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 PDF

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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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phosphorus
acid
compound
base
chloro
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PCT/CN2018/084008
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关保川
张天浩
盛秋菊
陈邦池
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迈克斯(如东)化工有限公司
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Priority to BR112019024933-8A priority Critical patent/BR112019024933B1/pt
Priority to EP18805928.1A priority patent/EP3632905B1/en
Publication of WO2018214685A1 publication Critical patent/WO2018214685A1/zh
Priority to US16/694,989 priority patent/US10807967B2/en

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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

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  • 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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  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

本发明公开了一种制备N-酰基邻氨基苯甲酰胺(I)的方法。该方法包括：将取代邻氨基苯甲酸化合物(II)和吡唑甲酸化合物(III)在磷试剂和碱的作用下反应得到苯并噁嗪酮中间体(IV)，后者与甲胺的质子酸盐反应开环，得到N-酰基邻氨基苯甲酰胺(I)，用反应式表示如上：其中X是氢、氯或氰基，HY是氢卤酸、硫酸、磷酸或羧酸。该方法操作简便、反应温和、三废少、总收率高、适合工业化生产。

Description

一种制备N-酰基邻氨基苯甲酰胺的方法 技术领域
本发明属于有机合成领域，具体涉及一种制备N-酰基邻氨基苯甲酰胺化合物的方法。
背景技术
N-酰基邻氨基苯甲酰胺(I)是一类重要的有机化合物，广泛应用于农药、医药等领域。例如，3-溴-N-(2-甲基-4-氯-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(X为氯，氯虫苯甲酰胺)和3-溴-N-(2-甲基-4-氰基-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(X为氰基，溴氰虫酰胺)是由杜邦公司开发的两种重要的N-酰基邻氨基苯甲酰胺类杀虫剂，主要作用于昆虫的鱼尼丁受体，用来防治大多数咀嚼式害虫，尤其是鳞翅目、鞘翅目、双翅目等害虫。适用作物包括果树、蔬菜、葡萄、棉花、甘蔗、水稻和草坪等。
目前，以取代邻氨基苯甲酸(II)和吡唑甲酸化合物(III)为原料来合成N-酰基邻氨基苯甲酰胺(I)的方法主要有以下三种：
方法一：将取代邻氨基苯甲酸(II)在甲酰氯化试剂(如氯甲酸甲酯、光气等)的作用下，脱水环合得到中间体靛红酸酐(V)。将吡唑甲酸化合物(III)在氯化亚砜和DMF的作用下，转化成吡唑甲酰氯(VI)。然后将靛红酸酐(V)和吡唑甲酰氯(VI)在吡啶等缚酸剂的作用下缩合，得到苯并噁嗪酮中间体(IV)，后者再与甲胺发生开环反应，得到N-酰基邻氨基苯甲酰胺(I)(WO2003/015519)，用反应式表示如下：
Figure PCTCN2018084008-appb-000001
方法二：将取代邻氨基苯甲酸(II)在甲酰氯化试剂(如氯甲酸甲酯、光气等)的作用下，脱水环合得到中间体靛红酸酐(V)，后者与甲胺发生开环反应得到邻氨基苯甲酰胺(VII)。将吡唑甲酸化合物(III)在氯化亚砜和DMF的作用下，转化成吡唑甲酰氯(VI)。然后将吡唑甲酰氯(VI)与邻氨基苯甲酰胺(VII)在缚酸剂的作用下缩合，得到N-酰基邻氨基苯甲酰胺(I)(WO2008/010897)，用反应式表示如下：
Figure PCTCN2018084008-appb-000002
方法一和方法二的路线都较长，而且要用到剧毒试剂氯甲酸甲酯或光气等，给操作带来不便，不利于工业化生产。
方法三：将取代邻氨基苯甲酸(II)和吡唑甲酸化合物(III)在甲磺酰氯和缚酸剂的作用下，先生成苯并噁嗪酮中间体(IV)，后者再与甲胺的四氢呋喃溶液反应得到N-酰基邻氨基苯甲酰胺(WO2003/015519)，用反应式表示如下：
Figure PCTCN2018084008-appb-000003
该方法虽然比方法一和方法二的步骤少，但是要用到过量的甲磺酰氯，会产生大量的含硫有机酸废水不易处理，三废严重，而且该方法收率很低(两步总收率约为20％)，不利于工业化生产。
发明内容
为克服现有技术的不足，本发明提供了一种更为简便、更加环保、更加高效的合成N-酰基邻氨基苯甲酰胺(I)的方法。
一种制备N-酰基邻氨基苯甲酰胺(I)的方法，其特征在于，该方法包括：第一步，将取代邻氨基苯甲酸化合物(II)和吡唑甲酸化合物(III)在磷试剂和碱的作用下反应得到苯并噁嗪酮中间体(IV)；第二步，苯并噁嗪酮中间体(IV)与甲胺的质子酸盐反应开环，得到N-酰基邻氨基苯甲酰胺(I)，用反应式表示如下：
Figure PCTCN2018084008-appb-000004
其中X是氢、氯或氰基；HY是氢卤酸、硫酸、磷酸或羧酸，优选是盐酸或硫酸。
所述的磷试剂是指含磷元素的化合物，如三氯氧磷、三溴氧磷、三氯化磷、三溴化磷、五氯化磷或五溴化磷等，优选为三氯氧磷或三溴氧磷。
第一步所述的碱可以是有机碱或无机碱，优选是有机碱，进一步优选是叔胺碱，如吡啶、3-甲基吡啶、N,N-二甲氨基吡啶、三乙胺等。
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)与碱的投料摩尔比是1:2～5。
在第二步开环反应中，还可以加入适量的碱。碱可以是有机碱或无机碱，优选是有机碱，如三乙胺、吡啶、3-甲基吡啶等，化合物(IV)与碱的投料摩尔比是1:1～3。
化合物(IV)与甲胺的质子酸盐的投料摩尔比是1:1～3。
按照本发明，其溶剂可选自N,N-二甲基甲酰胺、丙酮、乙腈，优选是乙腈。
与现有技术相比，本发明提供的N-取代酰胺的制备方法具有以下优点：
(1)工艺简单，反应条件温和；
(2)避免了使用氯甲酸甲酯或光气等剧毒品，操作方便；
(3)避免了使用甲磺酰氯等有机试剂带来的含硫有机酸废水问题，三废少；
(4)收率高，适合工业化。
具体实施方式
下面的实施例进一步举例说明了本发明的一些特征，但本发明所申请保护的内容和范围并不受下述实施例的限制。
实施例1：3-溴-N-(2-甲基-4-氯-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(氯虫苯甲酰胺)的制备
