WO2018214685A1 - 一种制备n-酰基邻氨基苯甲酰胺的方法 - Google Patents
一种制备n-酰基邻氨基苯甲酰胺的方法 Download PDFInfo
- Publication number
- WO2018214685A1 WO2018214685A1 PCT/CN2018/084008 CN2018084008W WO2018214685A1 WO 2018214685 A1 WO2018214685 A1 WO 2018214685A1 CN 2018084008 W CN2018084008 W CN 2018084008W WO 2018214685 A1 WO2018214685 A1 WO 2018214685A1
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- WIPO (PCT)
- Prior art keywords
- phosphorus
- acid
- compound
- base
- chloro
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- 0 Cc(cc(*)cc1C(O)=O)c1N Chemical compound Cc(cc(*)cc1C(O)=O)c1N 0.000 description 7
- FORBXGROTPOMEH-UHFFFAOYSA-N OC(c1cc(Br)n[n]1-c(nccc1)c1Cl)=O Chemical compound OC(c1cc(Br)n[n]1-c(nccc1)c1Cl)=O FORBXGROTPOMEH-UHFFFAOYSA-N 0.000 description 2
- MOXMPWAWQLBNGS-UHFFFAOYSA-N O=C(c1cc(Br)n[n]1-c(nccc1)c1Cl)Cl Chemical compound O=C(c1cc(Br)n[n]1-c(nccc1)c1Cl)Cl MOXMPWAWQLBNGS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 invention belongs to the field of organic synthesis, and in particular relates to a method for preparing an N-acyl anthranilamide compound.
- N-acyl anthranilamide (I) is an important class of organic compounds widely used in pesticides, pharmaceuticals and other fields.
- Method 1 Substituting the substituted anthranilic acid (II) with a formyl chloride reagent (such as methyl chloroformate, phosgene, etc.), dehydration and cyclization to obtain the intermediate isatoic anhydride (V).
- a formyl chloride reagent such as methyl chloroformate, phosgene, etc.
- the pyrazolecarboxylic acid compound (III) is converted to pyrazolecarbonyl chloride (VI) by the action of thionyl chloride and DMF.
- the isatoic anhydride (V) and the pyrazolecarbonyl chloride (VI) are condensed under the action of an acid such as pyridine to obtain a benzoxazinone intermediate (IV), which is then subjected to a ring opening reaction with methylamine.
- the N-acyl anthranilamide (I) (WO 2003/015519) is obtained, which is represented by the following formula:
- Method 2 Substituting the substituted anthranilic acid (II) with a formyl chloride reagent (such as methyl chloroformate, phosgene, etc.), dehydration and cyclization to obtain an intermediate isatoic anhydride (V), the latter and methylamine The ring opening reaction occurs to give anthranilamide (VII).
- a formyl chloride reagent such as methyl chloroformate, phosgene, etc.
- the routes of method one and method two are long, and the highly toxic reagents such as methyl chloroformate or phosgene are used, which brings inconvenience to the operation and is not conducive to industrial production.
- the method has fewer steps than the first method and the second method, an excessive amount of methanesulfonyl chloride is used, which generates a large amount of sulfur-containing organic acid wastewater, which is difficult to handle, and the three wastes are serious, and the yield of the method is very low (two-step total collection) The rate is about 20%), which is not conducive to industrial production.
- the present invention provides a simpler, more environmentally friendly, and more efficient method for synthesizing N-acyl anthranilamide (I).
- Formamide (I) is expressed by the reaction formula as follows:
- X is hydrogen, chlorine or cyano
- HY is hydrohalic acid, sulfuric acid, phosphoric acid or a carboxylic acid, preferably hydrochloric acid or sulfuric acid.
- the phosphorus reagent refers to a compound containing a phosphorus element, such as phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide, etc., preferably trichloroox Phosphorus or phosphorus oxybromide.
- a phosphorus element such as phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide, etc., preferably trichloroox Phosphorus or phosphorus oxybromide.
