JP2011513282A - 2−アルコキシメチレン−4,4−ジフルオロ−3−オキソ酪酸アルキルの製造方法 - Google Patents
2−アルコキシメチレン−4,4−ジフルオロ−3−オキソ酪酸アルキルの製造方法 Download PDFInfo
- Publication number
- JP2011513282A JP2011513282A JP2010548124A JP2010548124A JP2011513282A JP 2011513282 A JP2011513282 A JP 2011513282A JP 2010548124 A JP2010548124 A JP 2010548124A JP 2010548124 A JP2010548124 A JP 2010548124A JP 2011513282 A JP2011513282 A JP 2011513282A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- acid
- iii
- difluoro
- formula
- 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.)
- Granted
Links
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- PBWZKZYHONABLN-UHFFFAOYSA-M difluoroacetate Chemical compound [O-]C(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-M 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002955 isolation Methods 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 3
- VEZQTLOPSQHWFT-UHFFFAOYSA-N 5-(difluoromethyl)-2-methyl-1h-pyrazole-5-carboxylic acid Chemical compound CN1NC(C(O)=O)(C(F)F)C=C1 VEZQTLOPSQHWFT-UHFFFAOYSA-N 0.000 claims abstract 3
- -1 alkyl 4,4-difluoroacetoacetate Chemical compound 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- HQZSNVHMLLTTRA-UHFFFAOYSA-N 4,4-difluoro-3-oxobutanoic acid Chemical compound OC(=O)CC(=O)C(F)F HQZSNVHMLLTTRA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 69
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 16
- 239000000725 suspension Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- CBDPWKVOPADMJC-UHFFFAOYSA-N ethyl 4,4-difluoro-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)C(F)F CBDPWKVOPADMJC-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 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 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 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 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002905 orthoesters Chemical class 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- PXOPQFNZDXJCDN-UHFFFAOYSA-N C(C)(=O)OC(C)=O.C(C)OC=C(C(=O)OCC)C(C(F)F)=O Chemical compound C(C)(=O)OC(C)=O.C(C)OC=C(C(=O)OCC)C(C(F)F)=O PXOPQFNZDXJCDN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000007966 viscous suspension Substances 0.000 description 2
- 0 *OC(C=C(C(F)F)O)=O Chemical compound *OC(C=C(C(F)F)O)=O 0.000 description 1
- ZVXKYWHJBYIYNI-UHFFFAOYSA-N 1h-pyrazole-4-carboxamide Chemical compound NC(=O)C=1C=NNC=1 ZVXKYWHJBYIYNI-UHFFFAOYSA-N 0.000 description 1
- SQHVPIAVRCMIDN-UHFFFAOYSA-N 4,4-difluoro-2-methylidene-3-oxobutanoic acid Chemical compound C=C(C(=O)C(F)F)C(=O)O SQHVPIAVRCMIDN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
【化1】
[式中、Rはメチルまたはエチルである]
を4,4-ジフルオロアセト酢酸アルキル(I)
【化2】
の粗な反応混合物から製造する方法であって、
a) 追加の溶媒なしに、酢酸アルキル(II)
【化3】
ROMアルコキシド(III)
[式中、Mはナトリウムまたはカリウムイオンである]
及び
ジフルオロ酢酸アルキル(IV)
【化4】
を反応させてエノラート(V)
【化5】
を形成し、
b)エノラート(V)から酸を用いて対応する4,4-ジフルオロアセト酢酸アルキル(I)を遊離させ、
c)カチオンM及び酸アニオンから形成された塩を固体として除去し、
d)(I)を、粗な反応混合物から単離することなく、2-アルコキシメチレン-4,4-ジフルオロ-3-オキソ酪酸アルキル(VI)に変換することを含む前記方法、並びに1-メチル-3-ジフルオロメチルピラゾール-3-イルカルボキシレート(VII)
【化6】
を製造するための(VI)の使用。
【選択図】 なし
Description
c)カチオンM及び酸アニオンから形成された塩を固体として除去し、
d)(I)を、粗な反応混合物から単離することなく、式(VI)を有する2-アルコキシメチレン-4,4-ジフルオロ-3-オキソ酪酸アルキルに変換させる
ことにより2-アルコキシメチレン-4,4-ジフルオロ-3-オキソ酪酸アルキル(VI)が高収率で得られることが知見された。
最初に酢酸エチル(733.1g,8.32モル)及びジフルオロ酢酸エチル(99.9%)(397.6g,3.2モル)を25℃で充填し、ナトリウムエトキシド(98%)(238.7g,3.437モル)を攪拌しながら25〜65℃で1.3時間かけて計量添加した。その後、反応混合物を65℃で更に2時間攪拌し、次いで25℃まで冷却した。
