WO2023197562A1 - 一种虫螨腈及类似物的制备方法 - Google Patents

一种虫螨腈及类似物的制备方法 Download PDF

Info

Publication number
WO2023197562A1
WO2023197562A1 PCT/CN2022/127763 CN2022127763W WO2023197562A1 WO 2023197562 A1 WO2023197562 A1 WO 2023197562A1 CN 2022127763 W CN2022127763 W CN 2022127763W WO 2023197562 A1 WO2023197562 A1 WO 2023197562A1
Authority
WO
WIPO (PCT)
Prior art keywords
preparation
chloride
reaction
acetate
add
Prior art date
Application number
PCT/CN2022/127763
Other languages
English (en)
French (fr)
Inventor
张通
张少武
张小航
Original Assignee
陕西美邦药业集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 陕西美邦药业集团股份有限公司 filed Critical 陕西美邦药业集团股份有限公司
Publication of WO2023197562A1 publication Critical patent/WO2023197562A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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

Definitions

  • This disclosure belongs to the technical field of pesticides and is based on 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile, chloride, dialkoxymethane or diene.
  • Propoxymethane is used as raw material, and in the presence of ester solvent and acid binding agent, fenfonitrile and its analogues are prepared.
  • Difentrile is a new type of azole insecticide and acaricide developed by the American Cyanamid Company. It acts on the mitochondria of cells in insects and works through the multifunctional oxidase in insects. It mainly inhibits adenosine diphosphate (ADP). Conversion to adenosine triphosphate (ATP). Adenosine triphosphate stores the energy necessary for cells to maintain their life functions. This medicine has stomach poisoning and contact effects. It has strong permeability on the leaf surface, has a certain systemic effect, and has the characteristics of broad insecticidal spectrum, high control effect, long-lasting effect and safety. Can control resistant pests.
  • ADP adenosine diphosphate
  • ATP adenosine triphosphate
  • chlorpyronil and its analogs such as those introduced in CN 110218170 A, CN 109438315 A, CN101591284, and CN1439634, which all use chloromethyl ether as raw materials, but chloromethyl ether is a dangerous goods catalog material. It is highly flammable and has carcinogenic risks and is harmful if inhaled, in contact with skin and if swallowed. There are great safety risks in procurement, transportation, storage and use.
  • toluene, diethoxymethane, and phosphorus trichloride (or phosphorus oxychloride) as raw materials introduced in CN104016899 solves the above problems.
  • Trichlorination Phosphorus and phosphorus oxychloride are toxic, irritating and highly corrosive. Reacts violently when exposed to water and may explode. Inhalation of phosphorus trichloride gas can cause conjunctival inflammation, sore throat and eye tissue damage, and can irritate the lungs and mucous membranes.
  • This product is highly corrosive and can cause burns when in contact with skin and may cause pollution to water bodies. Combustion produces toxic nitrogen oxides and chloride fumes, which can generate heat or even explode when exposed to water or acid. 2
  • This process produces a large amount of phosphorus-containing wastewater that is difficult to treat and has high environmental costs.
  • the present disclosure aims to provide a clean, safe, efficient, and suitable industrial production method for fenfonitrile synthesis.
  • First mix B and Z in the reaction bottle add the catalyst, react at the set temperature, and then add 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H- to the reaction system Pyrrole-3-carbonitrile reacts with the acid-binding agent, and after the reaction is completed, the pyrrole-3-carbonitrile and its analogues are obtained by quenching and separation.
  • the preparation steps of this method are as follows: first mix B and Z in a reaction bottle, add a catalyst, react at a set temperature, and then add 4-bromo-2-(4-chlorophenyl)-5- to the reaction system. Trifluoromethyl-1H-pyrrole-3-carbonitrile reacts with an acid-binding agent. After the reaction is completed, fenfennitrile and its analogues are obtained by quenching and separation. After purification, fine fenfennitrile and its analogues can be obtained.
  • the chloride described in the above steps can be acetyl chloride, benzoyl chloride, thionyl chloride, ethyl chloroformate, oxalyl chloride, optionally acetyl chloride, 4-bromo-2-(4-chlorophenyl)
