WO2021033172A1 - Procédé de préparation de chlorantraniliprole - Google Patents

Procédé de préparation de chlorantraniliprole Download PDF

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Publication number
WO2021033172A1
WO2021033172A1 PCT/IB2020/059172 IB2020059172W WO2021033172A1 WO 2021033172 A1 WO2021033172 A1 WO 2021033172A1 IB 2020059172 W IB2020059172 W IB 2020059172W WO 2021033172 A1 WO2021033172 A1 WO 2021033172A1
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WO
WIPO (PCT)
Prior art keywords
reaction mixture
acid
chlorantraniliprole
amino
methyl
Prior art date
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PCT/IB2020/059172
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English (en)
Inventor
Ashwin V
Ashok Kumar Pradhan
Sanjay Sambhajirao PALIMKAR
Avinash Sheshrao MANE
Syam Kumar Unniaran KUNHIMON
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Eurofins Advinus Limited
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Publication of WO2021033172A1 publication Critical patent/WO2021033172A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a field of agricultural pesticides, and more specifically to Insecticides acting on an insect ryanodine receptor.
  • Anthranilic diamide are new important class of insecticides. This class of insecticides is highly potent, selective, less toxic, and safe. These insecticides work through an action on a novel target, a ryanodine receptor. Chlorantraniliprole, an anthranilic diamide, developed and commercialized worldwide by DuPont has excellent control over lepidopteran pests, low mammalian toxicity and a favorable environmental profile. A pesticide is applicable for a broad range of crops to control a wide range of pests belonging to Lepidoptera, Coleoptera, Diptera and Isoptera species. Few of its derivatives, example Cyantraniliprole (2) is also highly effective against insects.
  • Chlorantraniliprole The reported routes for preparation of Chlorantraniliprole include a patent application WO/2003/015519 filed by DuPont claiming Chlorantraniliprole as a product. This patent application describes its preparation using two of its advanced intermediates in two steps.
  • Chlorantraniliprole can be prepared by reacting 3-bromo-l-(3-chloropyridin-2-yl)-lH- pyrazole-5 -carboxylic acid (3) with 2-amino-5-chloro-N, 3- dimethylbenzamide (8) using methane sulfonyl chloride as a reagent for amide coupling in the presence of pyridine and/or substituted pyridine such as 2-picoline, 3-picoline, 2,6-lutidine as bases in acetonitrile as a solvent (Scheme 3).
  • Agrochemicals in the year 2012 discloses preparation of Chlorantraniliprole Scheme 4 by reacting 3-bromo-l-(3-chloropyridin- 2-yl)-4,5-dihydro-lH-pyrazole-5-carboxylic acid (9) with 2-amino-5- chloro-N, 3-dimethylbenzamide (8) with simultaneous acyl halide formation and oxidation of dihydro pyrazole ring using thionyl chloride followed by reaction with anthranilamide (8) to get Chlorantraniliprole.
  • Another patent US8871939 (B2) granted to DuPont discloses a method of preparation of one of the advanced intermediate anthranilamide 2- amino-5-chloro-N, 3-dimethylbenzamide (8) by carbonylative amidation of substituted halo anilines (10) using palladium catalyst for example palladium (II) acetate and ligand 1,4- bis(diphenylphosphino)butane (dppb) Scheme 5.
  • the disclosed method for the synthesis is cumbersome and requires use of certain toxic gases and expensive catalyst.
  • US8153844 (B2) granted to FMC Corp. discloses a method of preparation one of the advanced intermediate anthranilamide for example 2-amino-5-chloro-N, 3-dimethylbenzamide (8) by converting carbamate derivatives of anthranilic acid (12) using phosphorus tribromide into isatoic anhydride (7) and thereafter ring opening by alkyl amine for example, methyl amine Scheme 6.
  • Phosphorus Tribromide is a corrosive chemical and its contact can severely irritate and bum the skin and eyes with possible eye damage. When heated to decomposition, it emits toxic fumes of hydrogen bromide and phosphorous oxides.