- the base described in the first step may be an organic base or an inorganic base, preferably an organic base, further preferably a tertiary amine base such as pyridine, 3-methylpyridine, N,N-dimethylaminopyridine, triethylamine or the like.
- a tertiary amine base such as pyridine, 3-methylpyridine, N,N-dimethylaminopyridine, triethylamine or the like.
- the molar ratio of the compound (II) to the compound (III) is 1:0.5 to 1.5, and the molar ratio of the compound (II) to the phosphorus reagent is 1:1 to 2, and the compound (II) and the base are used.
- the molar ratio of feed is 1:2-5.
- the base may be an organic base or an inorganic base, preferably an organic base such as triethylamine, pyridine, 3-methylpyridine or the like, and the molar ratio of the compound (IV) to the base is 1:1 to 3.
- the molar ratio of the compound (IV) to the protonate of methylamine is 1:1 to 3.
- the solvent may be selected from the group consisting of N,N-dimethylformamide, acetone, acetonitrile, preferably acetonitrile.
- the preparation method of the N-substituted amide provided by the invention has the following advantages:
- the second step 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H obtained in the first step -3,1-Benzothoxazin-4-one 4.16 g was dissolved in 20 ml of acetonitrile, then 0.92 g of methylamine hydrochloride was added, and stirred at room temperature for 4 hours. The solvent was removed under reduced pressure, washed with water and dried to give chlorobenzene. The benzamide was 3.56 g in a yield of 80%.
- the second step 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H obtained in the first step -3,1-benzoxazin-4-one 4.16 g was dissolved in 20 ml of acetonitrile, then 1.11 g of triethylamine and 0.92 g of methylamine hydrochloride were added, and the mixture was stirred at room temperature for 2 hours, and the solvent was removed under reduced pressure and washed with water. Drying, the chlorantraniliprole was 4.18 g, and the yield was 94%.
- the second step 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H obtained in the first step -3,1-Benzothoxazin-4-one 4.07g was dissolved in 20ml of acetonitrile, then 2.73g of triethylamine and 1.82g of methylamine hydrochloride were added, and stirred at room temperature for 2 hours. The solvent was removed under reduced pressure and washed with water. Drying gave 4.77 g of chlorantraniliproleamide in a yield of 96%.
- the second step 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H obtained in the first step -3,1-Benzothoxazin-4-one 4.2g was dissolved in 20ml of acetonitrile, then 1.23g of 4-dimethylaminopyridine and 2.18g of methylamine sulfate were added, stirred at room temperature for 2.5 hours, solvent was removed under reduced pressure, and water was added. Washing and drying gave 4.27 g of chlorantraniliprole with a yield of 95%.
- the second step 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H obtained in the first step -3,1-benzoxazin-4-one 4.16 g was dissolved in 20 ml of acetonitrile, then 0.79 g of pyridine and 0.92 g of methylamine hydrochloride were added, and stirred at room temperature for 1.5 hours. The solvent was removed under reduced pressure, washed with water and dried. , chlorantraniliprole 4g, yield 90%.
- the second step 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-cyano-8-methyl- 4H-3,1-benzoxazin-4-one 3.81 g was dissolved in 20 ml of acetonitrile, then 1.11 g of triethylamine and 2.18 g of methylamine sulfate were added, and stirred at room temperature for 2.5 hours. The solvent was removed under reduced pressure and washed with water. Drying gave 3.77 g of bromidazamide with a yield of 95%.
