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WO2021115400A1 - 一种咪唑啉酮化合物的制备方法 - Google Patents

一种咪唑啉酮化合物的制备方法 Download PDF

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Publication number
WO2021115400A1
WO2021115400A1 PCT/CN2020/135521 CN2020135521W WO2021115400A1 WO 2021115400 A1 WO2021115400 A1 WO 2021115400A1 CN 2020135521 W CN2020135521 W CN 2020135521W WO 2021115400 A1 WO2021115400 A1 WO 2021115400A1
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compound
imidazolinone
reaction
preparing
general formula
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French (fr)
Inventor
关云飞
王徵
陈霖
英君伍
梁爽
杨辉斌
于海波
邓旭
李子亮
朱建荣
金守征
李斌
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Shenyang Sciencreat Chemicals Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Sciencreat Chemicals Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • the present invention relates to compound synthesis, in particular to a method for preparing imidazolinone compound (I).
  • imidazolinone compounds are developed by the American Cyanamid Company. They have high herbicidal activity, high efficiency, broad spectrum and low toxicity. Patents US4798619 and US5334576 disclose that imidazolinone compounds are highly effective broad-spectrum herbicides that are beneficial to the environment.
  • Imidazolinone compound (I) is a soybean field herbicide developed by American Cyanamid Company. It is used as an ALS inhibitor to inhibit the biosynthesis of side chain amino acids. It has high activity, low dosage, and broad herbicidal spectrum, so it has a high The value of use, can be used for pre-emergence and post-emergence application.
  • the purpose of the present invention is to provide a simple, environmentally friendly, and low-cost method for preparing imidazolinone compounds.
  • the quaternary ammonium salt compound of general formula II is reacted with 2-amino-2,3-dimethylbutanamide in a suitable solvent in the presence of a base at a temperature ranging from 0°C to the boiling point of a suitable solvent, and acidified after the reaction to obtain imidazoline Ketone compound (I).
  • the quaternary ammonium salt compound represented by the general formula II and 2-amino-2,3-dimethylbutanamide undergo a condensation reaction in a suitable solvent in the presence of a base at a temperature ranging from 0°C to the boiling point of the suitable solvent 0.5-10 hours, acidification to prepare imidazolinone compound (I);
  • the molar ratio of the quaternary ammonium salt compound represented by the general formula II to 2-amino-2,3-dimethylbutanamide is 1:1-1.5; the molar ratio of the quaternary ammonium salt compound represented by the general formula II to the base addition is 1:2-4.
  • the suitable base is selected from sodium methoxide, potassium methoxide or lithium methoxide;
  • the acid is selected from one or more of hydrochloric acid, sulfuric acid and acetic acid;
  • the solvent is selected from dichloromethane, dichloroethane, toluene or chlorobenzene .
  • the molar ratio of the quaternary ammonium salt compound represented by the general formula II to 2-amino-2,3-dimethylbutanamide is 1:1 to 1.2; the quaternary ammonium salt compound represented by the general formula II and the base are fed by moles The ratio is 1:3-4;
  • the reaction temperature is 20° C. to the boiling point of a suitable solvent; the condensation reaction is 0.5-8 hours; the solvent is selected from toluene or chlorobenzene, and the acid is selected from hydrochloric acid or sulfuric acid.
  • R 1 and R 2 are each independently selected from C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl, halogenated phenyl, phenyl C 1 -C 6 alkane Group or halophenyl C 1 -C 6 alkyl group;
  • X is selected from chlorine or bromine
  • Q is selected from the following groups:
  • R 3 , R 4 , and R 5 are each independently selected from C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl C 1 -C 6 alkyl;
  • R 6 is selected from halogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 1 -C 6 alkoxy;
  • n is selected from 0-5;
  • n is selected from 0-4;
  • p is selected from 0-3.
  • the tetra-substituted pyridine compound 1 is obtained in the reaction process for preparing imidazolinone compound (I), and its structural formula is as follows:
  • One such compound 1 is used to identify the use of the synthesis method of the imidazolinone compound represented by the above general formula (I).
  • the combination is imidazolinone compound (I) and compound 1; compound 1 accounts for 0.01%-10% of the composition by mass.