  • the equivalent ratio of -5-trifluoromethyl-1H-pyrrole-3-carbonitrile to chloride is 1.0:1.0-3.0.
  • Z described in the above steps can be dialkoxymethane, diallyloxymethane, 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-methyl
  • the equivalent ratio of nitrile to Z is 1.0:1.0-3.0
  • the acid binding agent described in the above steps is selected from one or more of inorganic bases and organic bases;
  • the inorganic base is selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates , one or more alkali metal bicarbonates, the optional inorganic base is potassium carbonate or a mixture of potassium carbonate and sodium hydroxide;
  • the organic base is selected from triethylamine, pyridine, diisopropyl ethyl One or more amines, the optional organic base is triethylamine.
  • the equivalent ratio of 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile and acid-binding agent is 1.0:1.0-5.0.
  • the ester solvent described in the above steps is selected from one or more of ethyl acetate, methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, tert-butyl acetate, and ethyl propionate.
  • the optional ester solvent is ethyl acetate
  • the weight ratio of 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile to the ester solvent is 1.0 :3.0-10.
  • reaction temperature described in the above steps is 0-80°C
  • the optional reaction temperature is 10°C-55°C
  • the optimal reaction temperature is 25-35°C.
  • the alcohol solvent used for the purification is selected from one or more types of methanol, ethanol, isopropanol, n-butanol or water, optionally a methanol aqueous solution, 4-bromo-2-(4-chlorophenyl)-
  • the weight ratio of 5-trifluoromethyl-1H-pyrrole-3-carbonitrile and alcohol solvent is 1.0:3.0-10.
  • the reaction time of this preparation method is 1-24 hours, and the optional reaction time is 2-8 hours.
  • the advantage of this disclosure is that it avoids the procurement, transportation and storage of toxic and dangerous chemicals such as chloromethyl ether, phosphorus trichloride, phosphorus oxychloride, etc., and the process is safe and environmentally friendly. Moreover, the reaction conditions are mild, the product yield and content are high, and the amount of three wastes is small, so it is suitable for industrial production.
  • toxic and dangerous chemicals such as chloromethyl ether, phosphorus trichloride, phosphorus oxychloride, etc.
  • Acetyl chloride (30.27g, 0.3856mol) and diethoxymethane (40.10g, 0.3856mol) were added to the four-necked flask, and concentrated sulfuric acid (0.3149g, 3.213mmol) was added to the system after reacting at 20-30°C for 2 hours.
  • Ethyl acetate (283.1g, 3.213mol), 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile (112.3g, 0.3213mol) were stirred and dissolved Afterwards, triethylamine (39.02g, 0.3856mol) was added dropwise to the system at 20-30°C, and reacted at this temperature for 2 hours.
  • Acetyl chloride (30.27g, 0.3856mol) and diethoxymethane (40.10g, 0.3856mol) were added to the four-necked flask, and concentrated sulfuric acid (0.3149g, 3.213mmol) was added to the system after reacting at 20-30°C for 2 hours.
  • n-Butyl acetate (298.5g, 2.570mol), 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile (112.3g, 0.3213mol) and then stir After dissolution, add a mixture of sodium hydroxide (8.996g, 0.2249mol) and potassium carbonate (79.93g, 0.5783mol) to the system at 20-30°C, and react at this temperature for 6 hours. Monitor the reaction to complete and add to the system. Add water to the mixture, wash with water, separate into layers, and remove the solvent.
  • the crude fenfentrile was obtained, and 80% isopropyl alcohol aqueous solution was added to the desolvated material for recrystallization to obtain 123.5g of fenfentrile technical material, with a content of 99.1% and a yield of 94.26%.
  • any combination of various embodiments of the present disclosure can also be carried out, and as long as they do not violate the idea of the present disclosure, they should also be regarded as the contents disclosed in the present disclosure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrrole Compounds (AREA)

