TW200846318A - Process for preparing alkyl dihaloacetoacetates - Google Patents
Process for preparing alkyl dihaloacetoacetates Download PDFInfo
- Publication number
- TW200846318A TW200846318A TW097103839A TW97103839A TW200846318A TW 200846318 A TW200846318 A TW 200846318A TW 097103839 A TW097103839 A TW 097103839A TW 97103839 A TW97103839 A TW 97103839A TW 200846318 A TW200846318 A TW 200846318A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- alkyl
- ethyl
- fluorine
- chlorine
- Prior art date
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- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- -1 1,1,2-trifluoro-2-(trifluoromethyl)ethyl Chemical group 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 239000000460 chlorine Chemical group 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Chemical group 0.000 claims description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 claims description 2
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 2
- 150000004795 grignard reagents Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- YMAWDYYHYWOGHI-UHFFFAOYSA-N CN(C)CC(F)Cl Chemical compound CN(C)CC(F)Cl YMAWDYYHYWOGHI-UHFFFAOYSA-N 0.000 claims 1
- XMRFSEPPGSJHFC-UHFFFAOYSA-N NN.C(C)NCC Chemical compound NN.C(C)NCC XMRFSEPPGSJHFC-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims 1
- HPTZACFYPLQYGS-UHFFFAOYSA-N anthracene N-ethylethanamine Chemical compound CCNCC.C1=CC=C2C=C3C=CC=CC3=CC2=C1 HPTZACFYPLQYGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 claims 1
- 229910052747 lanthanoid Inorganic materials 0.000 claims 1
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims 1
- 235000019439 ethyl acetate Nutrition 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000052 vinegar Substances 0.000 description 6
- 235000021419 vinegar Nutrition 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- VIRGYRZBWQFJGJ-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-n,n-dimethylethanamine Chemical compound CN(C)C(F)(F)C(F)F VIRGYRZBWQFJGJ-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- ZOZNCAMOIPYYIK-UHFFFAOYSA-N 1-aminoethylideneazanium;acetate Chemical compound CC(N)=N.CC(O)=O ZOZNCAMOIPYYIK-UHFFFAOYSA-N 0.000 description 1
