ES2540211T3 - Proceso para preparar una amida de un ácido carboxílico pirazólico - Google Patents
Proceso para preparar una amida de un ácido carboxílico pirazólico Download PDFInfo
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- ES2540211T3 ES2540211T3 ES12700859.7T ES12700859T ES2540211T3 ES 2540211 T3 ES2540211 T3 ES 2540211T3 ES 12700859 T ES12700859 T ES 12700859T ES 2540211 T3 ES2540211 T3 ES 2540211T3
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/56—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by doubly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/02—Monothiocarbonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/02—Monothiocarbonic acids; Derivatives thereof
- C07C329/04—Esters of monothiocarbonic acids
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Communicable Diseases (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Oncology (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
Un proceso para preparar el compuesto de formula I**Fórmula** comprendiendo el proceso acilar el oxígeno de la oxima del compuesto de fórmula VIII**Fórmula** en presencia de un disolvente y un agente acilante de fórmula XI R1-C(X)-Cl (XI), donde X es oxígeno o azufre; R1 es cloro si X es oxígeno o azufre; o R1 es alcoxi C1-C6, CH3-C(>=CH2)-O-, fenoxi o triclorometoxi si X es oxígeno; y a) si R1 es cloro y el compuesto de fórmula XI se añadió al compuesto de fórmula VIII; hacer reaccionar el producto obtenido de este modo de fórmula XIIa**Fórmula** donde X es oxígeno o azufre; con el compuesto de fórmula IX**Fórmula** b) si R1 es cloro y el compuesto de fórmula VIII se añadió al compuesto de fórmula XI; o R1 es alxoxi C1-C6, CH3- C(>=CH2)-O-, fenoxi o triclorometoxi si X es oxígeno; hacer reaccionar el producto obtenido de este modo de fórmula XII**Fórmula** donde X es oxígeno o azufre; R1 es cloro si X es oxígeno o azufre; o R1 es alcoxi C1-C6, CH3-C(>=CH2)-O-, fenoxi o triclorometoxi si X es oxígeno; con el compuesto de fórmula IX**Fórmula**
Description
5
10
15
20
25
30
35
40
E12700859
22-06-2015
reacción se repartió entre acetato de etilo (500 ml) y agua (500 ml). La fase orgánica se separó, se lavó dos veces con agua (500 ml) y se evaporó. El residuo cristalino remanente se secó al vacío. Rendimiento 25.6 g (99%).
1H RMN (DMSO-d6, 400 MHz) δ (isómero mayoritario) 1.17 (m, 1H), 1.32 (m, 1H), 1.67 (m, 2H), 1.77 – 1.92 (m, 2H),
Ejemplo P6: Preparación del compuesto de fórmula XIIb: Cl
Una mezcla del compuesto de fórmula VIII (104.2 g, 0.40 mol) y trietilamina (44.7 g, 0.44 mol) en tolueno (400 g) se trató con una solución de cloroformiato de etilo (53.2 g, 0.49 mol) en tolueno (200 g) a 25 °C durante 60 min y se agitó a 25 °C durante 50 min más. La mezcla de reacción se trató con agua (150 g). La fase orgánica se separó, se lavó con agua (50 g) y salmuera (30 g) y se evaporó a sequedad. El aceite amarillo remanente se disolvió en etanol caliente (700 g) y se enfrió lentamente hasta 5 °C. El precipitado resultante se separó por filtración, se lavó con etanol frío y se secó al vacío. Rendimiento 90.1 g (68%, 99+% de pureza, que se determinó mediante análisis cuantitativos de 1H RMN y LC).
Las aguas madres se evaporaron para obtener 43 g de material, que se cristalizó nuevamente en etanol caliente (150 g). El precipitado se separó por filtración, se lavó con etanol frío y se secó al vacío para obtener 25.7 g adicionales (19%, 99+% de pureza, que se determinó mediante análisis cuantitativos de 1H RMN y LC) del producto deseado XIIb.
P. f. 110 °C.
1H RMN (CDCl3, 400 MHz) δ (isómero mayoritario) 1.24 – 1.38 (m, 2H), 1.36 (t, J = 7.0 Hz, 3H), 1.77 – 1.85 (m, 2H),
1.87 – 2.01 (m, 2H), 2.24 (td, J = 6.8 y 18.4 Hz, 1H), 2.35 – 2.51 (m, 2H), 2.75 (td, J = 5.8 y 17.2 Hz, 1H), 3.41 (dd, J = 0.8 y 3.3 Hz, 1H), 3.98 (d, J = 3.0 Hz, 1H), 4.31 (c, J = 7.1 Hz, 2H).
13C RMN (CDCl3, 100 MHz) δ (isómero mayoritario) 14.29, 21.01, 23.46, 23.67, 25.89, 26.08, 43.39, 49.29, 64.52, 101.49, 134.21, 149.42, 153.94, 156.89, 157.45.
