JP5763179B2 - 1−アルキル−3−ジフルオロメチル−5−ヒドロキシピラゾール類の製造方法 - Google Patents
1−アルキル−3−ジフルオロメチル−5−ヒドロキシピラゾール類の製造方法 Download PDFInfo
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- JP5763179B2 JP5763179B2 JP2013510575A JP2013510575A JP5763179B2 JP 5763179 B2 JP5763179 B2 JP 5763179B2 JP 2013510575 A JP2013510575 A JP 2013510575A JP 2013510575 A JP2013510575 A JP 2013510575A JP 5763179 B2 JP5763179 B2 JP 5763179B2
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- alkyl
- formula
- represented
- difluoroacetoacetate
- iii
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- 238000000034 method Methods 0.000 title claims description 14
- -1 alkyl difluoroacetoacetate Chemical compound 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 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
- CBDPWKVOPADMJC-UHFFFAOYSA-N ethyl 4,4-difluoro-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)C(F)F CBDPWKVOPADMJC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001983 dialkylethers Chemical class 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 claims 1
- OHTZSGZMMOMLKA-UHFFFAOYSA-N methyl 4,4-difluoro-3-oxobutanoate Chemical compound COC(=O)CC(=O)C(F)F OHTZSGZMMOMLKA-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- VEIPKLIIXBPVCG-UHFFFAOYSA-N 5-(difluoromethyl)-2-methyl-1h-pyrazol-3-one Chemical compound CN1NC(C(F)F)=CC1=O VEIPKLIIXBPVCG-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RVNUTJVNGHHOLG-UHFFFAOYSA-N 3-(difluoromethyl)-2-methyl-1,3-dihydropyrazol-5-ol Chemical class CN1NC(O)=CC1C(F)F RVNUTJVNGHHOLG-UHFFFAOYSA-N 0.000 description 1
- HQZSNVHMLLTTRA-UHFFFAOYSA-N 4,4-difluoro-3-oxobutanoic acid Chemical compound OC(=O)CC(=O)C(F)F HQZSNVHMLLTTRA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
式(III)
NH2−NH−R1 (III)
で表されるアルキルヒドラジンと、有機酸および溶媒の存在下で反応させることによって得られることが判明した。
R1ラジカルは、1から5個の炭素原子を有する直鎖又は分岐アルキル基であり、好ましくはメチル及びエチルである。
生成物の収率は、一般的に、90−95%であり、位置選択性は100%である。
実施例
製造実施例
実施例1:1−メチル−3−ジフルオロメチル−5−ヒドロキシ−1H−ピラゾール
実施例2:1−メチル−3−ジフルオロメチル−5−ヒドロキシ−1H−ピラゾール
初めにエチルジフルオロアセトアセテート(166g(1mol))をメチルtert−ブチルエーテル(500ml)に導入し、酢酸(60g)を加えた。当該混合物を5℃に冷却した後、メチルヒドラジン(119g)(40%水溶液)を加えた。当該混合物を22℃でさらに20時間攪拌した。相を分離をして、有機相を水(200ml)で洗浄し、MgSO4で乾燥した。減圧下で溶媒を除去した後、生成物(140g)を黄色固体(融点:133℃、純度:96%)として得た。収率は91%であった。
実施例3.WO2007/013536による反応
初めにエチルジフルオロアセトアセテート(166g(1mol))を酢酸(400ml)に導入した。当該混合物を5℃に冷却した後、メチルヒドラジン(119g)(40%水溶液)を加えた。当該混合物を22℃でさらに20時間攪拌した。LC−MSは、55面積%の生成物、15面積%の2−メチル−3−ジフルオロメチル−5−ヒドロキシ−1H−ピラゾール異性体、及び30面積%の多くの副生成物を示した。
Claims (6)
- 式(I)
(ここで、R1は、直鎖又は分岐C1〜C6−アルキル基である)で表される1−アルキル−3−ジフルオロメチル−5−ヒドロキシピラゾールの製造方法であって、式(II)
(ここで、R2は、直鎖又は分岐C1〜C6−アルキル基である)で表されるアルキルジフルオロアセトアセテートと、
式(III)
NH2−NH−R1 (III)
で表されるアルキルヒドラジンとの、ギ酸及び酢酸から選択される有機酸及びジアルキルエーテル、テトラヒドロフラン、ジオキサン、ジクロロメタン、ジクロロエタン、トリクロロエタン、アセトニトリル、プロピオニトリル、n−若しくはi−ブチロニトリル、メチルtert−ブチルエーテル、トルエン及びクロロベンゼンから選択される溶媒存在下における反応を含む、製造方法。 - 式(II)で表されるアルキルジフルオロアセトアセテートが、メチルジフルオロアセトアセテート及びエチルジフルオロアセトアセテートから選択される、請求項1に記載の方法。
- 式(III)で表されるアルキルヒドラジンが、メチルヒドラジン及びエチルヒドラジンから選択される、請求項1又は2に記載の方法。
- 式(II)で表されるアルキルジフルオロアセトアセテート1モルあたり、0.8から1.8モルの間の式(III)で表されるアルキルヒドラジンおよび0.1から1.2モルの間の有機酸が使用される、請求項1から3のいずれかに記載の方法。
- 溶媒が、テトラヒドロフラン、メチルtert−ブチルエーテル、トルエン及びクロロベンゼンから選択される、請求項1から4のいずれかに記載の方法。
- 溶媒が、メチルtert−ブチルエーテルである、請求項1から4のいずれかに記載の方法。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10163420.2 | 2010-05-20 | ||
EP10163420 | 2010-05-20 | ||
US34836110P | 2010-05-26 | 2010-05-26 | |
US61/348,361 | 2010-05-26 | ||