- LNWXJXSQQHQHAY-UHFFFAOYSA-N 2,2-difluoroacetic acid ethyl acetate Chemical compound C(C)(=O)OCC.FC(C(=O)O)F LNWXJXSQQHQHAY-UHFFFAOYSA-N 0.000 description 1
- WXVJXHSXFUYRFB-UHFFFAOYSA-N 2,2-difluoroindole Chemical compound FC1(N=C2C=CC=CC2=C1)F WXVJXHSXFUYRFB-UHFFFAOYSA-N 0.000 description 1
- AYUPOTWFYYVIGE-UHFFFAOYSA-N 2,7-dichloropyrene Chemical compound C1=C(Cl)C=C2C=CC3=CC(Cl)=CC4=CC=C1C2=C43 AYUPOTWFYYVIGE-UHFFFAOYSA-N 0.000 description 1
- OOJZGFFJNPGACA-UHFFFAOYSA-N 2-chloro-1,1,2-trifluoro-n,n-dimethylethanamine Chemical compound CN(C)C(F)(F)C(F)Cl OOJZGFFJNPGACA-UHFFFAOYSA-N 0.000 description 1
- XSJVWZAETSBXKU-UHFFFAOYSA-N 2-ethoxypropane Chemical compound CCOC(C)C XSJVWZAETSBXKU-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- FGTPQGXNZZZONI-UHFFFAOYSA-N ClC1(N=C2C=CC=CC2=C1)Cl Chemical compound ClC1(N=C2C=CC=CC2=C1)Cl FGTPQGXNZZZONI-UHFFFAOYSA-N 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 240000001980 Cucurbita pepo Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 241001529936 Murinae Species 0.000 description 1
- 125000000520 N-substituted aminocarbonyl group Chemical group [*]NC(=O)* 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 238000003434 Perkow synthesis reaction Methods 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- ZEXBOHFMOMKHQA-UHFFFAOYSA-N acetic acid 2,2-difluoroacetic acid Chemical compound FC(C(=O)O)F.C(C)(=O)O ZEXBOHFMOMKHQA-UHFFFAOYSA-N 0.000 description 1
- XBMGHVJWJAIHKS-UHFFFAOYSA-N acetic acid ethyl 2,2,2-trifluoroacetate Chemical compound C(C)(=O)O.FC(C(=O)OCC)(F)F XBMGHVJWJAIHKS-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000015114 espresso Nutrition 0.000 description 1
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GLVAUDGFNGKCSF-UHFFFAOYSA-N mercaptopurine Chemical compound S=C1NC=NC2=C1NC=N2 GLVAUDGFNGKCSF-UHFFFAOYSA-N 0.000 description 1
- 229960001428 mercaptopurine Drugs 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DGJTZXXNXZVULP-UHFFFAOYSA-N undecanoyl undecanoate Chemical compound CCCCCCCCCCC(=O)OC(=O)CCCCCCCCCC DGJTZXXNXZVULP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
