WO2019128872A1 - 一种具有杀虫活性的吡唑酰胺类化合物及其应用 - Google Patents

一种具有杀虫活性的吡唑酰胺类化合物及其应用 Download PDF

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WO2019128872A1
WO2019128872A1 PCT/CN2018/122724 CN2018122724W WO2019128872A1 WO 2019128872 A1 WO2019128872 A1 WO 2019128872A1 CN 2018122724 W CN2018122724 W CN 2018122724W WO 2019128872 A1 WO2019128872 A1 WO 2019128872A1
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compound
formula
chlorine
halogen
methyl
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PCT/CN2018/122724
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English (en)
French (fr)
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冯美丽
李宏举
石欣欣
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江苏中旗科技股份有限公司
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Priority claimed from CN201811502022.2A external-priority patent/CN109988149B/zh
Application filed by 江苏中旗科技股份有限公司 filed Critical 江苏中旗科技股份有限公司
Priority to EP18896218.7A priority Critical patent/EP3719011B1/en
Priority to US16/958,739 priority patent/US20200329707A1/en
Priority to BR112020013313-2A priority patent/BR112020013313B1/pt
Publication of WO2019128872A1 publication Critical patent/WO2019128872A1/zh

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    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/36—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl groups

Definitions

  • the invention relates to the field of insecticides, in particular to a benzamide compound having insecticidal activity and application thereof.
  • the problem of insect pest resistance to insecticides is often a potential problem that plagues people, which is one of the most important reasons why pesticide researchers have been seeking to develop insecticides with special mechanisms of action. For many years, pesticide researchers have been working hard to find insecticides with special mechanisms of action.
  • the o-formylaminobenzamides developed by DuPont are a new class of compounds targeting the nitinin receptor, representing the compound chlorantraniliprole (RynaxypyrTM), which exhibits excellent insecticidal activity. Evaluation results with field effects, low toxicity to mammals, and good environmental compatibility.
  • a 2-benzamide-propionamide compound is reported in the patent CN 104447688, in which the compounds KC1 and KC2 have the following structural formulas, and have good control effects against Plutella xylostella, armyworm and aphids.
  • the invention provides a benzamide compound with novel structure and higher insecticidal effect, which can be applied to the control of pests.
  • R 1 is selected from chlorine or CN;
  • R 2 is selected from H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 5 alkoxyalkyl;
  • R 3 is selected from halogen or C 1 -C 3 haloalkyl;
  • R 4 is selected from halogen;
  • R 5 is selected from H or halogen.
  • Preferred compounds of the invention are those of formula I:
  • R 1 is selected from chlorine or CN
  • R 2 is selected from H, C 1 -C 3 alkyl, CH 2 OCH 3 , CH 2 OCH 2 CH 3 , CH 2 CH 2 OCH 3 , CF 3 , CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CF 2 CF 3 or CF(CF 3 ) 2
  • R 3 is selected from chlorine, bromine or trifluoromethyl
  • R 4 is selected from chlorine
  • R 5 is selected from H or chlorine.
  • R 1 is selected from chlorine; R 6 is H or methyl; R 3 is selected from chlorine or bromine; R 4 is selected from chlorine; and R 5 is selected from H.
  • the invention also includes intermediates which are directly employed in the preparation of compounds of formula I which have not previously been reported and have the structure shown in formula II:
  • R 1 is selected from halogen or CN; and R 2 is selected from H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 5 alkoxyalkyl.
  • R 2 is selected from H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 5 alkoxyalkyl.
  • the compound of the formula I can be prepared by the reaction formula 1, wherein the substituent is as defined above unless otherwise specified.
  • the compound of formula II is reacted with a compound of formula III in a suitable solvent in the presence or absence of a base to provide a compound of formula I.
  • a base substance is advantageous for the reaction, and examples thereof include an organic base such as pyridine, triethylamine, potassium t-butoxide, 4-dimethylaminopyridine or N-methylmorpholine, and an inorganic base such as sodium hydride. , sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, and the like.
  • the reaction can be carried out in a suitable inert solvent such as tetrahydrofuran, acetonitrile, toluene, dichloromethane or the like.
  • reaction mixture containing the desired product is subjected to separation treatment according to an ordinary method, and if necessary, purification by recrystallization, column chromatography or the like, whereby the intended product can be obtained.
  • the compound of the formula II can be prepared by the reaction formula 2, wherein the substituent is as defined above unless otherwise specified.
  • the compound of formula IV is reacted with hydrogen peroxide under basic conditions to provide a compound of formula III.
  • the base is selected from sodium hydroxide, potassium hydroxide and the like.
  • the reaction can be carried out in a suitable inert solvent such as tetrahydrofuran, acetonitrile, toluene, dichloromethane or the like.
  • a suitable inert solvent such as tetrahydrofuran, acetonitrile, toluene, dichloromethane or the like.
  • the reaction mixture containing the desired product is subjected to separation treatment according to an ordinary method, and if necessary, purification by recrystallization, column chromatography or the like, whereby the intended product can be obtained.
  • the compound of the formula IV can be prepared from the reaction formula 3, wherein the substituents are as defined above unless otherwise specified.
  • the compound represented by the general formula V is prepared by a known general method (for example, Organic Syntheses, 9, 32 (1929).), and a general formula V is easily obtained by a commercially available acid chloride reagent such as thionyl chloride, oxalyl chloride or the like. Compound.
  • the compounds represented by the formula VII or VII' are partially commercially available and partly prepared by a known general method, for example, J. Am. Chem. Soc., 75, 4841-4842 (1953), Chemical Communications, 48 (50), 6253. -6255 (2012) and so on.