Abstract

本公开提供一种虫螨腈及类似物的制备方法。其特征在于：所述的制备方法以4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈、氯化物、二烷氧基甲烷或二烯丙氧基甲烷为原料，在酯类溶剂和缚酸剂的存在下，制备虫螨腈及其类似物。本公开方法所制备的虫螨腈原药含量高，粒度分布均匀，同时工艺中有效避免了危险化学品的运输储存，具有生产工艺条件简单、反应条件温和、生产成本低廉且三废量少、环境友好等优点，具有良好的规模化工业生产应用前景。

Description

一种虫螨腈及类似物的制备方法
相关申请的交叉引用
本公开要求于2022年04月15日提交中国专利局的申请号为CN202210400151.0、名称为“一种虫螨腈及类似物的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开属于农药技术领域，是以4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈、氯化物、二烷氧基甲烷或二烯丙氧基甲烷为原料，在酯类溶剂和缚酸剂的存在下，制备虫螨腈及其类似物。
背景技术
虫螨腈，又名溴虫腈、除尽、专攻，化学名：4-溴-2-(4-氯苯基)-1-(乙氧基甲烷)-5-三氟甲基吡咯-3-甲腈，英文名：chlorfenapyr，化学式如下：
Figure PCTCN2022127763-appb-000001
虫螨腈是由美国氰胺公司开发的新型吡咯类杀虫、杀螨剂，作用于昆虫体内细胞的线粒体上，通过昆虫体内的多功能氧化酶起作用，主要抑制二磷酸腺苷(ADP)向三磷酸腺苷(ATP)的转化。而三磷酸腺苷贮存细胞维持其生命机能所必须的能量。该药具有胃毒及触杀作用。在叶面渗透性强，有一定的内吸作用，且具有杀虫谱广、防效高、持效长、安全的特点。可以控制抗性害虫。
现行的虫螨腈及其类似物的合成工艺较多，如CN 110218170 A、CN 109438315 A、CN101591284、CN1439634中介绍的均以氯甲基乙醚作为原料，但氯甲基乙醚为危险品目录物料，其高度易燃，且有致癌风险，吸入、皮肤接触及吞食有害。在采购、运输、储存、使用方面均存在非常大的安全隐患。CN104016899中介绍的以甲苯、二乙氧基甲烷、三氯化磷(或三氯氧磷)为原料解决了上述问题，是目前比较常见的生产工艺，但该工艺的缺点是：①三氯化磷和 三氯氧磷有毒，有刺激性和强腐蚀性。遇水发生激烈反应，可引起爆炸。吸入三氯化磷气体后能使结膜发炎，喉痛及眼睛组织破坏，对肺和黏膜都有刺激作用。该品腐蚀性强，与皮肤接触容易灼伤，对水体可造成污染。燃烧产生有毒氮氧化物和氯化物烟雾，遇水或酸即发热乃至爆炸。②该工艺产生大量难以处理的含磷废水，环境成本高。
发明内容
针对上述虫螨腈生产工艺中存在的问题，本公开旨在提供一个清洁、安全、高效、适合工业化生产的虫螨腈合成方法。
本公开采用下面的技术方案：
先将B与Z于反应瓶中混合，加入催化剂，在设定温度下反应，再向反应体系中加入4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈和缚酸剂进行反应，反应结束，淬灭分离得到虫螨腈及其类似物。
反应式如下：
Figure PCTCN2022127763-appb-000002
B为：氯化物
Z为：
Figure PCTCN2022127763-appb-000003
(R＝氢或C1—C3的烷基或乙烯基)。
本方法的制备步骤如下：先将B与Z于反应瓶中混合，加入催化剂，在设定温度下反应，再向反应体系中加入4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈和缚酸剂进行反应，反应结束，淬灭分离得到虫螨腈及其类似物，经纯化后可得精品虫螨腈及其类似物。
