WO2005044804A1 - Verfahren zum herstellen von fluormethyl-substituierten heterocyclen - Google Patents

Verfahren zum herstellen von fluormethyl-substituierten heterocyclen Download PDF

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Publication number
WO2005044804A1
WO2005044804A1 PCT/EP2004/011809 EP2004011809W WO2005044804A1 WO 2005044804 A1 WO2005044804 A1 WO 2005044804A1 EP 2004011809 W EP2004011809 W EP 2004011809W WO 2005044804 A1 WO2005044804 A1 WO 2005044804A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
chlorine
fluorine
alkoxy
substituted
Prior art date
Application number
PCT/EP2004/011809
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German (de)
English (en)
French (fr)
Inventor
Reinhard Lantzsch
Sergiy Pazenok
Frank Memmel
Original Assignee
Bayer Cropscience Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Cropscience Gmbh filed Critical Bayer Cropscience Gmbh
Priority to BRPI0416112-2A priority Critical patent/BRPI0416112A/pt
Priority to KR1020067008293A priority patent/KR101123745B1/ko
Priority to CN2004800322480A priority patent/CN1875006B/zh
Priority to EP04765988.3A priority patent/EP1682515B1/de
Priority to US10/576,742 priority patent/US7501527B2/en
Priority to DK04765988.3T priority patent/DK1682515T3/en
Priority to JP2006537130A priority patent/JP4936895B2/ja
Priority to ES04765988.3T priority patent/ES2524597T3/es
Publication of WO2005044804A1 publication Critical patent/WO2005044804A1/de
Priority to IL175148A priority patent/IL175148A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to a new process for the preparation of fluoromethyl-substituted heterocycles by reacting the corresponding c ormethyl-substituted compound with a fluorinating agent.
  • the present invention thus relates to a process for the preparation of fluoromethyl-substituted heterocycles of the formula (I)
  • R 1 represents hydrogen, fluorine or chlorine
  • R 2 represents hydrogen, fluorine or chlorine
  • R 3 represents Ci-CValkyl
  • A stands for a 5-membered heterocycle, selected from the series pyrazole, which is substituted in the 1-position by R 4 , thiazole, which is substituted in the 2-position by R 4 , and oxazole, which is in the 2-position by R 4 is substituted,
  • R 4 is Ci- -alkyl, C 3 -C 6 -cycloalkyl, Ct- -M lMo-Cr -alkyl, C r C 4 -alkoxy-CrC 4 -alkyl or phenyl, characterized in that a) cMormethyl-substituted heterocycles of the formula (13)
  • R 1 , R 2 , R 3 and A have the meanings given above, in the presence of a fluorinating agent and optionally in the presence of a diluent.
  • the fluoromethyl-substituted heterocycles of the formula (!) Can be prepared with good yields in high purity and selectivity under the conditions according to the invention.
  • the production of trifluoromethyl, difluoromethyl or monofluoromethyl-substituted aromatic compounds from the corresponding chlorinated compounds by halogen exchange is known for phenyl and some 3-trihaloalkyl-pyridine derivatives, but drastic conditions such as the use of HF, high temperature and pressure can be applied.
  • process (a) according to the invention can be illustrated by the following formula.
  • Formula (IT) generally defines the chloromethyl-substituted heterocycles used as starting materials in carrying out the process according to the invention.
  • the substituents have the following preferred meanings:
  • R 1 preferably represents hydrogen, fluorine or chlorine.
  • R 2 preferably represents hydrogen, fluorine or chlorine.
  • R 3 preferably represents CC 4 alkyl, particularly preferably methyl, ethyl, n-propyl, isopropyl,. n-butyl, sec-butyl, iso-butyl or tert-butyl, very particularly preferably for methyl or ethyl.
  • A preferably represents a 5-membered heterocycle selected from the series
  • R 4 preferably represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclopentyl, cyclohexyl or phenyl, particularly preferably for methyl, ethyl, isopropyl or phenyl, very particularly preferably for methyl.
  • Chloromethyl-substituted heterocycles of the formula (H) are preferably used as starting material, in which R 1 is chlorine and R 2 is hydrogen.