  • a method for controlling weeds of a herbicidal composition comprises applying a herbicidal effective dose of the herbicidal composition to the weeds or the growth medium or places of the weeds.
  • Alkyl refers to linear or branched form, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, N-hexyl and other groups.
  • Cycloalkyl refers to including cyclic chain forms, such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • Alkenyl refers to straight-chain or branched alkenyl, such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, and hexenyl groups.
  • Alkynyl refers to straight-chain or branched alkynyl groups, such as 1-propynyl, 2-propynyl, butynyl, pentynyl, and hexynyl groups.
  • Alkoxy refers to a group with an oxygen atom attached to the end of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, and t-butoxy.
  • a 5-7 membered heterocyclic ring containing 1-4 heteroatoms refers to a 5-7 membered heterocyclic compound containing 1-4 heteroatoms without aromatic characteristics, such as tetrahydrofuran, imidazolinone, caprolactam and the like.
  • the present invention has the following characteristics:
  • the present invention carries out methoxylation and cyclization reaction through a one-step method to prepare imidazolinone compound (I).
  • the present invention reduces reaction steps, simplifies operation technology, mild reaction conditions, reduces the amount of three wastes, and has high product content.
  • compound 1 when the imidazolinone compound (I) of the present invention is obtained, compound 1 can also be obtained.
  • the obtained compound 1 can be used as a marker to identify the synthesis of the imidazolinone compound (I), and the obtained compound 1 has herbicidal activity.
  • the dichloroethane solution prepared in Example 1 was heated to 50°C, and triethylamine (6.2g, 0.06mol) was added dropwise to the reaction system. After the addition, the reaction was kept for 3 hours, and the temperature was lowered and filtered to obtain (2,3 -Diethoxycarbonylpyridine-5-methyl)triethylammonium bromide 21.9g, the content is 93.6%, and the yield is 49.2% based on ethyl 5-methylpyridine-2,3-dicarboxylate.
  • the above product contains a small amount of compound 1.
  • 1.3g of white solid can be obtained by recrystallization, with a melting point of 197-199°C.
  • the above product contains a small amount of compound 1, and 1.5 g of white solid can be obtained by recrystallization.
