CN101133031B - 1-取代-3-氟代烷基吡唑-4-羧酸酯的制造方法 - Google Patents
1-取代-3-氟代烷基吡唑-4-羧酸酯的制造方法 Download PDFInfo
- Publication number
- CN101133031B CN101133031B CN2006800061009A CN200680006100A CN101133031B CN 101133031 B CN101133031 B CN 101133031B CN 2006800061009 A CN2006800061009 A CN 2006800061009A CN 200680006100 A CN200680006100 A CN 200680006100A CN 101133031 B CN101133031 B CN 101133031B
- Authority
- CN
- China
- Prior art keywords
- methyl
- carboxylic acid
- solution
- ethyl ester
- carboxylicesters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 150000002429 hydrazines Chemical class 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 103
- 125000004494 ethyl ester group Chemical group 0.000 description 91
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 87
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 44
- 238000003756 stirring Methods 0.000 description 42
- 238000001035 drying Methods 0.000 description 36
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 36
- FZNKJQNEJGXCJH-UHFFFAOYSA-N 1-methyl-3-(trifluoromethyl)pyrazole-4-carboxylic acid Chemical compound CN1C=C(C(O)=O)C(C(F)(F)F)=N1 FZNKJQNEJGXCJH-UHFFFAOYSA-N 0.000 description 33
- 239000000706 filtrate Substances 0.000 description 33
- 238000004817 gas chromatography Methods 0.000 description 33
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 33
- 239000012044 organic layer Substances 0.000 description 33
- 239000011541 reaction mixture Substances 0.000 description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 22
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 238000004821 distillation Methods 0.000 description 19
- 238000000605 extraction Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 235000019439 ethyl acetate Nutrition 0.000 description 15
- -1 methylene radical acyl acetic acid ester Chemical class 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 230000006837 decompression Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- FFGKJFAGLCONJF-UHFFFAOYSA-N 1-(2-methylpropyl)-3-(trifluoromethyl)pyrazole-4-carboxylic acid Chemical compound C(C(C)C)N1N=C(C(=C1)C(=O)O)C(F)(F)F FFGKJFAGLCONJF-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- UGXKLEYJWXQPHC-UHFFFAOYSA-N 1-ethyl-3-(trifluoromethyl)pyrazole-4-carboxylic acid Chemical compound CCN1C=C(C(O)=O)C(C(F)(F)F)=N1 UGXKLEYJWXQPHC-UHFFFAOYSA-N 0.000 description 3
- VAKOSNKAXYJZRG-UHFFFAOYSA-N 1-methyl-5-(trifluoromethyl)pyrazole-4-carboxylic acid Chemical compound CN1N=CC(C(O)=O)=C1C(F)(F)F VAKOSNKAXYJZRG-UHFFFAOYSA-N 0.000 description 3
- RLOHOBNEYHBZID-UHFFFAOYSA-N 3-(difluoromethyl)-1-methylpyrazole-4-carboxylic acid Chemical compound CN1C=C(C(O)=O)C(C(F)F)=N1 RLOHOBNEYHBZID-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 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 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- NGSOWKPBNFOQCR-UHFFFAOYSA-N 2-methylpropylhydrazine Chemical compound CC(C)CNN NGSOWKPBNFOQCR-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 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 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical class OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- WKQBXUUNRHKCGH-UHFFFAOYSA-N 1-(2-methylpropyl)-5-(trifluoromethyl)pyrazole-4-carboxylic acid Chemical compound CC(C)CN1N=CC(C(O)=O)=C1C(F)(F)F WKQBXUUNRHKCGH-UHFFFAOYSA-N 0.000 description 1