  • the starting materials of the formula (H) are particularly preferably chloromethyl-substituted heterocycles of the formula (Ha) in which R> 1, o R2 "u_ndj ⁇ R 1 3 have the meanings given above.
  • R 1 , R 2 and R 3 have the meanings given above.
  • Chloromethyl-substituted heterocycles of the formula (II-c) are also particularly preferred as starting materials of the formula (H)
  • R 1 , R 2 and R 3 have the meanings given above.
  • Preferred starting materials of the formula (E) are likewise cWormethyl-substituted heterocycles of the formula (Hd) in which R, R and R have the meanings given above.
  • Chloromethyl-substituted heterocycles of the formula (II) are known in some cases (cf. WO 92/12970, WO 93/11117 and The Chemistry of Heterocyclic Compounds: Thiazole and its derivatives, Jaques Metzger (ed.), Vol. 34, Part 1- 3, John Wiley and Sons, New York, 1979).
  • 3-halomethyl-1H-pyrazole-4-carboxylic acid esters can be prepared by b) acid halides of the formula (HI)
  • shark represents fluorine, chlorine or bromine, with dialkylaminoacrylic acid esters of the formula (IV)
  • R 5 and R 6 independently of one another are -C 4 -alkyl, in a water-immiscible organic solvent (for example toluene) in the presence of a base (for example sodium hydroxide or pyridine) , and the 2-dihaloacyl-3-arnino-acrylic acid esters of the formula (V) thus obtained
  • R 1 , R 2 , R 3 , R 5 and R 6 have the meanings indicated above, with hydrazine derivatives of the formula (VT) R — NH-NH 2 (VI) in which R 4 has the meanings indicated above, in the presence of a diluent (for example toluene).
  • a diluent for example toluene
  • Process (a) according to the invention is carried out in the presence of a fluorinating agent.
  • fluorinating agents customary for such reactions can be used.
  • alkali metal fluorides such as sodium fluoride, potassium fluoride and cesium fluoride, cobalt (i ⁇ ) fluoride, halogen fluorides, antimony fluorides, molybdenum fluoride, hydrogen fluoride, hydrogen fluoride, pyridine mixtures, tertiary ammonium hydrofluorides or trialkylamine hydrofluorides (general formula HF) (where the general formula n) (HF) n (general formula n) are (HF) n (general formula HF) n (general formula HF) (general formula 3 ) stands for 1, 2, or 3, preferably for 2 or 3, and Alk for -CC alkyl, preferably for ethyl or n-butyl).
  • 3 HF / N (Et) 3 (Franz reagent), 3 HF / N (n-Bu) 3 and HF / pyridine (Olah's reagent) are particularly preferably used.
  • 3 HF / N (Et) 3 (Franz Reagenz) or 3 HF / N (n-Bu) 3 are very particularly preferably used.
  • Nitriles such as acetonitrile can preferably be used; halogenated hydrocarbons, e.g. Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trifluorochloromethane, l, l, 2-trifluoro-l, 2,2-trichloroethane, l, l, l-trifluoro-2,2,2-trichloroethane or trichloroethane; aromatic hydrocarbons, e.g.
  • Petroleum ether such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Diethylene glycol.
  • Acetonitrile, toluene, chlorobenzene, trifluorochloromethane, l, l, 2-trifluoro-l, 2,2-trichloroethane, l, l, l-trifluoro-2,2,2-trichloroethane, dioxane or diethylene glycol are particularly preferably used.
  • temperatures from 80 ° C. to 170 ° C. or in the range from 20 ° C. to 170 ° C., preferably at temperatures from 120 ° C. to 150 ° C. or 100 ° C. to 150 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under elevated or reduced pressure - generally between 0.1 bar and 50 bar, preferably between 1 bar and 10 bar.
  • the reaction time is not critical and, depending on the batch size, can be chosen within a wide range from 1 h to 20 h, preferably from 6 h to 12 h.
  • 1 mol of cMormethyl-substituted heterocycles of the formula (ET) are generally employed between 1 mol and 3 mol of bound HF, preferably between 1 mol and 1.5 mol per chlorine atom of fluorinating agent.