最初に無水酢酸(2274.9g,22.08モル)を攪拌容器に充填し、110℃に加熱した。2時間以内に、合成例1a)からの4,4-ジフルオロアセト酢酸エチル溶液(エタノール/酢酸エチル中22.6%溶液)(2171g)及びオルトギ酸トリエチル(98%)(822.7g,5.44モル)を平行して計量添加した。約半分を供給した後、還流を始めた。計量添加が終了したとき、内部温度は95℃であった。混合物を還流温度で更に7時間攪拌した後、25℃まで冷却した。150ミリバールの圧力下で、低沸点物(酢酸エチル、酢酸、無水酢酸、オルトギ酸トリエチル)を40〜90℃の内部温度で留去させた。完全に除去するために、圧力を90℃で5ミリバールに下げ、次いで蒸留残液を95℃/5ミリバールで0.5時間攪拌した。得られた蒸留残渣(658.8g)は95.5重量%の所望の2-エトキシメチレン-4,4-ジフルオロ-3-オキソ酪酸エチルを含んでいた。これは、実施例1a)で使用したジフルオロ酢酸エチルに基づいて88.5%の2つの合成工程を通した全収率に相当する。
最初に酢酸エチル(141.2g,1.6モル)を25℃で充填し、ナトリウムエトキシド(98%)(45.9g,0.66モル)を攪拌しながら添加した。懸濁液を5℃まで冷却した後、ジフルオロ酢酸エチル(97%)(76.7g,0.6モル)を5〜13℃の内部温度で2.83時間以内に計量添加した。その後、反応混合物を65℃に加熱し、この温度で更に2時間攪拌した後、20℃まで冷却した(264.3gの溶液)。
最初に無水酢酸(427.8g,4.15モル)を攪拌容器に充填し、110℃に加熱した。2時間以内に、合成例2からの粗な4,4-ジフルオロアセト酢酸エチル(エタノール/酢酸エチル中20.9%溶液)(438g)及びオルトギ酸トリエチル(145.3g,0.96モル)を平行して計量添加した。約半分を供給した後、還流を106℃で始めた。計量添加が終了したとき、内部温度は94℃であった。混合物を還流温度で更に6時間攪拌した後、25℃まで冷却した。150ミリバールの圧力下で、低沸点物(酢酸エチル、酢酸、無水酢酸、オルトギ酸トリエチル)を40〜90℃の内部温度で留去させた。完全に除去するために、圧力を90℃で10ミリバールに下げ、次いで蒸留残液を95℃/10ミリバールで1時間攪拌した。蒸留残渣(125.7g)は89.7重量%の所望の2-エトキシメチレン-4,4-ジフルオロ-3-オキソ酪酸エチルを含んでいた。これは、実施例2で使用したジフルオロ酢酸エチルに基づいて84.6%の2つの合成工程を通した全収率に相当する。
最初に酢酸エチル(47.06g,0.533モル)を25℃で充填し、ナトリウムエトキシド(98%)(15.3g,0.22モル)を攪拌しながら添加した。懸濁液を5℃まで冷却した後、ジフルオロ酢酸エチル(97%)(25.6g,0.2モル)を5〜13℃の内部温度で2.83時間以内に計量添加した。その後、反応混合物を65℃に加熱し、この温度で更に2時間攪拌し、次いで20℃まで冷却した(88.1gの溶液)。
最初に酢酸エチル(45.9g,0.53モル)を25℃で充填し、ナトリウムエトキシド(98%)(14.96g,0.22モル)を攪拌しながら添加した。懸濁液を5℃まで冷却した後、ジフルオロ酢酸エチル(99.88%)(24.9g,0.2モル)を10〜25℃の内部温度で2.0時間以内に計量添加した。その後、反応混合物を65℃に加熱し、この温度で更に2時間攪拌し、次いで20℃まで冷却した。
最初に酢酸エチル(47.06g,0.533モル)を25℃で充填し、ナトリウムエトキシド(98%)(15.3g,0.22モル)を攪拌しながら添加した。懸濁液を5℃まで冷却した後、ジフルオロ酢酸エチル(97%)(25.6g,0.2モル)を5〜13℃の内部温度で2.83時間以内に計量添加した。その後、反応混合物を65℃に加熱し、この温度で更に2時間攪拌し、次いで20℃まで冷却した(88.1gの溶液)。
最初に酢酸エチル(137.8g,1.56モル)を25℃で充填し、ナトリウムエトキシド(98%)(44.9g,0.65モル)を攪拌しながら添加した。懸濁液を5℃まで冷却した後、ジフルオロ酢酸エチル(99.88%)(74.8g,0.6モル)を10〜25℃の内部温度で2.0時間以内に計量添加した。その後、反応混合物を65℃に加熱し、この温度で更に2時間攪拌し、次いで20℃まで冷却した(256.8gの溶液)。
最初に無水酢酸(365.2g,3.54モル)を攪拌容器に充填し、110℃に加熱した。2時間以内に、合成例7からの粗な4,4-ジフルオロアセト酢酸エチル(エタノール/酢酸エチル中26.5%の4,4-ジフルオロアセト酢酸エチル溶液)(356.3g)及びオルトギ酸トリエチル(154.4g,1.02モル)を平行して計量添加した。約半分を供給した後、還流を106℃で始めた。計量添加が終了したとき、内部温度は92℃であった。混合物を還流温度で更に5時間攪拌した後、25℃まで冷却した。150ミリバールの圧力で、低沸点物(酢酸エチル、酢酸、無水酢酸、オルトギ酸トリエチル)を40〜90℃の内部温度で留去させた。完全に除去するために、圧力を90℃で5ミリバールに下げた後、蒸留残液を95℃/5ミリバールで1時間攪拌した。生じた蒸留残渣(127.5g)は90.7重量%の所望の2-エトキシメチレン-4,4-ジフルオロ-3-オキソ酪酸エチルを含んでいた。これは、(実施例7で使用したジフルオロ酢酸エチルに基づいて)86.6%の2つの合成工程を通した全収率に相当する。
Claims (10)
- 式(VI)
を有する2-アルコキシメチレン-4,4-ジフルオロ-3-オキソ酪酸アルキルを4,4-ジフルオロアセト酢酸アルキル(I)
a)最初に以下の成分(II)、(III)及び(IV)
ROM アルコキシド(III)
[式中、Mはリチウム、ナトリウムまたはカリウムイオンである]
及び
のうちの2つを充填し、この混合物を第3成分と反応させて、式(V)
b)エノラート(V)から酸を用いて式(I)を有する対応する4,4-ジフルオロアセト酢酸アルキルを遊離させる工程、
c)カチオンM及び酸アニオンから形成された塩を固体として除去する工程、及び
d)(I)を、粗な反応混合物から単離することなく、式(VI)を有する2-アルコキシメチレン-4,4-ジフルオロ-3-オキソ酪酸アルキルに変換する工程、
を含む前記方法。 - 工程a)を最初に酢酸アルキル(II)及びジフルオロ酢酸アルキル(IV)を充填し、アルコキシド(III)を計量添加することにより実施する、請求項1に記載の方法。
- (I)を水の非存在下または少量の水の存在下で(V)から遊離させる、請求項1に記載の方法。
- 工程b)において(V)から(I)を遊離させるために使用される酸が塩化水素、臭化水素、ヨウ化水素、硫酸、ギ酸、酢酸、シュウ酸、クエン酸、メタンスルホン酸またはp-トルエンスルホン酸である、請求項1に記載の方法。
- 工程b)における(V)から(I)の遊離を少量の水の存在下で実施する、請求項1〜4のいずれか1項に記載の方法。
- 酢酸アルキル(II)のアルコキシド(III)に対するモル比が0.8:1〜10:1である、請求項1〜4のいずれか1項に記載の方法。
- ジフルオロ酢酸アルキル(IV)の酢酸アルキル(II)に対するモル比が1:0.8〜1:20である、請求項1〜4のいずれか1項に記載の方法。
- アルコキシド(III)の酸に対するモル比が1:0.7〜1:5である、請求項1〜4のいずれか1項に記載の方法。
- (II)、(III)及び(IV)の反応の反応温度が-20℃〜70℃である、請求項1〜4のいずれか1項に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08102197.4 | 2008-02-29 | ||
EP08102197 | 2008-02-29 | ||
