DK2247577T3 - Fremgangsmåde til regioselektiv synthese af 1-alkyl-3-haloalkyl-pyrazol-4-carboxylsyrederivater - Google Patents
Fremgangsmåde til regioselektiv synthese af 1-alkyl-3-haloalkyl-pyrazol-4-carboxylsyrederivater Download PDFInfo
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- DK2247577T3 DK2247577T3 DK09715350.6T DK09715350T DK2247577T3 DK 2247577 T3 DK2247577 T3 DK 2247577T3 DK 09715350 T DK09715350 T DK 09715350T DK 2247577 T3 DK2247577 T3 DK 2247577T3
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- Prior art keywords
- group
- methyl
- formula
- groups
- alkyl
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- 238000000034 method Methods 0.000 title claims description 33
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 3
- -1 tetrafluoroborate Chemical compound 0.000 claims description 111
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 33
- 125000005842 heteroatom Chemical group 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 17
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000000543 intermediate Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- KJASTBCNGFYKSR-UHFFFAOYSA-N prop-2-enehydrazide Chemical compound NNC(=O)C=C KJASTBCNGFYKSR-UHFFFAOYSA-N 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 150000007857 hydrazones Chemical class 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 6
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- 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 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 4
- 150000001266 acyl halides Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- KURKJXZWCPWPFX-UHFFFAOYSA-N 2,2-difluoroacetyl chloride Chemical compound FC(F)C(Cl)=O KURKJXZWCPWPFX-UHFFFAOYSA-N 0.000 claims description 2
- CRLSHTZUJTXOEL-UHFFFAOYSA-N 2,2-difluoroacetyl fluoride Chemical compound FC(F)C(F)=O CRLSHTZUJTXOEL-UHFFFAOYSA-N 0.000 claims description 2
- SLNOZWZCYJQTKJ-UHFFFAOYSA-N 2-hydrazinylprop-2-enoic acid Chemical class NNC(=C)C(O)=O SLNOZWZCYJQTKJ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PXOITZCMXGJWMD-UHFFFAOYSA-M [(e)-3-(dimethylamino)-2-ethoxycarbonyl-4,4,5,5-tetrafluoropent-2-enylidene]-dimethylazanium;chloride Chemical compound [Cl-].CCOC(=O)C(=CN(C)C)C(=[N+](C)C)C(F)(F)C(F)F PXOITZCMXGJWMD-UHFFFAOYSA-M 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- JXBLPDIZGMZWNB-UHFFFAOYSA-N ethyl 2-(dimethylaminomethylidene)-4,4,4-trifluoro-3-oxobutanoate Chemical compound CCOC(=O)C(=CN(C)C)C(=O)C(F)(F)F JXBLPDIZGMZWNB-UHFFFAOYSA-N 0.000 claims description 2
- KOCXCPHEKSLCMQ-UHFFFAOYSA-N n-(1-phenylethylideneamino)methanamine Chemical compound CNN=C(C)C1=CC=CC=C1 KOCXCPHEKSLCMQ-UHFFFAOYSA-N 0.000 claims description 2
- VBCGYWVDRKKFET-UHFFFAOYSA-N n-(butan-2-ylideneamino)methanamine Chemical compound CCC(C)=NNC VBCGYWVDRKKFET-UHFFFAOYSA-N 0.000 claims description 2
- JXSSEZYJBTUIGX-UHFFFAOYSA-N n-(propan-2-ylideneamino)methanamine Chemical compound CNN=C(C)C JXSSEZYJBTUIGX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 5
- 229910052760 oxygen Inorganic materials 0.000 claims 5
- 125000002820 allylidene group Chemical group [H]C(=[*])C([H])=C([H])[H] 0.000 claims 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims 1
- 125000006539 C12 alkyl 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])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000520 N-substituted aminocarbonyl group Chemical group [*]NC(=O)* 0.000 claims 1
- 150000008360 acrylonitriles Chemical class 0.000 claims 1