第一步：在100mL的三口瓶中，加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸3.02g、3-甲基吡啶1.95g和乙腈15mL，-5℃条件下滴加POBr 35.73g，滴毕保温搅拌半小时，再加入2-氨基-3-甲基-5-氯苯甲酸1.86g，室温反应1小时。加入20mL水搅拌0.5小时，过滤，滤饼用3:2的乙腈-水洗涤，干燥得2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.16g，收率92％。
第二步：将第一步得到的2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.16g溶于20ml乙腈，然后加入甲胺盐酸盐0.92g，室温搅拌4小时，减压脱除溶剂，加水洗涤，烘干，得氯虫苯甲酰胺3.56g，收率80％。
实施例2：3-溴-N-(2-甲基-4-氯-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(氯虫苯甲酰胺)的制备
第一步：在100mL的三口瓶中，加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸3.02g、3-甲基吡啶1.95g和乙腈15mL，-5℃条件下滴加POBr 35.73g，滴毕保温搅拌半小时，再加入2-氨基-3-甲基-5-氯苯甲酸1.86g，室温反应1小时。加入20mL水搅拌0.5小时，过滤，滤饼用3:2的乙腈-水洗涤，干燥得2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.16g，收率92％。
第二步：将第一步得到的2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.16g溶于20ml乙腈，然后加入三乙胺1.11g、甲胺盐 酸盐0.92g，室温搅拌2小时，减压脱除溶剂，加水洗涤，烘干，得氯虫苯甲酰胺4.18g，收率94％。
实施例3：3-溴-N-(2-甲基-4-氯-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(氯虫苯甲酰胺)的制备
第一步：在100mL的三口瓶中，加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸4.53g、吡啶1.58g和乙腈15mL，-5℃条件下滴加POCl 33.07g，滴毕保温搅拌半小时，再加入2-氨基-3-甲基-5-氯苯甲酸1.86g，室温反应0.5小时。加入20mL水搅拌0.5小时，过滤，滤饼用3:2的乙腈-水洗涤，干燥得2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.07g，收率90％。
第二步：将第一步得到的2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.07g溶于20ml乙腈，然后加入三乙胺2.73g、甲胺盐酸盐1.82g，室温搅拌2小时，减压脱除溶剂，加水洗涤，烘干，得氯虫苯甲酰胺4.17g，收率96％。
实施例4：3-溴-N-(2-甲基-4-氯-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(氯虫苯甲酰胺)的制备
第一步：在100mL的三口瓶中，加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸3.02g、3-甲基吡啶4.87g和乙腈30mL，-5℃条件下滴加POBr 35.73g，滴毕保温搅拌半小时，再加入2-氨基-3-甲基-5-氯苯甲酸1.86g，室温反应1.5小时。加入20mL水搅拌0.5小时，过滤，滤饼用3:2的乙腈-水洗涤，干燥得2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.2g，收率93％。
第二步：将第一步得到的2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.2g溶于20ml乙腈，然后加入4-二甲氨基吡啶1.23g、甲胺硫酸盐2.18g，室温搅拌2.5小时，减压脱除溶剂，加水洗涤，烘干，得氯虫苯甲酰胺4.27g，收率95％。
实施例5：3-溴-N-(2-甲基-4-氯-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(氯虫苯甲酰胺)的制备
第一步：在100mL的三口瓶中，加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸3.02g、3-甲基吡啶1.95g和乙腈15mL，-5℃条件下滴加POBr 35.73g，滴毕保温搅拌半小时，再加入2-氨基-3-甲基-5-氯苯甲酸1.86g，室温反应1小时。加入20mL水搅拌0.5小时，过滤，滤饼用3:2的乙腈-水洗涤，干燥得2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.16g，收率92％。
第二步：将第一步得到的2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氯-8-甲基-4H-3,1-苯并噁嗪-4-酮4.16g溶于20ml乙腈，然后加入吡啶0.79g、甲胺盐酸盐0.92g，室温搅拌1.5小时，减压脱除溶剂，加水洗涤，烘干，得氯虫苯甲酰胺4g，收率90％。
实施例6：3-溴-N-(2-甲基-4-氰基-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(溴氰虫酰胺)的制备
第一步：在100mL的三口瓶中，加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸3.02g、3-甲基吡啶1.95g和乙腈15mL，-5℃条件下滴加POCl 33.23g，滴毕保温搅拌半小时，再加入2-氨基-3-甲基-5-氰基苯甲酸1.94g，室温反应2小时。加入20mL水搅拌0.5小时，过滤，滤饼用3:2的乙腈-水洗涤，干燥得2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氰基-8-甲基-4H-3,1-苯并噁嗪-4-酮3.81g，收率86％。 1H NMR(500MHz,DMSO)δ8.63(dd,1H),8.40–8.33(m,2H),8.10(s,1H),7.77(dd,1H),7.60(s,1H),1.73(s,3H).4.16g。
第二步：将第一步得到的2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氰基-8-甲基-4H-3,1-苯并噁嗪-4-酮3.81g溶于20ml乙腈，然后加入三乙胺1.11g、甲胺硫酸盐2.18g，室温搅拌2.5小时，减压脱除溶剂，加水洗涤，烘干，得溴腈虫酰胺3.87g，收率95％。
实施例7：3-溴-N-(2-甲基-4-氰基-6-(甲氨酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(溴氰虫酰胺)的制备
第一步：在100mL的三口瓶中，加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸3.02g、3-甲基吡啶1.95g和乙腈15mL，-5℃条件下滴加POCl 31.62g，滴毕保温搅拌半小时，再加入2-氨基-3-甲基-5-氰基苯甲酸3.88g，室温反应1.5小时。加 入20mL水搅拌0.5小时，过滤，滤饼用3:2的乙腈-水洗涤，干燥得2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氰基-8-甲基-4H-3,1-苯并噁嗪-4-酮4.17g，收率88％。
第二步：将第一步得到的2-[3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基]-6-氰基-8-甲基-4H-3,1-苯并噁嗪-4-酮4.17g溶于20ml乙腈，然后加入三乙胺1.78g、甲胺硫酸盐2.82g，室温搅拌2.5小时，减压脱除溶剂，加水洗涤，烘干，得溴腈虫酰胺4.08g，收率98％。

