WO2015003289A1 - Acide 3-fluoroalkyl-pyrazole 1-substitué-4-carboxylique et son procédé de préparation - Google Patents
Acide 3-fluoroalkyl-pyrazole 1-substitué-4-carboxylique et son procédé de préparation Download PDFInfo
- Publication number
- WO2015003289A1 WO2015003289A1 PCT/CN2013/000848 CN2013000848W WO2015003289A1 WO 2015003289 A1 WO2015003289 A1 WO 2015003289A1 CN 2013000848 W CN2013000848 W CN 2013000848W WO 2015003289 A1 WO2015003289 A1 WO 2015003289A1
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- WIPO (PCT)
- Prior art keywords
- formula
- hydrazine
- derivative
- reaction
- dimethyl
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title abstract description 7
- IMBBXSASDSZJSX-UHFFFAOYSA-N 4-Carboxypyrazole Chemical class OC(=O)C=1C=NNC=1 IMBBXSASDSZJSX-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000003869 acetamides Chemical class 0.000 claims abstract description 4
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical class OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims abstract description 3
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims abstract 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 88
- -1 3-fluorodecyl-1-substituted pyrazole-4-carboxylic acid Chemical class 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 36
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 21
- 239000008346 aqueous phase Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 8
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 8
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 8
- IGQNDARULCASRN-UHFFFAOYSA-N Fluxapyroxad (bas 700 f)-tp cscd465008 Chemical compound OC(=O)C1=CNN=C1C(F)F IGQNDARULCASRN-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical class CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 abstract description 18
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 238000004128 high performance liquid chromatography Methods 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000012544 monitoring process Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 235000019439 ethyl acetate Nutrition 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 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 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 4
- PFFIDZXUXFLSSR-UHFFFAOYSA-N 1-methyl-N-[2-(4-methylpentan-2-yl)-3-thienyl]-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound S1C=CC(NC(=O)C=2C(=NN(C)C=2)C(F)(F)F)=C1C(C)CC(C)C PFFIDZXUXFLSSR-UHFFFAOYSA-N 0.000 description 3
- XTDZGXBTXBEZDN-UHFFFAOYSA-N 3-(difluoromethyl)-N-(9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl)-1-methylpyrazole-4-carboxamide Chemical compound CC(C)C1C2CCC1C1=C2C=CC=C1NC(=O)C1=CN(C)N=C1C(F)F XTDZGXBTXBEZDN-UHFFFAOYSA-N 0.000 description 3
- XQJQCBDIXRIYRP-UHFFFAOYSA-N N-{2-[1,1'-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)-1-methyl-1pyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1C1C(C2CC2)C1 XQJQCBDIXRIYRP-UHFFFAOYSA-N 0.000 description 3
- KDVPGBVZKTVEIS-UHFFFAOYSA-N ethyl 2-(ethoxymethylidene)-4,4-difluoro-3-oxobutanoate Chemical compound CCOC=C(C(=O)C(F)F)C(=O)OCC KDVPGBVZKTVEIS-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 0 *C(*)(C(O*)=O)F Chemical compound *C(*)(C(O*)=O)F 0.000 description 2
- ARUMUDGORHCWRM-UHFFFAOYSA-N 2-(ethoxymethylidene)-4,4-difluoro-3-oxobutanoic acid Chemical compound CCOC=C(C(O)=O)C(=O)C(F)F ARUMUDGORHCWRM-UHFFFAOYSA-N 0.000 description 2
- ZPAJAVGZZKPCTN-UHFFFAOYSA-N 5-methyl-1h-pyrazole-4-carboxamide Chemical compound CC1=NNC=C1C(N)=O ZPAJAVGZZKPCTN-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- MRQQMVMIANXDKC-UHFFFAOYSA-N ethyl 3-(difluoromethyl)-1-methylpyrazole-4-carboxylate Chemical compound CCOC(=O)C1=CN(C)N=C1C(F)F MRQQMVMIANXDKC-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ZMIBIIAWFMCVFD-UHFFFAOYSA-N 2,2-difluoroacetamide Chemical compound NC(=O)C(F)F ZMIBIIAWFMCVFD-UHFFFAOYSA-N 0.000 description 1
- HFHXXHXFSWXOFG-UHFFFAOYSA-N 3-(difluoromethyl)-1,5-dimethylpyrazole-4-carboxamide Chemical compound CC1=C(C(=NN1C)C(F)F)C(=O)N HFHXXHXFSWXOFG-UHFFFAOYSA-N 0.000 description 1
- 239000005799 Isopyrazam Substances 0.000 description 1
- 239000005816 Penthiopyrad Substances 0.000 description 1
- 239000005834 Sedaxane Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-M difluoroacetate Chemical compound [O-]C(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 description 1
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001256 steam distillation Methods 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
Definitions
- the present invention relates to a 3-fluorodecyl-1-substituted pyrazole-4-carboxylic acid and a process for the preparation thereof.