  • the above product contains a small amount of compound 1, and 1.2 g of white solid can be obtained by recrystallization.
  • the above product contains a small amount of compound 1, and 1.1 g of white solid can be obtained by recrystallization.
  • the weed test material was sprayed on the crawler crop sprayer.
  • test materials After the test materials are processed, they are placed in the operation hall. After the liquid is naturally dried, it is placed in the greenhouse for management according to conventional methods. Observe and record the response of weeds to the drug. After processing, regularly visually observe the control effect of the test drug on weeds. It is represented by 0-100, with “0" representing no prevention effect and "100” representing 100% prevention effect.
  • the control effect of Compound 1 on Zinnia, Setaria, and Barnyardgrass at an applied dose of 1000 g ai/hm 2 is 70%, 90%, and 90%, respectively.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

提供一种一步法进行甲氧基化和成环反应制备咪唑啉酮化合物(I)，通式II季铵盐化合物与2-氨基-2,3-二甲基丁酰胺，于适宜的溶剂中，在碱的存在下于0℃至适宜溶剂沸点范围内反应，反应后酸化得到咪唑啉酮化合物(I)，所述方法减少反应步骤，简化操作工艺、反应条件温和，降低三废量，产品含量高。

Description

一种咪唑啉酮化合物的制备方法 技术领域
本发明涉及化合物合成，具体的说是一种制备咪唑啉酮化合物(I)的方法。
背景技术
咪唑啉酮类化合物是由美国氰胺公司开发，其除草活性高，具有高效广谱低毒的特点。专利US4798619和US5334576中公开了咪唑啉酮类化合物是高效广谱、对环境有益的除草剂。咪唑啉酮化合物(I)是由美国氰胺公司开发的大豆田除草剂，其用作ALS抑制剂从而抑制侧链氨基酸的生物合成，其活性高、用量低、杀草谱宽，所以具有很高的使用价值，可用于出苗前和出苗后施用。
Figure PCTCN2020135521-appb-000001
美国氰胺公司在专利US5288866、US5973154，巴斯夫公司在专利WO2010054954中均公开了该类化合物的制备方法，专利中报道制备的铵盐类中间体先与甲醇钠进行醚化反应，再与氨基丁酰胺反应制备此类化合物，或通过水解成二酸再转化为酸酐的方法来制备咪唑啉酮化合物(I)，存在反应步骤多和废水量大的问题。
安道麦公司专利WO2018091964中也公开该类化合物的制备方法，仍存在反应步骤多，反应收率低等关键工艺问题。
尽管咪唑啉酮类化合物的工业生产一直在进行，但从工艺角度出发仍有改进的空间，尤其是在经济和环保两方面，比如简化反应工艺、提高反应收率以及避免使用特殊的溶剂等。
一直以来，技术人员致力于不断研究开发新的、更为先进合理、更加环保的制备方法，以期获得质量更优、价格更低的高效、安全的除草剂。
发明内容
本发明的目的在于提供一种简便、环保，低成本的制备咪唑啉酮类化合物的方法。
为实现上述目的，本发明采用技术方案为：
一种制备咪唑啉酮化合物(I)的方法，反应为
Figure PCTCN2020135521-appb-000002
通式II季铵盐化合物与2-氨基-2,3-二甲基丁酰胺，于适宜的溶剂中，在碱的存在下于0℃至适宜溶剂沸点范围内反应，反应后酸化得到咪唑啉酮化合物(I)。
所述通式II所示的季铵盐化合物与2-氨基-2,3-二甲基丁酰胺，在碱存在下于适宜的溶剂中，在0℃至适宜溶剂沸点范围内，进行缩合反应0.5-10个小时，酸化制得咪唑啉酮化合物(I)；
通式II所示的季铵盐化合物与2-氨基-2,3-二甲基丁酰胺的摩尔比为1:1-1.5；通式II所示的季铵盐化合物与碱加料摩尔比为1:2-4。
所述适宜的碱选自甲醇钠、甲醇钾或甲醇锂；酸选自盐酸、硫酸、乙酸中的一种或几种；所述溶剂选自二氯甲烷、二氯乙烷、甲苯或氯苯。
所述通式II所示的季铵盐化合物与2-氨基-2,3-二甲基丁酰胺的摩尔比为1:1-1.2；通式II所示的季铵盐化合物与碱加料摩尔比为1:3-4；
所述反应温度为20℃至适宜溶剂沸点；所述缩合反应0.5-8小时；所述溶剂选自甲苯或氯苯，所述的酸选自盐酸或硫酸。
所述通式II中