  • the fluoromethyl-substituted heterocycles of the formula (I) which can be prepared by the process according to the invention are valuable precursors for the preparation of halogenomethyl-substituted pyrazolyl-, thiazolyl- and oxazolylcarboxamides which are fungicidal active ingredients (cf. WO 03/070705).
  • fungicidally active carboxamides of the formula (VTT) For example, fungicidally active carboxamides of the formula (VTT)
  • R 1 , R 2 and A have the meanings given above,
  • R 7 is hydrogen, CC 8 alkyl, CC 6 alkylsulfmyl, CC 6 alkylsulfonyl, C_ -C 4 alkoxy-C C 4 alkyl, C 3 -C 8 cycloalkyl; C 1 -C 6 haloalkyl, C ⁇ -C4-haloalkylthio, C ⁇ -C 4 haloalkyl sulf nyl, C r C 4 -haloalkylsulfonyl, halo-C ⁇ -C 4 -alkoxy-C r C 4 alkyl, C 3 ⁇ C 3 -Ha- • logencycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms; Formyl, formyl-C 3 -alkyl, (-C-C 3 alkyl) carbonyl-C -C 3 ⁇ alkyl, (-C-C 3 alkoxy) carbonyl-C C 3
  • R 11 and R 12 each independently are hydrogen, C 8 -alkyl, C 4 -alkoxy-C ⁇ -C 4 alkyl, C 3 -C 8 cycloalkyl; -Cs-haloalkyl, halogen- - -aD ⁇ xy-Ci- -alkyl, C 3 -C 8 -halo-cycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms,
  • R ⁇ and R 12 together with the nitrogen atom to which they are attached, form a saturated heterocycle with 5 to 8 ring atoms, optionally mono- or polysubstituted, identically or differently, by halogen or CC 4 alkyl, the heterocycle 1 or 2 more , can contain non-adjacent heteroatoms from the series oxygen, sulfur or NR 15 ,
  • R 13 and R 14 are independently hydrogen, C r C 8 alkyl, C 3 -C 8 cycloalkyl; -C-C 8 halo alkyl, C 3 -C 8 halocycloalkyl each having 1 to 9 fluorine, chlorine and or bromine atoms, R 13 and R 14 are also given together with the nitrogen atom to which they are attached - If necessary, form one or more, identical or different, halogen or C 1 -C 6 -substituted saturated heterocycle with 5 to 8 ring atoms, where the heterocycle can contain 1 or 2 further, non-adjacent heteroatoms from the series oxygen, sulfur or NR 15 , R 15 represents hydrogen or - alkyl, obtained by fluoromethyl-substituted heterocycles of the formula (I)
  • Ethyl 3- (picMormethyl) -l-methyl-1H-pyrazole-4-carboxylate (37.9 g, 0.16 mol) and triethylamine tris (hydrofluoride) (80 g, 0.49 mol) were heated in an autoclave at 145 ° C. for 8 h.
  • the reaction mixture was then diluted with 200 ml of water.
  • the precipitated product was filtered off, washed and dried.
  • Ethyl 4- (dichloromethyl) -l-methyl-1H-pyrazole-3-carboxylate 37.9 g (0.16 mol) and triethylamine tris (hydrofluoride) 80 g (0.49 mol) were heated in an autoclave at 160 ° C. for 8 h.
  • the reaction mixture was then diluted with 200 ml of water and the product extracted with ethyl acetate.