- YQDOHRFWXFAPHX-UHFFFAOYSA-N n-(benzhydrylideneamino)methanamine Chemical compound C=1C=CC=CC=1C(=NNC)C1=CC=CC=C1 YQDOHRFWXFAPHX-UHFFFAOYSA-N 0.000 claims 1
- GIJRMWNCLATMHL-UHFFFAOYSA-N n-(cyclohexylideneamino)methanamine Chemical compound CNN=C1CCCCC1 GIJRMWNCLATMHL-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 23
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 238000007363 ring formation reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 150000001408 amides Chemical class 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical group 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 8
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 8
- 150000003568 thioethers Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 230000010933 acylation Effects 0.000 description 5
- 238000005917 acylation reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010626 work up procedure Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 229960004132 diethyl ether Drugs 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229940052303 ethers for general anesthesia Drugs 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PYHOFAHZHOBVGV-UHFFFAOYSA-N triazane Chemical class NNN PYHOFAHZHOBVGV-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical class OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FHNCCAGEZMNIHZ-UHFFFAOYSA-N 3,4,5,5a,6,7,8,9-octahydro-2h-1,2-benzodiazepine Chemical compound N1CCCC2CCCCC2=N1 FHNCCAGEZMNIHZ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 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
- IWKUMHNTQRFTRT-SABKRDHFSA-N ethyl (e)-3-[(3,3-dimethylbutan-2-ylideneamino)-methylamino]prop-2-enoate Chemical compound CCOC(=O)\C=C\N(C)N=C(C)C(C)(C)C IWKUMHNTQRFTRT-SABKRDHFSA-N 0.000 description 2
- WXOLGYSOZAUTRR-VOTSOKGWSA-N ethyl (e)-3-[methyl-(propan-2-ylideneamino)amino]prop-2-enoate Chemical compound CCOC(=O)\C=C\N(C)N=C(C)C WXOLGYSOZAUTRR-VOTSOKGWSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- MQXTZFQVRCKEGA-UHFFFAOYSA-N methyl 3-[ethyl-(propan-2-ylideneamino)amino]prop-2-enoate Chemical compound CC(C)=NN(CC)C=CC(=O)OC MQXTZFQVRCKEGA-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- SWADNLFRTHBCLE-UHFFFAOYSA-N n,n-diethyl-1,1,2,2-tetrafluoroethanamine Chemical compound CCN(CC)C(F)(F)C(F)F SWADNLFRTHBCLE-UHFFFAOYSA-N 0.000 description 2
- BNTFCVMJHBNJAR-UHFFFAOYSA-N n,n-diethyl-1,1,2,3,3,3-hexafluoropropan-1-amine Chemical compound CCN(CC)C(F)(F)C(F)C(F)(F)F BNTFCVMJHBNJAR-UHFFFAOYSA-N 0.000 description 2
- XXCMGYNVDSOFHV-UHFFFAOYSA-N n-(benzylideneamino)methanamine Chemical compound CNN=CC1=CC=CC=C1 XXCMGYNVDSOFHV-UHFFFAOYSA-N 0.000 description 2
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- IYXUFOCLMOXQSL-UHFFFAOYSA-N (2,2-difluoroacetyl) 2,2-difluoroacetate Chemical compound FC(F)C(=O)OC(=O)C(F)F IYXUFOCLMOXQSL-UHFFFAOYSA-N 0.000 description 1
- IFCCXJXADBSREN-UHFFFAOYSA-N 1,1,1-trifluoro-4-(2-methylpropoxy)but-3-en-2-one Chemical compound CC(C)COC=CC(=O)C(F)(F)F IFCCXJXADBSREN-UHFFFAOYSA-N 0.000 description 1
- COLOHWPRNRVWPI-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound [CH2]C(F)(F)F COLOHWPRNRVWPI-UHFFFAOYSA-N 0.000 description 1
- DLDBAVFXKUQZOE-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoro-n,n-dimethylpropan-1-amine Chemical compound CN(C)C(F)(F)C(F)C(F)(F)F DLDBAVFXKUQZOE-UHFFFAOYSA-N 0.000 description 1
- 125000001607 1,2,3-triazol-1-yl group Chemical group [*]N1N=NC([H])=C1[H] 0.000 description 1
- 125000001766 1,2,4-oxadiazol-3-yl group Chemical group [H]C1=NC(*)=NO1 0.000 description 1
