WO2014111449A1 - Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyrazole-4-carbaldehyde - Google Patents
Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyrazole-4-carbaldehyde Download PDFInfo
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- WO2014111449A1 WO2014111449A1 PCT/EP2014/050767 EP2014050767W WO2014111449A1 WO 2014111449 A1 WO2014111449 A1 WO 2014111449A1 EP 2014050767 W EP2014050767 W EP 2014050767W WO 2014111449 A1 WO2014111449 A1 WO 2014111449A1
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- Prior art keywords
- pyrazole
- carbaldehyde
- difluoromethyl
- methyl
- fluoro
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- 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.)
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- 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
- C07D231/16—Halogen atoms or nitro radicals
Definitions
- the present invention relates to a novel process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde (I), a useful intermediate in the manufacture of fungicides.
- 5-fluoro-1-alkyl-3-fluoroalkyl-1 H-pyrazole-4-carbonyl chlorides can be prepared by reacting in a first step 5-chloro-1-alkyl-3-fluoroalkyl-1 H-pyrazole-4- carbaldehyde with metal fluorides like KF as fluorinating reagent to obtain 5-fluoro-1-alkyl-3- fluoroalkyl-1 H-pyrazole-4-carbaldehyde , followed by a second reaction with a chlorinating agent to obtain the acyl chloride derivatives.
- the present invention relates to a process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde of formula (I)
- phase transfer catalyst selected among tetrabutylammonium chloride, bromide or hydrogen sulphate, preferably tetrabutylammonium hydrogen sulphate, in dimethylformamide or dimethylacetamide as solvent.
- phase transfer catalyst selected among tetrabutylammonium chlorid, bromid or hydrogen sulphate, preferably tetrabutylammonium hydrogen sulphate, in dimethylformamide or dimethylacetamide as solvent.
- 5-Chloro-1-alkyl-3-fluoroalkyl-1 H-pyrazole-4-carbaldehydes are known or obtainable by known methods (cf. J. Het. Chem. 1990, 27, 243, WO 2006/018725).
- 5-Chloro-1-alkyl-3-difluoroalkyl-1 H-pyrazole-4-carbaldehyde of formula (II) can be be prepared according to WO 201 1/061205.
- Potassium fluoride is a known synthesis chemical.
- Reaction temperature in the process according to the invention is from 130°C to 160°C, preferably from 145°C to 155°C.
- Reaction time is from 2 to 4 hours, preferably 3 hours.
- the process according to the invention is carried out by using generally from 1 to 1.5 mol, preferably from 1.1 to 1.5 mol, of potassium fluoride per mole of 5-chloro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde of formula (II).
- the process according to the invention is carried out by using generally from 1 to 5 mol % of the phase transfer catalyst per mole of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde of formula (II).
- the process is preferably performed in equipment which is not a glass equipment, because KF can react under the reaction conditions with the glass equipment to produce side products (H2O). Teflon or stainless steel equipment is preferable.
- the process can be performed under normal atmosphere or under pressure (in closed vessel).
- the potassium fluoride is generally used as a spray-dried.
- Example 1 preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in presence of the catalyst Bu4N + HS04 ⁇ in dimethylacetamide
- Example 3 preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in presence of the catalyst Bu4N + HS04 " in dimethylformamide. 19.4 g (100 mmol) of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (11-1 ) were initially charged in 120 ml dimethylformamide. This was followed by the addition of 6,84 g (120 mmol) of spry dried potassium fluoride and 1 g (3 mol %) of Bu4N + HS04 " , heating to 150°C and subsequent stirring at that temperature for 3 hours. GC of the reaction mixture shows 100 % conversion.
- Example 4 The reaction was performed similar to example 3, but without the catalyst Bu4N + HS04 " . In these conditions, GC of the reaction mixture shows 52% of conversion after 3 hours, 73% of conversion after 6 hours, 83% of conversion after 9 hours and 93% of conversion after 15h.
- Example 6 The reaction was performed similar to experiment 5, but without the catalyst Bu4N + HS04 " . In these conditions, GC of the reaction mixture shows 35% of conversion after 3 hours, 50% of conversion after 6 hours, and 65% of conversion after 15h.