- the second step 2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-cyano-8-methyl- 4H-3,1-benzoxazin-4-one 4.17 g was dissolved in 20 ml of acetonitrile, then 1.78 g of triethylamine and 2.82 g of methylamine sulfate were added, and stirred at room temperature for 2.5 hours. The solvent was removed under reduced pressure and washed with water. Drying gave 4.08 g of bromidazamide with a yield of 98%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
Claims (10)
- 根据权利要求1所述的方法,其特征在于,第一步所述的磷试剂是三氯氧磷、三溴氧磷、三氯化磷、三溴化磷、五氯化磷或五溴化磷。
- 根据权利要求2所述的方法,其特征在于,所述的磷试剂优选是三氯氧磷或三溴氧磷。
- 根据权利要求1所述的方法,其特征在于,第一步所述的碱为有机碱。
- 根据权利要求4所述的方法,其特征在于,所述的有机碱优选为吡啶、3-甲基吡啶、N,N-二甲氨基吡啶或三乙胺。
- 根据权利要求1所述的方法,其特征在于,所述的HY优选是盐酸或硫酸。
- 根据权利要求1所述的方法,其特征在于,第一步反应中化合物(II)与化合物(III)的投料摩尔比是1:0.5~1.5;化合物(II)与磷试剂的投料摩尔比是1:1~2;化合物(II)与碱的投料摩尔比为1:2~5。
- 根据权利要求1所述的方法,其特征在于,第二步反应在碱的作用下进行。
- 根据权利要求8所述的方法,其特征在于,所述的碱优选为三乙胺、吡啶或3-甲基吡啶。
- 根据权利要求1所述的方法,其特征在于,第二步反应中化合物(IV)与甲胺的质子酸盐的投料摩尔比是1:1~3,化合物(IV)与碱的投料摩尔比是1:1~3。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18805928.1A EP3632905B1 (en) | 2017-05-26 | 2018-04-23 | Method for preparing n-acyl ortho-aminobenzamide |
BR112019024933-8A BR112019024933B1 (pt) | 2017-05-26 | 2018-04-23 | Método para preparar antranilamida de n-acila |
US16/694,989 US10807967B2 (en) | 2017-05-26 | 2019-11-25 | Method of preparing N-acyl anthranilamide |
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CN201710386998.7 | 2017-05-26 | ||
CN201710386998.7A CN107089970B (zh) | 2017-05-26 | 2017-05-26 | 一种制备n-酰基邻氨基苯甲酰胺的方法 |
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US16/694,989 Continuation US10807967B2 (en) | 2017-05-26 | 2019-11-25 | Method of preparing N-acyl anthranilamide |
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US (1) | US10807967B2 (zh) |
EP (1) | EP3632905B1 (zh) |
CN (1) | CN107089970B (zh) |
WO (1) | WO2018214685A1 (zh) |
Cited By (1)
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JP2022529475A (ja) * | 2019-04-19 | 2022-06-22 | アダマ・マクテシム・リミテッド | 置換ピラゾールの調製およびアントラニルアミド前駆体としてのそれらの使用 |
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CN107033135B (zh) * | 2017-05-26 | 2020-09-11 | 浙江省诸暨合力化学对外贸易有限公司 | 一种制备异噁嗪酮化合物的方法及其应用 |
CN107089970B (zh) | 2017-05-26 | 2020-06-16 | 迈克斯(如东)化工有限公司 | 一种制备n-酰基邻氨基苯甲酰胺的方法 |
CN110835331A (zh) * | 2018-08-15 | 2020-02-25 | 海利尔药业集团股份有限公司 | 一种具有杀虫活性的取代水杨酰胺类化合物的制备方法 |
CN112574190B (zh) * | 2020-12-21 | 2022-11-11 | 江苏快达农化股份有限公司 | 一种氯虫苯甲酰胺的合成方法 |
CN114957211B (zh) * | 2022-05-31 | 2024-04-09 | 山东友道化学有限公司 | 一种氯虫苯甲酰胺的生产方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003015519A1 (en) | 2001-08-13 | 2003-02-27 | E.I. Du Pont De Nemours And Company | Arthropodicidal anthranilamides |
CN1541063A (zh) * | 2001-08-13 | 2004-10-27 | ��Ļ���Ű˾ | 使用邻氨基苯甲酰胺化合物防治特殊害虫的方法 |
WO2008010897A2 (en) | 2006-07-19 | 2008-01-24 | E. I. Du Pont De Nemours And Company | Process for making 3-substituted 2-amino-5-halobenzamides |