- 125000004505 1,2,4-oxadiazol-5-yl group Chemical group O1N=CN=C1* 0.000 description 1
- 125000004515 1,2,4-thiadiazol-3-yl group Chemical group S1N=C(N=C1)* 0.000 description 1
- 125000001305 1,2,4-triazol-3-yl group Chemical group [H]N1N=C([*])N=C1[H] 0.000 description 1
- 125000004509 1,3,4-oxadiazol-2-yl group Chemical group O1C(=NN=C1)* 0.000 description 1
- 125000004521 1,3,4-thiadiazol-2-yl group Chemical group S1C(=NN=C1)* 0.000 description 1
- BRJHIUPNDYVERF-UHFFFAOYSA-N 1-(1,3-dimethylpyrazol-4-yl)ethanone Chemical class CC(=O)C1=CN(C)N=C1C BRJHIUPNDYVERF-UHFFFAOYSA-N 0.000 description 1
- 125000006083 1-bromoethyl group Chemical group 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
- FZOPNNJWLMFBPO-UHFFFAOYSA-N 2,2,2-trifluoro-1-[1-methyl-3-(trifluoromethyl)pyrazol-4-yl]ethanone Chemical compound CN1C=C(C(=O)C(F)(F)F)C(C(F)(F)F)=N1 FZOPNNJWLMFBPO-UHFFFAOYSA-N 0.000 description 1
- VHYWBLSTWYJZDS-UHFFFAOYSA-N 2,2,2-trifluoro-1-[1-phenyl-3-(trifluoromethyl)pyrazol-4-yl]ethanone Chemical compound N1=C(C(F)(F)F)C(C(=O)C(F)(F)F)=CN1C1=CC=CC=C1 VHYWBLSTWYJZDS-UHFFFAOYSA-N 0.000 description 1
- DCEPGADSNJKOJK-UHFFFAOYSA-N 2,2,2-trifluoroacetyl fluoride Chemical compound FC(=O)C(F)(F)F DCEPGADSNJKOJK-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004781 2,2-dichloro-2-fluoroethyl group Chemical group [H]C([H])(*)C(F)(Cl)Cl 0.000 description 1
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 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
- 125000004779 2-chloro-2-fluoroethyl group Chemical group [H]C([H])(*)C([H])(F)Cl 0.000 description 1
- BDZHKUAKSMWSAJ-UHFFFAOYSA-N 2-chloro-n,n-diethyl-1,1,2-trifluoroethanamine Chemical compound CCN(CC)C(F)(F)C(F)Cl BDZHKUAKSMWSAJ-UHFFFAOYSA-N 0.000 description 1
- XSJVWZAETSBXKU-UHFFFAOYSA-N 2-ethoxypropane Chemical compound CCOC(C)C XSJVWZAETSBXKU-UHFFFAOYSA-N 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- ITTXGKOHFZJUEX-UHFFFAOYSA-N 3-(ethoxymethylidene)pentane-2,4-dione Chemical compound CCOC=C(C(C)=O)C(C)=O ITTXGKOHFZJUEX-UHFFFAOYSA-N 0.000 description 1
- IVOBJSCASJZDKF-UHFFFAOYSA-N 3-[[methyl-(propan-2-ylideneamino)amino]methylidene]pentane-2,4-dione Chemical compound CC(C)=NN(C)C=C(C(C)=O)C(C)=O IVOBJSCASJZDKF-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- BRSGXDFFFPRLLW-UHFFFAOYSA-N 4,4-dichloro-2-(dimethylaminomethylidene)-3-oxobutanoic acid Chemical compound CN(C)C=C(C(O)=O)C(=O)C(Cl)Cl BRSGXDFFFPRLLW-UHFFFAOYSA-N 0.000 description 1
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical group [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004775 chlorodifluoromethyl group Chemical group FC(F)(Cl)* 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 125000004774 dichlorofluoromethyl group Chemical group FC(Cl)(Cl)* 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- RCKLFYPBAKDSFI-UHFFFAOYSA-N ethyl 2-(dimethylaminomethylidene)-4,4-difluoro-3-oxobutanoate Chemical compound CCOC(=O)C(=CN(C)C)C(=O)C(F)F RCKLFYPBAKDSFI-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 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
- 238000002955 isolation Methods 0.000 description 1
- KQGUFAUAVIHRNS-UHFFFAOYSA-N methyl 3-[(3,3-dimethylbutan-2-ylideneamino)-methylamino]prop-2-enoate Chemical compound COC(=O)C=CN(C)N=C(C)C(C)(C)C KQGUFAUAVIHRNS-UHFFFAOYSA-N 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- PUJNJVNLKTXFMI-UHFFFAOYSA-N n-(3,3-dimethylbutan-2-ylideneamino)methanamine Chemical compound CNN=C(C)C(C)(C)C PUJNJVNLKTXFMI-UHFFFAOYSA-N 0.000 description 1