上述步骤中所述的氯化物可以为乙酰氯、苯甲酰氯、氯化亚砜、氯甲酸乙酯、草酰氯，可选地为乙酰氯，4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈与氯化物的当量比为1.0：1.0—3.0。
上述步骤中所述的Z可以为二烷氧基甲烷、二烯丙氧基甲烷，4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈与Z的当量比为1.0：1.0—3.0
上述步骤中所述的缚酸剂选自无机碱、有机碱中的一种或多种；所述的无机碱选自碱金属的氢氧化物、碱金属的氧化物、碱金属的碳酸盐、碱金属的碳酸氢盐中的一种或多种，可选的无机碱为碳酸钾或碳酸钾和氢氧化钠混合物；所述的有机碱选自三乙胺、吡啶、二异丙基乙基胺中的一种或多种，可选的有机碱为三乙胺。4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈与缚酸剂的当量比为1.0：1.0—5.0。
上述步骤中所述的酯类溶剂选自乙酸乙酯、乙酸甲酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸叔丁酯、丙酸乙酯中的一种或多种，可选的酯类溶剂为乙酸乙酯，4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈与酯类溶剂的重量比为1.0：3.0—10。
上述步骤中所述的反应温度为0-80℃，可选的反应温度为10℃—55℃，最佳反应温度为25-35℃。
所述提纯所用醇类溶剂选自甲醇、乙醇、异丙醇、正丁醇或水中的一种或多种，可选地为甲醇水溶液，4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈与醇类溶剂的重量比为1.0：3.0—10。
本制备方法的反应时间为1-24小时，可选的反应时间为2-8小时。
本公开的优点在于，本公开的优点在于避免了有毒、危险化学品氯甲基乙醚、三氯化磷、三氯氧磷等的采购、运输和储存，工艺安全、环保。且反应条件温和，产品收率和含量高、三废量少，适宜工业化生产。
具体实施方式
以下对本公开的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本公开，并不用于限制本公开。
实施例中的百分比均为重量百分比。
实施例1
四口瓶中加入乙酰氯(30.27g,0.3856mol)和二乙氧基甲烷(40.10g,0.3856mol)，浓硫酸(0.3149g,3.213mmol)于20-30℃反应2h后，向体系中加入乙酸乙酯(283.1g,3.213mol)、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯 -3-甲腈(112.3g,0.3213mol)后搅拌溶解后，于20-30℃，向体系中滴加三乙胺(39.02g,0.3856mol)，并在该温度下反应2h，监控反应结束，向体系中加入水，水洗，分层，脱溶。得到虫螨腈粗品，在脱溶后的物料中加入80％的甲醇水溶液进行重结晶，得到虫螨腈原药125.5g，含量99.1％，收率95.85％。
实施例2
四口瓶中加入乙酰氯(40.43g,0.5150mol)和二乙氧基甲烷(53.56g,0.5150mol)，对甲苯磺酸(1.109g,6.438mmol)于30-40℃反应3h后，再向体系中加入乙酸甲酯(349.75g,4.721mol)、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈(150.0g,0.4292mol)后搅拌溶解后，于20-30℃，向体系中加入碳酸钾(148.3g,1.073mol)，并在该温度下反应7h，监控反应结束，向体系中加入水，水洗，分层，脱溶。得到虫螨腈粗品，在脱溶后的物料中加入85％的异丙醇水溶液进行重结晶，得到虫螨腈原药164.7g，含量99.0％，收率94.13％。
