JP5802213B2 - 5−フッ素−1−アルキル−3−フルオロアルキル−1h−ピラゾール−4−カルボン酸クロライドの製造方法 - Google Patents
5−フッ素−1−アルキル−3−フルオロアルキル−1h−ピラゾール−4−カルボン酸クロライドの製造方法 Download PDFInfo
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- JP5802213B2 JP5802213B2 JP2012539308A JP2012539308A JP5802213B2 JP 5802213 B2 JP5802213 B2 JP 5802213B2 JP 2012539308 A JP2012539308 A JP 2012539308A JP 2012539308 A JP2012539308 A JP 2012539308A JP 5802213 B2 JP5802213 B2 JP 5802213B2
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- pyrazole
- alkyl
- fluoroalkyl
- carbaldehyde
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Finger-Pressure Massage (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Description
(c)最後の段階でこれらを、希釈剤(例えばトルエン)の存在下に、そしてジメチルホルムアミドの存在下に塩素化剤(例えばホスホリルクロライド)と反応させることで得ることができる。
塩素をフッ素に交換する工程(ハレックス工程)は、特に5−クロロ−1,3−ジアルキル−1H−ピラゾール−4−カルボニルクロライドに関して公知である(例えばWO2007/031212およびEP−A0776889参照)。そのアシルクロライドはアシルフルオリドに変換させ、結果的にフッ素化がさらに促進される。しかしながら、活性化基がアシルクロライドCOClではなく、そしてアシルフルオリドCOFではなくアルデヒドCHOである場合、フッ化カリウムとの反応では非常に低い収量しか得られない。例えば、5−フルオロ−1,3−ジメチル−1H−ピラゾール−4−カルボアルデヒドは、1,3−ジメチル−5−クロロピラゾール−4−カルボアルデヒドとフッ化カリウムとの反応によって、24%の収率でしか得られない(EP−A0776946参照)。その低収率についての一つの可能な理由は、ピラゾールアルデヒドの熱安定性が低いことにある(EP−A1364946参照)。5−クロロ−1−アルキル−3−フルオロアルキル−1H−ピラゾール−4−カルボアルデヒドの金属フッ化物によるフッ素化が奏功するか否かは予測できない。
原料として必要とされる式(IV)の5−フルオロ−1−アルキル−3−フルオロアルキル−1H−ピラゾール−4−カルボアルデヒド類のうちの一部は新規である(例えば、5−フルオロ−1−アルキル−3−トリフルオロメチル−1H−ピラゾール−4−カルボアルデヒドはWO−A2004/014138に記載されている)。
噴霧乾燥フッ化カリウム96.3g(1660mmol)を注意深く高真空下で乾燥させた。DMF(1リットル)中の5−クロロ−1−メチル−3−ジフルオロメチル−1H−ピラゾール−4−カルボアルデヒド(II−1)129.2g(664mmol)を加えた。反応混合物を高撹拌しながら加熱して150℃とした。反応は3時間後に完了する(GCチェック)。反応混合物を冷却して室温とし、水で増量して総体積を4リットルとする。反応混合物を酢酸エチル2000mLずつで2回洗浄する。次に、合わせた有機相を飽和塩化ナトリウム溶液で洗浄し、硫酸ナトリウムで脱水し、濃縮して、5−フルオロ−1−メチル−3−ジフルオロメチル−1H−ピラゾール−4−カルボアルデヒド(IV−1)117.6g(理論量の90%、純度90%)を褐色固体の形態で得て、それをそれ以上精製せずにさらに反応に供した。
Claims (4)
- 下記式(I)の5−フルオロ−1−アルキル−3−フルオロアルキル−1H−ピラゾール−4−カルボニルクロライド:
(R1はC1−C6−アルキルを表し、R2はC1−C5−フルオロアルキルを表す。)の製造方法であって、下記式(II)の5−クロロ−1−アルキル−3−フルオロアルキル−1H−ピラゾール−4−カルボアルデヒド:
(R1およびR2はそれぞれ上記で定義の通りである。)を最初に下記式(III)のフッ素化剤:
(M+はLi+、Na+、K+、Cs+ またはAlk4N+(AlkはC1−C4−アルキルを表す。)と、場合により相間移動触媒存在下において、反応させて(段階1)、下記式(IV)の5−フルオロ−1−アルキル−3−フルオロアルキル−1H−ピラゾール−4−カルボアルデヒド:
(R1およびR2はそれぞれ上記で定義の通りである。)を形成し、次に式(IV)の化合物を塩素化剤との反応(段階2)によって式(I)のアシルクロライドに変換することを特徴とする方法。 - 使用される前記5−クロロ−1−アルキル−3−フルオロアルキル−1H−ピラゾール−4−カルボアルデヒドが、R1がメチル、エチル、n−プロピル、イソプロピル、ブチルまたはペンチルを表し、R2がCF2H、CF3、CF2Cl、CCl2F、C2F5 またはC3F7を表す式(II)のものである請求項1に記載の方法。
- 使用される前記5−クロロ−1−アルキル−3−フルオロアルキル−1H−ピラゾール−4−カルボアルデヒドが、R1がメチルを表し、R2がCF2HまたはCF3を表す式(II)のものである請求項1に記載の方法。