- JGOAZQAXRONCCI-SDNWHVSQSA-N n-[(e)-benzylideneamino]aniline Chemical compound C=1C=CC=CC=1N\N=C\C1=CC=CC=C1 JGOAZQAXRONCCI-SDNWHVSQSA-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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 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
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- DINLPSGSJVTAMS-UHFFFAOYSA-N propyl 3-[methyl-(propan-2-ylideneamino)amino]prop-2-enoate Chemical compound CCCOC(=O)C=CN(C)N=C(C)C DINLPSGSJVTAMS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/76—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/10—Hydrazines
- C07C243/12—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms
- C07C243/16—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C243/18—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/78—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/80—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Claims (14)
1. Fremgangsmåde til fremstilling af l-alkyl-3-haloalkyl-pyrazol-4-carboxylsyre-derivater med formel (I)
(0 hvor R1 er udvalgt af Ci_i2-alkyl-, C3-8_cycloalkyl-, C2-i2-alkenyl-, C2_i2-alkynyl-, C6_8-aryl-, C7-i9-arylalkyl- eller C7-19-alkylarylgrupper, som hver især kan være substitueret med en eller flere grupper, der er udvalgt af gruppen bestående af -R', -X, -OR', -SR', -NR'2, -SiR'3, -C00R', -(C=0)R', -CN og -CONR2', idet R' er hydrogen eller en Ci-12-alkylgruppe; R2 er udvalgt af Ci-C4-alkylgrupper, som kan være substitueret med et, to eller tre halogenatomer udvalgt af F, Cl og Br eller en CF3-gruppe; Y er udvalgt af gruppen bestående af (C=0)0R , CN og (C=0)NR4R5, idet R3, R4 og R5 uafhængigt af hinanden er udvalgt af Ci-i2-alkyl-, C3-8_cycloalkyl-, C2-i2_alkenyl-, C2- 12-alkynyl-, C6-8_aryl-, C7_i9-arylalkyl- eller C7-19-alkylarylgrupper, som hver især kan være substitueret med en eller flere grupper, der er udvalgt af gruppen bestående af -R', -X, -OR', -SR', -NR'2, -SiR's, -C00R', -(C=0)R', -CN og -CONR2', idet R' er hydrogen eller en Ci-12-alkylgruppe, og R4 og R5 sammen med det nitrogenatom, som de er bundet til, kan danne en 5- til β-leddet ring, som i givet fald kan indeholde et eller to yderligere heteroatomer udvalgt af 0, S og en S02-gruppe, og som kan være substitueret med en eller flere grupper, der er udvalgt af gruppen bestående af -R', -X, -OR', -SR', -NR'2, -SiR's, -C00R', -(C=0)R', -CN og -C0NR2' , idet R' er hydrogen eller en Ci_i2-alkylgruppe; omfattende i det mindste en af reaktionssekvenserne, som består af de følgende trin (A) og (D), (B) og (D) eller (C) og (D): (A) omsætning af et 2-acyleret eller 2-iminoalkyleret acrylsyrederivat med formel (II),
(Π), hvor Ζ er udvalgt af 0, S og N+R10RX1, idet R10 og R11 uafhængigt af hinanden er udvalgt af Ci-i2_alkyl-, C3_8-cycloalkyl-, C2- 12-alkenyl-, C2-i2-alkynyl-, C6-8-aryl-, C7-i9-arylalkyl- eller C7-i9-alkylarylgrupper, som hver især kan være substitueret med en eller flere grupper, der er udvalgt af gruppen bestående af -R', -X, -OR', -SR', -NR'2, -SiR'3, -C00R', (C=0) R' , -CN og -CONR2', idet R' er hydrogen eller en C1-12-alkylgruppe, og R10 og R11 sammen med det nitrogenatom, som de er bundet til, kan danne en 5- til 6-leddet ring, som i givet fald kan indeholde et eller to yderligere heteroatomer udvalgt af 0, S og en S02-gruppe, og som kan være substitueret med en eller flere grupper, som er udvalgt af gruppen bestående af - R', -X, -OR', -SR', -NR'2, -SiR'3, -CONR', - (C=0) R' , -CN og - C0NR2' , idet R' er