实施例3
四口瓶中加入氯化亚砜(76.59g,0.6438mol)和二甲氧基甲烷(39.19g,0.5150mol)，浓硫酸(0.4206g,4.292mmol)于40-50℃反应3.5h后，再向体系中加入乙酸甲酯(318.0g,4.292mol)、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈(150.0g,0.4292mol)后搅拌溶解后，于20-30℃，向体系中滴加三乙胺(65.15g,0.6438mol)，并在该温度下反应5h，监控反应结束，向体系中加入水，水洗，分层，脱溶。得到4-溴-2-(4-氯苯基)-1-甲氧基甲基-5-三氟甲基吡咯-3-腈粗品，在脱溶后的物料中加入80％的乙醇水溶液进行重结晶，得到4-溴-2-(4-氯苯基)-1-甲氧基甲基-5-三氟甲基吡咯-3-腈，156.0g，含量98.7％，收率92.37％。
实施例4
四口瓶中加入乙酰氯(30.27g,0.3856mol)和二乙氧基甲烷(40.10g,0.3856mol)，浓硫酸(0.3149g,3.213mmol)于20-30℃反应2h后，向体系中加入乙酸正丁酯(298.5g,2.570mol)、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯 -3-甲腈(112.3g,0.3213mol)后搅拌溶解后，于20-30℃，向体系中加入氢氧化钠(8.996g,0.2249mol)和碳酸钾(79.93g,0.5783mol)的混合物，并在该温度下反应6h，监控反应结束，向体系中加入水，水洗，分层，脱溶。得到虫螨腈粗品，在脱溶后的物料中加入80％的异丙醇醇水溶液进行重结晶，得到虫螨腈原药123.5g，含量99.1％，收率94.26％。
实施例5
四口瓶中加入乙酰氯(44.21g,0.5632mol)和二烯丙氧基甲烷(56.39g,0.5632mol)，浓硫酸(0.849g,8.664mmol)于60-70℃反应5h后，再向体系中加入乙酸丙酯(398.2g,3.899mol)、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈(151.4g,0.4332mol)后搅拌溶解后，于60-65℃，向体系中二异丙基乙基胺(83.99g,0.6498mol)，并在该温度下反应4h，监控反应结束，向体系中加入水，水洗，分层，脱溶。得到4-溴-2-(4-氯苯基)-1-二烯丙氧基甲基-5-三氟甲基吡咯-3-腈粗品，在脱溶后的物料中加入95％的甲醇水溶液进行重结晶，得到4-溴-2-(4-氯苯基)-1-二烯丙氧基甲基-5-三氟甲基吡咯-3-腈，153.1g，含量98.4％，收率87.41％。
实施例6
四口瓶中加入乙酰氯(32.61g,0.4154mol)和二乙氧基甲烷(43.20g,0.4154mol)，对甲苯磺酸(0.8942g,5.193mmol)于20-30℃反应3h，监控反应结束，向体系中加入乙酸叔丁酯(321.8g,2.770mol)、4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈(121.0g,0.3462mol)后搅拌溶解后，于40-50℃，向体系中滴加吡啶(35.60g,0.4500mol)，并在该温度下反应6h，监控反应结束，向体系中加入水，水洗，分层，脱溶。得到虫螨腈粗品，在脱溶后的物料中加入80％的异丙醇水溶液进行重结晶，得到虫螨腈原药127.8g，含量99.0％，收率90.53％。
以上详细描述了本公开的可选的实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。