- 5−クロロ−1−メチル−3−ジフルオロメチル−1H−ピラゾール−4−カルボアルデヒド(II−1)を用いる請求項1に記載の方法。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US26264109P | 2009-11-19 | 2009-11-19 | |
US61/262,641 | 2009-11-19 | ||
EP09176426A EP2325173A1 (de) | 2009-11-19 | 2009-11-19 | Verfahren zum Herstellen von 5-Fluor-1-alkyl-3-fluoralkyl-1H-pyrazol-4-carbonsäurechloriden |
EP09176426.6 | 2009-11-19 | ||
PCT/EP2010/067630 WO2011061205A1 (de) | 2009-11-19 | 2010-11-17 | Verfahren zum herstellen von 5-fluor-1-alkyl-3-fluoralkyl-1h-pyrazol-4-carbonsäurechloriden |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013511485A JP2013511485A (ja) | 2013-04-04 |
JP5802213B2 true JP5802213B2 (ja) | 2015-10-28 |
Family
ID=42077022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012539308A Active JP5802213B2 (ja) | 2009-11-19 | 2010-11-17 | 5−フッ素−1−アルキル−3−フルオロアルキル−1h−ピラゾール−4−カルボン酸クロライドの製造方法 |
Country Status (13)
Country | Link |
---|---|
US (2) | US8436191B2 (ja) |
EP (2) | EP2325173A1 (ja) |
JP (1) | JP5802213B2 (ja) |
KR (2) | KR101635046B1 (ja) |
CN (1) | CN102666492B (ja) |
BR (1) | BR112012011961B1 (ja) |
DK (1) | DK2501682T3 (ja) |
ES (1) | ES2600864T3 (ja) |
IL (1) | IL219682A (ja) |
IN (1) | IN2012DN04414A (ja) |
MX (2) | MX2012005676A (ja) |
TW (1) | TWI510473B (ja) |
WO (1) | WO2011061205A1 (ja) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR076839A1 (es) * | 2009-05-15 | 2011-07-13 | Bayer Cropscience Ag | Derivados fungicidas de pirazol carboxamidas |
EP2325173A1 (de) | 2009-11-19 | 2011-05-25 | Bayer CropScience AG | Verfahren zum Herstellen von 5-Fluor-1-alkyl-3-fluoralkyl-1H-pyrazol-4-carbonsäurechloriden |
JP5819938B2 (ja) | 2010-04-23 | 2015-11-24 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Intellectual Property GmbH | 5−フルオロ−1−アルキル−3−フルオロアルキル−1h−ピラゾール−4−カルボニルクロリドおよびフルオリドの調製方法 |
MX348274B (es) | 2012-05-14 | 2017-06-02 | Bayer Cropscience Ag | Procedimiento de preparacion de cloruros de 1-alquil-3-fluoroalqui l-1h-pirazol-4-carbonilo. |
ES2628332T3 (es) | 2012-08-07 | 2017-08-02 | Bayer Cropscience Ag | Procedimiento de preparación de pirazoles carboxilatos que contienen perfluoroalquilos |
CN104918916A (zh) * | 2013-01-17 | 2015-09-16 | 拜尔农作物科学股份公司 | 5-氟-1-甲基-3-二氟甲基-1h-吡唑-4-甲醛的制备方法 |
US9951023B2 (en) | 2013-09-20 | 2018-04-24 | Bayer Cropscience Aktiengesellschaft | Process for preparing 5-fluoro-1-alkyl-3-fluoroalkyl-1H-pyrazole-4-carbaldehyde |
US9656966B2 (en) | 2014-01-24 | 2017-05-23 | Bayer Cropscience Aktiengesellschaft | Method for preparing 1-alkyl-3-difluoromethyl-5-fluor-1H-pyrazole-4-carbaldehydes and 1-alkyl-3-difluoromethyl-5-fluor-1H-pyrazole-4-carboxylates |