hydrogen eller en Ci_i2-alkylgruppe ; A er en udgangsgruppe NR12R13, idet R12 og R13 uafhængigt af hinanden er udvalgt af Ci_i2-alkyl-, C3_8-cycloalkyl-, C2-i2_ alkenyl-, C2-i2-alkynyl-, C6-8~aryl-, C7_i9-arylalkyl- eller C7_i9-alkylarylgrupper, som hver især kan være substitueret med en eller flere grupper, der er udvalgt af gruppen bestående af -R', -X, -OR', -SR', -NR'2, -SiR'3, -C00R', " (C=0)R', —CN og — CONR2 ' , idet R' hydrogen eller en Ci-12 alkylgruppe, og R12 og R13 sammen med det nitrogenatom, som de er bundet til, kan danne en 5- til 6-leddet ring, som i givet fald kan indeholde et eller to yderligere heteroatomer udvalgt af 0, S og en S02-gruppe, og som kan være substitueret med en eller flere grupper, som er udvalgt af gruppen bestående af -R', -x, -OR', -SR', -NR'2, -SiR'3, -CONR', ~(C=0)R', -CN og -C0NR2 ' , idet R' er hydrogen eller en Ci-12-alkylgruppe; med en N-alkyl-hydrazon med formel (III)
(HI); hvor R8 og R9 uafhængigt af hinanden er udvalgt af H, Ci-i2-alkyl-, C3-8-cyclcoalkyl-, C2-i2-alkenyl-, C2-i2-alkynyl-, C6-s-aryl-, C7-i9-arylalkyl- eller C7_i9-alkylaryl-grupper, som hver især kan være substitueret med en eller flere grupper, der er udvalgt af gruppen bestående af -R', -X, -OR', -SR', -NR'2, -SiR'3, -COOR', -(C-O)R', -CN og 'CONR2 ' , idet R' er hydrogen eller en Ci-i2-alkylgruppe, og R8 og R9 sammen med det carbonatom, som de er bundet til, kan danne en 5- til 6-leddet ring, som i givet fald kan indeholde et eller to yderligere heteroatomer udvalgt af 0, S og en S02-gruppe, og som kan være substitueret med en eller flere grupper, der er udvalgt af gruppen bestående af -R', -X, -OR', -SR', -NR'2, -SiR'3, -COOR', - (C=0)R', -CN og -C0NR2 ' , idet R' er hydrogen eller en Ci_i2-alkylgruppe; (B) acylering af en acrylsyrehydrazon med formel (VI);
(VI) med et acylhalogenid med formel (X) , idet X er udvalgt af F, Cl, Br eller 1;
(X); (C) iminoalkylering af en acrylsyrehydrazon med den ovenstående formel (VI) med en a,α-dihalogenamin med formel (XI), idet X er udvalgt af F, Cl, Br eller I,
(Xi); (D) cyklisering af de i trin (A) , (B) eller (C) opnåede mellemprodukter til 3-haloalkyl-pyrazol-4- carboxylsyrederivatet med formel (I).
2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at grupperne i formlerne (III), (VIII) og (IX) har følgende betegnelser: R1 er methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl; R8 er udvalgt af H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, phenyl, tolyl, cyclohexyl; R9 er udvalgt af H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, tolyl, cyclohexyl, idet R8 og R9 sammen md det C-atom, som de er knyttet til, kan danne en 5- eller 6-leddet ring.
3. Fremgangsmåde ifølge krav 1 eller 2, kendetegnet ved, at der som mellemprodukt i trinnene (A) , (B) eller (C) dannes et 2-acyleret eller et 2-iminoalkyleret hydrazinoacrylsyrederivat med formel (VII),
(VID, hvor grupperne R1, R2, R8' R9, Y og Z har de ovenfor beskrevne betegnelser.
4. Fremgangsmåde ifølge et af kravene 1 til 3, kendetegnet ved, at reaktionssekvensen består af trinnene (A) og (D).
5. Fremgangsmåde ifølge et af kravene 1 til 3, kendetegnet ved, at reaktionssekvensen består af trinnene (B) og (D).
6. Fremgangsmåde ifølge et af kravene 1 til 3, kendetegnet ved, at reaktionssekvensen består af trinnene (C) og (D).
7. Fremgangsmåde ifølge et af kravene 1 til 3 eller 5, kendetegnet ved, at acylhalogenidet med formel (X) i trin (B) er udvalgt af gruppen bestående af difluoreddikesyrefluorid eller difluoreddikesyrechlorid.