R 1、R 2分别独立的选自C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、苯基、卤代苯基、苯基C 1-C 6烷基或卤代苯基C 1-C 6烷基；
式中X选自氯或溴；
式中Q选自如下基团：
Figure PCTCN2020135521-appb-000003
R 3、R 4、R 5分别独立的选自C 1-C 6烷基、C 3-C 6环烷基、C 1-C 6烷氧基C 1-C 6烷基或C 3-C 6环烷基C 1-C 6烷基；
或者R 3与R 4、或R 3与R 5、或R 4与R 5与它们相连氮原子一起组成含有1-4个杂原子的5-7元杂环；
R 6选自卤素、C 1-C 6烷基、C 3-C 6环烷基或C 1-C 6烷氧基；
n选自0-5；
m选自0-4；
p选自0-3。
上述通式II可市购获得，或是按照US5288866A中记载制备获得。
所述制备咪唑啉酮化合物(I)反应过程中获得化合物1四取代吡啶，其结构式如下：
Figure PCTCN2020135521-appb-000004
一种所述的方法获得的四取代吡啶化合物，化合物1结构如下式所示：
Figure PCTCN2020135521-appb-000005
一种所述的化合物1在用来鉴定按照上述通式(I)所示咪唑啉酮化合物的合成方法的用途。
一种除草组合物，组合物含所得的咪唑啉酮化合物(I)和/或化合物1。
所述组合为咪唑啉酮化合物(I)和化合物1；化合物1占组合物质量的0.01％-10％。
一种除草组合物的控制杂草的方法，向杂草或杂草的生长介质或地点上施用除草有效剂量的所述的除草组合物。
上面给出的通式I化合物的定义中，汇集所用术语定义如下：
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、正己基等基团。环烷基是指包括环状链形式，例如环丙基、甲基环丙基、环丙基环丙基、环丁基、环戊基、环己基等基团。烯基是指直链或支链烯基，如乙烯基、1-丙烯基、2-丙烯基、丁烯基、戊烯基和已烯基等基团。炔基是指直链或支链炔基，如1-丙炔基、2-丙炔基、丁炔基、戊炔基和己炔基等基团。烷氧基是指烷基末端连有氧原子的基团，例如甲氧基、乙氧基、正丙氧基、异丙氧基、特丁氧基等。含有1-4个杂原子的5-7元杂环是指含有1-4个杂原子的5-7元没有芳香特征的杂环化合物，如四氢呋喃、咪唑啉酮、己内酰胺等。
与现有技术相比，本发明具有以下特点：
本发明通过一步法进行甲氧基化和成环反应，制备咪唑啉酮化合物(I)，本发明减少反应步骤，简化操作工艺、反应条件温和，降低三废量，产品含量高。
同时，获得本发明咪唑啉酮化合物(I)时还可获得化合物1，所得化合物1可作为标志物用于鉴定咪唑啉酮化合物(I)的合成，并且所得化合物1具有除草活性。
具体实施方式
以下结合实例对本发明的具体实施方式做进一步说明，应当指出的是，此处所描述的具体实施方式只是为了说明和解释本发明，并不局限于本发明。
实施例1
1)5-溴甲基吡啶-2,3-二甲酸乙酯的制备：
Figure PCTCN2020135521-appb-000006
将(23.7g，0.1mol)5-甲基吡啶-2,3-二甲酸乙酯溶于1,2-二氯乙烷中，升温至回流。加入二溴海因(11.7g，0.04mol)、AIBN(2g，0.0114)的混合物，加入结束后保温2小时，降温过滤得5-溴甲基吡啶-2，3-二甲酸乙酯的二氯乙烷溶液溶液。
2)(2,3-二乙氧羰基吡啶-5-甲基)三甲基溴化铵的制备：
Figure PCTCN2020135521-appb-000007
将上述制得的5-溴甲基吡啶-2，3-二甲酸乙酯二氯乙烷溶液升温至50℃，向反应体系内滴加三甲胺甲醇溶液(11g，0.06mol)，滴加结束后保温3小时，降温过滤得，干燥得固体19.5g，含量95％，以5-甲基吡啶-2,3-二甲酸乙酯计收率为49.3％。
在有机滤液中加入5-甲基吡啶-2,3-二甲酸乙酯(11.9g，0.05mol)后，循环至下一批溴化物料，重复实施例1和2五次，共得到季铵盐87.9g，含量90％，收率60.2％。
3)(2,3-二乙氧羰基吡啶-5-甲基)三乙基溴化铵的制备：
Figure PCTCN2020135521-appb-000008
将实施例1制得的二氯乙烷溶液升温至50℃，向反应体系内滴加三乙胺(6.2g，0.06mol)，滴加结束后保温反应3小时，降温过滤得(2,3-二乙氧羰基吡啶-5-甲基)三乙基溴化铵21.9g，含量93.6％，以5-甲基吡啶-2,3-二甲酸乙酯计收率为49.2％。
实施例2
2-(4-异丙基-4-甲基-5-氧-2-咪唑啉-2-基)-5-甲氧基甲基烟酸(I)的制备：
Figure PCTCN2020135521-appb-000009
在室温下加入(2,3-二乙氧羰基吡啶-5-甲基)三甲基溴化铵(39.5g，0.1mol)，2-氨基-2,3-二甲基丁酰胺(19.5g，0.15mol)，溶剂甲苯150mL。搅拌下滴加30％甲醇钠溶液(72g，0.4mol)，滴毕后升温至110℃回流，保温反应2小时；反应后冷却至室温，用水稀释，分离得到水相。水相用硫酸酸化到pH＝3，过滤干燥得白色固体咪唑啉酮化合物(I)25.6g，含量98％，收率82％。上述产品中含少量化合物1，通过重结晶可得到白色固体1.3g，熔点197-199℃。其 1H NMR(600MHz，CDCl 3)数据如下：9.61(br s,1H),8.64(s,1H),4.10(s,3H),2.33(s,3H),2.17(hept,J＝7.2Hz,1H),1.52(s,3H),1.13(d,J＝7.2Hz,3H),0.92(d,J＝7.2Hz,3H).