  • Ethyl chloroformate used in this reaction is highly toxic and is a strong eye and skin irritant.
  • Chlorantraniliprole is specific in its action, has low toxicity for other living beings, excellent environmental safety profile, high efficacy, and unique mode of action, therefore, an increasing global demand of Chlorantraniliprole has been observed over the years.
  • QY Research titled “Global Chlorantraniliprole Sales Market Report 2018”
  • the global chlorantraniliprole market is expected to expand at a moderate CAGR of 4.4% during the seven-year forecast period 2018-2025.
  • the market is expected to attain a valuation of US$ 2,120 Mn. In 2017, it was valued at a US$ 1,500 Mn.
  • the primary object of the invention is to develop an efficient, telescopic, and environment friendly process for the preparation of chlorantraniliprole and its intermediates.
  • Another object of the invention is to disclose efficient/novel schemes for the in-situ production of a key raw material and key starting material essentially used for the production of chlorantraniliprole.
  • Another object of the invention is to disclose use of novel intermediate compounds to achieve production process efficiency.
  • It is therefore a further object of the present invention is to develop a process that uses ecofriendly reagents having low toxicity for the production of chlorantraniliprole.
  • Yet another object of the invention is to develop a process that produces fewer by-products and can be carried out in a single pot.
  • the present invention therefore also provides methods to reduce the production cost of chlorantraniliprole and improve its quality.
  • the invention discloses two novel, efficient and one-pot method for synthesizing chlorantraniliprole, and its intermediates.
  • Chlorantraniliprole is prepared by a novel telescopic process starting from 3-Bromo-l-(3-chloropyridin-2-yl)-lH-pyrazole-5- carboxylic acid (3).
  • the process steps use a novel variant of pyrazolic acid (Methyl 2-amino-5-chloro- 3-methylbenzoate), to get Chlorantraniliprole.
  • the invention provides two novel, efficient and one-pot method for synthesizing chlorantraniliprole.
  • the invention also provides efficient/novel schemes for the in-situ production of the KRMs viz. 3- Bromo-1 -(3 -chloropyridin-2-yl)-lH-pyrazole-5 -carboxylic acid (3), 2- Amino-5-chloro-N,3-dimethylbenzamide (8), Methyl 2-amino-5- chloro-3-methylbenzoate (13).
  • Chlorantraniliprole is prepared by a novel telescopic process starting from 3-Bromo-l-(3- chloropyridin-2-yl)-lH-pyrazole-5-carboxylic acid (3), the process steps include in-situ preparation of acid chloride (6) using stoichiometric amount of oxalyl chloride or thionyl chloride at ambient temperature followed by coupling with anthranilic amide without using any base.
  • the process steps include in-situ preparation of acid chloride, methyl ester of chlorantraniliprole (14) followed by reaction with methyl amine to get Chlorantraniliprole in one-pot.
  • This scheme uses a novel variant of pyrazolic acid (Methyl 2- amino-5-chloro-3-methylbenzoate) (13) to get Chlorantraniliprole.
  • all the in-situ steps of the disclosed synthesis method obtain good yield, without using any base or harsh reaction conditions, which makes the process simple, environmentally benign and more cost effective.
  • the production cost of chlorantraniliprole and its intermediates is substantially reduced; fewer by-products are formed during its synthesis and since it is a one-pot reaction, isolation and purification are easy to achieve.
  • Scheme-7.1 Provides the details of reactants and reaction conditions for the in-situ preparation of chlorantraniliprole using 2 -amino-5 - chloro-N, 3 -dimethylbenzamide .
  • Scheme-7.2 Provides the details of reactants and reaction conditions for the in-situ preparation of chlorantraniliprole using methyl 2-amino- 5 -chloro-3 -methylbenzoate .
  • Scheme-8 Provides the details of reactants and reaction conditions for the preparation of pyrazole acid (3) using dichloropyridine (DCP).