- ZRJYUDXJXUVNFC-UHFFFAOYSA-N 1-ethyl-5-(trifluoromethyl)pyrazole-4-carboxylic acid Chemical compound CCN1N=CC(C(O)=O)=C1C(F)(F)F ZRJYUDXJXUVNFC-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CTTXMUZEFPPHGD-UHFFFAOYSA-N 5-(difluoromethyl)-1-methylpyrazole-4-carboxylic acid Chemical compound CN1N=CC(C(O)=O)=C1C(F)F CTTXMUZEFPPHGD-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 238000003512 Claisen condensation reaction Methods 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940045984 antineoplastic methylhydrazine Drugs 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 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 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000003438 dodecyl 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 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims (6)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005052004 | 2005-02-25 | ||
JP052006/2005 | 2005-02-25 | ||
JP2005052006 | 2005-02-25 | ||
JP052004/2005 | 2005-02-25 | ||
PCT/JP2006/303269 WO2006090778A1 (ja) | 2005-02-25 | 2006-02-23 | 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101133031A CN101133031A (zh) | 2008-02-27 |
CN101133031B true CN101133031B (zh) | 2010-07-21 |
Family
ID=36927416
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2006800061009A Active CN101133031B (zh) | 2005-02-25 | 2006-02-23 | 1-取代-3-氟代烷基吡唑-4-羧酸酯的制造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US7863460B2 (zh) |
EP (1) | EP1854788B8 (zh) |
JP (1) | JP4114754B2 (zh) |
CN (1) | CN101133031B (zh) |
WO (1) | WO2006090778A1 (zh) |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5260636B2 (ja) * | 2007-05-31 | 2013-08-14 | シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト | ピラゾールを生産するプロセス |
EP1997808A1 (en) * | 2007-05-31 | 2008-12-03 | Syngeta Participations AG | Process for the production of pyrazoles |
EP2008996A1 (en) * | 2007-06-27 | 2008-12-31 | Syngeta Participations AG | Process for the production of pyrazoles |
EP2133341A1 (de) * | 2008-02-25 | 2009-12-16 | Bayer CropScience AG | Verfahren zur regioselektiven Synthese von 1-Alkyl-3-haloalkyl-pyrazol-4-carbonsäure-Derivaten |
KR20100133392A (ko) * | 2008-02-29 | 2010-12-21 | 바스프 에스이 | 알킬 2-알콕시메틸렌-4,4-디플루오로-3-옥소부티레이트의 제조 방법 |
EP2100883A1 (de) * | 2008-03-10 | 2009-09-16 | Bayer CropScience AG | Verfahren zur regioselektiven Synthese von 1-Alkyl-3-haloalkyl-pyrazol-4carbonsäure-Derivaten |
EP2297111B1 (de) | 2008-05-02 | 2012-06-20 | Basf Se | Verfahren zur herstellung halogensubstituierter 2-(aminomethyliden)-3-oxobuttersäureester |
PL2300417T3 (pl) | 2008-05-02 | 2015-12-31 | Basf Se | Sposób wytwarzania estrów kwasu 2-(aminometylideno)-4,4-difluoro-3-oksomasłowego |
MX2010011433A (es) | 2008-05-05 | 2010-11-12 | Basf Se | Procedimiento para la preparacion de compuestos pirazolicos sustituidos en posiciones 1,3,4. |
JP5558467B2 (ja) * | 2008-07-21 | 2014-07-23 | ビーエーエスエフ ソシエタス・ヨーロピア | 1,3−二置換ピラゾールカルボン酸エステルの調製方法 |
GB0908435D0 (en) * | 2009-05-15 | 2009-06-24 | Syngenta Ltd | Processes |
BR112012001990B1 (pt) * | 2009-07-28 | 2021-02-23 | Syngenta Participations Ag | processos relacionados à alquilação de pirazóis |
AR077332A1 (es) * | 2009-07-31 | 2011-08-17 | Syngenta Participations Ag | Procesos para la alquilacion de pirazoles |
GB201004299D0 (en) | 2010-03-15 | 2010-04-28 | Syngenta Participations Ag | Process |
GB201004301D0 (en) | 2010-03-15 | 2010-04-28 | Syngenta Participations Ag | Process |
TWI562985B (en) * | 2010-07-13 | 2016-12-21 | Lonza Ag | Process for the preparation of enolate salts of 4-fluoro-2-hydroxymethylene-3-oxobutyrates |
WO2012010692A1 (en) | 2010-07-23 | 2012-01-26 | Solvay Sa | Process for the preparation of esters of 1-substituted-3-fluoroalkyl-pyrazole-4-carboxylic acids |
CA2806436C (en) * | 2010-08-10 | 2019-09-10 | Syngenta Participations Ag | Process for the preparation of 3-haloalkylpyrazoles |