200846318 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種藉使式(ΠΙ)之α，α-二鹵胺與式(II) 之羧酸酯於鹼的存在下反應以製備式（I)之烷基二鹵乙醯 5 醋酸酯之方法。 【先前技術】 烷基二氟乙醯醋酸酯係製備活性農業化學成分，特別係 用於製備吡唑基叛醯苯胺之重要合成單位。 10 Tetrahedron 2001，57, 2689-2700 揭示 4,4_二氟乙醯醋酸 酯可藉使二氟乙醯醋乙酸酯與醋酸乙酯在氫化鈉(NaH)的存 在下反應獲得。此反應25%之產率係令人極不滿意。此外， Tetrahedron 1996, 52, 119-130 陳述 4,4-二氟乙醯醋酸酯可藉 使二氟醋酸乙酯與溴醋酸乙酯在Zn的存在下反應製得。 15 WO-A-2005/003077教導一種藉以三烷氧基膦(P(0Alk)3) _ 還原氯原子(其亦為已知的Perkow反應）由氯二氟乙醯醋酸 酯進行烷基二氟乙醯醋酸酯之製備的三階段方法。 WO-A-2006/005612 教導一種藉使 2,2-二氟·Ν,Ν·二烷基 乙醯胺與醋酸酯在鹼的存在下反應以製備4,4_二氟-3_侧氧 20 基丁酸酯之方法。如JACS, 73, 3684(1951)所述般，該烷基 4,4-二氟-3-侧氧基丁酸酯接著與三曱基原曱酸酯及醋酸酐 反應以獲得乙基(2-乙氧基亞曱基)-4,4-二氟曱基乙醯醋酸 醋，根據US-A-5,489,624，其可利用曱基胼轉化成乙基3-二氟曱基甲基-4-。比嗤叛酸酯。首先，所述路徑包括多個 5 200846318 反應步驟，其次，所用之2,2-二氟-_-二燒基乙隨胺 產品並僅可藉由敗化2,2-二氯-Ν，队二燒基乙_ ^ 之小產率獲得。 ° 先前技術中早已描述過之方法具有下舰點：所用之二 5 氟羰基鹵化物、幽烧基羧酸酐及鹵丙烯酸醋係昂貴的、引^ 腐姓問題及/或僅可以高度技術複雜性進行純化。 因此，本發明目的係提供一種較簡單並更經濟可行之製 備烧基二鹵乙酿酸酸醋的方法。
I 10 【發明内容】 令人驚訝地，該目的係藉由一種製備式(I)之烷基二齒乙 醯醋酸酯之方法達到， 〇 ρ 其中 X 係氣、氯或CF3 ’ 15 X’係氟、氯或溴， R1係選自Η、（^12-烧基、C5-18-芳基、氯、溴及氟，且 R3獨立於R1係選自Cwy烷基、C5-18-芳基或c7_19-芳基 烧基， 其係藉使式(III)之α，α-二鹵胺 6 20 200846318 V'* , ϊΦ A ν +声 ^^SSSSSSB：㈣ .^C:’ ^\.·Α. oW r%
其中 R4係選自Cm2-烷基、C5_18-芳基或C7_19-芳基烷基，
R5獨立於R4係選自CW2-烷基、C 5-18, 芳基或 C7-I9- 芳基 烧基，
與式（II)之羧酸酯 其中 R2係選自氳、Cm2-烷基、C5-18-芳基、氯、溴及氟)反應。 在一本發明之較佳具體實施例中， t X 係選自氟、氯或CF3 ; X’係選自氟或氯； R1係選自烷基； R2獨立於R1係選自（^_4-烷基； R3獨立於R1係選自C 1-4" 烷基； R4係選自Ck烷基； R5獨立於R4係選自Cm-烷基。 7 15 200846318 在一本發明之特佳具體實施例中， X 係選自氟或氯； X’係氟； R1係選自氫或氟； 5 R2係氫； R3 係選自甲基或乙基； R4係選自甲基或乙基； R5係選自甲基或乙基。
I 本發明之其他具體實施例可採自所附申請專利範圍 ίο 及描述。 根據本發明方法可藉由下列流程(I)說明：
m 流程(I) 一般定義 15 與本發明有關之術語「鹵素」（X)涵蓋彼等選自由氟、 氯、溴及碘組成之群之元素，較佳係利用氟、氯及溴，特 8 200846318 佳係利用氟及氯。 視情況經取代基團可為經單-或多取代且該等取代基 在多取代之情況下可為相同或不同的。 除非另外定義，與本發明有關之烷基係直鏈、分枝鏈 或環狀烴基’其可視情況具有…二❹鮮或雙不飽和 度或一、二或多個選自由0、n、ms之雜原子。而且， 本發明烷基可視情況經選自以下各者之其他基團取代： 、-CN 及 _COK[R2,
10 15