- Example 7 preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in presence of the catalyst Bu4N + Br " in dimethylformamide 19.4 g (100 mmol) of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (11-1 ) were initially charged in 120 ml dimethylformamide. This was followed by the addition of 6,27 g (110 mmol) of spry dried potassium fluoride and 0,96 g (3 mol %) of Bu4N + Br ⁇ , heating to 150°C and subsequent stirring at that temperature for 3 hours. GC of the reaction mixture shows 98 % conversion.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a novel process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1H-pyrazole-4-carbaldehyde, a useful intermediate in the manufacture of fungicides.
Description
Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehvde
The present invention relates to a novel process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde (I), a useful intermediate in the manufacture of fungicides.
Processes for exchanging chlorine for fluorine (halex processes) are known particularly for 5-chloro- 1 ,3-dialkyl-1 H-pyrazole-4-carbonyl chlorides (cf. for example WO 2007/031212 and EP-A 0 776 889). It is also known from WO 201 1/061205 that 5-fluoro-1-alkyl-3-fluoroalkyl-1 H-pyrazole-4-carbonyl chlorides can be prepared by reacting in a first step 5-chloro-1-alkyl-3-fluoroalkyl-1 H-pyrazole-4- carbaldehyde with metal fluorides like KF as fluorinating reagent to obtain 5-fluoro-1-alkyl-3- fluoroalkyl-1 H-pyrazole-4-carbaldehyde , followed by a second reaction with a chlorinating agent to obtain the acyl chloride derivatives.
It has now been found that the fluorination occurring in the preparation of 5-fluoro-1-methyl-3- difluoromethyl-1 H-pyrazole-4-carbaldehyde from 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4- carbaldehyde can be significantly and surprisingly accelerated and improved by the utilization of a phase transfer catalysts selected among tetrabutylammonium chloride, bromide or hydrogen sulphate in dimethylformamide or dimethylacetamide as solvent. Under such conditions, it is possible to reduce both the reaction time and the amount of potassium fluoride used for the fluorination, leading to a cheaper and more sustainable process.
The present invention relates to a process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde of formula (I)
characterized in that 5-chloro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carbaldehyde of formula (II)
(II)
is reacted with potassium fluoride of formula (III)
K+ F~ (III) in the presence of a phase transfer catalyst selected among tetrabutylammonium chloride, bromide or hydrogen sulphate, preferably tetrabutylammonium hydrogen sulphate, in dimethylformamide or dimethylacetamide as solvent.
The process according to the invention can be illustrated by the following formula scheme:
5-Chloro-1-alkyl-3-fluoroalkyl-1 H-pyrazole-4-carbaldehydes are known or obtainable by known methods (cf. J. Het. Chem. 1990, 27, 243, WO 2006/018725).
5-Chloro-1-alkyl-3-difluoroalkyl-1 H-pyrazole-4-carbaldehyde of formula (II) can be be prepared according to WO 201 1/061205.
Potassium fluoride is a known synthesis chemical. Reaction temperature in the process according to the invention is from 130°C to 160°C, preferably from 145°C to 155°C.
Reaction time is from 2 to 4 hours, preferably 3 hours.
The process according to the invention is carried out by using generally from 1 to 1.5 mol, preferably from 1.1 to 1.5 mol, of potassium fluoride per mole of 5-chloro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde of formula (II).
The process according to the invention is carried out by using generally from 1 to 5 mol % of the phase transfer catalyst per mole of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde of formula (II).
The process is preferably performed in equipment which is not a glass equipment, because KF can react under the reaction conditions with the glass equipment to produce side products (H2O). Teflon or stainless steel equipment is preferable.
The process can be performed under normal atmosphere or under pressure (in closed vessel). The potassium fluoride is generally used as a spray-dried.