Claims (9)

  1. 一种虫螨腈及类似物的制备方法，其特征在于：以4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈、B、Z为原料，在酯类溶剂和缚酸剂的存在下，制备虫螨腈及其类似物，其反应式如下：
    Figure PCTCN2022127763-appb-100001
    B为：氯化物；
    Z为：
    Figure PCTCN2022127763-appb-100002
    (R＝氢或C1—C3的烷烃基或乙烯基)。
  2. 根据权利要求1所述虫螨腈及类似物的制备方法，其特征在于：具体操作步骤是，先将B与Z于反应瓶中混合，加入催化剂，在设定温度下反应，再向反应体系中加入4-溴-2-(4-氯苯基)-5-三氟甲基-1H-吡咯-3-甲腈和缚酸剂进行反应，反应结束，淬灭分离得到虫螨腈及其类似物。
  3. 根据权利要求1或2所述虫螨腈及类似物的制备方法，其特征在于：所述的催化剂选自有机酸、无机酸、固体酸中的一种或多种。
  4. 根据权利要求1或2所述虫螨腈及类似物的制备方法，其特征在于：所述的缚酸剂选自无机碱、有机碱中的一种或多种；
    所述的无机碱选自碱金属的氢氧化物、碱金属的氧化物、碱金属的碳酸盐、碱金属的碳酸氢盐中的一种或多种；
    所述的有机碱选自三乙胺、吡啶、二异丙基乙基胺中的一种或多种。
  5. 根据权利要求1所述虫螨腈及类似物的制备方法，其特征在于：酯类溶剂选自乙酸乙酯、乙酸甲酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸叔丁酯、丙酸乙酯中的一种或多种。
  6. 根据权利要求1或2所述虫螨腈及类似物的制备方法，其特征在于：所述的B选自乙酰氯、苯甲酰氯、氯化亚砜、氯甲酸乙酯、草酰氯中的一种或多种。
  7. 根据权利要求1或2所述虫螨腈及类似物的制备方法，其特征在于：所述的Z选自二烷氧基甲烷或二烯丙氧基甲烷。
  8. 根据权利要求2所述虫螨腈及类似物的制备方法，其特征在于：制备方法中反应温度为0℃—80℃；
    优选的反应温度为10℃—55℃。
  9. 根据权利要求1至8任一项所述虫螨腈及类似物的制备方法的提纯工艺，其特征在于：制得的虫螨腈及其类似物用甲醇、乙醇、异丙醇、正丁醇和水中的一种或多种进行提纯。
PCT/CN2022/127763 2022-04-15 2022-10-26 一种虫螨腈及类似物的制备方法 WO2023197562A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210400151.0 2022-04-15
CN202210400151.0A CN115286551A (zh) 2022-04-15 2022-04-15 一种虫螨腈及类似物的制备方法

Publications (1)

Publication Number Publication Date
WO2023197562A1 true WO2023197562A1 (zh) 2023-10-19

Family

ID=83820747

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/127763 WO2023197562A1 (zh) 2022-04-15 2022-10-26 一种虫螨腈及类似物的制备方法

Country Status (2)

Country Link
CN (1) CN115286551A (zh)
WO (1) WO2023197562A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117586167A (zh) * 2024-01-18 2024-02-23 山东潍坊双星农药有限公司 一种虫螨腈新合成工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116082211B (zh) * 2023-04-10 2023-07-28 山东新龙农化有限公司 一种溴虫腈的合成方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358047A2 (en) * 1988-09-08 1990-03-14 American Cyanamid Company Method of controlling phytopathogenic fungi
CN101591284A (zh) * 2009-06-29 2009-12-02 湖南化工研究院 溴虫腈及其类似物的制备方法
CN102617439A (zh) * 2012-02-27 2012-08-01 山东潍坊双星农药有限公司 一种溴虫腈的制备方法
CN104016899A (zh) * 2014-05-16 2014-09-03 浙江师范大学 一种溴虫腈的合成方法
CN109169668A (zh) * 2018-09-11 2019-01-11 江苏省血吸虫病防治研究所 2-芳基取代吡咯类化合物在杀小泡螺药物中的应用
CN109438315A (zh) * 2018-11-14 2019-03-08 江苏宝众宝达药业有限公司 一种虫螨腈的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5359090A (en) * 1993-12-29 1994-10-25 American Cyanamid Company Alkoxymethylation of pyrroles
JP4693840B2 (ja) * 2005-03-30 2011-06-01 大塚化学株式会社 ハロアルキルエーテル化合物の製造方法
CN104710286B (zh) * 2015-04-01 2016-07-06 中国科学院上海有机化学研究所 一种氯甲基甲基醚及其甲氧甲基保护的化合物的合成方法
CN110218170A (zh) * 2019-07-03 2019-09-10 山东潍坊双星农药有限公司 一种混合型催化剂催化合成虫螨腈的生产工艺