20 -X、-OR’、-SR，、-NR，2、-SiR，3、-COOR， 基’其中R可為鼠或Cl4_烧基。 「Cuu-烷基」之定義涵蓋本文針對烷基所定義之最 寬範圍。此定義特別涵蓋（例如）甲基、乙基、正丙基、異 丙基、正丁基、異丁基、第二丁基及第三丁基、正戊基 正己基、1，3-二曱基丁基、3,3-二甲基丁基、正庚基、正 壬基、正癸基、正十一基、正十二基之意義。 除非另外定義，與本發明有關之芳基係可具有一、二 或多個選自0、Ν、Ρ及S之雜原子並可視情況經選自: 下各者之其他基團取代之芳族烴基：、七R，、、 -NR’2、-SiR，3、-C00R，、-CN 及,CONR2,基，其中厌，可 為氫或Cm-烷基。 「Ch8-芳基」之定義涵蓋本文所定義具有5至18個 骨架碳原子之芳基之最寬範圍。此定義特別涵蓋(例如）環 戊烯基、苯基、環庚三烯基、環辛四烯基、萘基及蒽基之 意義。 土 9 200846318 除非另外定義，鱼太恭 -、二或多個選自〇:、；：有：之芳基烧基係可具有 鏈之環狀芳族烴基，其中該侧鏈可視情況與 另一侧鏈形成四-、五一戎丄 ^ # AU ^/、貝辰並可視情況經選自以下各 者之其他基®取代：·χ、领，、_SR，、视,2、掀，3、 -COOR n -CN ^-CONl?，装苷丄 「p — R2基，其中R，可為氫或Cm-烷基。 10 15 心」7ΓΓ基絲」之定㈣蓋本文所定義骨架及侧 一“至19個碳原子之芳基烧基之最寬範圍。此 疋我4寸別涵蓋(例如）曱苯基、鄰、二甲苯基、間-二甲苯基、 對-二曱苯基及乙基苯基之意義。 /本發明化合物視情況可以不同可能異構物形式，特別 係立體異構物，例如Ε及Ζ、蘇及赤以及光學異構物，但 右適合以及互變異構物之混合物形式存在。主張Ε及ζ 異構物，以及蘇及赤異構物，以及光學異構物、這些異構 物之任何混合物及可能互變異構物形式。 八 羧酸酯
在該等酯中，R2及R3基係各獨立地選自H、Cl_12-烧基、Csi芳基或Cw-芳基烷基，較佳係選自d8-烷 基，更佳係選自C3_6_烷基。 20 200846318 適S的緩酉夂酉曰之貝例係醋酸曱醋、酷酸乙醋、氣醋酸 乙醋、漠醋酸乙醋、丙歲己酯、苯基醋酸乙酯、苯曱酸乙 酯。 5 根據本毛明’較佳係错酸酯，特佳係醋酸乙醋。 α，α-二鹵胺 根據本發明所用之α，α、二鹵胺係通式⑽之化合物 mm
V
其中 10
15 R4係選自Ciw烧基、C5 i8_芳基或Cw芳基烧基，較 佳係選自烷基，更佳係選自C3 6_烷基； R5獨立於R4係選自Cllre烷基、C518_芳基或c7_19-芳基 烧基，較佳係選自C2_8_烷基，更佳係選自c3_6-烷基； X係CF3、氟或氯，較佳係氟，且 X’係氟、氯或溴，較佳係氟。 §亥專化合物可根據Petrov等人於Journal of Fluorine Chemistry 109(2001) 25-31 及 Dmowski 等人在 Chemistry of Organic Fluorine Compounds II，A Critical Review，ACS， Washington DC(1995) 263藉由經氟化/經鹵化烯與二級胺 反應獲得並係（例如)由DuPont商業販售的。 11 20 200846318 根據本發明偏好使用之…齒胺係（例如 1，1，2,2-四氟乙基-队义二曱基胺、u，2,2,=
10 二乙基胺、l，u-三氟-2_(三氟甲基）乙基二甲土灵脸队 1 1 2-三氟-2-(三氣f基）乙基.N，N_:乙基胺_二g 劑）、1，1，2-三氟-2-氯乙基-N，N-二甲基胺及u，2_三氟$ 氯乙基乙基胺(Yar〇venk〇試劑）組成之群，較H U，2,2-四氟乙基-N，N-二甲基胺及u，2,2_四氟乙基 二乙基胺，特佳係1，1，2,2-四氟乙基-N，N-二甲基胺。’ 可製備氣胺或其鹽（類似Vilsmeier複合物)形式，例如 n，n-二曱基二氟乙醯胺及(例如）草醯基氯、光氣或p〇cl3:
P0CI3
式（111)之α，α_二鹵胺典型地與式（II)之羧酸酯在鹼的 存在下反應，其將羧酸酯之…位置去質子化成羰基。 根據本發明，適合的鹼係所有彼等具有鹼性以使該羧 酸酯去質子化者。實例包括鹼金屬氫氧化物，例如氫氧化 鐘、氫氧化鈉或氫氧化鉀，鹼金屬烷氧化物，例如 200846318
NaOMe、NaOEt' NaOt-Bu、KOt-Bu、氫化物，例如 NaH、 KH、烷基鋰試劑，例如n BuU或卜仙以、、
Grignard试劑，例如CHyVigCl;磷氮烯及i，8-二氮雜雙環 [5·4·0]十一烯(DBU)。 5 α，α·一鹵胺典型係在-5〇至6(TC，較佳係-20至40°C， 更佳係-1G至30 C之溫度下與該特酸醋反應。 該反應可在較低壓力下、在標準壓力或在高壓下，較 佳係在標準壓力下進行。 釀敍應可絲或在溶射進行。較㈣在—溶劑中進 10 行反應。適合溶劑係（例如）選自由下列各者組成之群：脂 族及芳族烴，例如正己烧、苯或甲苯，其可經氟及氣原子 取代，例如二氯曱烧、二氯乙烧、氣苯、氯苯或二氣苯； 醚，例如二乙基醚、二苯基醚、甲基第三丁基醚、異丙基 乙基醚、二口等烧、二甘二甲鱗、二甲甘醇、二甲氧基乙统 15 (DME)4THF;腈如曱腈、丁腈或笨基腈；醯胺如二甲基 f醯胺(DMF)或N·甲基驾σ定酮(NMp)或此等溶劑之混 » 合物，特㈣™F、讓E、二⑽。該反應可在過量缓 酸酯（如在乙基醋酸酯）中進行。 較佳係使用等莫耳量之驗及竣酸醋。或者，亦可使用 20 過量之驗。根據本發明，鹼：竣酸酿之比例係介於L5:! 與0.9 : 1之間’較佳係介於〗4 :卜更佳係介於丨3 :】 與1·05 : 1之間。 