Preparation examples
Example 1 : preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in presence of the catalyst Bu4N+ HS04~ in dimethylacetamide
19.4 g (l OO mmol) of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (II) were initially charged in 120 ml dimethylacetamide. This was followed by the addition of 6,84 g (120 mmol) of spry dried potassium fluoride and 1 g (3 mol %) of Bu4N+ HS04", heating to 150°C and subsequent stirring at that temperature for 3 hours. GC (gas chromatography) of the reaction mixture shows 100 % conversion This was followed by dilution of the mixture with toluene, filtration and removal of the solvent in vacuo at 1 mbar and 70°C to obtain 18,5 g of 5-fluoro-1-methyl-3- difluoromethyl-1 H-pyrazole-4-carbaldehyde having a purity w.w. % of 90 . H NMR (CD3CN): δ = 9.8 (1 H, s), 6.88 (1 H, t), 3.7 (3H, s) ppm.
9F NMR (CD3CN): δ = -114.75 (2F, t), -124.06 (1 F, s) ppm. Example 2: the reaction was performed similar to example 1 but without the catalyst Bu4N+ HS04~. In these conditions, GC of the reaction mixture shows 55% of conversion after 3 hours, 65% of conversion after 6 hours, 75% of conversion after 9 hours and 78% of conversion after 15h.
Example 3 : preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in presence of the catalyst Bu4N+ HS04" in dimethylformamide.
19.4 g (100 mmol) of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (11-1 ) were initially charged in 120 ml dimethylformamide. This was followed by the addition of 6,84 g (120 mmol) of spry dried potassium fluoride and 1 g (3 mol %) of Bu4N+ HS04", heating to 150°C and subsequent stirring at that temperature for 3 hours. GC of the reaction mixture shows 100 % conversion. This was followed by dilution of the mixture with toluene, filtration and removal of the solvent in vacuo at 0.5 mbar and 70°C to obtain 18,3 g of 5-fluoro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde having a purity w.w. % of 92.
Example 4: The reaction was performed similar to example 3, but without the catalyst Bu4N+ HS04". In these conditions, GC of the reaction mixture shows 52% of conversion after 3 hours, 73% of conversion after 6 hours, 83% of conversion after 9 hours and 93% of conversion after 15h.
Example 5. preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in presence of the catalyst Bu4N+ HS04" in dimethylformamide.
19.4 g (100 mmol) of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (11-1 ) were initially charged in 120 ml dimethylformamide. This was followed by the addition of 6,27 g (110 mmol) of spry dried potassium fluoride and 1 g (3 mol %) of Bu4N+ HS04", heating to 150°C and subsequent stirring at that temperature for 3 hours. GC of the reaction mixture shows 99 % conversion. This was followed by dilution of the mixture with toluene, filtration and removal of the solvent in vacuo at 1 mbar and 70°C to obtain 18,1g of 5-fluoro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde having a purity w.w. % of 89.
Example 6 : The reaction was performed similar to experiment 5, but without the catalyst Bu4N+ HS04". In these conditions, GC of the reaction mixture shows 35% of conversion after 3 hours, 50% of conversion after 6 hours, and 65% of conversion after 15h.
Example 7 : preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in presence of the catalyst Bu4N+ Br " in dimethylformamide 19.4 g (100 mmol) of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (11-1 ) were initially charged in 120 ml dimethylformamide. This was followed by the addition of 6,27 g (110 mmol) of spry dried potassium fluoride and 0,96 g (3 mol %) of Bu4N+ Br ~, heating to 150°C and subsequent stirring at that temperature for 3 hours. GC of the reaction mixture shows 98 % conversion. This was followed by dilution of the mixture with toluene, filtration and removal of the solvent in vacuo at 0.5 mbar and 70°C to obtain 17,8 g of 5-fluoro-1-methyl-3-difluoromethyl-1 H- pyrazole-4-carbaldehyde having a purity w.w. % of 89.
Example 8 : preparation of 5-fluoro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (I) in dimethylacetamide
19.4 g (100 mmol) of 5-chloro-1-methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde (11-1 ) were initially charged in 120 ml dimethylacetamide. This was followed by the addition of 8,55 g (150 mmol) of spry dried potassium fluoride, heating to 150°C and subsequent stirring at that temperature for 3 hours. GC shows only 55 % conversion.
Claims
1 . Process for preparing 5-fluoro-1 -methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde formula (I)
characterized in that 5-chloro-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carbaldehyde of formula (II)
is reacted with potassium fluoride of formula (II I)
K+ (III) in the presence of a phase transfer catalyst selected among tetrabutylammonium chloride, bromide or hydrogen sulphate in dimethylformamide or dimethylacetamide as solvent.