8. Fremgangsmåde ifølge et af kravene 1 til 3 eller 6, kendetegnet ved, at ex,α-dihalogenaminen med formel (XI) i trin (C) er 1,1,2,2-tetrafluorethyl-N,N-di-methylamin.
9. Fremgangsmåde ifølge et af kravene 1 til 4, kendetegnet ved, at det 2-acylerede eller 2- iminoalkylerede aerylsyrederivat med formel (II) er udvalgt af gruppen bestående af N-l-(trifluormethyl)-3- (dimethylamino)-2-(ethoxycarbonyl)-prop-2-en-l-ylidene]-N-methylmethanaminiumchlorid, N-l-(difluormethyl)-3- (dimethylamino)-2-(ethoxycarbonyl)prop-2-en-l-ylidene]-N- methylmethanaminium tetrafluorborat og N-[3- (dimethylamino)-2-(ethoxycarbonyl)-1-(1,1,2,2-tetrafluoroethyl)prop-2-en-l-ylidene]-N-methylmethanaminiumchlorid.
10. Fremgangsmåde ifølge et af kravene 1 til 4 eller 9, kendetegnet ved, at N-alkyl-hydrazonen med formel (III) er udvalgt af gruppen bestående af l-methyl-2-(1-methylethylidene)hydrazin, 1-methyl-2-(1- phenylethylidene)hydrazin, l-methyl-2 - (1,2,2 - trimethylpropylidene)hydraxin, l-methyl-2- (1- methylpropylidene)hydrazin, l-cyclohexylidene-2- methylhydrazin, l-methyl-2-(phenylmethylidene)hydraxin, 1-(diphenylmethylidene)-2-methylhydrazin, ethyl-2- [(dimethylamino) methylidene]-4,4,4-trifluoro-3-oxobutanoat.
11.
Fremgangsmåde ifølge et af kravene 1 til 3 eller 5 til 8, kendetegnet ved, at aerylsyrehydrazonen med formel (VI) i trinnene (B) og (C) er udvalgt af gruppen bestående af ethyl (2E)-3-[l-methyl-2-(propan-2-ylidene)- hydrazinyl]prop-2-enoate, ethyl (2Z)-3-[l-methyl-2-(propan-2-ylidene)hydrazinyl]prop-2-enoate, methyl -3-[l-methyl-2-(propan-2-ylidene)hydrazinyl]prop-2-enoate, propyl-3-[1- methyl-2-(propan-2-ylidene)hydrazinyl]prop-2-enoate, ethyl (2E)-3-[l-methyl-2-(3,3-dimethylbutan-2- ylidene)hydrazinyl]prop-2-enoate, methyl 3-[l-methyl-2-(3,3-dimethylbutan-2-ylidene)hydraxinyl]prop-2-enoate, methyl-3-[l-methyl-2-(phenylmethylidene)-hydrazinyl]prop-2-enoate, (2E)-3-[l-methyl-2- (phenylmethylidene)hydrazinyl]prop-2-enenitriler og methyl -3 - [l-ethyl-2-(propan-2-ylidene)hydrazinyl]prop-2-enoate. 12. 2-acyleret eller 2-iminoalkyleret acrylsyrehydrazon med formel (VII)
(VII), hvori grupperne R1, R2, R8' R9, Y og Z har de ovenfor beskrevne betegnelser.
13. 2-acylacrylhydrazon med formel (Vila)
(Vila), hvori grupperne R1, R2, R8, R9 og Y har de ovenfor beskrevne betegnelser.
14. Salte med formel (Vllb) Aniorr
(viib), hvori grupperne R1 til R8 og Y har de ovenfor beskrevne betegnelser, og anionen er udvalgt af gruppen bestående af Cl”, BF4”, PF6”, SbF6” og A1C14”.