PCT/EP2009/052378 WO2009106619A1 (en) | 2008-02-29 | 2009-02-27 | Process for preparing alkyl 2-alkoxymethylene-4,4-difluoro-3-oxobutyrates |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2011513282A true JP2011513282A (ja) | 2011-04-28 |
JP5559066B2 JP5559066B2 (ja) | 2014-07-23 |
Family
ID=39645697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010548124A Active JP5559066B2 (ja) | 2008-02-29 | 2009-02-27 | 2−アルコキシメチレン−4,4−ジフルオロ−3−オキソ酪酸アルキルの製造方法 |
Country Status (15)
Country | Link |
---|---|
US (1) | US8207354B2 (ja) |
EP (1) | EP2262756B1 (ja) |
JP (1) | JP5559066B2 (ja) |
KR (1) | KR20100133392A (ja) |
CN (1) | CN101959840B (ja) |
AR (1) | AR072447A1 (ja) |
AU (1) | AU2009218414B2 (ja) |
BR (1) | BRPI0908252A2 (ja) |
CA (1) | CA2715668A1 (ja) |
EA (1) | EA019427B1 (ja) |
IL (1) | IL207408A (ja) |
MX (1) | MX2010008627A (ja) |
UA (1) | UA102386C2 (ja) |
WO (1) | WO2009106619A1 (ja) |
ZA (1) | ZA201006842B (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015522536A (ja) * | 2012-05-16 | 2015-08-06 | ソルヴェイ(ソシエテ アノニム) | 1−置換メチリデン化合物の製造 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201004301D0 (en) * | 2010-03-15 | 2010-04-28 | Syngenta Participations Ag | Process |
GB201004299D0 (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 |
IT1401696B1 (it) * | 2010-09-10 | 2013-08-02 | Miteni Spa | Procedimento per la preparazione di esteri dell acido 4,4-difluoroacetilacetico |
CN102206155A (zh) * | 2011-04-19 | 2011-10-05 | 巨化集团公司 | 一种4,4-二氟乙酰乙酸乙酯的合成方法 |
EP2731426A2 (en) | 2011-07-15 | 2014-05-21 | Basf Se | Pesticidal methods using substituted 3-pyridyl thiazole compounds and derivatives for combating animal pests ii |
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 |
CN104744256B (zh) * | 2013-12-27 | 2017-01-04 | 北京乐威泰克医药技术有限公司 | 制备2-(烷氧基亚烷基)-3-氧代羧酸酯、嘧啶化合物的方法及铁作为催化剂的用途 |
JP2018087142A (ja) * | 2015-03-30 | 2018-06-07 | 旭硝子株式会社 | 3−ハロゲン化アルキルピラゾール誘導体の製造方法 |
WO2017054112A1 (zh) | 2015-09-28 | 2017-04-06 | 常州市卜弋科研化工有限公司 | 3-氟代烷基-1-甲基吡唑-4-羧酸的制备方法 |
CN106554311B (zh) * | 2015-09-28 | 2019-03-01 | 常州市卜弋科研化工有限公司 | 3-氟代烷基-1-甲基吡唑-4-羧酸的制备方法 |
WO2019220962A1 (ja) | 2018-05-18 | 2019-11-21 | 富士フイルム株式会社 | 3-ジフルオロメチルピラゾール化合物の製造方法及び3-ジフルオロメチルピラゾール-4-カルボン酸化合物の製造方法、並びに、ピラゾリジン化合物 |
JP6911143B2 (ja) | 2018-11-07 | 2021-07-28 | 福建永晶科技股▲ふん▼有限公司Fujian Yongjing Technology Co., Ltd | ピラゾール又はピリミジノンの新しい製造方法 |
CN111116364B (zh) * | 2019-12-30 | 2022-11-11 | 浙江本立科技股份有限公司 | 2-多卤代乙酰基-3-烷氧基丙烯酸酯的制备方法 |
CN117384096A (zh) * | 2023-12-13 | 2024-01-12 | 山东国邦药业有限公司 | 一种二氟吡唑酸的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07501549A (ja) * | 1991-12-06 | 1995-02-16 | モンサント・カンパニー | ピラゾールカルボキサニリド殺菌剤 |
WO2006090778A1 (ja) * | 2005-02-25 | 2006-08-31 | Sagami Chemical Research Center | 1-置換-3-フルオロアルキルピラゾール-4-カルボン酸エステルの製造方法 |
WO2007115766A1 (en) * | 2006-04-06 | 2007-10-18 | Syngenta Participations Ag | Fungicidal compositions |
Family Cites Families (100)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2831123A (en) * | 1956-07-11 | 1958-04-15 | Webster J Daly | X-ray fluoroscopic device |
USRE28544E (en) * | 1971-07-07 | 1975-09-02 | Radiant energy imaging with scanning pencil beam | |
US3784837A (en) * | 1972-05-08 | 1974-01-08 | Siemens Ag | X-ray device with a stand |
DE2532218C2 (de) * | 1975-07-18 | 1982-09-02 | Heimann Gmbh, 6200 Wiesbaden | Vorrichtung zum Prüfen von Gepäckstücken mittels Röntgenstrahlung |
DE2532300C3 (de) * | 1975-07-18 | 1979-05-17 | Heimann Gmbh, 6200 Wiesbaden | Anlage zum Prüfen von Gepäckstücken mittels Röntgenstrahlung |