Ejemplo P7: Preparación del compuesto de fórmula XIIc: imagen9
Una mezcla del compuesto de fórmula VIII (10.43 g, 0.040 mol) y trietilamina (4.47 g, 0.044 mol) en tolueno (50 g) se trató con una solución de cloroformiato de metilo (4.20 g, 0.044 mol) en tolueno (10 g) a 25 °C durante 60 min y se agitó a 25 °C durante 90 min más. La mezcla de reacción se trató con agua (60 g). La fase orgánica se separó y la fase acuosa se extrajo con tolueno (30 g). Las fases orgánicas combinadas se lavaron con agua (50 g) y se evaporaron. El sólido amarillo remanente se secó al vacío. Rendimiento 5.80 g (41%, aproximadamente un 90% de pureza, que se determinó mediante análisis de LC).
El material crudo (5.50 g) se recristalizó en metanol caliente (90 g) con fines analíticos. El precipitado se separó por filtración, se lavó dos veces con metanol frío y se secó al vacío. Rendimiento 4.70 g (95%, 99+% de pureza, que se determinó mediante análisis cuantitativos de 1H RMN y LC).
P. f. 159 °C.
1H RMN (CDCl3, 400 MHz) δ (isómero mayoritario) 1.23 – 1.37 (m, 2H), 1.77 – 1.85 (m, 2H), 1.86 – 2.01 (m, 2H),
- 2.24
- (td, J = 6.8 y 18.4 Hz, 1H), 2.37 – 2.50 (m, 2H), 2.75 (td, J = 5.8 y 17.2 Hz, 1H), 3.42 (dd, J = 1.3 y 3.3 Hz, 1H),
- 3.88
- (s, 3H), 3.98 (d, J = 3.0 Hz, 1H).
13C RMN (CDCl3, 100 MHz) δ (isómero mayoritario) 21.01, 23.46, 23.64, 25.89, 26.10, 43.39, 49.31, 55.15, 101.56, 134.16, 149.40, 154.54, 157.08, 157.61.
Ejemplo P8: Preparación del compuesto de fórmula XIId:
9
Claims (1)
-
imagen1 imagen2 imagen3
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11151965 | 2011-01-25 | ||
| EP11151965 | 2011-01-25 | ||
| PCT/EP2012/051075 WO2012101139A1 (en) | 2011-01-25 | 2012-01-25 | Process for the preparation of pyrazole carboxylic acid amide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2540211T3 true ES2540211T3 (es) | 2015-07-09 |
Family
ID=45524566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES12700859.7T Active ES2540211T3 (es) | 2011-01-25 | 2012-01-25 | Proceso para preparar una amida de un ácido carboxílico pirazólico |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US8895757B2 (es) |
| EP (1) | EP2668166B1 (es) |
| JP (2) | JP6133788B2 (es) |
| KR (1) | KR101851781B1 (es) |
| CN (1) | CN103339113B (es) |
| AR (1) | AR084915A1 (es) |
| AU (1) | AU2012210547B2 (es) |
| BR (1) | BR112013018533A2 (es) |
| CA (1) | CA2824730C (es) |
| CO (1) | CO6751253A2 (es) |
| ES (1) | ES2540211T3 (es) |
| HR (1) | HRP20150658T1 (es) |
| IL (1) | IL227317A (es) |
| MX (1) | MX352697B (es) |
| PL (1) | PL2668166T3 (es) |
| PT (1) | PT2668166E (es) |
| TW (1) | TWI534126B (es) |
| UY (1) | UY33879A (es) |
| WO (1) | WO2012101139A1 (es) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI534126B (zh) * | 2011-01-25 | 2016-05-21 | 先正達合夥公司 | 用於製備吡唑羧酸醯胺之方法 |
| TWI510472B (zh) | 2012-02-15 | 2015-12-01 | Syngenta Participations Ag | 立體選擇性製備吡唑羧醯胺之方法 |
| EP3575030B1 (en) | 2017-03-31 | 2024-01-03 | NSK Ltd. | Laser welding device, laser processing device, laser welding method, bearing manufacturing method, machine manufacturing method, vehicle manufacturing method, bearing, machine, and vehicle |
| AU2023309261A1 (en) | 2022-07-22 | 2024-12-12 | Syngenta Crop Protection Ag | Solid form of a heterocyclic amide derivative |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58194853A (ja) * | 1982-05-11 | 1983-11-12 | Showa Denko Kk | シクロヘキセン−アセチルオキシム誘導体 |
| US5093347A (en) | 1991-01-28 | 1992-03-03 | Monsanto Company | 3-difluoromethylpyrazolecarboxamide fungicides, compositions and use |