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| PCT/EP2009/000958 WO2009106230A2 (de) | 2008-02-25 | 2009-02-12 | Verfahren zur regioselektiven synthese von 1-alkyl-3-haloalkyl-pyrazol-4-carbonsäur e-derivaten |
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Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2181087B1 (en) | 2007-08-16 | 2015-10-14 | Solvay Sa | 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 |
| EP2100883A1 (de) * | 2008-03-10 | 2009-09-16 | Bayer CropScience AG | Verfahren zur regioselektiven Synthese von 1-Alkyl-3-haloalkyl-pyrazol-4carbonsäure-Derivaten |
| CA2725446A1 (en) * | 2008-05-05 | 2009-11-12 | Basf Se | Method for preparing 1,3,4-substituted pyrazol compounds |
| MX2013014312A (es) | 2011-06-21 | 2014-01-31 | Bayer Ip Gmbh | Procedimiento para la preparacion de pirazolilcarboxanilidas. |
| US9012657B2 (en) | 2011-06-22 | 2015-04-21 | Central Glass Company, Limited | Method for producing pyrazole compound |
| EP2623496A1 (de) | 2012-02-01 | 2013-08-07 | Bayer CropScience AG | Verfahren zur Herstellung von 3,5-bis (fluoralkyl)-pyrazol-4-carbonsäure-Derivaten und 3,5-bis(fluoralkyl)-pyrazolen |
| EP2644598A1 (en) | 2012-03-30 | 2013-10-02 | Solvay Sa | Method for the manufacture of heterocycles |
| EP2644593A1 (en) * | 2012-03-30 | 2013-10-02 | Solvay Sa | Dialkoxymethyl oxobutyric acid esters, their manufacture and use |
| CN104284879A (zh) | 2012-05-16 | 2015-01-14 | 索尔维公司 | 1-取代甲叉基化合物的制备 |
| EP2671873A1 (en) | 2012-06-06 | 2013-12-11 | Solvay Sa | Method for the cyclization of hydrazinoacrylic acid derivatives |
| EP2671874B1 (en) | 2012-06-06 | 2016-01-13 | Solvay Sa | Preparation of esters of 1-substituted-3-fluoroalkyl-pyrazole-4-carboxylic acids |
| US8871947B2 (en) | 2013-02-04 | 2014-10-28 | KingChem LLC | Preparation of alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ester |
| BR112015027707B1 (pt) | 2013-05-22 | 2021-02-09 | Bayer Cropscience Aktiengesellschaft | método de preparação de derivados de 3,5-bis(fluoroalquil)pirazole e compostos intermediários envolvidos nesse método |
| BR112015028751B1 (pt) * | 2013-05-22 | 2021-01-12 | Bayer Cropscience Aktiengesellschaft | Processo para a preparação de derivados de 3,5-bis (fluoralquil)pirazol a partir de alfa, alfa-dihaloaminas e uso destes para preparação de ingredientes fungicidas ativos |
| CN103360313A (zh) * | 2013-07-12 | 2013-10-23 | 雅本化学股份有限公司 | 3-氟代烷基-1-取代吡唑-4-羧酸及其制备方法 |
| TWI647215B (zh) * | 2013-11-11 | 2019-01-11 | 德商拜耳作物科學股份有限公司 | 自α,α－二鹵胺製備３,５－雙鹵烷基吡唑衍生物之方法 |
| CN104379551B (zh) | 2013-12-09 | 2017-03-08 | 金凯有限责任公司 | 3‑二氟甲基‑1‑甲基‑1h‑吡唑‑4‑羧酸烷基酯及其类似物的制备方法 |
| EP3015458A1 (en) | 2014-11-03 | 2016-05-04 | Bayer CropScience AG | Process for preparing 3,5-bis(haloalkyl)pyrazole derivatives from a,a-dihaloamines and ketimines |
| WO2015144578A1 (en) * | 2014-03-24 | 2015-10-01 | Bayer Cropscience Ag | PROCESS FOR PREPARING 3,5-BIS(HALOALKYL)PYRAZOLE DERIVATIVES FROM α,α-DIHALOAMINES AND KETIMINES |
| CN106458918B (zh) | 2014-06-11 | 2019-07-09 | 拜耳作物科学股份公司 | 经由酮亚胺的酰化来制备3,5-双(卤代烷基)吡唑的方法 |
| DK3154946T3 (da) * | 2014-06-11 | 2018-06-18 | Bayer Cropscience Ag | Fremgangsmåde til fremstilling af 3,5-bis(halogenalkyl)pyrazolderivater ved hjælp af acylering af hydrazoner |