EP3015458A1 (en) * | 2014-11-03 | 2016-05-04 | Bayer CropScience AG | Process for preparing 3,5-bis(haloalkyl)pyrazole derivatives from a,a-dihaloamines and ketimines |
TWI651306B (zh) | 2014-03-24 | 2019-02-21 | 德商拜耳作物科學股份有限公司 | 自α,α-二鹵胺類與酮亞胺類製備3,5-雙(鹵烷基)吡唑衍生物之方法 |
TWI705055B (zh) | 2015-04-29 | 2020-09-21 | 德商拜耳作物科學公司 | 製備5-氟-1h-吡唑-4-羰基氟化物之方法 |
WO2020093715A1 (en) | 2018-11-07 | 2020-05-14 | Fujian Yongjing Technology Co., Ltd | New process for manufacture of pyrazoles or pyrimidones |
EP4052576A4 (en) | 2019-10-29 | 2023-10-11 | Shenyang Sinochem Agrochemicals R & D Co., Ltd. | AMIDE COMPOUND CONTAINING FRAGMENT OF SUBSTITUTED ACETOPHENONE STRUCTURE, PREPARATION METHOD THEREFOR AND USE THEREOF |
WO2022233129A1 (en) | 2021-05-05 | 2022-11-10 | Fujian Yongjing Technology Co., Ltd | New process for the synthesis of 5-fluoro-3- (difuoromethyl) -5-fluoro-1-methyl-1h-pyrazole-4-carboxylic acid derivatives and the free acid thereof |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5223526A (en) * | 1991-12-06 | 1993-06-29 | Monsanto Company | Pyrazole carboxanilide fungicides and use |
DE19544800A1 (de) | 1995-12-01 | 1997-06-05 | Bayer Ag | Verfahren zur Herstellung von 1,3-Dimethyl-5-fluor-pyrazol-4-carboxaniliden |
JP4465133B2 (ja) * | 2001-02-08 | 2010-05-19 | クミアイ化学工業株式会社 | イソオキサゾリン誘導体及びこれを有効成分とする除草剤 |
WO2003000686A1 (fr) * | 2001-06-21 | 2003-01-03 | Kumiai Chemical Industry Co., Ltd. | Dérivés d'isoxazoline et herbicides |
UA78071C2 (en) | 2002-08-07 | 2007-02-15 | Kumiai Chemical Industry Co | Herbicidal composition |
RU2346996C2 (ru) | 2004-06-29 | 2009-02-20 | ЮРОПИЭН НИКЕЛЬ ПиЭлСи | Усовершенствованное выщелачивание основных металлов |
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. |
BRPI0611707A2 (pt) | 2005-06-29 | 2012-04-24 | Compumedics Ltd | conjunto de sensor com ponte condutiva |
DE102005044451A1 (de) | 2005-09-17 | 2007-03-22 | Bayer Cropscience Gmbh | Verfahren zum Herstellen von 5-Fluor-1,3-dialkyl-1H-pyrazol-4-carbonsäurefluoriden |
EP1767353B1 (en) * | 2005-09-27 | 2011-04-20 | FUJIFILM Corporation | Lithographic printing method |
AR056882A1 (es) | 2006-02-01 | 2007-10-31 | Bayer Cropscience Sa | Derivados del fungicida n- cicloalquil- bencil- amida |
DE102007002674A1 (de) * | 2007-01-18 | 2008-07-24 | Bayer Cropscience Ag | Verfahren zum Herstellen von substituierten Pyrazolcarbonsäurechloriden |