WO2012025469A1 (en) | 2010-08-24 | 2012-03-01 | Solvay Sa | Improved process for the preparation of esters of 1-h-pyrazole-4-carboxylic acids |
WO2012176717A1 (ja) * | 2011-06-22 | 2012-12-27 | セントラル硝子株式会社 | ピラゾール化合物の製造方法 |
JP5915004B2 (ja) * | 2011-06-22 | 2016-05-11 | セントラル硝子株式会社 | ピラゾール化合物の製造方法 |
CN102702104B (zh) * | 2012-06-08 | 2015-02-25 | 巨化集团公司 | 一种3-二氟甲基-1-甲基吡唑-4-甲酸乙酯的连续化合成方法 |
PT2885277T (pt) * | 2012-07-19 | 2016-12-12 | Bayer Cropscience Ag | Processo para a preparação de 5-fluoro-1h-pirazóis |
CN102766096A (zh) * | 2012-07-20 | 2012-11-07 | 苏州汉德创宏生化科技有限公司 | 合成3-二氟甲基-1-甲基-1-氢-吡唑-4-甲酸及其酯类的方法 |
JP5140776B1 (ja) | 2012-09-05 | 2013-02-13 | タマ化学工業株式会社 | 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 |
JP5232335B1 (ja) * | 2013-01-29 | 2013-07-10 | タマ化学工業株式会社 | 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 |
CN105027683A (zh) | 2013-01-30 | 2015-11-04 | 卢米娜拉全球有限责任公司 | 用于控制多个电蜡烛的***和方法 |
US8871947B2 (en) * | 2013-02-04 | 2014-10-28 | KingChem LLC | Preparation of alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ester |
US9139507B2 (en) | 2013-12-09 | 2015-09-22 | KingChem LLC. | Process for the preparation of alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylate and its analogs |
CN110891940A (zh) | 2017-08-28 | 2020-03-17 | 日本凡凯姆股份有限公司 | 吡唑-4-甲酰胺衍生物的制备方法 |
CN115403524A (zh) * | 2021-05-26 | 2022-11-29 | 浙江省化工研究院有限公司 | 3-氟代吡唑羧酸酯、3-氟代烷基-1-取代吡唑-4-羧酸的制备方法 |
CN113387863B (zh) * | 2021-07-08 | 2022-11-22 | 康化(上海)新药研发有限公司 | 一种3-(三氟甲基)-4-吲哚甲酸的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5438070A (en) * | 1992-09-21 | 1995-08-01 | Basf Aktiengesellschaft | Carboxanilides, their preparation and compositions containing them for controlling harmful fungi |
JP2000212166A (ja) * | 1999-01-26 | 2000-08-02 | Mitsui Chemicals Inc | 1,3―ジアルキルピラゾ―ル―4―カルボン酸エステルの製造法 |
JP2002128763A (ja) * | 2000-10-27 | 2002-05-09 | Mitsui Chemicals Inc | 1,3−ジアルキルピラゾール−4−カルボン酸の精製法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0822853B2 (ja) | 1987-10-23 | 1996-03-06 | 三井東圧化学株式会社 | ピラゾール−4−カルボン酸類およびその製造方法 |
JP3655342B2 (ja) * | 1995-03-28 | 2005-06-02 | 日本ヒドラジン工業株式会社 | ピラゾール類の製造方法 |
JP3719318B2 (ja) * | 1996-10-18 | 2005-11-24 | 宇部興産株式会社 | 1−エチル−5−ヒドロキシピラゾールの製法 |
JP2000128763A (ja) | 1998-10-28 | 2000-05-09 | Kose Corp | 抗菌剤組成物及びこれを含有する皮膚外用剤 |
JP4190701B2 (ja) * | 1999-06-18 | 2008-12-03 | 三井化学株式会社 | 5−アミノピラゾール−4−カルボン酸エステル誘導体及びその製造方法 |
WO2004060877A1 (ja) * | 2002-12-27 | 2004-07-22 | Sankyo Agro Company, Limited | 4−アミノ−5−メチルピラゾール誘導体及びその製造方法 |
JP4584908B2 (ja) * | 2003-02-12 | 2010-11-24 | ロレアル | 皮膚または皮膚付属物の色素沈着を刺激するための15−ヒドロキシプロスタグランジンデヒドロゲナーゼの阻害剤の使用 |
WO2005003077A1 (de) * | 2003-07-01 | 2005-01-13 | Bayer Cropscience Aktiengesellschaft | Verfahren zum herstellen von difluoracetessigsäurealkylestern |
BRPI0512118A (pt) * | 2004-06-18 | 2008-02-06 | Basf Ag | composto, processo para combater fungos nocivos, e, agente fungicida |
-
2006
- 2006-02-23 JP JP2007504769A patent/JP4114754B2/ja active Active
- 2006-02-23 CN CN2006800061009A patent/CN101133031B/zh active Active
- 2006-02-23 WO PCT/JP2006/303269 patent/WO2006090778A1/ja active Application Filing
- 2006-02-23 EP EP06714409A patent/EP1854788B8/en active Active
- 2006-02-23 US US11/884,665 patent/US7863460B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5438070A (en) * | 1992-09-21 | 1995-08-01 | Basf Aktiengesellschaft | Carboxanilides, their preparation and compositions containing them for controlling harmful fungi |
JP2000212166A (ja) * | 1999-01-26 | 2000-08-02 | Mitsui Chemicals Inc | 1,3―ジアルキルピラゾ―ル―4―カルボン酸エステルの製造法 |