US4210811A (en) * | 1975-11-03 | 1980-07-01 | Heimann Gmbh | Drive for moveable shield in luggage screening apparatus |
DE2735400C2 (de) * | 1977-08-05 | 1979-09-20 | Heimann Gmbh, 6200 Wiesbaden | Vorrichtung zum Prüfen von Gepäckstücken mitteis Röntgenstrahlung |
JPS5756740A (en) * | 1980-09-22 | 1982-04-05 | Mitsubishi Electric Corp | Object inspecting device |
DE3145227A1 (de) * | 1981-11-13 | 1983-05-19 | Heimann Gmbh, 6200 Wiesbaden | Verfahren und vorrichtung zur untersuchung des inhaltes von containern |
US4599740A (en) * | 1983-01-06 | 1986-07-08 | Cable Arthur P | Radiographic examination system |
DE3431082A1 (de) * | 1984-08-23 | 1986-02-27 | Heimann Gmbh, 6200 Wiesbaden | Schaltungsanordnung zur hochspannungsversorung einer roentgenroehre |
US4817123A (en) * | 1984-09-21 | 1989-03-28 | Picker International | Digital radiography detector resolution improvement |
CN85107860A (zh) * | 1985-04-03 | 1986-10-01 | 海曼股份公司 | X-射线扫描仪 |
US4799247A (en) * | 1986-06-20 | 1989-01-17 | American Science And Engineering, Inc. | X-ray imaging particularly adapted for low Z materials |
US4825454A (en) * | 1987-12-28 | 1989-04-25 | American Science And Engineering, Inc. | Tomographic imaging with concentric conical collimator |
DE58902570D1 (de) * | 1989-08-09 | 1992-12-03 | Heimann Gmbh | Vorrichtung zum durchstrahlen von gegenstaenden mit faecherfoermiger strahlung. |
US5022062A (en) * | 1989-09-13 | 1991-06-04 | American Science And Engineering, Inc. | Automatic threat detection based on illumination by penetrating radiant energy using histogram processing |
US5179581A (en) * | 1989-09-13 | 1993-01-12 | American Science And Engineering, Inc. | Automatic threat detection based on illumination by penetrating radiant energy |
US5098640A (en) * | 1990-01-10 | 1992-03-24 | Science Applications International Corporation | Apparatus and method for detecting contraband using fast neutron activation |
US4991189A (en) * | 1990-04-16 | 1991-02-05 | General Electric Company | Collimation apparatus for x-ray beam correction |
US5181234B1 (en) * | 1990-08-06 | 2000-01-04 | Rapiscan Security Products Inc | X-ray backscatter detection system |
US5247561A (en) * | 1991-01-02 | 1993-09-21 | Kotowski Andreas F | Luggage inspection device |
US5093347A (en) * | 1991-01-28 | 1992-03-03 | Monsanto Company | 3-difluoromethylpyrazolecarboxamide fungicides, compositions and use |
US5224144A (en) * | 1991-09-12 | 1993-06-29 | American Science And Engineering, Inc. | Reduced mass flying spot scanner having arcuate scanning lines |
US5182764A (en) * | 1991-10-03 | 1993-01-26 | Invision Technologies, Inc. | Automatic concealed object detection system having a pre-scan stage |
US5221843A (en) * | 1992-04-23 | 1993-06-22 | Alvarez Robert E | Active energy selective x-ray image detection |
US5237598A (en) * | 1992-04-24 | 1993-08-17 | Albert Richard D | Multiple image scanning X-ray method and apparatus |
EP0579848B1 (de) * | 1992-07-20 | 1995-10-04 | Heimann Systems GmbH | Prüfanlage für Gegenstände |
JPH06277207A (ja) * | 1993-03-25 | 1994-10-04 | Toshiba Corp | 非破壊検査装置、x線ct用データ検出装置及びx線ct用画像処理装置 |
DE4311174C2 (de) * | 1993-04-05 | 1996-02-15 | Heimann Systems Gmbh & Co | Röntgenprüfanlage für Container und Lastkraftwagen |
FR2705786B1 (fr) * | 1993-05-28 | 1995-08-25 | Schlumberger Ind Sa | Procédé et dispositif pour la reconnaissance de matériaux déterminés dans la composition d'un objet. |