EP2325173A1 (de) | 2009-11-19 | 2011-05-25 | Bayer CropScience AG | Verfahren zum Herstellen von 5-Fluor-1-alkyl-3-fluoralkyl-1H-pyrazol-4-carbonsäurechloriden |
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2009
- 2009-11-19 EP EP09176426A patent/EP2325173A1/de not_active Ceased
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2010
- 2010-11-17 IN IN4414DEN2012 patent/IN2012DN04414A/en unknown
- 2010-11-17 EP EP10782247.0A patent/EP2501682B1/de active Active
- 2010-11-17 JP JP2012539308A patent/JP5802213B2/ja active Active
- 2010-11-17 BR BR112012011961A patent/BR112012011961B1/pt active IP Right Grant
- 2010-11-17 MX MX2012005676A patent/MX2012005676A/es active IP Right Grant
- 2010-11-17 KR KR1020127015772A patent/KR101635046B1/ko active IP Right Grant
- 2010-11-17 MX MX2013009578A patent/MX344246B/es unknown
- 2010-11-17 WO PCT/EP2010/067630 patent/WO2011061205A1/de active Application Filing
- 2010-11-17 CN CN201080052388.XA patent/CN102666492B/zh active Active
- 2010-11-17 ES ES10782247.0T patent/ES2600864T3/es active Active
- 2010-11-17 DK DK10782247.0T patent/DK2501682T3/en active
- 2010-11-17 KR KR1020167011442A patent/KR101749561B1/ko active IP Right Grant
- 2010-11-18 TW TW099139630A patent/TWI510473B/zh active
- 2010-11-19 US US12/950,849 patent/US8436191B2/en active Active
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2012
- 2012-05-09 IL IL219682A patent/IL219682A/en active IP Right Grant
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- 2013-02-19 US US13/770,720 patent/US8765971B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
IN2012DN04414A (ja) | 2015-08-07 |
BR112012011961A2 (pt) | 2015-09-08 |
KR20120084325A (ko) | 2012-07-27 |
ES2600864T3 (es) | 2017-02-13 |
TW201127817A (en) | 2011-08-16 |
JP2013511485A (ja) | 2013-04-04 |
TWI510473B (zh) | 2015-12-01 |
KR101749561B1 (ko) | 2017-06-21 |
MX344246B (es) | 2016-12-07 |
MX2012005676A (es) | 2012-06-19 |
WO2011061205A1 (de) | 2011-05-26 |
EP2501682B1 (de) | 2016-08-03 |
IL219682A0 (en) | 2012-07-31 |
BR112012011961B1 (pt) | 2018-05-08 |
US20130165664A1 (en) | 2013-06-27 |
CN102666492B (zh) | 2016-03-23 |
US8765971B2 (en) | 2014-07-01 |
IL219682A (en) | 2016-08-31 |
KR20160054041A (ko) | 2016-05-13 |
US20110207940A1 (en) | 2011-08-25 |
CN102666492A (zh) | 2012-09-12 |
EP2501682A1 (de) | 2012-09-26 |
EP2325173A1 (de) | 2011-05-25 |
US8436191B2 (en) | 2013-05-07 |
KR101635046B1 (ko) | 2016-07-01 |
DK2501682T3 (en) | 2016-11-14 |
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