在一根據本發明方法讀佳具體實關巾，起初將缓 酸醋整批裝人聽於適合溶射錢漸與鹼混合，然後與 13 200846318 α，α-二齒胺反應。 由於α，α-二鹵胺之水解敏感性，該反應應在惰性氣體 氛圍下無水裝置中進行。 本發明將參照下列工作實例詳細說明，但不受其所 5 限0 【實施方式】 製備實例 _ 實例1 ··乙基三氟乙醯醋酸酯之製備 ίο 起初裝入之48克醋酸乙酯在RT下與10%32.4克乙 氧化鈉於乙醇中之溶液混合。該混合物在RT下攪拌1小 時，然後與36克1，1，2,2-四氟乙基二曱基胺混合。揍著， 該溶液在30°C下攪拌2小時，與Η20混合並調整至pH 5。 以醋酸乙酯萃取並接著蒸餾後，獲得27克(65%)二氟乙醯 15 醋酸乙酯（沸點90-94°C/100毫巴）。 _ 實例2 : 類似實例1，除了使用氳化鈉取代乙氧化鈉。所得產 率為79%。 20 實例3 : 類似實例1，除了使用1,1-二氯-2,2-二氟乙基二曱基 胺（由N，N-二曱基二氟乙醯胺與草醯基氯在80°C下製得) 之外。所得產率為63%。 14 200846318 【圖式簡單說明】 益 【主要元件符號說明】 5
Claims (1)
- 200846318 十、申請專利範圍： 1. 一種製備式(I)之烷基二鹵乙醯醋酸酯之方法 X’期gm 其中 X 係氟、氯或CF3， 4 ίο X’係氟、氯或溴， R 係選自Η、Ci_i2-烧基、C5W芳基、氯、>臭及氣’ 且 R3 獨立於R1係選自Cm-烷基、C5_18-芳基或C7_19-芳基烧基， 其係藉使式(III)之α，α-二鹵胺χ\ +乂.. mm' ~ V其中 R4 係選自Cur烷基、C 5-18- 芳基或 C7-I9- 芳基烷基， R5 獨立於R4係選自Cur烷基、C5_18-芳基或C7_19-芳基烧基，16 200846318 與式(Π)之羧酸酯 其中 R係選自H、CW烷基、c5，_芳基、α、溴及 反應。 、 2·根據申請專利範圍第1項之方法，其特徵在於 χ 係選自氟、氯或cf3 ; ' X’係選自氟或Cl ; Rl係選自Ck烷基； 10 R2獨立於R1係選自Cu-烷基； r3獨立於R1係選自Cu·烷基； r4係選自Cw烷基且 r5獨立於R4係選自Cm-烷基。 3·根據申請專利範圍第1及2項中任一項之方法，其 特徵在於 15 X 係選自氟或氯； x’係氟； R 係選自氮或氟； r2係氫； 20 r3係選自甲基或乙基； r4係選自甲基或乙基； ^ 係選自曱基或乙基。 4·根據申請專利範圍第1至3項中任一項之方法，其 特徵在於該反應係在鹼的存在下進行。 5·根據申請專利範圍第1至4項中任一項之方法，其 17 200846318 4寸徵在於該等α，α-二鹵胺係選自由ι，ι，2,2-四氟乙基 -N，N-二曱基胺、l，i，2,2-四氟乙基-Ν，Ν·二乙基胺、 1，1，2-三氟-2-(三氟甲基）乙基_队>^二甲基胺、ι，ι，2-三氟-2-(三氟甲基）乙基_N，N_:乙基胺（Ishikawa試 5 劑）、込1，2·三氟-2-氯乙基-N，N-二甲基胺及1，1，2-三 氟-2-氣乙基-Ν，Ν-二乙基胺(Yarovenk〇試劑）組成之 群。 6.根據申睛專利範圍第1至5項中任一項之方法，其 ❿ 特徵在於該驗係選自由驗金屬氫氧化物、驗金屬烧 1〇 氧化物、氫化物、烷基鋰試劑及Grignard試劑或其 混合物組成之群。 7·根據申請專利範圍第1至6項中任一項之方法，其 特徵在於該等緩酸酯係選自乙酸甲酯、乙酸乙酯、 氟醋酸乙酯、溴醋酸乙酯、丙酸乙酯、苯基醋酸乙 15 酯及苯甲酸乙酯。 18 200846318 ^ 七、指定代表圖： (一) 本案指定代表圖為：第（無）圖。 (二) 本代表圖之元件符號簡單說明： 無10 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：15 4
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| TWI409252B TWI409252B (zh) | 2013-09-21 |
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| TW097103839A TWI409252B (zh) | 2007-02-02 | 2008-02-01 | 製備烷基二鹵乙醯醋酸酯之方法 |
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| EP (1) | EP2114855B1 (zh) |
| JP (1) | JP5264780B2 (zh) |
| CN (1) | CN101595081B (zh) |
| DE (1) | DE102007005296A1 (zh) |
| DK (1) | DK2114855T3 (zh) |
| ES (1) | ES2597853T3 (zh) |
| TW (1) | TWI409252B (zh) |