FR2708751B1 (fr) * | 1993-07-30 | 1995-10-06 | Schlumberger Ind Sa | Procédé et dispositif pour détecter la présence d'un objet, comportant un matériau donné, non accessible à la vue. |
US5493596A (en) * | 1993-11-03 | 1996-02-20 | Annis; Martin | High-energy X-ray inspection system |
KR100344363B1 (ko) | 1993-11-30 | 2002-11-30 | 일라이 릴리 앤드 캄파니 | 2,2-디플루오로케텐실릴아세탈의제조방법 |
US5666393A (en) * | 1994-02-17 | 1997-09-09 | Annis; Martin | Method and apparatus for reducing afterglow noise in an X-ray inspection system |
US5548123A (en) * | 1994-12-06 | 1996-08-20 | Regents Of The University Of California | High resolution, multiple-energy linear sweep detector for x-ray imaging |
DE19510168C2 (de) * | 1995-03-21 | 2001-09-13 | Heimann Systems Gmbh & Co | Verfahren und Vorrichtung zur Bestimmung von kristallinen und polykristallinen Materialien in einem Untersuchungsbereich |
US5642393A (en) * | 1995-09-26 | 1997-06-24 | Vivid Technologies, Inc. | Detecting contraband by employing interactive multiprobe tomography |
US6507025B1 (en) * | 1995-10-23 | 2003-01-14 | Science Applications International Corporation | Density detection using real time discrete photon counting for fast moving targets |
US6255654B1 (en) * | 1995-10-23 | 2001-07-03 | Science Applications International Corporation | Density detection using discrete photon counting |
US5764683B1 (en) * | 1996-02-12 | 2000-11-21 | American Science & Eng Inc | Mobile x-ray inspection system for large objects |
US5642394A (en) * | 1996-04-03 | 1997-06-24 | American Science And Engineering, Inc. | Sidescatter X-ray detection system |
US5638420A (en) * | 1996-07-03 | 1997-06-10 | Advanced Research And Applications Corporation | Straddle inspection system |
US5930326A (en) * | 1996-07-12 | 1999-07-27 | American Science And Engineering, Inc. | Side scatter tomography system |
US5910973A (en) * | 1996-07-22 | 1999-06-08 | American Science And Engineering, Inc. | Rapid X-ray inspection system |
US5940468A (en) * | 1996-11-08 | 1999-08-17 | American Science And Engineering, Inc. | Coded aperture X-ray imaging system |
US6058158A (en) * | 1997-07-04 | 2000-05-02 | Eiler; Peter | X-ray device for checking the contents of closed cargo carriers |
US6192101B1 (en) * | 1997-08-21 | 2001-02-20 | American Science & Engineering, Inc. | X-ray determination of the mass distribution in containers |
EP1012586A2 (en) * | 1997-09-09 | 2000-06-28 | American Science & Engineering, Inc. | A tomographic inspection system |
EP1040489A1 (en) * | 1997-12-19 | 2000-10-04 | American Science & Engineering, Inc. | X-ray ambient level safety system |
DE19802668B4 (de) * | 1998-01-24 | 2013-10-17 | Smiths Heimann Gmbh | Röntgenstrahlungserzeuger |
DE19812055C2 (de) * | 1998-03-19 | 2002-08-08 | Heimann Systems Gmbh & Co | Bildverarbeitung zur Materialerkennung mittels Röntgenstrahlungen |
US6218943B1 (en) * | 1998-03-27 | 2001-04-17 | Vivid Technologies, Inc. | Contraband detection and article reclaim system |
US6094472A (en) * | 1998-04-14 | 2000-07-25 | Rapiscan Security Products, Inc. | X-ray backscatter imaging system including moving body tracking assembly |
DE19826062B4 (de) * | 1998-06-12 | 2006-12-14 | Smiths Heimann Gmbh | Verfahren und Anordnung zur Detektion von Röntgenstrahlen |
US6442233B1 (en) * | 1998-06-18 | 2002-08-27 | American Science And Engineering, Inc. | Coherent x-ray scatter inspection system with sidescatter and energy-resolved detection |
US6278115B1 (en) * | 1998-08-28 | 2001-08-21 | Annistech, Inc. | X-ray inspection system detector with plastic scintillating material |