| AU2006308128B2 (en) * | 2005-10-25 | 2011-07-28 | Syngenta Crop Protection Ag | Heterocyclic amide derivatives useful as microbiocides |
| US8227619B2 (en) | 2008-05-14 | 2012-07-24 | Syngenta Limited | Process for the preparation of amides |
| WO2010072631A1 (en) * | 2008-12-24 | 2010-07-01 | Syngenta Limited | Methods for the preparation of fungicides |
| AU2010280923B2 (en) | 2009-08-06 | 2014-08-07 | Syngenta Crop Protection Ag | Process for the preparation of pyrazole carboxylic acid amides |
| CN102906072B (zh) | 2010-04-20 | 2014-07-02 | 先正达参股股份有限公司 | 吡唑羧酸酰胺的制备方法 |
| WO2011131546A1 (en) | 2010-04-20 | 2011-10-27 | Syngenta Participations Ag | Process for the preparation of pyrazole carboxylic acid amides |
| JP6153864B2 (ja) | 2010-04-20 | 2017-06-28 | シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト | ピラゾールカルボン酸アミドの調製方法 |
| TWI534126B (zh) * | 2011-01-25 | 2016-05-21 | 先正達合夥公司 | 用於製備吡唑羧酸醯胺之方法 |
-
2012
- 2012-01-20 TW TW101102374A patent/TWI534126B/zh active
- 2012-01-23 AR ARP120100211A patent/AR084915A1/es active IP Right Grant
- 2012-01-25 WO PCT/EP2012/051075 patent/WO2012101139A1/en not_active Ceased
- 2012-01-25 AU AU2012210547A patent/AU2012210547B2/en active Active
- 2012-01-25 CA CA2824730A patent/CA2824730C/en active Active
- 2012-01-25 UY UY0001033879A patent/UY33879A/es active IP Right Grant
- 2012-01-25 KR KR1020137022399A patent/KR101851781B1/ko active Active
- 2012-01-25 CN CN201280006384.7A patent/CN103339113B/zh active Active
- 2012-01-25 JP JP2013549849A patent/JP6133788B2/ja active Active
- 2012-01-25 MX MX2013007914A patent/MX352697B/es active IP Right Grant
- 2012-01-25 ES ES12700859.7T patent/ES2540211T3/es active Active
- 2012-01-25 HR HRP20150658TT patent/HRP20150658T1/hr unknown
- 2012-01-25 EP EP12700859.7A patent/EP2668166B1/en active Active
- 2012-01-25 US US13/981,913 patent/US8895757B2/en active Active
- 2012-01-25 BR BR112013018533A patent/BR112013018533A2/pt active IP Right Grant
- 2012-01-25 PT PT127008597T patent/PT2668166E/pt unknown
- 2012-01-25 PL PL12700859T patent/PL2668166T3/pl unknown
-
2013
- 2013-07-04 IL IL227317A patent/IL227317A/en active IP Right Grant
- 2013-07-23 CO CO13173578A patent/CO6751253A2/es unknown
-
2016
- 2016-11-07 JP JP2016217091A patent/JP6419131B2/ja active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US8895757B2 (en) | 2014-11-25 |
| AU2012210547A1 (en) | 2013-08-01 |
| HRP20150658T1 (hr) | 2015-07-31 |
| CA2824730C (en) | 2018-10-23 |
| TW201245114A (en) | 2012-11-16 |
| US20130310592A1 (en) | 2013-11-21 |
| MX2013007914A (es) | 2013-08-29 |
| PT2668166E (pt) | 2015-08-27 |
| UY33879A (es) | 2012-08-31 |
| EP2668166A1 (en) | 2013-12-04 |
| MX352697B (es) | 2017-12-05 |
| BR112013018533A2 (pt) | 2016-07-12 |
| CO6751253A2 (es) | 2013-09-16 |
| JP6133788B2 (ja) | 2017-05-24 |
| IL227317A (en) | 2014-11-30 |
| WO2012101139A1 (en) | 2012-08-02 |
| CN103339113A (zh) | 2013-10-02 |
| CA2824730A1 (en) | 2012-08-02 |
| TWI534126B (zh) | 2016-05-21 |
| KR101851781B1 (ko) | 2018-04-24 |
| EP2668166B1 (en) | 2015-05-13 |
| AU2012210547B2 (en) | 2016-04-14 |
| JP6419131B2 (ja) | 2018-11-07 |
| JP2017071614A (ja) | 2017-04-13 |
| IL227317A0 (en) | 2013-09-30 |
| PL2668166T3 (pl) | 2015-09-30 |
| KR20140019333A (ko) | 2014-02-14 |
| CN103339113B (zh) | 2015-07-22 |
| AR084915A1 (es) | 2013-07-10 |
| JP2014504596A (ja) | 2014-02-24 |
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