  • Scheme-9 Provides the details of the reactants and reaction conditions for the preparation of 2 -amino-5 -chloro-N, 3 -dimethylbenzamide using m-Toluic acid.
  • Scheme-10 Provides the details of the reactants and reaction conditions for the preparation of methyl 2-amino-5-chloro-3-methylbenzoate using 3-methyl-2-nitrobenzoic acid.
  • the terms “includes,” “including,” “has,” “having,” “contains”, “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • a process, method that comprises a list of compounds is not necessarily limited to only those compounds but may include other compounds not expressly listed or inherent to such process, method.
  • a telescopic process for the preparation of Chlorantraniliprole takes place in the following manner:
  • reaction mixture was stirred for 3-4 h at 60-70°C.
  • the progress of the reaction was monitored by HPLC.
  • Acetonitrile was recovered at a reduced pressure.
  • Product was isolated by adding water to a residue and filtration of resulting solid to get crude product. Crude product was purified by slurry wash with acetone. Yield: 78% and purity: 98%.
  • Step-2 Preparation of ethyl 2-(3-chloropyridin-2-yl)-5- oxopyrazolidine-3-carboxylate
  • Step-3 Preparation of Ethyl 3-bromo-l-(3-chloropyridin-2-yl)-4, 5-dihydro-lH-pyr azole- 5-carboxylate
  • Step-4 Preparation of ethyl 3-bromo-l-(3-chloropyridin-2-yl)-lH- pyrazole-5-carboxylate
  • Step-5 Preparation of 3-bromo-l-(3-chloropyridin-2-yl)-lH- pyrazole-5-carboxylic acid
  • Step-1 3-Methyl-2-nitrobenzoic acid (Scheme 9) m-Toluic acid (100 g) was added to fuming nitric acid (200 ml) at -10 to -5°C in portion wise manner. After addition, the reaction mixture was stirred for 2-3 h at -10 to -5°C. The progress of the reaction was monitored by HPLC. After completion of the reaction, the reaction mixture was poured into ice water and stirred for 1-2 h. The solid product was isolated by filtration and washed with water to get crude product. The crude product was purified by crystallization in ethanol to get pure 3-methyl-2-nitrobenzoic acid. Yield: 45% and purity: 97%.
  • Step-4 2-Amino-5-chloro-N,3-dimethylbenzamide
  • Step-3 Preparation of methyl 2-amino-5-chloro-3-methylbenzoate
  • 2-Amino-5-chloro-3-methylbenzoic acid (175 g, 0.95 mol) and K2CO3 (137.06 g, 0.99 mol) in DMF (525 ml) was added Dimethyl sulfate (119 g, 0.95 mol) at room temperature.
  • the reaction mixture was heated and stirred for 9-10 h at 100-110°C. The progress of the reaction was monitored by HPLC. After completion of the reaction, DMF was recovered under reduced pressure at 60-70°C. Water was added to the residue and product was isolated by extraction in ethyl acetate and recovering of ethyl acetate. Yield: 78%, purity: 98%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne deux procédés nouveaux, efficaces et monotopes pour synthétiser du chlorantraniliprole. Dans le premier schéma, le chlorantraniliprole est préparé par un nouveau procédé télescopique à partir d'acide 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylique, une matière première clé-A (RM-A clé). Dans le second schéma, à partir de la RM-A clé, les étapes de procédé utilisent une nouvelle variante d'acide anthranilique (2-amino-5-chloro-3-méthylbenzoate de méthyle), pour obtenir du chlorantraniliprole. En outre, la présente invention concerne également la synthèse d'une matière première clé pour la synthèse de chlorantraniliprole in situ. Toutes les étapes in-situ des procédés de synthèse décrits permettent d'obtenir un bon rendement, sans utiliser de réactif ou de base onéreux ou de conditions de réaction difficiles, ce qui rend le procédé simple, respectueux de l'environnement et plus rentable. Avec ce procédé, le coût de production du chlorantraniliprole et de ses intermédiaires est sensiblement réduit; moins de sous-produits sont formés pendant sa synthèse et étant donné qu'il s'agit d'une réaction monotope, l'isolement et la purification sont faciles à obtenir.
PCT/IB2020/059172 2019-08-20 2020-09-30 Procédé de préparation de chlorantraniliprole WO2021033172A1 (fr)