实施例3
Figure PCTCN2020135521-appb-000010
2-(4-异丙基-4-甲基-5-氧-2-咪唑啉-2-基)-5-甲氧基甲基烟酸(I)的制备：
在室温下加入(2,3-二甲氧羰基吡啶-5-甲基)三乙基溴化铵(41g，0.1mol)，2-氨基-2,3-二甲基丁酰胺(19.5g，0.15mol)，溶剂甲苯150mL。搅拌下滴加30％甲醇钠溶液(72g，0.4mol)，滴毕后升温至110℃回流，保温反应2小时；反应后冷却至室温，用水稀释，分离得到水相。水相用盐酸酸化pH＝3，过滤干燥得白色固体咪唑啉酮化合物(I)25g，含量97％，收率80％。上述产品中含少量化合物1，通过重结晶可得到白色固体1.5g。
实施例4
Figure PCTCN2020135521-appb-000011
2-(4-异丙基-4-甲基-5-氧-2-咪唑啉-2-基)-5-甲氧基甲基烟酸(I)的制备：
在室温下加入(2,3-二甲氧羰基吡啶-5-甲基)三乙基溴化铵(41g，0.1mol)，2-氨基-2,3-二甲基丁酰胺(19.5g，0.15mol)，溶剂二氯乙烷150mL。搅拌下滴加30％甲醇钠溶液(72g，0.4mol)，滴毕后升 温至50℃，保温反应6小时；反应后冷却至室温，用水稀释，分离得到水相。水相用盐酸酸化pH＝3，过滤干燥得白色固体咪唑啉酮化合物(I)25g，含量97％，收率80％。上述产品中含少量化合物1，通过重结晶可得到白色固体1.2g。
实施例5
Figure PCTCN2020135521-appb-000012
2-(4-异丙基-4-甲基-5-氧-2-咪唑啉-2-基)-5-甲氧基甲基烟酸(I)的制备：
在室温下加入(2,3-二乙氧羰基吡啶-5-甲基)三甲基溴化铵(39.5g，0.1mol)，2-氨基-2,3-二甲基丁酰胺(19.5g，0.15mol)，溶剂氯苯烷150mL。搅拌下滴加30％甲醇钠溶液(72g，0.4mol)，滴毕后升温至80℃，保温反应4小时；反应后冷却至室温，用水稀释，分离得到水相。水相用硫酸酸化pH＝3，过滤干燥得白色固体咪唑啉酮化合物(I)26g，含量98％，收率83％。上述产品中含少量化合物1，通过重结晶可得到白色固体1.1g。
由上述各实施例可见，在制备获得唑啉酮化合物(I)时含0.01％-10％的化合物1的存在，即可以判定为制备唑啉酮化合物(I)采用的方法为本发明所述的制备方法。
应用例
化合物1除草活性的测定
Figure PCTCN2020135521-appb-000013
将阔叶杂草(百日草、苘麻)和禾本科杂草(狗尾草、稗草)种子分别播于直径为7cm的装有营养土的纸杯中，播后覆土1cm，镇压、淋水后在温室按常规方法培养，待杂草2-3叶期后进行茎叶喷雾处理。
原药用丙酮溶解后，按试验要求用1‰的吐温80静置自来水配制所需浓度的待测液。按试验设计剂量，在履带式作物喷雾机上对杂草试材进行喷雾处理。
试材处理后置于操作大厅，待药液自然阴干后，放于温室内按常规方法管理，观察并记录杂草对药剂的反应情况，处理后定期目测供 试药剂对杂草的防除效果，用0-100来表示，以“0”代表无防效和“100”代表100％防效。
按照以上测试方法，化合物1在施用剂量为1000g a.i/hm 2对百日草、狗尾草、稗草的防效分别为70％、90％、90％。

Claims (11)

  1. 一种制备咪唑啉酮化合物(I)的方法，其特征在于：反应为
    Figure PCTCN2020135521-appb-100001
