、アリールアルキル、チオアルキル、アルキルチオアルキル、アルキルスルホニルアルキル、シアノアルキル、ハロアルキル、ニトロアルキル又はアリールを表し;
R1は、好ましくは、メチル、エチル、(C5−C12)アルキル又はアリールを表し;
R1は、さらに好ましくは、メチル、エチル、ペンチル、ヘキシル又は2−エチルヘキシルを表し;
R1は、最も好ましくは、ペンチル、ヘキシル又は2−エチルヘキシルを表す〕
で表される2−アミノ−5−シアノ−3−メチル安息香酸エステル、又は、式(III)
Aは、アルキレン及びアルコキシアルキレンを表し;
Aは、好ましくは、メチレン、エチレン又はヘキシレンを表し;
Aは、さらに好ましくは、エチレン又はヘキシレンを表す〕
で表される2−アミノ−5−シアノ−3−メチル安息香酸ジエステルを、MeNH2と、それ以上混合させることなく又は少なくとも1種類の塩基(例えば、ナトリウムアミド、水素化ナトリウム、水酸化ナトリウム、シアン化ナトリウム、シアン化カリウム、炭酸カリウム、炭酸ナトリウム、炭酸セシウム、ナトリウムメトキシド、及び、トリエチルアミン)用いて、反応させることによる。
で表される化合物をシアン化銅(I)と反応させることによって得ることができる。
で表される化合物を臭化水素と過酸化水素の混合物と反応させることによって得ることができる。
本発明に関連して、用語「ハロゲン」(X)は、特に異なって定義されていない限り、フッ素、塩素、臭素及びヨウ素からなる群から選択されるハロゲン元素を包含し、ここで、フッ素、塩素及び臭素を使用するのが好ましく、フッ素及び塩素を使用するのが特に好ましい。置換される基は、1以上の置換基で置換されることができ、それら置換基のうちの2つ以上が存在している場合、それら置換基は同一であっても又は異なっていてもよい。
以下の調製実施例によって本発明について例証するが、該調製実施例は本発明を限定するものではない。
2−アミノ−3−メチル安息香酸メチル
1H NMR(600MHz,(d6−DMSO):δ=7.64(dd,1H),7.19(d,1H),6.50(pq,3H,Ar−H,NH2),3.79(s,3H),2.12(s,3H))。
2−アミノ−3−メチル安息香酸メチル(142.1g、0.843mol、純度:98% 定量的NMR)を240mLのH2Oに溶解させた溶液に、30℃で臭化水素(H2O中48%、149.2g、0.885mol)を滴下して加え、徐々に混合させる。得られた懸濁液に2時間かけて過酸化水素(H2O中30%、105.1g、0.927mol)を滴下して加え、混合させ、温度を70℃未満に維持する。その後1時間撹拌した後、NaHSO3(H2O中39%、33.7g、0.126mol)を少量ずつ添加する(過酸化物試験は陰性であった)。得られた懸濁液を、Na2CO3(0.1eq.、9.0g、0.084mol)を少量ずつ添加して、pH7−8に調節する。濾過して真空乾燥キャビネット内で乾燥させた後、2−アミノ−5−ブロモ−3−メチル安息香酸メチルが薄茶色の固体として単離される。収量:204.2g、理論値の97.7%、純度:98.5%(定量的NMR)。
2−アミノ−5−ブロモ−3−メチル安息香酸メチル(100g、0.393mol、96% 定量的NMR)、シアン化銅(I)(36.3g、0.401mol)及びN−メチル−2−ピロリジノン(NMP)(206g、200mL、2.084mol)を撹拌しながら4時間170℃に加熱する。その反応バッチを120℃まで冷却し、350mLのH2O(90℃)を30分間かけて滴下して加え、得られた懸濁液を濾過する。得られた固体をアンモニア(200g、H2O中12%)で2回洗浄し、及び、100mLの水で2回洗浄する。真空乾燥キャビネット内で50℃で乾燥させた後、2−アミノ−5−シアノ−3−メチル安息香酸メチルが灰色の固体として得られる。収量:69.0g、理論値の88.2%、純度:95.6% 定量的NMR、1500ppm Cu)。
2−アミノ−5−シアノ−N,3−ジメチルベンズアミド
2−アミノ−5−シアノ−3−メチル安息香酸エチル(50g、0.251mol)をメタノール(175mL)に溶解させた溶液にメチルアミン(117g、3.77mol)を入れ、ナトリウムメトキシド(1.13g、メタノール中30%強度、6.28mmol)を添加し、その反応混合物を室温で一晩撹拌する。その後、100mLの22%強度NaOHを添加し、バッチを10℃まで冷却する。得られた懸濁液を濾過し、得られた固体をメタノール:水(1:1)で1回洗浄し、次いで、50mLの水で洗浄する。固体を真空乾燥キャビネット内で50℃で乾燥させる。2−アミノ−5−シアノ−N,3−ジメチルベンズアミドが僅かにベージュ色の固体として単離される。収率:理論値の80.3%、純度:94.9% 定量的LC、73ppm Cu)。
Claims (11)
- 式(I)
(A) 式(II)