DE69924001T2 (de) * | 1998-11-30 | 2006-02-09 | American Science & Engineering, Inc., Billerica | Röntgenstrahluntersuchungssystem mit kegel- und bleistiftstrahlen aus einer gemeinsamen quelle |
US6453007B2 (en) * | 1998-11-30 | 2002-09-17 | American Science And Engineering, Inc. | X-ray inspection using co-planar pencil and fan beams |
DE19855213C2 (de) * | 1998-11-30 | 2001-03-15 | Siemens Ag | Röntgenaufnahmeeinrichtung |
US6249567B1 (en) * | 1998-12-01 | 2001-06-19 | American Science & Engineering, Inc. | X-ray back scatter imaging system for undercarriage inspection |
US6421420B1 (en) * | 1998-12-01 | 2002-07-16 | American Science & Engineering, Inc. | Method and apparatus for generating sequential beams of penetrating radiation |
US6282260B1 (en) * | 1998-12-14 | 2001-08-28 | American Science & Engineering, Inc. | Unilateral hand-held x-ray inspection apparatus |
WO2000037928A2 (en) * | 1998-12-22 | 2000-06-29 | American Science And Engineering, Inc. | Unilateral hand-held x-ray inspection apparatus |
US6256369B1 (en) * | 1999-03-31 | 2001-07-03 | Analogic Corporation | Computerized tomography scanner with longitudinal flying focal spot |
US6456684B1 (en) * | 1999-07-23 | 2002-09-24 | Inki Mun | Surgical scanning system and process for use thereof |
US6356620B1 (en) * | 1999-07-30 | 2002-03-12 | American Science & Engineering, Inc. | Method for raster scanning an X-ray tube focal spot |
US6546072B1 (en) * | 1999-07-30 | 2003-04-08 | American Science And Engineering, Inc. | Transmission enhanced scatter imaging |
DE19954663B4 (de) * | 1999-11-13 | 2006-06-08 | Smiths Heimann Gmbh | Verfahren und Vorrichtung zur Bestimmung eines Materials eines detektierten Gegenstandes |
US6542578B2 (en) * | 1999-11-13 | 2003-04-01 | Heimann Systems Gmbh | Apparatus for determining the crystalline and polycrystalline materials of an item |
US6763635B1 (en) * | 1999-11-30 | 2004-07-20 | Shook Mobile Technology, Lp | Boom with mast assembly |
DE10196075B3 (de) * | 2000-03-01 | 2015-08-20 | Tsinghua University | Containeruntersuchungsvorrichtung |
US6839403B1 (en) * | 2000-07-24 | 2005-01-04 | Rapiscan Security Products (Usa), Inc. | Generation and distribution of annotation overlays of digital X-ray images for security systems |
US6434219B1 (en) * | 2000-07-24 | 2002-08-13 | American Science And Engineering, Inc. | Chopper wheel with two axes of rotation |
US6837422B1 (en) * | 2000-09-01 | 2005-01-04 | Heimann Systems Gmbh | Service unit for an X-ray examining device |
DE10044357A1 (de) * | 2000-09-07 | 2002-03-21 | Heimann Systems Gmbh & Co | Detektoranordnung zur Detektion von Röntgenstrahlen |
DE10062214B4 (de) * | 2000-12-13 | 2013-01-24 | Smiths Heimann Gmbh | Vorrichtungen zur Durchleuchtung von Objekten |
US6477417B1 (en) * | 2001-04-12 | 2002-11-05 | Pacesetter, Inc. | System and method for automatically selecting electrode polarity during sensing and stimulation |
US6580778B2 (en) * | 2001-05-23 | 2003-06-17 | Heimann Systems Gmbh | Inspection device |
US6597760B2 (en) * | 2001-05-23 | 2003-07-22 | Heimann Systems Gmbh | Inspection device |
US7505557B2 (en) * | 2006-01-30 | 2009-03-17 | Rapiscan Security Products, Inc. | Method and system for certifying operators of x-ray inspection systems |
DE10139672A1 (de) * | 2001-08-11 | 2003-03-06 | Heimann Systems Gmbh & Co | Verfahren und Anlage zur Inspektion eines Objektes, insbesondere eines Gepäckstückes |