    通式II季铵盐化合物与2-氨基-2,3-二甲基丁酰胺，于适宜的溶剂中，在碱的存在下于0℃至适宜溶剂沸点范围内反应，反应后酸化得到咪唑啉酮化合物(I)。
  2. 按权利要求1所述的制备咪唑啉酮化合物(I)的方法，其特征在于：所述通式II所示的季铵盐化合物与2-氨基-2,3-二甲基丁酰胺，在碱存在下于适宜的溶剂中，在0℃至适宜溶剂沸点范围内，进行缩合反应0.5-10个小时，酸化制得咪唑啉酮化合物(I)；
    通式II所示的季铵盐化合物与2-氨基-2,3-二甲基丁酰胺的摩尔比为1:1-1.5；通式II所示的季铵盐化合物与碱加料摩尔比为1:2-4。
  3. 按权利要求1所述的制备咪唑啉酮化合物(I)的方法，其特征在于：所述适宜的碱选自甲醇钠、甲醇钾或甲醇锂；酸选自盐酸、硫酸、乙酸中的一种或几种；所述溶剂选自二氯甲烷、二氯乙烷、甲苯或氯苯。
  4. 按权利要求1-3任意一项所述的制备咪唑啉酮化合物(I)的方法，其特征在于：所述通式II所示的季铵盐化合物与2-氨基-2,3-二甲基丁酰胺的摩尔比为1:1-1.2；通式II所示的季铵盐化合物与碱加料摩尔比为1:3-4；
    所述反应温度为20℃至适宜溶剂沸点；所述缩合反应0.5-8小时；所述溶剂选自甲苯或氯苯，所述的酸选自盐酸或硫酸。
  5. 按权利要求1所述的制备咪唑啉酮化合物(I)的方法，其特征在于：所述通式II中
    R 1、R 2分别独立的选自C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、苯基、卤代苯基、苯基C 1-C 6烷基或卤代苯基C 1-C 6烷基；
    式中X选自氯或溴；
    式中Q选自如下基团：
    Figure PCTCN2020135521-appb-100002
    R 3、R 4、R 5分别独立的选自C 1-C 6烷基、C 3-C 6环烷基、C 1-C 6烷氧基C 1-C 6烷基或C 3-C 6环烷基C 1-C 6烷基；
    或者R 3与R 4、或R 3与R 5、或R 4与R 5与它们相连氮原子一起组成含有1-4个杂原子的5-7元杂环；
    R 6选自卤素、C 1-C 6烷基、C 3-C 6环烷基或C 1-C 6烷氧基；
    n选自0-5；
    m选自0-4；
    p选自0-3。
  6. 按权利要求1所述的制备咪唑啉酮化合物(I)的方法，其特征在于：所述制备咪唑啉酮化合物(I)反应过程中获得化合物1四取代吡啶，其结构式如下：
    Figure PCTCN2020135521-appb-100003
  7. 一种权利要求1所述的方法获得的四取代吡啶化合物，其特征在于：化合物1结构如下式所示：
    Figure PCTCN2020135521-appb-100004
  8. 一种权利要求7所述的化合物1在用来鉴定权利要求1制备咪唑啉酮化合物(I)方法的用途。
  9. 一种除草组合物，其特征在于：组合物含权利要求1方法所得的咪唑啉酮化合物(I)和/或化合物1。
  10. 按权利要求9所述的除草组合物，其特征在于：所述组合为咪唑啉酮化合物(I)和化合物1；化合物1占组合物质量的0.01％-10％。
  11. 一种权利要求9所述的除草组合物的控制杂草的方法，其特征在于：向杂草或杂草的生长介质或地点上施用除草有效剂量的如权利要求9所述的除草组合物。
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