- 3-Fluoroindolyl-1-substituted pyrazole-4-carboxylic acid is an important intermediate for some new pesticides, such as books
- Isopyrazam (CAS: 881685-58-1), Sedaxane (CAS ⁇ 874967-67-6), Penthiopyrad (CAS: 183675-82-3). Therefore, it is suitable for industrial production.
- the technical problem to be solved by the present invention is to provide a 3-fluorodecyl-1-substituted pyrazole-4-carboxylic acid and a process for the preparation thereof.
- the present invention provides a 3-fluorodecyl-1-substituted pyrazole-4-carboxylic acid having the structure of the following formula VI:
- R 2 is hydrogen or a fluorine atom
- R 8 is a lower or lower hydrocarbon of H or C1 to C4.
- the 3-fluorodecyl-1-substituted pyrazole-4-carboxylic acid is 3-difluoromethyl-1-methylpyrazole-4-carboxylic acid of formula VII and/or 3-Difluoromethyl-1H-pyrazole-4-carboxylic acid shown
- the present invention also provides a process for producing the above 3-fluorodecyl-1-substituted pyrazole-4-carboxylic acid, which
- R 2 is hydrogen or a fluorine atom
- R 3 , R 4 , R 5 , and R 6 are H or a C1 to C4 lower indole hydrocarbon
- R 3 , R 4 , R 5 , and R 7 are H or C1 to C4 lower indole hydrocarbons; Wherein, R 2 is hydrogen or a fluorine atom;
- R 4 , R 5 , R 7 , R 8 are H or a C1 to C4 lower indole hydrocarbon
- R 4 , R 5 and R 8 are H or a C1 to C4 lower indole hydrocarbon.
- the fluoroacetic acid derivative of the formula I is ethyl difluoroacetate; the acetamide derivative of the formula II is acetamide; the fluoroacetic acetamide derivative of the formula ⁇ is ⁇ , ⁇ - ⁇ Methyl difluoroacetoacetamide.
- the condensation reaction is carried out in a solventless, organic ether solvent or organic alcohol solvent system, wherein the organic ether solvent is THF or dioxane; and the organic alcohol solvent is methanol or ethanol.
- the 2-nonoxymethylenefluoroacetamide derivative of the formula IV is hydrazine, hydrazine-dimethyl-2-ethoxymethylene difluoroacetoacetyl;
- the molar ratio of the orthoformate to the fluoroacetoacetamide derivative of the formula III is from 0.8 to 5:1; the molar ratio of the acetic anhydride to the fluoroacetoacetamide derivative of the formula III is from 1 to 6:1.
- the reaction is carried out in a hydrocarbon solvent or an organic ether solvent system, wherein the hydrocarbon solvent is benzene, toluene or xylene; and the organic ether solvent is THF, dioxane or methyl tert. Ether.
- the 1-substituted-3-fluorodecylpyrazole-4-amide derivative of the formula V is hydrazine, ⁇ -dimethyl-3-difluoromethyl-1-methyl Pyrazole-3-amide and/or hydrazine, hydrazine-dimethyl-3-difluoromethyl-1 ⁇ -pyrazole-4-amide.
- the hydrolysis reaction is carried out by acid hydrolysis or alkali hydrolysis, and the reaction is carried out in an aqueous phase or a water and an organic alcohol solvent system, wherein the acid is hydrochloric acid, hydrobromic acid or sulfuric acid:
- the base is lithium hydroxide, sodium hydroxide or potassium hydroxide, and the organic alcohol is methanol or ethanol.
- step 1) the condensation reaction occurs at -10 ° C to 60 ° C; the reaction in step 2) occurs at 80 ° C to 120 ° C; the reaction of step 3) occurs at -20 ° C to 50 ° °C; The reaction of step 4) occurs at 20 ° C ⁇ 100 ° C.