US8502699B2 (en) * | 2001-09-28 | 2013-08-06 | Mct Technology, Llc | Integrated detection and monitoring system |
US6542580B1 (en) * | 2002-01-15 | 2003-04-01 | Rapiscan Security Products (Usa), Inc. | Relocatable X-ray imaging system and method for inspecting vehicles and containers |
DE10215292A1 (de) | 2002-02-19 | 2003-08-28 | Bayer Cropscience Ag | Disubstitutierte Pyrazolylcarbocanilide |
US6843599B2 (en) * | 2002-07-23 | 2005-01-18 | Rapiscan, Inc. | Self-contained, portable inspection system and method |
CN1181336C (zh) * | 2002-10-16 | 2004-12-22 | 清华大学 | 一种车载移动式集装箱检查系统 |
US7099434B2 (en) * | 2002-11-06 | 2006-08-29 | American Science And Engineering, Inc. | X-ray backscatter mobile inspection van |
US6785357B2 (en) * | 2003-01-16 | 2004-08-31 | Bio-Imaging Research, Inc. | High energy X-ray mobile cargo inspection system with penumbra collimator |
US20050117700A1 (en) * | 2003-08-08 | 2005-06-02 | Peschmann Kristian R. | Methods and systems for the rapid detection of concealed objects |
DE10351088A1 (de) | 2003-10-31 | 2005-06-02 | Bayer Cropscience Gmbh | Verfahren zum Herstellen von fluormethyl-substituierten Heterocyclen |
CN1627061A (zh) * | 2003-12-10 | 2005-06-15 | 清华同方威视技术股份有限公司 | 一种组合移动式低靶点集装箱检查系统 |
US7039159B2 (en) * | 2004-01-30 | 2006-05-02 | Science Applications International Corporation | Method and system for automatically scanning and imaging the contents of a moving target |
US7166844B1 (en) * | 2004-06-01 | 2007-01-23 | Science Applications International Corporation | Target density imaging using discrete photon counting to produce high-resolution radiographic images |
JP2008502636A (ja) | 2004-06-18 | 2008-01-31 | ビーエーエスエフ アクチェンゲゼルシャフト | N−(オルト−フェニル)−1−メチル−3−ジフルオロメチルピラゾール−4−カルボキシアニリドおよびそれらの殺菌剤としての使用 |
US7738687B2 (en) * | 2005-04-07 | 2010-06-15 | L-3 Communications Security And Detection Systems, Inc. | Method of registration in a contraband detection system |
AU2006291419B2 (en) | 2005-09-16 | 2012-06-14 | Syngenta Limited. | Process for the production of amides |
JP5284266B2 (ja) | 2006-11-03 | 2013-09-11 | ビーエーエスエフ ソシエタス・ヨーロピア | ジフルオロメチルピラゾリルカルボキシレートの調製方法 |
AU2007338031B2 (en) | 2006-12-21 | 2012-08-16 | Basf Se | Process for preparing fluoromethyl-substituted heterocyclic compounds |
EP1997808A1 (en) * | 2007-05-31 | 2008-12-03 | Syngeta Participations AG | Process for the production of pyrazoles |
-
2009
- 2009-02-27 JP JP2010548124A patent/JP5559066B2/ja active Active
- 2009-02-27 KR KR1020107021594A patent/KR20100133392A/ko not_active Application Discontinuation
- 2009-02-27 EP EP09715410.8A patent/EP2262756B1/en active Active
- 2009-02-27 AU AU2009218414A patent/AU2009218414B2/en not_active Ceased
- 2009-02-27 UA UAA201011338A patent/UA102386C2/ru unknown
- 2009-02-27 US US12/919,842 patent/US8207354B2/en active Active
- 2009-02-27 CN CN200980106768.4A patent/CN101959840B/zh active Active
- 2009-02-27 CA CA2715668A patent/CA2715668A1/en not_active Abandoned
- 2009-02-27 WO PCT/EP2009/052378 patent/WO2009106619A1/en active Application Filing
- 2009-02-27 AR ARP090100715A patent/AR072447A1/es unknown
- 2009-02-27 EA EA201001360A patent/EA019427B1/ru not_active IP Right Cessation
- 2009-02-27 MX MX2010008627A patent/MX2010008627A/es active IP Right Grant
- 2009-02-27 BR BRPI0908252-2A patent/BRPI0908252A2/pt not_active IP Right Cessation
-
2010
- 2010-08-04 IL IL207408A patent/IL207408A/en not_active IP Right Cessation