CN103601718A (zh) * | 2013-12-05 | 2014-02-26 | 江西天人生态股份有限公司 | 一类基于鱼泥丁受体的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途 |
CN104003976A (zh) * | 2014-05-07 | 2014-08-27 | 肇庆市真格生物科技有限公司 | 多取代吡啶基吡唑酰胺及其制备方法和用途 |
CN107089970A (zh) * | 2017-05-26 | 2017-08-25 | 迈克斯(如东)化工有限公司 | 一种制备n‑酰基邻氨基苯甲酰胺的方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200724033A (en) * | 2001-09-21 | 2007-07-01 | Du Pont | Anthranilamide arthropodicide treatment |
SI1717237T1 (sl) * | 2004-02-18 | 2011-03-31 | Ishihara Sangyo Kaisha | Antranilamidi, postopek za njihovo proizvodnjo in sredstva za zatiranje škodljivcev, ki jih vsebujejo |
CN103304508A (zh) * | 2012-03-14 | 2013-09-18 | 山东科技大学 | 一种双苯并恶嗪酮类紫外吸收剂的新合成方法 |
CN103058993B (zh) * | 2013-01-08 | 2014-06-04 | 河南师范大学 | 一种氯虫苯甲酰胺的制备方法 |
CN105669643A (zh) * | 2013-12-05 | 2016-06-15 | 江西天人生态股份有限公司 | 一类基于鱼泥丁受体的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途 |
CN107033135B (zh) * | 2017-05-26 | 2020-09-11 | 浙江省诸暨合力化学对外贸易有限公司 | 一种制备异噁嗪酮化合物的方法及其应用 |
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2017
- 2017-05-26 CN CN201710386998.7A patent/CN107089970B/zh active Active
-
2018
- 2018-04-23 EP EP18805928.1A patent/EP3632905B1/en active Active
- 2018-04-23 WO PCT/CN2018/084008 patent/WO2018214685A1/zh unknown
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2019
- 2019-11-25 US US16/694,989 patent/US10807967B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003015519A1 (en) | 2001-08-13 | 2003-02-27 | E.I. Du Pont De Nemours And Company | Arthropodicidal anthranilamides |
CN1541063A (zh) * | 2001-08-13 | 2004-10-27 | ��Ļ���Ű˾ | 使用邻氨基苯甲酰胺化合物防治特殊害虫的方法 |
CN100425607C (zh) * | 2001-08-13 | 2008-10-15 | 纳幕尔杜邦公司 | 使用邻氨基苯甲酰胺化合物防治特殊害虫的方法 |
WO2008010897A2 (en) | 2006-07-19 | 2008-01-24 | E. I. Du Pont De Nemours And Company | Process for making 3-substituted 2-amino-5-halobenzamides |
CN103601718A (zh) * | 2013-12-05 | 2014-02-26 | 江西天人生态股份有限公司 | 一类基于鱼泥丁受体的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途 |
CN104003976A (zh) * | 2014-05-07 | 2014-08-27 | 肇庆市真格生物科技有限公司 | 多取代吡啶基吡唑酰胺及其制备方法和用途 |
CN107089970A (zh) * | 2017-05-26 | 2017-08-25 | 迈克斯(如东)化工有限公司 | 一种制备n‑酰基邻氨基苯甲酰胺的方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3632905A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022529475A (ja) * | 2019-04-19 | 2022-06-22 | アダマ・マクテシム・リミテッド | 置換ピラゾールの調製およびアントラニルアミド前駆体としてのそれらの使用 |
Also Published As
Publication number | Publication date |
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CN107089970A (zh) | 2017-08-25 |
EP3632905A4 (en) | 2020-11-25 |
EP3632905B1 (en) | 2021-12-01 |
BR112019024933A2 (pt) | 2020-06-23 |
US10807967B2 (en) | 2020-10-20 |
CN107089970B (zh) | 2020-06-16 |
EP3632905A1 (en) | 2020-04-08 |
US20200087278A1 (en) | 2020-03-19 |
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