  • the desired product was purified by chromatography and isolated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
PCT/EP2004/011809 2003-10-31 2004-10-19 Verfahren zum herstellen von fluormethyl-substituierten heterocyclen WO2005044804A1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BRPI0416112-2A BRPI0416112A (pt) 2003-10-31 2004-10-19 preparação de heterociclos substituìdo por fluormetila
KR1020067008293A KR101123745B1 (ko) 2003-10-31 2004-10-19 플루오로메틸-치환된 헤테로사이클의 제조방법
CN2004800322480A CN1875006B (zh) 2003-10-31 2004-10-19 氟甲基取代的杂环的制备方法
EP04765988.3A EP1682515B1 (de) 2003-10-31 2004-10-19 Verfahren zum herstellen von fluormethyl-substituierten heterocyclen
US10/576,742 US7501527B2 (en) 2003-10-31 2004-10-19 Method for the production of fluoromethyl-substituted heterocycles
DK04765988.3T DK1682515T3 (en) 2003-10-31 2004-10-19 PROCEDURE FOR PREPARING FLUORMETHYL-SUBSTITUTED HETEROCYCLES
JP2006537130A JP4936895B2 (ja) 2003-10-31 2004-10-19 フルオロメチル−置換された複素環
ES04765988.3T ES2524597T3 (es) 2003-10-31 2004-10-19 Procedimiento para la preparación de heterociclos sustituidos con fluorometilo
IL175148A IL175148A (en) 2003-10-31 2006-04-25 Process for the preparation of alkyl esters of lumethyl pyrazoles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10351088.5 2003-10-31
DE10351088A DE10351088A1 (de) 2003-10-31 2003-10-31 Verfahren zum Herstellen von fluormethyl-substituierten Heterocyclen

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EP (1) EP1682515B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JP4936895B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
KR (1) KR101123745B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CN (1) CN1875006B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
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DE (1) DE10351088A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DK (1) DK1682515T3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES2524597T3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IL (1) IL175148A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
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MX (1) MXPA06004605A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
TW (1) TWI359141B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO2005044804A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

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WO2008077907A1 (de) * 2006-12-21 2008-07-03 Basf Se Verfahren zur herstellung fluormethylsubstituierter heterocyclischer verbindungen
WO2008145740A1 (de) 2007-06-01 2008-12-04 Basf Se Verfahren zur herstellung n-substituierter (3-dihalomethyl-1-methyl-pyrazol-4-yl)carboxamide
WO2008152138A3 (de) * 2007-06-15 2009-05-28 Basf Se Verfahren zur herstellung difluormethylsubstituierter pyrazolverbindungen
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
US8115012B2 (en) 2006-11-03 2012-02-14 Basf Se Process for preparing difluoromethylpyrazolyl carboxylates
US8207354B2 (en) 2008-02-29 2012-06-26 Basf Se Process for preparing alkyl 2-alkoxymethylene-4,4-difluoro-3-oxobutyrates
US8314233B2 (en) 2008-05-02 2012-11-20 Basf Se Process for preparing 2-(aminomethylidene)-4,4-difluoro-3-oxobutyric esters
WO2012163896A1 (fr) * 2011-06-01 2012-12-06 Rhodia Operations Procede de preparation d'un compose fluoromethylpyrazole sous forme acide carboxylique ou derivee
WO2012163905A1 (fr) * 2011-06-01 2012-12-06 Rhodia Operations Procede de préparation d'un compose organique fluore
US8344157B2 (en) 2008-07-21 2013-01-01 Basf Se Process for preparing 1,3-disubstituted pyrazolecarboxylic esters
US8350046B2 (en) 2008-05-08 2013-01-08 Basf Se Method for manufacturing aryl carboxamides
US8586750B2 (en) 2008-05-02 2013-11-19 Basf Se Method for the production of halogen-substituted 2-(aminomethylidene)-3-oxobutyric acid esters
US8598222B2 (en) 2008-05-05 2013-12-03 Basf Se Method for preparing 1,3,4-substituted pyrazol compounds