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IN201941033579 2019-08-20
IN201941033579 2019-08-20

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113480518A (zh) * 2021-07-08 2021-10-08 江西汇和化工有限公司 一种合成氯虫苯甲酰胺的方法
CN113896714A (zh) * 2021-11-23 2022-01-07 江西汇和化工有限公司 一种氯虫苯甲酰胺的合成方法
CN114085208A (zh) * 2021-11-30 2022-02-25 重庆华歌生物化学有限公司 一种利于溶剂循环套用的氯虫苯甲酰胺化合物的制备方法
WO2022149098A1 (fr) * 2021-01-11 2022-07-14 Upl Limited Procédé de préparation d'anthranilamides à action insecticide
CN114874185A (zh) * 2022-03-18 2022-08-09 青岛恒宁生物科技有限公司 一种制备邻甲酰胺基苯甲酰胺类化合物的方法
WO2022232366A1 (fr) * 2021-04-30 2022-11-03 Fmc Corporation Hydrogénation d'acide nitrobenzoïque et de nitrobenzamide
CN115583895A (zh) * 2022-12-08 2023-01-10 苏州开元民生科技股份有限公司 一种2-氨基-5-氯-n,3-二甲基苯甲酰胺的合成方法
CN115611746A (zh) * 2022-11-02 2023-01-17 天津大学浙江绍兴研究院 一种3-甲基-2-硝基苯甲酸连续硝化生产的工艺及设备
CN116983927A (zh) * 2023-09-27 2023-11-03 天津凯莱英医药科技发展有限公司 连续生产氯虫苯甲酰胺的系统及方法
WO2024116196A1 (fr) * 2022-11-30 2024-06-06 Natco Pharma Limited Procédé amélioré pour la préparation d'intermédiaires de chlorantraniliprole

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003015519A1 (fr) * 2001-08-13 2003-02-27 E.I. Du Pont De Nemours And Company Anthranilamides arthropodicides
US8217179B2 (en) * 2008-04-01 2012-07-10 Sinochem Corporation Preparation method of phenylcarboxamides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003015519A1 (fr) * 2001-08-13 2003-02-27 E.I. Du Pont De Nemours And Company Anthranilamides arthropodicides
US8217179B2 (en) * 2008-04-01 2012-07-10 Sinochem Corporation Preparation method of phenylcarboxamides

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022149098A1 (fr) * 2021-01-11 2022-07-14 Upl Limited Procédé de préparation d'anthranilamides à action insecticide
WO2022232366A1 (fr) * 2021-04-30 2022-11-03 Fmc Corporation Hydrogénation d'acide nitrobenzoïque et de nitrobenzamide
CN113480518A (zh) * 2021-07-08 2021-10-08 江西汇和化工有限公司 一种合成氯虫苯甲酰胺的方法
CN113896714A (zh) * 2021-11-23 2022-01-07 江西汇和化工有限公司 一种氯虫苯甲酰胺的合成方法
CN114085208A (zh) * 2021-11-30 2022-02-25 重庆华歌生物化学有限公司 一种利于溶剂循环套用的氯虫苯甲酰胺化合物的制备方法
CN114085208B (zh) * 2021-11-30 2023-03-14 重庆华歌生物化学有限公司 一种利于溶剂循环套用的氯虫苯甲酰胺化合物的制备方法
CN114874185A (zh) * 2022-03-18 2022-08-09 青岛恒宁生物科技有限公司 一种制备邻甲酰胺基苯甲酰胺类化合物的方法
CN115611746A (zh) * 2022-11-02 2023-01-17 天津大学浙江绍兴研究院 一种3-甲基-2-硝基苯甲酸连续硝化生产的工艺及设备
WO2024116196A1 (fr) * 2022-11-30 2024-06-06 Natco Pharma Limited Procédé amélioré pour la préparation d'intermédiaires de chlorantraniliprole
CN115583895A (zh) * 2022-12-08 2023-01-10 苏州开元民生科技股份有限公司 一种2-氨基-5-氯-n,3-二甲基苯甲酰胺的合成方法
CN116983927A (zh) * 2023-09-27 2023-11-03 天津凯莱英医药科技发展有限公司 连续生产氯虫苯甲酰胺的系统及方法
CN116983927B (zh) * 2023-09-27 2024-01-19 天津凯莱英医药科技发展有限公司 连续生产氯虫苯甲酰胺的系统及方法

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