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358047A2 (en) * 1988-09-08 1990-03-14 American Cyanamid Company Method of controlling phytopathogenic fungi
CN101591284A (zh) * 2009-06-29 2009-12-02 湖南化工研究院 溴虫腈及其类似物的制备方法
CN102617439A (zh) * 2012-02-27 2012-08-01 山东潍坊双星农药有限公司 一种溴虫腈的制备方法
CN104016899A (zh) * 2014-05-16 2014-09-03 浙江师范大学 一种溴虫腈的合成方法
CN109169668A (zh) * 2018-09-11 2019-01-11 江苏省血吸虫病防治研究所 2-芳基取代吡咯类化合物在杀小泡螺药物中的应用
CN109438315A (zh) * 2018-11-14 2019-03-08 江苏宝众宝达药业有限公司 一种虫螨腈的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHENG DONGQING, CAO WEI, MA HAIYAN, DING KAI: "Efficient Synthesis of Chloromethyl Methyl Ether and One-Pot Hydroxyl Protection", CHINESE JOURNAL OF ORGANIC CHEMISTRY, SCIENCE PRESS, BEIJING., CN, vol. 36, no. 5, 16 January 2016 (2016-01-16), CN , pages 1122, XP093098260, ISSN: 0253-2786, DOI: 10.6023/cjoc201512013 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117586167A (zh) * 2024-01-18 2024-02-23 山东潍坊双星农药有限公司 一种虫螨腈新合成工艺

Also Published As

Publication number Publication date
CN115286551A (zh) 2022-11-04

Similar Documents

Publication Publication Date Title
WO2023197562A1 (zh) 一种虫螨腈及类似物的制备方法
JP3145220B2 (ja) 新規の１，２，４−トリアミノベンゼン誘導体およびその製造方法
DE1595915A1 (de) Verfahren zur Herstellung von heterocyclischen Benzamiden
US3014063A (en) 3-amino-2, 5-dichlorobenzoates
Parker Chemistry of dinitroacetonitrile—IV: Preparation and properties of esters of dinitrocyanoacetic acid
US7592462B2 (en) Explosive complexes
KR19990082249A (ko) 퍼플루오로(알콕시시클로알칸)카르보닐 플루오리드 조성물 및그 용도
DE2029299B2 (de) Neue Aminophenylamidine, Verfahren zu ihrer Herstellung und diese enthaltende Arzneimittel
Gunther Aspects of the chemistry of DDT
DE2031227A1 (de) Neue substituierte Sahcylsauren und Verfahren zu ihrer Herstellung
ITMI942362A1 (it) Procedimento per la preparazione di una combinazione chimica farmacologicamente attiva
Kikugawa et al. Selective reduction of oximes with pyridine-borane
EP1076643A1 (de) Biphenylderivate
US3278600A (en) alpha-amine-p-methoxyisobutyrophenone and salts thereof
US3471523A (en) Conjugated vinyl azides and their preparation
EP0001051B1 (de) Benzolsulfonamidderivate, Verfahren zu ihrer Herstellung und diese enthaltende pharmazeutische Präparate
CH629757A5 (en) Process for the preparation of cyanoacetanilide derivatives
DE2409313A1 (de) Neue pyrrolyl-verbindungen und verfahren zu ihrer herstellung
DE2718871C3 (de) N-(2-Furylmethyl)-5-sulfamoylorthanilsäuren und deren physiologisch verträgliche Salze und Verfahren zu ihrer Herstellung und ihre Verwendung bei der Bekämpfung von Oedemkrankheiten und Bluthochdruck
US3481979A (en) Propargyl benzamides
PL97785B1 (pl) Sposob wytwarzania nowych pochodnych 1-sulfonylobenzimidazolu
BE633594A (zh)
CA1153387A (en) Substituted amino acids, their use and production and pharmaceutical products containing same
KR790001895B1 (ko) 치환된 페닐구아니딘류의 제조방법
EP2188245B1 (en) Nitric oxide releasing derivatives of paracetamol

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22937195

Country of ref document: EP

Kind code of ref document: A1