PCT/EP2011/057828 WO2011144549A1 (en) | 2010-05-20 | 2011-05-16 | Method for manufacturing 1 - alkyl - 3 - difluormethyl - 5 - hydroxypyrazoles |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013530945A JP2013530945A (ja) | 2013-08-01 |
JP5763179B2 true JP5763179B2 (ja) | 2015-08-12 |
Family
ID=42290055
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013510575A Active JP5763179B2 (ja) | 2010-05-20 | 2011-05-16 | 1−アルキル−3−ジフルオロメチル−5−ヒドロキシピラゾール類の製造方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US8455664B2 (ja) |
EP (1) | EP2571854B1 (ja) |
JP (1) | JP5763179B2 (ja) |
KR (2) | KR20170102581A (ja) |
CN (1) | CN102906073B (ja) |
BR (1) | BR112012029363B1 (ja) |
DK (1) | DK2571854T3 (ja) |
ES (1) | ES2528646T3 (ja) |
IL (1) | IL222531A (ja) |
MX (1) | MX2012013388A (ja) |
TW (1) | TWI535703B (ja) |
WO (1) | WO2011144549A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101901556B1 (ko) * | 2015-11-16 | 2018-09-21 | 론자 리미티드 | 1-메틸-3-(트리플루오로메틸)-1h-피라졸-5-올을 제조하는 방법 |
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 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0113524D0 (en) * | 2001-06-04 | 2001-07-25 | Hoffmann La Roche | Pyrazole derivatives |
TW200409758A (en) * | 2002-08-01 | 2004-06-16 | Ihara Chemical Ind Co | Pyrazole derivatives and process for production thereof |
UA78071C2 (en) | 2002-08-07 | 2007-02-15 | Kumiai Chemical Industry Co | Herbicidal composition |
JP4621939B2 (ja) * | 2004-03-31 | 2011-02-02 | イハラケミカル工業株式会社 | 5−ヒドロキシ−4−チオメチルピラゾール化合物の製造方法 |
MX2007001527A (es) * | 2004-08-18 | 2007-03-27 | Pfizer | Inhibidores de la arn polimerasa dependiente de arn del virus de la hepatitis c y composiciones y tratamientos que los usan. |
JP2007031342A (ja) | 2005-07-27 | 2007-02-08 | Ihara Chem Ind Co Ltd | 5−ヒドロキシ−1−アルキルピラゾール誘導体の製造方法 |
US20100016396A1 (en) * | 2007-01-29 | 2010-01-21 | Hiroshi Imoto | Pyrazole compound |
-
2011
- 2011-05-16 JP JP2013510575A patent/JP5763179B2/ja active Active
- 2011-05-16 KR KR1020177024428A patent/KR20170102581A/ko not_active Application Discontinuation
- 2011-05-16 BR BR112012029363-0A patent/BR112012029363B1/pt active IP Right Grant
- 2011-05-16 MX MX2012013388A patent/MX2012013388A/es active IP Right Grant
- 2011-05-16 EP EP11719279.9A patent/EP2571854B1/en active Active
- 2011-05-16 ES ES11719279.9T patent/ES2528646T3/es active Active
- 2011-05-16 KR KR1020127032615A patent/KR102011648B1/ko active IP Right Grant
- 2011-05-16 WO PCT/EP2011/057828 patent/WO2011144549A1/en active Application Filing
- 2011-05-16 CN CN201180025028.5A patent/CN102906073B/zh active Active
- 2011-05-16 DK DK11719279.9T patent/DK2571854T3/en active
- 2011-05-19 TW TW100117507A patent/TWI535703B/zh active
- 2011-05-19 US US13/111,582 patent/US8455664B2/en active Active
-
2012
- 2012-10-18 IL IL222531A patent/IL222531A/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
KR102011648B1 (ko) | 2019-08-19 |
BR112012029363A2 (pt) | 2015-10-13 |
US20110288304A1 (en) | 2011-11-24 |
CN102906073A (zh) | 2013-01-30 |
BR112012029363B1 (pt) | 2018-04-17 |
TWI535703B (zh) | 2016-06-01 |
MX2012013388A (es) | 2012-12-10 |
EP2571854B1 (en) | 2014-11-05 |
US8455664B2 (en) | 2013-06-04 |
WO2011144549A1 (en) | 2011-11-24 |
TW201209039A (en) | 2012-03-01 |
KR20130109965A (ko) | 2013-10-08 |
DK2571854T3 (en) | 2015-02-09 |
EP2571854A1 (en) | 2013-03-27 |
KR20170102581A (ko) | 2017-09-11 |
IL222531A (en) | 2014-05-28 |
ES2528646T3 (es) | 2015-02-11 |
CN102906073B (zh) | 2015-11-25 |
JP2013530945A (ja) | 2013-08-01 |
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