| WO (1) | WO2008092583A2 (zh) |
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| JP5514549B2 (ja) * | 2006-10-27 | 2014-06-04 | バイエル・クロップサイエンス・アーゲー | ２−フルオロプロピオネートの製造のための立体選択的一段階フッ素化法 |
| WO2009021987A1 (en) | 2007-08-16 | 2009-02-19 | Solvay (Société Anonyme) | Process for the preparation of esters of 4-fluorosubstituted 3-oxo-alcanoic acids |
| EP2133341A1 (de) * | 2008-02-25 | 2009-12-16 | Bayer CropScience AG | Verfahren zur regioselektiven Synthese von 1-Alkyl-3-haloalkyl-pyrazol-4-carbonsäure-Derivaten |
| CN102206155A (zh) * | 2011-04-19 | 2011-10-05 | 巨化集团公司 | 一种4,4-二氟乙酰乙酸乙酯的合成方法 |
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| US5489624A (en) | 1992-12-01 | 1996-02-06 | Minnesota Mining And Manufacturing Company | Hydrophilic pressure sensitive adhesives |
| US5567856A (en) * | 1995-05-30 | 1996-10-22 | Hoechst Celanese Corporation | Synthesis of and hydroformylation with fluoro-substituted bidentate phosphine ligands |
| DE10331496A1 (de) * | 2003-07-01 | 2005-01-27 | Bayer Cropscience Ag | Verfahren zum Herstellen von Difluoracetessigsäurealkylestern |
| EP1644314B1 (de) * | 2003-07-01 | 2011-08-10 | Bayer Cropscience AG | Verfahren zum herstellen von difluoracetessigs urealkylestern |
| GB0415764D0 (en) | 2004-07-14 | 2004-08-18 | Syngenta Participations Ag | Chemical process |
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- 2008-01-22 CN CN200880003534.2A patent/CN101595081B/zh active Active
- 2008-02-01 TW TW097103839A patent/TWI409252B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| DK2114855T3 (en) | 2016-11-07 |
| EP2114855A2 (de) | 2009-11-11 |
| WO2008092583A2 (de) | 2008-08-07 |
| WO2008092583A8 (de) | 2009-12-03 |
| CN101595081A (zh) | 2009-12-02 |
| US8044231B2 (en) | 2011-10-25 |
| CN101595081B (zh) | 2014-04-23 |
| JP2010517950A (ja) | 2010-05-27 |
| DE102007005296A1 (de) | 2008-08-07 |
| EP2114855B1 (de) | 2016-07-27 |
| WO2008092583A3 (de) | 2008-09-18 |
| ES2597853T3 (es) | 2017-01-23 |
| JP5264780B2 (ja) | 2013-08-14 |
| TWI409252B (zh) | 2013-09-21 |
| US20100121095A1 (en) | 2010-05-13 |
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