2. Process according to claim 1 wherein the phase transfer catalyst is tetrabutylammonium hydrogen sulphate.
3. Process according to claim 1 or 2 wherein the reaction temperature is from 130°C to 160°C.
4. Process according to anyone of claims 1 to 3 wherein the reaction time is from 2 to 4 hours.
5. Process according to anyone of claims 1 to 4 wherein from 1 to 1 .5 mol of potassium fluoride per mole of 5-chloro-1 -methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde of formula (II) is used.
6. Process according to anyone of claims 1 to 5 wherein from 1 to 5 mol % of the catalyst per mole of 5-chloro-1 -methyl-3-difluoromethyl-1 H-pyrazole-4-carbaldehyde of formula (II) is used.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/760,674 US9932312B2 (en) | 2013-01-17 | 2014-01-16 | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1H-pyrazole-4-carbaldehyde |
| JP2015553068A JP6349329B2 (en) | 2013-01-17 | 2014-01-16 | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1H-pyrazole-4-carbaldehyde |
| BR112015015833A BR112015015833B1 (en) | 2013-01-17 | 2014-01-16 | preparation process of 5-fluoro-1-methyl-3-difluoromethyl-1 h-pyrazol-4-carbaldehyde |
| ES14701001.1T ES2610380T3 (en) | 2013-01-17 | 2014-01-16 | Preparation procedure for 5-fluoro-1-methyl-3-difluoromethyl-1H-pyrazol-4-carbaldehyde |
| CN201480005100.1A CN104918916A (en) | 2013-01-17 | 2014-01-16 | Preparation method of 5-fluoro-1-methyl-3-difluoromethyl-1H-pyrazole-4-carbaldehyde |
| DK14701001.1T DK2945933T3 (en) | 2013-01-17 | 2014-01-16 | METHOD OF PREPARING 5-FLUORO-1-METHYL-3-DIFLUORMETHYL-1H-PYRAZOL-4-CARBALDEHYDE |
| KR1020157021772A KR102261967B1 (en) | 2013-01-17 | 2014-01-16 | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyrazole-4-carbaldehyde |
| MX2015009114A MX361768B (en) | 2013-01-17 | 2014-01-16 | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyraz ole-4-carbaldehyde. |
| EP14701001.1A EP2945933B1 (en) | 2013-01-17 | 2014-01-16 | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyrazole-4-carbaldehyde |
| IL239993A IL239993A (en) | 2013-01-17 | 2015-07-16 | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyrazole-4-carbaldehyde |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13151564 | 2013-01-17 | ||
| EP13151564.5 | 2013-01-17 |
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| Publication Number | Publication Date |
|---|---|
| WO2014111449A1 true WO2014111449A1 (en) | 2014-07-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2014/050767 Ceased WO2014111449A1 (en) | 2013-01-17 | 2014-01-16 | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyrazole-4-carbaldehyde |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US9932312B2 (en) |
| EP (1) | EP2945933B1 (en) |
| JP (1) | JP6349329B2 (en) |
| KR (1) | KR102261967B1 (en) |
| CN (1) | CN104918916A (en) |
| BR (1) | BR112015015833B1 (en) |
| DK (1) | DK2945933T3 (en) |
| ES (1) | ES2610380T3 (en) |
| IL (1) | IL239993A (en) |
| MX (1) | MX361768B (en) |
| TW (1) | TWI597270B (en) |
| WO (1) | WO2014111449A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0776889A1 (en) | 1995-12-01 | 1997-06-04 | Bayer Ag | Process for the production of 1,3-dimethyl-5-fluoro-pyrazol-4-carboxanilides |
| WO2006018725A1 (en) | 2004-08-18 | 2006-02-23 | Pfizer Inc. | Inhibitors of hepatitis c virus rna-dependent rna polymerase, and compositions and treatments using the same |