- the above preparation method is cheap and easy to obtain; the preparation process is simple, the equipment requirements are low, and it is suitable for industrial production.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
L'invention concerne un acide 3-fluoroalkyl-pyrazole 1-substitué-4-carboxylique et son procédé de préparation. Selon le procédé, un dérivé d'acide fluoroacétique, en tant que matière première, est condensé avec un dérivé d'acétamide pour former un dérivé de fluoroacétoacétamide, qui est mis à réagir avec un orthoformiate pour former un dérivé de 2-alcoxyméthylènefluoroacylacétamide, puis avec un réactif hydrazine pour obtenir un dérivé de 3-fluoroalkylpyrazole 1-substitué-4-amide, qui est hydrolysé pour obtenir l'acide 3-fluoroalkyl-pyrazole 1-substitué -4-carboxylique. Le procédé utilise des matières premières peu onéreuses et facilement disponibles, est facile à réaliser, nécessite peu d'équipement et convient pour une production industrielle à grande échelle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2013/000848 WO2015003289A1 (fr) | 2013-07-12 | 2013-07-12 | Acide 3-fluoroalkyl-pyrazole 1-substitué-4-carboxylique et son procédé de préparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2013/000848 WO2015003289A1 (fr) | 2013-07-12 | 2013-07-12 | Acide 3-fluoroalkyl-pyrazole 1-substitué-4-carboxylique et son procédé de préparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015003289A1 true WO2015003289A1 (fr) | 2015-01-15 |
Family
ID=52279275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2013/000848 WO2015003289A1 (fr) | 2013-07-12 | 2013-07-12 | Acide 3-fluoroalkyl-pyrazole 1-substitué-4-carboxylique et son procédé de préparation |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2015003289A1 (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016152886A1 (fr) * | 2015-03-26 | 2016-09-29 | 旭硝子株式会社 | Procédé de fabrication d'un dérivé pyrazole |
| WO2019220962A1 (fr) * | 2018-05-18 | 2019-11-21 | 富士フイルム株式会社 | Procédé de production d'un composé 3-difluorométhylpyrazole, procédé de production d'un composé d'acide 3-difluorométhylpyrazole-4-carboxylique, et composé de pyrazolidine |
| WO2019224677A1 (fr) | 2018-05-21 | 2019-11-28 | Pi Industries Ltd. | Procédé de préparation de composés hétérocycliques substitués |
| WO2024040995A1 (fr) * | 2022-08-24 | 2024-02-29 | 绍兴上虞新银邦生化有限公司 | Procédé de synthèse d'un dérivé de méthyl-4-pyrazolecarboxamide n-méthyl-3-substitué et d'acide formique de méthyl-4-pyrazole n-méthyl-3-substitué |
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| CN102718712A (zh) * | 2012-06-29 | 2012-10-10 | 上海康鹏化学有限公司 | 3-二氟甲基吡唑-4-羧酸和3-三氟甲基吡唑-4-羧酸的制备方法 |
| 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 |
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2013
- 2013-07-12 WO PCT/CN2013/000848 patent/WO2015003289A1/fr active Application Filing
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|---|---|---|---|---|
| CN1078234A (zh) * | 1991-12-06 | 1993-11-10 | 孟山都公司 | 吡唑甲酰苯胺类杀真菌剂 |
| CN101679281A (zh) * | 2007-05-31 | 2010-03-24 | 先正达参股股份有限公司 | 吡唑的制备方法 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016152886A1 (fr) * | 2015-03-26 | 2016-09-29 | 旭硝子株式会社 | Procédé de fabrication d'un dérivé pyrazole |
| US10239841B2 (en) | 2015-03-26 | 2019-03-26 | AGC Inc. | Method for producing pyrazole derivative |
| WO2019220962A1 (fr) * | 2018-05-18 | 2019-11-21 | 富士フイルム株式会社 | Procédé de production d'un composé 3-difluorométhylpyrazole, procédé de production d'un composé d'acide 3-difluorométhylpyrazole-4-carboxylique, et composé de pyrazolidine |
| CN112119063A (zh) * | 2018-05-18 | 2020-12-22 | 富士胶片株式会社 | 3-二氟甲基吡唑化合物的制造方法及3-二氟甲基吡唑-4-羧酸化合物的制造方法以及吡唑烷化合物 |
| US11149010B2 (en) | 2018-05-18 | 2021-10-19 | Fujifilm Corporation | Producing method for 3-difluoromethylpyrazole compound, producing method for 3-difluoromethylpyrazole-4-carboxylic acid compound, and pyrazolidine compound |
| CN112119063B (zh) * | 2018-05-18 | 2023-10-17 | 富士胶片株式会社 | 3-二氟甲基吡唑化合物的制造方法及3-二氟甲基吡唑-4-羧酸化合物的制造方法以及吡唑烷化合物 |
| WO2019224677A1 (fr) | 2018-05-21 | 2019-11-28 | Pi Industries Ltd. | Procédé de préparation de composés hétérocycliques substitués |
| WO2024040995A1 (fr) * | 2022-08-24 | 2024-02-29 | 绍兴上虞新银邦生化有限公司 | Procédé de synthèse d'un dérivé de méthyl-4-pyrazolecarboxamide n-méthyl-3-substitué et d'acide formique de méthyl-4-pyrazole n-méthyl-3-substitué |
| US12134603B2 (en) | 2022-08-24 | 2024-11-05 | Shaoxing Shangyu Xin Yinbang Biochemical Co., Ltd. | Synthesis method for N-methyl-3-substituted methyl-4-pyrazolamide derivative and N-methyl-3-substituted methyl-4-pyrazolic acid |
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