| CN105541716B (zh) | 2015-03-26 | 2024-02-23 | Ａｇｃ株式会社 | 吡唑衍生物的制造方法 |
| CN107960078A (zh) | 2015-06-26 | 2018-04-24 | 拜耳作物科学股份公司 | 由α,α-二卤代烷基胺和酮亚胺制备含有卤代烷氧基和卤代烷硫基的取代的吡唑的方法 |
| CN106467492B (zh) * | 2015-08-14 | 2019-12-17 | 联化科技(盐城)有限公司 | 多氟甲基吡唑类化合物的制备方法、中间体及制备方法 |
| EP3416949A1 (en) * | 2016-02-18 | 2018-12-26 | Solvay Sa | Process for the manufacture of carboxamides |
| CN109790126A (zh) * | 2016-08-02 | 2019-05-21 | 索尔维公司 | 用于制造吡唑甲酸及衍生物的肼基化合物的制造、肼基化合物及其用途 |
| ES2849960T3 (es) | 2016-09-21 | 2021-08-24 | Bayer Cropscience Ag | Procedimiento para la preparación de 3-fluoroalquil-5-pirazolcarboxilatos y ácidos 3-fluoroalquil-5-pirazolcarboxílicos |
| CN111566093A (zh) * | 2017-12-22 | 2020-08-21 | 索尔维公司 | 吡唑甲酸衍生物及其前体的制造方法 |
| KR20200103744A (ko) * | 2017-12-22 | 2020-09-02 | 솔베이(소시에떼아노님) | 이미늄 화합물의 제조 방법 및 피라졸 유도체 제조에서의 이의 응용 |
| BR112020024625A2 (pt) | 2018-06-18 | 2021-03-02 | Bayer Aktiengesellschaft | 3-pirazol carboxilatos dissubstituídos e um processo para preparação dos mesmos via acilação de enolatos |
| WO2020093715A1 (en) | 2018-11-07 | 2020-05-14 | Fujian Yongjing Technology Co., Ltd | New process for manufacture of pyrazoles or pyrimidones |
| CN112480007B (zh) * | 2020-12-08 | 2022-11-18 | 宿迁市科莱博生物化学有限公司 | 一种1，3-二甲基-1h-吡唑-4-羧酸的合成方法 |
| CN114195678A (zh) * | 2021-12-24 | 2022-03-18 | 江苏七洲绿色科技研究院有限公司 | 一种中间体、其制备方法及用其制备3-二氟甲基-1-甲基吡唑-4-甲酸乙酯的方法 |
| CN114195715B (zh) * | 2021-12-31 | 2024-05-10 | 福建永晶科技股份有限公司 | 1-甲基-3-二氟甲基-4-吡唑酸和1-甲基-3-三氟甲基-4-吡唑酸的制备方法 |
| CN117447401B (zh) * | 2023-12-26 | 2024-04-19 | 山东国邦药业有限公司 | 一种二氟吡唑酸的合成方法 |
Family Cites Families (11)
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| KR20000035081A (ko) | 1998-11-10 | 2000-06-26 | 마크 에스. 아들러 | 2-(트리할로아세틸)-3-(치환된 아미노)-2-프로페노에이트 제조방법 |
| DE10215292A1 (de) | 2002-02-19 | 2003-08-28 | Bayer Cropscience Ag | Disubstitutierte Pyrazolylcarbocanilide |
| DE10349500A1 (de) | 2003-10-23 | 2005-06-02 | Bayer Cropscience Ag | Verfahren zum Herstellen von 2-Dihalogenacyl-3-amino-acrylsäureestern und 3-Dihalogenmethyl-pyrazol-4-carbonsäureestern |
| CN101044119B (zh) * | 2004-10-21 | 2012-03-14 | 辛根塔参与股份公司 | 制备吡唑类化合物的方法 |
| WO2006090778A1 (ja) | 2005-02-25 | 2006-08-31 | Sagami Chemical Research Center | １－置換－３－フルオロアルキルピラゾール－４－カルボン酸エステルの製造方法 |
| DE102006039909A1 (de) | 2006-08-25 | 2008-03-13 | Bayer Cropscience Ag | Verfahren zum Herstellen von 3-Dihalomethyl-pyrazol-4-carbonsäurederivaten |
| DE102007005296A1 (de) | 2007-02-02 | 2008-08-07 | Bayer Cropscience Ag | Verfahren zum Herstellen von Dihaloacetessigsäurealkylestern |
| EP2008996A1 (en) * | 2007-06-27 | 2008-12-31 | Syngeta Participations AG | Process for the production of pyrazoles |
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| CA2725446A1 (en) * | 2008-05-05 | 2009-11-12 | Basf Se | Method for preparing 1,3,4-substituted pyrazol compounds |
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- 2013-07-24 RU RU2013134651A patent/RU2661192C2/ru active
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2014
- 2014-11-07 JP JP2014227243A patent/JP2015071615A/ja active Pending
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