- 2010-09-27 ZA ZA2010/06842A patent/ZA201006842B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07501549A (ja) * | 1991-12-06 | 1995-02-16 | モンサント・カンパニー | ピラゾールカルボキサニリド殺菌剤 |
WO2006090778A1 (ja) * | 2005-02-25 | 2006-08-31 | Sagami Chemical Research Center | 1-置換-3-フルオロアルキルピラゾール-4-カルボン酸エステルの製造方法 |
WO2007115766A1 (en) * | 2006-04-06 | 2007-10-18 | Syngenta Participations Ag | Fungicidal compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015522536A (ja) * | 2012-05-16 | 2015-08-06 | ソルヴェイ(ソシエテ アノニム) | 1−置換メチリデン化合物の製造 |
JP2018118982A (ja) * | 2012-05-16 | 2018-08-02 | ソルヴェイ(ソシエテ アノニム) | 1−置換メチリデン化合物の製造 |
Also Published As
Publication number | Publication date |
---|---|
US20110004002A1 (en) | 2011-01-06 |
EA201001360A1 (ru) | 2011-04-29 |
AR072447A1 (es) | 2010-09-01 |
IL207408A (en) | 2014-04-30 |
IL207408A0 (en) | 2010-12-30 |
BRPI0908252A2 (pt) | 2015-07-21 |
CN101959840B (zh) | 2014-04-16 |
AU2009218414A1 (en) | 2009-09-03 |
AU2009218414B2 (en) | 2013-05-16 |
EP2262756A1 (en) | 2010-12-22 |
CN101959840A (zh) | 2011-01-26 |
ZA201006842B (en) | 2011-12-28 |
CA2715668A1 (en) | 2009-09-03 |
KR20100133392A (ko) | 2010-12-21 |
WO2009106619A1 (en) | 2009-09-03 |
UA102386C2 (ru) | 2013-07-10 |
MX2010008627A (es) | 2010-08-31 |
EA019427B1 (ru) | 2014-03-31 |
JP5559066B2 (ja) | 2014-07-23 |
US8207354B2 (en) | 2012-06-26 |
EP2262756B1 (en) | 2016-08-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5559066B2 (ja) | 2−アルコキシメチレン−4,4−ジフルオロ−3−オキソ酪酸アルキルの製造方法 | |
US9783506B2 (en) | Process for the large scale production of 1H-[1,2,3]triazole and its intermediate 1-benzyl-1H-[1,2,3]triazole | |
JP2013522266A (ja) | 2−アルコキシメチレン−4,4−ジフルオロ−3−オキソ酪酸アルキルの製造方法 | |
JP6702623B2 (ja) | メデトミジンの合成に有用な3−アリールブタナールなどの化合物の調製方法 | |
CN107801390B (zh) | 用于制造1-环丙基萘的方法 | |
RU2423343C2 (ru) | Способ получения высокочистого, свободного от галогенов о-фталальдегида | |
JP4968066B2 (ja) | 4−アミノ−2−アルキルチオ−5−ピリミジンカルバルデヒドの製法 | |
US10358415B2 (en) | Processes for the preparation of unsaturated malonates | |
Menicagli et al. | Triisobutylaluminum assisted reductive rearrangement of 2-ethoxy-4-alkyl-2, 3-dihydrofurans | |
TWI551592B (zh) | 以兩步驟來製備3,5-二側氧己酸酯 | |
JP3838682B2 (ja) | 2−メチル−4−オキソ−2−シクロヘキセンカルボン酸エステル及びその新規中間体の製法 | |
CN104961722B (zh) | 一种使用反应助剂制备依普罗沙坦中间体的方法 | |
JP2010530859A (ja) | 2−ヒドロキシアセタールおよび相当する2−ヒドロキシアルカナールの製造方法 | |
WO2012063791A1 (ja) | ピラゾリノン塩の製造方法 | |
JPH0584298B2 (ja) | ||
KR101142052B1 (ko) | 자나미비어의 제조방법 | |
JP2011190216A (ja) | (トリフルオロメチル)アルキルケトンの製造方法 | |
WO2007086559A1 (ja) | テトラヒドロピラン化合物の製造方法 | |
CZ281994A3 (en) | Process for preparing alkyl esters of high purity and yields from fluorobenzoic acid | |
JP2006315972A (ja) | 3−アミノイソオキサゾールの硫酸塩及びその製法 | |
JP2000053622A (ja) | 3―アミノ―2,2,3―トリメチルブタン酸エステルの製造方法 | |
JP2006257027A (ja) | トリフルオロアセトアルデヒドの水和物および/又はヘミアセタールの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120222 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130822 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130827 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131122 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20131217 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140417 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20140424 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140513 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140605 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5559066 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |