WO2022028258A1 - 一种溴代吡唑羧酸酯类化合物的制备方法 - Google Patents

一种溴代吡唑羧酸酯类化合物的制备方法 Download PDF

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WO2022028258A1
WO2022028258A1 PCT/CN2021/108021 CN2021108021W WO2022028258A1 WO 2022028258 A1 WO2022028258 A1 WO 2022028258A1 CN 2021108021 W CN2021108021 W CN 2021108021W WO 2022028258 A1 WO2022028258 A1 WO 2022028258A1
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bromide
bromopyrazole
carboxylate
preparation
compound
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PCT/CN2021/108021
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French (fr)
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于海波
王学玲
赵贵民
杨浩
任忠宝
董燕
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沈阳中化农药化工研发有限公司
江苏扬农化工股份有限公司
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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
    • 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
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • 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
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D231/08—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen or sulfur atoms directly attached to ring carbon atoms

Definitions

  • the invention belongs to the field of organic synthesis, and in particular relates to a preparation method of a bromopyrazole carboxylate compound.
  • Benzamides are a new class of efficient and safe insecticides.
  • 3-bromo-N-(2-methyl-4-chloro-6-(carbamoyl)phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (Common name is tetrachlorantraniliprole)
  • 3-bromo-N-(2-methyl-4-cyano-6-(carbamoyl)phenyl)-1-(3-chloro-2-pyridyl) -1H-Pyrazole-5-carboxamide (common name cyantraniliprole) is an insecticide with high insecticidal activity by DuPont. Ishihara Sangyo Co., Ltd.
  • 3-Bromo-1H-pyrazole-5-carboxylate is a key intermediate in the synthesis of chlorantraniliprole, cyantraniliprole, cyclotraniliprole, and tetrachlorantraniliprole.
  • WO2003015518 discloses a synthesis method of 3-bromo-1-(pyridin-2-yl)-3-pyrazole-5-carboxylate, which consists of 1-(pyridin-2-yl)-3-pyrazolidone- 5-carboxylate reacts with phosphine tribromide or phosphine pentabromide to obtain bromopyrazole carboxylate.
  • phosphine tribromide or phosphine pentabromide will produce a large amount of phosphorus- and bromine-containing wastewater, causing serious environmental pollution.
  • the reaction formula is as follows:
  • CN101607957A also discloses a method for synthesizing 3-bromo-1-(pyridin-2-yl)-3-pyrazole-5-carboxylate, 1-(pyridin-2-yl)-3-pyrazolidone- 5-carboxylate reacts with p-toluenesulfonyl chloride, and then reacts with hydrogen bromide to obtain bromopyrazole carboxylate.
  • Hydrogen bromide gas or an acetic acid solution of hydrogen bromide can be used as a brominating reagent during the bromination reaction.
  • the purpose of the present invention is to provide a simpler and more efficient preparation method of brominated pyrazole carboxylate compounds.
  • the technical scheme adopted in the present invention is:
  • a kind of preparation method of bromopyrazole carboxylic acid ester compound, reaction formula is as follows:
  • R 1 is selected from alkyl, haloalkyl, optionally 1-3 selected from alkyl-substituted phenyl, halogen-substituted phenyl, nitro-substituted phenyl;
  • R 2 is selected from C 1 -C 6 Alkyl, C2 - C4alkenyl, C2 - C4alkynyl , C3- C6cycloalkyl , benzyl, halogen-substituted benzyl or substituted with up to 6 C1 - C4 alkyl groups Benzyl;
  • R 3 is selected from H, chlorine.
  • 3-Substituted sulfonyloxypyrazole carboxylate (II) is added to a suitable organic solvent, and a brominating reagent is added to obtain bromopyrazole carboxylate compound (I); the brominating reagent is inorganic bromine one or more of the salts.
  • the inorganic bromide salt is one of sodium bromide, potassium bromide, lithium bromide, ammonium bromide, magnesium bromide, calcium bromide, zinc bromide, barium bromide, iron bromide, copper bromide and nickel bromide or several kinds; the addition amount is 0.5-3 times the molar amount of the compound represented by the general formula (II).
  • the reaction temperature is 0-130°C, and the reaction is performed for 0.5-24 hours.
  • the 3-substituted sulfonyloxypyrazole carboxylate (II) is added to a suitable organic solvent, and a bromination reagent with a molar amount of 0.7-2 times the compound represented by the general formula (II) is added, and the bromination reagent is added at 20-110 At °C, the reaction is carried out for 1-18 hours, and the bromopyrazole carboxylate compound (I) is obtained by the reaction.
  • 3-substituted sulfonyloxypyrazole carboxylate (II) is added to a suitable organic solvent, and a bromination reagent of 1-1.5 times the molar amount of the compound represented by the general formula (II) is added, and the bromination reagent is added to 40- At 90° C., the reaction is carried out for 2-12 hours to obtain the bromopyrazole carboxylate compound (I).
  • the inorganic bromide salt is selected from sodium bromide, magnesium bromide, calcium bromide, zinc bromide or copper bromide.
  • the organic solvent is selected from ether, methyl butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, toluene, xylene, chlorobenzene, dichlorobenzene, pentane, hexane, cyclohexane, heptane , dichloromethane, dichloroethane, chloroform, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or N-methylpyrrolidone.
  • the suitable solvent is selected from tetrahydrofuran, toluene, xylene, chlorobenzene, methyl ethyl ketone, acetonitrile or N,N-dimethylformamide.
  • Alkyl refers to straight or branched chain forms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, etc. group. Cycloalkyl is meant to include cyclic chain forms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopropyl, cyclopropylcyclopropyl, and the like.
  • Alkenyl refers to straight or branched chain alkenyl groups such as 1-propenyl, 2-propenyl and the various butenyl groups, and the like.
  • Alkynyl refers to straight or branched chain alkynes such as 1-propynyl, 2-propynyl and the various butynyls, and the like.
  • the present invention has the characteristics: the present invention adopts inexpensive inorganic bromide salt as the bromination reagent for synthesizing bromopyrazole carboxylate, which is through the substitution reaction of 3-substituted sulfonyloxypyrazole carboxylate and inorganic bromide salt Furthermore, a high yield of bromopyrazole carboxylate was obtained, thereby completing the present invention.
  • the inorganic bromine salt avoids the generation of a large amount of phosphine-containing wastewater and reduces environmental pollution.
  • hydrogen bromide gas it has more cost advantages, and is easier to operate and use in the reaction process, and is more safe and reliable, so the present invention is easier to industrialize production.
  • the present invention adopts inexpensive inorganic bromine salt as the bromination reagent for synthesizing bromopyrazole carboxylate, which is by the substitution reaction of 3-substituted sulfonyloxy pyrazole carboxylate and inorganic bromine salt. Furthermore, a high yield of bromopyrazole carboxylate was obtained, thereby completing the present invention.
  • inorganic bromide salts avoid the generation of a large amount of phosphine-containing wastewater, reduce environmental pollution, have more cost advantages, and are easier to operate and use during the reaction process. Safe and reliable.
  • the method of the present invention is more simple and feasible for post-processing, and high-content bromopyrazole carboxylate can be obtained in high yield only by filtering and concentrating.
  • 3-p-toluenesulfonate-1-pyridylpyrazole-5-carboxyethyl ester prepared in the above example is subjected to bromination, hydrolysis, acylation and oxidation to obtain pyrazole acid chloride, which is then mixed with 2-Amino-3-methyl-5-chlorobenzamide was reacted to obtain a commercial variety of chlorantraniliprole (common name chlorantraniliprole), the content was 98%, and the total yield of the reaction was 73.8% (with 3- p-toluenesulfonate-1-pyridylpyrazole-5-carboxyethyl ester).
  • the present invention adopts inexpensive inorganic bromine salt as the bromination reagent for synthesizing bromopyrazole carboxylate, which is replaced by 3-substituted sulfonyloxy pyrazole carboxylate and inorganic bromine salt.
  • the reaction further obtains bromopyrazole carboxylate in high yield, and simultaneously using it as an intermediate for preparing bisamide insecticides, high-content commercial insecticide chlortetracycline can be prepared in high yield formamide.
  • the method improves the quality of the product, reduces the production cost, and also reduces the discharge of the three wastes, so the present invention is easier for industrial production.

Abstract

一种溴代吡唑羧酸酯类化合物的制备方法。反应式如下，式（I），式（II），式中各基团定义见说明书。一种制备苯甲酰胺类杀虫剂关键中间体溴代吡唑羧酸酯类化合物的方法，采用上述方法操作简单易行，更加安全可靠，更易于工业化生产。

Description

一种溴代吡唑羧酸酯类化合物的制备方法 技术领域
本发明属于有机合成领域，具体地涉及一种溴代吡唑羧酸酯类化合物的制备方法。
背景技术
苯甲酰胺类化合物是一类高效、安全的新型杀虫剂。其中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(通用名为四氯虫酰胺)、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(通用名为溴氰虫酰胺)为杜邦公司具有较高杀虫活性的杀虫剂。石原产业株式会社正在开发的双酰胺类化合物3-溴-N-(2-氯-4-溴-6-((1-环丙基乙基)酰基)苯基)-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺的(通用名为环溴虫酰胺)，具有广谱的杀虫活性。沈阳化工研究院发现了具有高杀虫活性的3-溴-N-(2,4-二氯-6-(甲氨酰基)苯基)-1-(3,5-二氯-2-吡啶基)-1H-吡唑-5-甲酰胺，也已经开发为杀虫剂，通用名为四氯虫酰胺。
Figure PCTCN2021108021-appb-000001
3-溴-1H-吡唑-5-羧酸酯是合成氯虫苯甲酰胺、溴氰虫酰胺、环溴虫酰胺、四氯虫酰胺的关键中间体。WO2003015518中公开了3-溴-1-(吡啶-2-基)-3-吡唑-5-羧酸酯的合成方法，由1-(吡啶-2-基)-3-吡唑烷酮-5-羧酸酯与三溴氧膦或五溴化膦反应制得溴代吡唑羧酸酯。使用三溴氧膦或五溴化膦，会产生大量含磷和含溴废水，环境污染严重。反应式如下：
Figure PCTCN2021108021-appb-000002
CN101607957A中也公开了合成3-溴-1-(吡啶-2-基)-3-吡唑-5-羧酸酯的方法，1-(吡啶-2-基)-3-吡唑烷酮-5-羧酸酯与对甲苯磺酰氯反应，再与溴化氢反应，制得溴代吡唑羧酸酯。在溴化反应过程中可以使用溴化氢气体或者溴化氢的乙酸溶液作为溴化试剂。如果使用溴化氢气体作为溴化试剂，需要在特定溶剂二溴甲烷中进行，可以高收率制得3-溴-1-(吡啶-2-基)-3-吡唑-5-羧酸酯。如果使用溴化氢乙酸溶液作为溴化试剂，也可以制得3-溴-1-(吡啶-2-基)-3-吡唑-5-羧酸酯，但收率低于溴化氢气体10％以上。反应式如下：
Figure PCTCN2021108021-appb-000003
虽然上述方法均可制备相应化合物，但随着市场需求不断更新技术人员致力于不断研究开发新的、更为先进合理的溴代吡唑羧酸酯类化合物制备方法，以期获得质量更优、价格更低的苯甲酰胺类杀虫剂。
发明内容
本发明的目的在于提供一种更为简便、更加高效地溴代吡唑羧酸酯类化合物的制备方法。
为实现上述目的，本发明采用的技术方案为：
一种溴代吡唑羧酸酯类化合物的制备方法，反应式如下：
Figure PCTCN2021108021-appb-000004
式中：R 1选自烷基、卤代烷基、任选1-3个选自烷基取代的苯基、卤素取代的苯基、硝基取代的苯基；R 2选自C 1-C 6烷基、C 2-C 4烯基、C 2-C 4炔基、C 3-C 6环烷基、苄基、卤素取代苄基或被至多6个C 1-C 4的烷基取代的苄基；R 3选自H、氯。
3-取代磺酰氧基吡唑羧酸酯(II)于适宜的有机溶剂中，加入溴化试剂，制得溴代吡唑羧酸酯类化合物(I)；所述溴化试剂为无机溴盐中的一种或几种。
所述无机溴盐为溴化钠、溴化钾、溴化锂、溴化铵、溴化镁、溴化钙、溴化锌、溴化钡、溴化铁、溴化铜、溴化镍其中一种或几种；其，添加量为通式(II)所示化合物摩尔量的0.5-3倍。
所述反应温度为0-130℃，反应0.5-24小时。
进一步的说，3-取代磺酰氧基吡唑羧酸酯(II)于适宜的有机溶剂中，加入通式(II)所示化合物摩尔量0.7-2倍的溴化试剂，于20-110℃下，反应1-18小时，反应制得溴代吡唑羧酸酯类化合物(I)。
再进一步的说，3-取代磺酰氧基吡唑羧酸酯(II)于适宜的有机溶剂中，加入通式(II)所示化合物摩尔量1-1.5倍的溴化试剂，于40-90℃下，反应2-12小时，反应制得溴代吡唑羧酸酯类化合物(I)。
所述无机溴盐选自溴化钠、溴化镁、溴化钙、溴化锌或溴化铜。
所述有机溶剂选自乙醚、甲基丁醚、四氢呋喃、二噁烷、二甲氧基乙烷、甲苯、二甲苯、氯苯、二氯苯、戊烷、已烷、环已烷、庚烷、二氯甲烷、二氯乙烷、氯仿、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮、甲基乙酮、环己酮、乙腈、丙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜或N-甲基吡咯烷酮。
所述适宜的溶剂选自四氢呋喃、、甲苯、二甲苯、氯苯、甲基乙酮、乙腈或N,N-二甲基甲酰胺。
上面给出的合成方法及各通式化合物中基团的定义中，汇集所用术语一般定义如下：
烷基是指直链或支链形式，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、特丁基、正戊基、异戊基等基团。环烷基是指包括环状链形式，例如环丙基、环丁基、环戊基、环己基、甲基环丙基、环丙基环丙基等基团。烯基是指直链或支链烯基，如1-丙烯基、2-丙烯基和不同的丁烯基等。炔基是指直链或支链炔烃，如1-丙炔基、2-丙炔基和不同的丁炔基等。
本发明所具有特点：本发明采用价格低廉的无机溴盐作为合成溴代吡唑羧酸酯的溴化试剂，其通过3-取代磺酰氧基吡唑羧酸酯与无机溴盐的取代反应进而获得高收率的溴代吡唑羧酸酯，从而完成了本发明。无机溴盐具相对于其他溴化试剂三溴氧膦而言，避免了大量含膦废水的产生，减少了环境污染。、相对于溴化氢气体，更具有成本优势，而且在反应过程中更易于操作使用，更加安全可靠，因此本发明更易于工业化生产。
具体实施方式
下面通过列举实施例来对本发明进行更详细的说明吡啶基吡唑烷 酮羧酸酯类化合物制备方法，但并不意味着限制本发明。
实施例1
3-溴-1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
Figure PCTCN2021108021-appb-000005
在1000mL反应瓶中依次加入500mL甲苯，吡唑羧酸乙酯(85.1g,98％,0.24mol)，溴化钠(27.4g，99％，0.264mol)，加热升温至90℃，保持温度90℃反应4小时，降温至室温25℃，过滤，滤液经减压蒸出甲苯，得到产品78.1g。外标法定量分析其含量为98.1％，收率95.9％。 1H-NMR(600MHz，CDCl 3):δ＝3.25-3.45(m,2H),δ＝5.28(t，1H)，δ＝6.88(t，1H)，δ＝7.67(d，1H)，δ＝8.10(d，1H)，δ＝1.20(t，3H)，δ＝4.18(q,2H)。
实施例2
3-溴-1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
Figure PCTCN2021108021-appb-000006
在1000mL反应瓶中依次加入500mL甲苯，吡唑羧酸乙酯(85.1g,98％,0.24mol)，溴化钾(31.7g，99％，0.264mol)，加热升温至90℃，保持温度90℃反应4小时，降温至室温25℃，过滤，滤液经减压蒸出甲苯，得到产品78.41g。外标法定量分析其含量为97.6％，收率95.9％。 1H-NMR(600MHz，CDCl 3):δ＝3.25-3.45(m,2H),δ＝5.28(t，1H)，δ＝6.88(t，1H)，δ＝7.67(d，1H)，δ＝8.10(d，1H)，δ＝1.20(t，3H)，δ＝4.18(q,2H)。
实施例3
3-溴-1-(3-氯吡啶-2-基)-3-吡唑烷酮-5-羧酸乙酯的合成
Figure PCTCN2021108021-appb-000007
在1000mL反应瓶中依次加入500mL二甲苯，吡唑羧酸乙酯(100.3g,98％,0.24mol)，溴化钾(31.7g，99％，0.264mol)，加热升温至100℃，保持温度100℃反应3小时，降温至室温25℃，过滤，滤液经减压蒸出二甲苯，得到产品77.7g。外标法定量分析其含量为97.6％，收率95％。 1H-NMR(600MHz，CDCl 3):δ＝3.25-3.45(m,2H),δ＝5.28(t，1H)，δ＝6.88(t，1H)，δ＝7.67(d，1H)，δ＝8.10(d，1H)，δ＝1.20(t，3H)，δ＝4.18(q,2H)。
实施例4
Figure PCTCN2021108021-appb-000008
在1000mL反应瓶中依次加入500mL二甲苯，吡唑羧酸乙酯(103.7g,98％,0.24mol)，溴化镍(58.2g，99％，0.264mol)，加热升温至80℃，保持温度80℃反应5小时，降温至室温25℃，过滤，滤液经减压蒸出二甲苯，得到产品78g。外标法定量分析其含量为97％，收率94.8％。 1H-NMR(600MHz，CDCl 3):δ＝3.25-3.45(m,2H),δ＝5.28(t，1H)，δ＝6.88(t，1H)，δ＝7.67(d，1H)，δ＝8.10(d，1H)，δ＝1.20(t，3H)，δ＝4.18(q,2H)。
实施例5
Figure PCTCN2021108021-appb-000009
在1000mL反应瓶中依次加入500mL二甲苯，吡唑羧酸乙酯(93.5g,98％,0.2mol)，溴化钙(48g，99％，0.24mol)，加热升温至80℃，保持温度80℃反应5小时，降温至室温25℃，过滤，滤液经减压蒸出二甲苯，得到产品71.92g。外标法定量分析其含量为98％，收率96％。 1H-NMR(600MHz，CDCl 3):δ＝3.25-3.45(m,2H),δ＝5.28(t，1H)，δ＝ 6.88(t，1H)，δ＝7.67(d，1H)，δ＝8.10(d，1H)，δ＝1.20(t，3H)，δ＝4.18(q,2H)。
由上述实施例可见，本发明采用价格低廉的无机溴盐作为合成溴代吡唑羧酸酯的溴化试剂，其通过3-取代磺酰氧基吡唑羧酸酯与无机溴盐的取代反应进而获得高收率的溴代吡唑羧酸酯，从而完成了本发明。无机溴盐相对于其他溴化试剂三溴氧膦、溴化氢而言，避免了大量含膦废水的产生，减少了环境污染，更具有成本优势，而且在反应过程中更易于操作使用，更加安全可靠。另外，采用本发明的方法后处理更加简单易行，只通过过滤、浓缩即可以高收率得到高含量的溴代吡唑羧酸酯。
应用实例
Figure PCTCN2021108021-appb-000010
按照上述反应式，将上述实施例制备所得3-对甲苯磺酸酯基-1-吡啶基吡唑-5-羧乙酯经过溴化、水解、酰化氧化，制得吡唑酰氯，再与2-氨基-3-甲基-5-氯苯甲酰甲胺反应制得商品化品种氯虫苯甲酰胺(通用名chlorantraniliprole)，含量98％，反应的总收率为73.8％(以3-对甲苯磺酸酯基-1-吡啶基吡唑-5-羧乙酯计)。
由上述应用实施例可见，本发明采用价格低廉的无机溴盐作为合成溴代吡唑羧酸酯的溴化试剂，其通过3-取代磺酰氧基吡唑羧酸酯与无机溴盐的取代反应进而以高收率的获得溴代吡唑羧酸酯，同时使用其再进一步作为制备双酰胺类杀虫剂的中间体，可以高收率地制备高含量的商品化杀虫剂氯虫苯甲酰胺。该方法提高了产品的品质，降低了生产成本，同时还减少了三废排放，因此本发明更易于工业化生产。

Claims (8)

  1. 一种溴代吡唑羧酸酯类化合物的制备方法，反应式如下：
    Figure PCTCN2021108021-appb-100001
    其特征在于：
    3-取代磺酰氧基吡唑羧酸酯(II)于适宜的有机溶剂中，加入溴化试剂，制得溴代吡唑羧酸酯类化合物(I)；所述溴化试剂为无机溴盐中的一种或几种。
  2. 按权利要求1所述的溴代吡唑羧酸酯类化合物的制备方法，其特征在于：所述无机溴盐为溴化钠、溴化钾、溴化锂、溴化铵、溴化镁、溴化钙、溴化锌、溴化钡、溴化铁、溴化铜、溴化镍其中一种或几种；其，添加量为通式(II)所示化合物摩尔量的0.5-3倍。
  3. 按权利要求1或2所述的溴代吡唑羧酸酯类化合物的制备方法，其特征在于：所述反应温度为0-130℃，反应0.5-24小时。
  4. 按权利要求3所述的溴代吡唑羧酸酯类化合物的制备方法，其特征在于：3-取代磺酰氧基吡唑羧酸酯(II)于适宜的有机溶剂中，加入通式(II)所示化合物摩尔量0.7-2倍的溴化试剂，于20-110℃下，反应1-18小时，反应制得溴代吡唑羧酸酯类化合物(I)。
  5. 按权利要求4所述的溴代吡唑羧酸酯类化合物的制备方法，其特征在于：3-取代磺酰氧基吡唑羧酸酯(II)于适宜的有机溶剂中，加入通式(II)所示化合物摩尔量1-1.5倍的溴化试剂，于40-90℃下，反应2-12小时，反应制得溴代吡唑羧酸酯类化合物(I)。
  6. 按权利要求2所述的溴代吡唑羧酸酯类化合物的制备方法，其特征在于：所述无机溴盐选自溴化钠、溴化镁、溴化钙、溴化锌或溴化铜。
  7. 按权利要求1所述的溴代吡唑羧酸酯类化合物的制备方法，其特征在于：所述有机溶剂选自乙醚、甲基丁醚、四氢呋喃、二噁烷、二甲氧基乙烷、甲苯、二甲苯、氯苯、二氯苯、戊烷、已烷、环已烷、庚烷、二氯甲烷、二氯乙烷、氯仿、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮、甲基乙酮、环己酮、乙腈、丙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜或N-甲基吡咯烷酮。
  8. 按权利要求7所述的溴代吡唑羧酸酯类化合物的制备方法，其 特征在于：所述适宜的溶剂选自四氢呋喃、甲苯、二甲苯、氯苯、甲基乙酮、乙腈或N,N-二甲基甲酰胺。
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