| WO2007031212A1 (en) | 2005-09-17 | 2007-03-22 | Bayer Cropscience Ag | Method for the production of 5-fluoro-1,3-dialkyl-1h-pyrazol-4-carbonyl fluorides |
| WO2010130767A2 (en) * | 2009-05-15 | 2010-11-18 | Bayer Cropscience Ag | Fungicide pyrazole carboxamides derivatives |
| WO2011061205A1 (en) | 2009-11-19 | 2011-05-26 | Bayer Cropscience Ag | Method for producing 5-fluorine-1-alkyl-3-fluoralkyl-1h-pyrazol-4 carbolic acid chlorides |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100096585A1 (en) * | 2007-03-16 | 2010-04-22 | Basf Se | Process for Preparing 2,6-Dichloro-4-(Trifluoromethyl)Phenylhydrazine Using Mixtures of Dichloro-Fluoro-Trifluoromethylbenzenes |
| MX2012012085A (en) * | 2010-04-23 | 2012-11-29 | Bayer Ip Gmbh | Process for preparing 5-fluoro-1-alkyl-3-fluoroalkyl-1h-pyrazole- 4-carbonyl chlorides and fluorides. |
-
2014
- 2014-01-16 US US14/760,674 patent/US9932312B2/en active Active
- 2014-01-16 MX MX2015009114A patent/MX361768B/en active IP Right Grant
- 2014-01-16 EP EP14701001.1A patent/EP2945933B1/en active Active
- 2014-01-16 ES ES14701001.1T patent/ES2610380T3/en active Active
- 2014-01-16 WO PCT/EP2014/050767 patent/WO2014111449A1/en not_active Ceased
- 2014-01-16 JP JP2015553068A patent/JP6349329B2/en active Active
- 2014-01-16 CN CN201480005100.1A patent/CN104918916A/en active Pending
- 2014-01-16 KR KR1020157021772A patent/KR102261967B1/en active Active
- 2014-01-16 TW TW103101660A patent/TWI597270B/en active
- 2014-01-16 DK DK14701001.1T patent/DK2945933T3/en active
- 2014-01-16 BR BR112015015833A patent/BR112015015833B1/en active IP Right Grant
-
2015
- 2015-07-16 IL IL239993A patent/IL239993A/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0776889A1 (en) | 1995-12-01 | 1997-06-04 | Bayer Ag | Process for the production of 1,3-dimethyl-5-fluoro-pyrazol-4-carboxanilides |
| WO2006018725A1 (en) | 2004-08-18 | 2006-02-23 | Pfizer Inc. | Inhibitors of hepatitis c virus rna-dependent rna polymerase, and compositions and treatments using the same |
| WO2007031212A1 (en) | 2005-09-17 | 2007-03-22 | Bayer Cropscience Ag | Method for the production of 5-fluoro-1,3-dialkyl-1h-pyrazol-4-carbonyl fluorides |
| WO2010130767A2 (en) * | 2009-05-15 | 2010-11-18 | Bayer Cropscience Ag | Fungicide pyrazole carboxamides derivatives |
| WO2011061205A1 (en) | 2009-11-19 | 2011-05-26 | Bayer Cropscience Ag | Method for producing 5-fluorine-1-alkyl-3-fluoralkyl-1h-pyrazol-4 carbolic acid chlorides |
Non-Patent Citations (1)
| Title |
|---|
| J. HET. CHEM., vol. 27, 1990, pages 243 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2945933A1 (en) | 2015-11-25 |
| ES2610380T3 (en) | 2017-04-27 |
| US20150353502A1 (en) | 2015-12-10 |
| TWI597270B (en) | 2017-09-01 |
| KR20150109396A (en) | 2015-10-01 |
| KR102261967B1 (en) | 2021-06-07 |
| IL239993A (en) | 2017-02-28 |
| MX361768B (en) | 2018-12-17 |
| BR112015015833B1 (en) | 2020-05-19 |
| IL239993A0 (en) | 2015-08-31 |
| EP2945933B1 (en) | 2016-10-12 |
| JP2016507517A (en) | 2016-03-10 |
| TW201441201A (en) | 2014-11-01 |
| BR112015015833A2 (en) | 2017-07-11 |
| MX2015009114A (en) | 2015-10-05 |
| US9932312B2 (en) | 2018-04-03 |
| JP6349329B2 (en) | 2018-06-27 |
| DK2945933T3 (en) | 2017-01-23 |
| CN104918916A (en) | 2015-09-16 |
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