JP2002128763A (ja) * | 2000-10-27 | 2002-05-09 | Mitsui Chemicals Inc | 1,3−ジアルキルピラゾール−4−カルボン酸の精製法 |
Non-Patent Citations (4)
Title |
---|
John L. Huppatz.The synthesis of certain pyrazole analogues of carboxin.Australian Journal of Chemistry 36.1983,(36),第135-147页. |
John L.Huppatz.The synthesis of certain pyrazole analogues of carboxin.Australian Journal of Chemistry 36.1983,(36),第135-147页. * |
熊振湖等.1-甲基-3-丙基吡唑-5-羧酸的新合成方法.合成化学9 6.2001,9(6),第553-555页. |
熊振湖等.1-甲基-3-丙基吡唑-5-羧酸的新合成方法.合成化学9 6.2001,9(6),第553-555页. * |
Also Published As
Publication number | Publication date |
---|---|
WO2006090778A1 (ja) | 2006-08-31 |
EP1854788A4 (en) | 2010-07-21 |
US20080154045A1 (en) | 2008-06-26 |
EP1854788A1 (en) | 2007-11-14 |
US7863460B2 (en) | 2011-01-04 |
EP1854788B1 (en) | 2012-06-13 |
JPWO2006090778A1 (ja) | 2008-07-24 |
EP1854788B8 (en) | 2012-12-26 |
JP4114754B2 (ja) | 2008-07-09 |
CN101133031A (zh) | 2008-02-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101133031B (zh) | 1-取代-3-氟代烷基吡唑-4-羧酸酯的制造方法 | |
CN101945861A (zh) | 一种苯甲酰胺类化合物的制备方法 | |
CN105541844B (zh) | 一种高纯度利拉利汀的简易制备方法 | |
JP2007326784A (ja) | 1−置換−5−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 | |
EP3137449B1 (en) | Process for the preparation of substituted cycloserines | |
CN102046573A (zh) | 卤代α-氟醚类的制造方法 | |
Yavari et al. | One-pot synthesis of 2, 6-diamino-4-sulfonamidopyrimidines from sulfonyl azides, terminal alkynes and cyanoguanidine | |
CN102424673B (zh) | 孟鲁司特钠中间体及孟鲁司特钠的合成方法 | |
EP2298756B1 (en) | Method for producing 3-methyl-2-thiophenecarboxylic acid | |
CN109293593A (zh) | 一种合成碘代异噁唑啉类化合物的方法 | |
CN107513056B (zh) | 一种含四氢呋喃基团的喹啉类化合物的合成方法 | |
JP4035166B2 (ja) | 4−メチレンピペリジンの製造方法 | |
CN105622613A (zh) | 一种合成伊鲁替尼的方法 | |
CN104447562A (zh) | 一种制备盐酸右美托咪定关键中间体的新方法 | |
AU2006240772A1 (en) | Method for producing nicotinic acid derivative or salt thereof | |
JP6477187B2 (ja) | 2−アミノ−6−メチルニコチン酸エステルの製造方法 | |
He et al. | One-pot three-component reaction of fluoroalkanesulfonyl azide, vinyl ether and aldehyde: the formation of polysubstituted fluorinated oxazolidines | |
EP3312161A1 (en) | Method for preparing pyrazolecarboxylic acid derivative, and intermediate thereof | |
WO2017186624A1 (en) | Process for the preparation of herbicidal pyridinylimidazolone compounds | |
JP5232335B1 (ja) | 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 | |
CN107459530A (zh) | 一种新型硅基取代的1,3‑异喹啉二酮衍生物及其制备方法 | |
CN105837401A (zh) | 光学活性1-溴-1-[3,5-双(三氟甲基)苯基]乙烷的制备方法 | |
CN101983187A (zh) | (s)-3-(1-氰基-1,1-二苯基甲基)吡咯烷的制备方法 | |
JP4165110B2 (ja) | 4−オキシピリミジン誘導体の製法 | |
WO2023104616A1 (de) | Verfahren zur herstellung von isoxazolincarbonsäure-derivaten |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C56 | Change in the name or address of the patentee | ||
CP01 | Change in the name or title of a patent holder |
Address after: Kanagawa Patentee after: SAGAMI CHEMICAL Research Institute Patentee after: JAPAN FINECHEM Co.,Inc. Address before: Kanagawa Patentee before: SAGAMI CHEM RES Patentee before: JAPAN FINECHEM Co.,Inc. |
|
C35 | Partial or whole invalidation of patent or utility model | ||
IP01 | Partial invalidation of patent right |
Commission number: 4W103973 Conclusion of examination: On the basis of the right of claim 1-4 submitted by the patent holder on 08 October 2015, the patent rights of the patent shall be maintained. Decision date of declaring invalidation: 20160331 Decision number of declaring invalidation: 28601 Denomination of invention: Method for producing 1-substituted-3-fluoroalkyl pyrazole-4-carboxylate Granted publication date: 20100721 Patentee: SAGAMI CHEMICAL Research Institute|JAPAN FINECHEM Co.,Inc. |