で表される2−アミノ−5−シアノ−3−メチル安息香酸エステルをMeNH2と反応させること;
又は、
(B) 式(III)
で表される2−アミノ−5−シアノ−3−メチル安息香酸ジエステルをMeNH2と反応させること;
を特徴とする、前記調製方法。 - 式(II)で表される2−アミノ−5−シアノ−3−メチル安息香酸エステル又は式(III)で表される2−アミノ−5−シアノ−3−メチル安息香酸ジエステルを少なくとも1種類の塩基を用いてMeNH2と反応させることを特徴とする、請求項1に記載の調製方法。
- 式(I)で表される化合物が式(II)で表される2−アミノ−5−シアノ−3−メチル安息香酸エステルを反応させることによって得られることを特徴とする、請求項1又は2に記載の調製方法。
- 式(I)で表される化合物が式(III)で表される2−アミノ−5−シアノ−3−メチル安息香酸ジエステルを反応させることによって得られることを特徴とする、請求項1又は2に記載の調製方法。
- 前記塩基がナトリウムアミド、水素化ナトリウム、水酸化ナトリウム、シアン化ナトリウム、シアン化カリウム、炭酸カリウム、炭酸ナトリウム、炭酸セシウム、ナトリウムメトキシド及びトリエチルアミンからなる群から選択されることを特徴とする、請求項2、3及び4の何れか一項に記載の調製方法。
- 式(IV)又は式(V)で表される化合物の1mol当たり、0.8mol〜1.4molのシアン化銅(I)を用いることを特徴とする、請求項6又は7に記載の調製方法。
- シアン化銅(I)を溶媒としてのN,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルホルムアニリド、N−メチルピロリドン、ヘキサメチルホスホルアミド又はジメチルスルホキシドの中で使用することを特徴とする、請求項6、7及び8の何れか一項に記載の調製方法。
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US61/506,263 | 2011-07-11 | ||
PCT/EP2012/063167 WO2013007603A1 (de) | 2011-07-08 | 2012-07-05 | Verfahren zur herstellung von 2-amino-5-cyano-n,3-dimethylbenzamid |
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JP2008523069A (ja) * | 2004-12-07 | 2008-07-03 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | N−フェニルピラゾール−1−カルボキサミドの製造法 |
JP2011513422A (ja) * | 2008-03-05 | 2011-04-28 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 2−アミノ−5−シアノ安息香酸誘導体を製造するための方法 |
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MX2014000317A (es) | 2014-02-19 |
BR112014000473B1 (pt) | 2020-04-14 |
BR112014000473A2 (pt) | 2017-02-21 |
ES2648308T3 (es) | 2017-12-29 |
KR20140039256A (ko) | 2014-04-01 |
TW201311618A (zh) | 2013-03-16 |
JP5955954B2 (ja) | 2016-07-20 |
CN107365263A (zh) | 2017-11-21 |
WO2013007603A1 (de) | 2013-01-17 |
CN103702978B (zh) | 2018-03-06 |
MX369283B (es) | 2019-11-04 |
DK2729444T3 (en) | 2017-12-04 |
US20140148611A1 (en) | 2014-05-29 |
TWI585069B (zh) | 2017-06-01 |
CN103702978A (zh) | 2014-04-02 |
EP2729444B1 (de) | 2017-08-23 |
KR101953407B1 (ko) | 2019-02-28 |
EP2729444A1 (de) | 2014-05-14 |
US9169198B2 (en) | 2015-10-27 |
IL230159A0 (en) | 2014-03-06 |
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