WO2015039877A1 (en) * 2013-09-20 2015-03-26 Bayer Cropscience Ag Process for preparing 5-fluoro-1-alkyl-3-fluoroalkyl-1h-pyrazole-4-carbaldehyde
WO2018032586A1 (zh) * 2016-08-15 2018-02-22 浙江永太科技股份有限公司 一种3-(二氟甲基)-1-甲基-1h-吡唑-4-羧酸的合成方法及其中间体

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CN105732376A (zh) 2007-08-16 2016-07-06 索尔维公司 制备4-氟取代的3-氧代-烷酸酯的方法
US20140128617A1 (en) * 2011-06-21 2014-05-08 Wahed Ahmed Moradi Method for producing pyrazolylcarboxanilides
US20150376135A1 (en) * 2013-02-15 2015-12-31 Syngenta Participations Ag Process for the preparation of bis-dihaloalkyl pyrazoles
CN115572210B (zh) * 2022-12-08 2023-03-21 暨南大学 一种(1,2,2,2-四氟乙基)芳烃衍生物及其制备方法和应用

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See also references of EP1682515A1

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Publication number Priority date Publication date Assignee Title
US8115012B2 (en) 2006-11-03 2012-02-14 Basf Se Process for preparing difluoromethylpyrazolyl carboxylates
WO2008077907A1 (de) * 2006-12-21 2008-07-03 Basf Se Verfahren zur herstellung fluormethylsubstituierter heterocyclischer verbindungen
JP2010513411A (ja) * 2006-12-21 2010-04-30 ビーエーエスエフ ソシエタス・ヨーロピア フルオロメチル置換複素環式化合物の調製方法
US7994207B2 (en) 2006-12-21 2011-08-09 Basf Se Process for preparing fluoromethyl-substituted heterocyclic compounds
WO2008145740A1 (de) 2007-06-01 2008-12-04 Basf Se Verfahren zur herstellung n-substituierter (3-dihalomethyl-1-methyl-pyrazol-4-yl)carboxamide
US8153820B2 (en) 2007-06-01 2012-04-10 Basf Se Method for the production of N-substituted (3-dihalomethyl-1-methylpyrazol-4-yl) carboxamides
EA016615B1 (ru) * 2007-06-01 2012-06-29 Басф Се Способ получения n-замещенных (3-дигалометил-1-метилпиразол-4-ил)карбоксамидов
WO2008152138A3 (de) * 2007-06-15 2009-05-28 Basf Se Verfahren zur herstellung difluormethylsubstituierter pyrazolverbindungen
JP2010529976A (ja) * 2007-06-15 2010-09-02 ビーエーエスエフ ソシエタス・ヨーロピア ジフルオロメチル置換ピラゾール化合物の製造方法
US8188295B2 (en) 2007-06-15 2012-05-29 Basf Se Method for producing difluoromethyl-substituted pyrazole compounds
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US8598222B2 (en) 2008-05-05 2013-12-03 Basf Se Method for preparing 1,3,4-substituted pyrazol compounds
US8350046B2 (en) 2008-05-08 2013-01-08 Basf Se Method for manufacturing aryl carboxamides
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US8981116B2 (en) 2010-07-23 2015-03-17 Solvay Sa Process for the preparation of esters of 1-substituted-3-fluoroalkyl-pyrazole-4-carboxylic acids
FR2975990A1 (fr) * 2011-06-01 2012-12-07 Rhodia Operations Procede de preparation d'un compose organique fluore
WO2012163905A1 (fr) * 2011-06-01 2012-12-06 Rhodia Operations Procede de préparation d'un compose organique fluore
WO2012163896A1 (fr) * 2011-06-01 2012-12-06 Rhodia Operations Procede de preparation d'un compose fluoromethylpyrazole sous forme acide carboxylique ou derivee
FR2975992A1 (fr) * 2011-06-01 2012-12-07 Rhodia Operations Procede de preparation d'un compose fluoromethylpyrazole sous forme acide carboxylique ou derivee
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WO2015039877A1 (en) * 2013-09-20 2015-03-26 Bayer Cropscience Ag Process for preparing 5-fluoro-1-alkyl-3-fluoroalkyl-1h-pyrazole-4-carbaldehyde
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WO2018032586A1 (zh) * 2016-08-15 2018-02-22 浙江永太科技股份有限公司 一种3-(二氟甲基)-1-甲基-1h-吡唑-4-羧酸的合成方法及其中间体
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IN2006DE01990A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2007-07-13
DK1682515T3 (en) 2014-11-17
CN1875006A (zh) 2006-12-06
KR101123745B1 (ko) 2012-03-15
IL175148A0 (en) 2006-09-05
MXPA06004605A (es) 2006-07-20
DE10351088A1 (de) 2005-06-02
US7501527B2 (en) 2009-03-10
EP1682515B1 (de) 2014-10-01
EP1682515A1 (de) 2006-07-26
US20060276656A1 (en) 2006-12-07
BRPI0416112A (pt) 2007-01-02
KR20060094534A (ko) 2006-08-29
TWI359141B (en) 2012-03-01
ES2524597T3 (es) 2014-12-10

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