Claims (10)

  1. 一种制备N-酰基邻氨基苯甲酰胺(I)的方法，其特征在于，该方法包括：第一步，将取代邻氨基苯甲酸化合物(II)和吡唑甲酸化合物(III)在磷试剂和碱的作用下反应得到苯并噁嗪酮中间体(IV)；第二步，苯并噁嗪酮中间体(IV)与甲胺的质子酸盐反应开环，得到N-酰基邻氨基苯甲酰胺(I)，用反应式表示如下：
    Figure PCTCN2018084008-appb-100001
    其中X是氢、氯或氰基，HY是氢卤酸、硫酸、磷酸或羧酸。
  2. 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。
  3. 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。
  4. 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。
  5. 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。
  6. 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。
  7. 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。
  8. 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。
  9. 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。
  10. 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。
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Cited By (1)

* Cited by examiner, † Cited by third party
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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200724033A (en) * 2001-09-21 2007-07-01 Du Pont Anthranilamide arthropodicide treatment
ES2560879T3 (es) * 2004-02-18 2016-02-23 Ishihara Sangyo Kaisha, Ltd. Antranilamidas, proceso para la producción de las mismas y controladores de plagas que contienen las mismas
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
See also references of EP3632905A4

Cited By (1)

* Cited by examiner, † Cited by third party
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

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