  • the compound of the formula VI can be obtained by reacting a compound of the formula V with a compound of the formula IV, which can be prepared by known methods, for example, J. Am. Chem. Soc., 135 (12), 4628-4631 (2013) and the like.
  • Typical methods include hydrogenation reduction in the presence of a metal catalyst such as Pd/C, platinum oxide or Ni in a hydroxyl solvent such as ethanol, methanol, isopropanol (eg Chinese Journal of Chemical Engineering, 24(9), 1195- 1200 (2016)). It can also be prepared by reduction of a metal such as zinc powder or iron powder under the catalysis of an acid.
  • a metal catalyst such as Pd/C, platinum oxide or Ni
  • a hydroxyl solvent such as ethanol, methanol, isopropanol
  • the fat solubility of the molecule can be changed.
  • the introduction of the methyl group in the present invention causes the molecules to be arranged in the space.
  • the fat solubility of molecules is closely related to the grooming of molecules in plants, insects and other organisms; the changes in molecular space structure also have an impact on the ability of molecules to bind to targets. These two points play an important role in the efficacy of drugs.
  • the effects of changes in molecular lipid solubility and spatial structure on the bioactive molecular grooming properties and binding ability to the target are unpredictable and require a large amount of creative labor to be known.
  • the compounds of the formula I according to the invention have an unexpectedly high insecticidal activity compared to known benzamides, and therefore the invention also includes compounds of the formula I for controlling pests. use.
  • the present invention also encompasses pesticidal compositions having a compound of formula I as an active ingredient.
  • the active ingredient in the pesticidal composition is present in an amount between 1 and 99% by weight.
  • Also included in the pesticidal composition are agricultural, forestry, and hygienic acceptable carriers.
  • compositions of the invention may be administered in the form of a formulation.
  • the compound of the formula I is dissolved or dispersed in the carrier as an active ingredient or formulated into a formulation for easier dispersion when used as an insecticide.
  • these chemicals can be formulated as wettable powders or emulsifiable concentrates.
  • at least one liquid or solid carrier is added, and a suitable surfactant may be added as needed.
  • the technical solution of the present invention also includes a method of controlling pests by applying the pesticidal composition of the present invention to the pest or the growth medium thereof.
  • a more suitable effective amount is usually selected from 10 grams to 1000 grams per hectare.
  • one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizers may be added to the pesticidal composition of the invention, thereby producing additional The advantages and effects.
  • An advantage of the present invention is that the two compounds disclosed in the present invention, wherein the compound of the formula I has a pest against the genus Spodoptera, the green leafhopper, the flower scorpion, the brown planthopper, the cotton bollworm, compared to the prior art. Higher insecticidal activity, even below 40ppm, has better insecticidal effect. Compared with similar compounds in the prior art, the amount of compound used in farmland is reduced, the residue of compound in farmland is reduced, and the environment is protected. .
  • the compound of the formula II is an intermediate for synthesizing the compound of the formula I, and the compound of the formula I and the formula II synthesized by the method of the invention; the problem of inconvenient synthesis of similar compounds in the prior art is solved, and is suitable for industrial use. Application, reducing the production cost of the enterprise.
  • Figure 1 is a physical property of a portion of the compound of formula I of the present invention.
  • Figure 2 is a physical property of a compound of the formula II of the present invention.
  • Figure 3 is a nuclear magnetic resonance spectrum test of a portion of a compound of formula I.
  • Alkyl means saturated aliphatic hydrocarbon groups, including straight-chain and branched forms, such as methyl, ethyl, propyl, isopropyl.
  • Base. means a group wherein the alkyl group is substituted by one or more halogen atoms, such as chloroethyl, trifluoromethyl and the like.
  • Alkoxyalkyl means a group having an oxygen atom bonded to the terminal of the alkyl group, such as methoxymethyl, methoxyethyl, ethoxymethyl and the like.
  • the reaction mixture was evaporated to dryness to dryness crystals crystals crystalssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss
  • reaction solution was poured into 50 ml of water and extracted with dichloromethane (3 ⁇ 20 ml).
  • the reaction mixture was evaporated to dryness to dryness crystals crystals crystalssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss
  • reaction solution was poured into 50 ml of water and extracted with dichloromethane (3 ⁇ 20 ml).
  • the remaining compounds can be synthesized by the above methods.
  • test agents were all dissolved in a 1000 mg/L solution using a mixture of acetone: N ⁇ N'-dimethylformamide.
  • 1% Tween-80 was added as an emulsifier to each of the drug solutions. These solutions were then diluted to the desired concentration of test solution with 1% Tween-20 aqueous solution. An aqueous solution containing 1% Tween-20 was used as a control.
  • Example 3 Insecticidal effect on Spodoptera litura
  • the 3rd instar larvae of Spodoptera litura were selected and tested for insecticidal effects by leaf-fed feeding.
  • the leaves of the leek that have not been exposed to the pesticide are made into scissors with about 40 mm square leaves. These leaves are immersed in the solution of each compound for 30 s, and the leaves are placed on the absorbent paper, and air-dried to the leaves. Stains. Place the leaf dish after the dipping in a Petri dish (7 cm) and place 3 leaf discs per dish.
  • the cover of the petri dish was placed on the back of the insect, placed in a larvae room at 25 ° C, and illuminated for 16 h / dark for 8 h. The number of dead insects on the 5d was investigated and the mortality was calculated.
  • Example 5 Insecticidal effect on flower thrips
  • the 60d-old seedlings were washed away from the roots, the leaves were cut off, air-dried, and then immersed in each test solution for 30 s, then taken out, air-dried on absorbent paper, wrapped around the neck and neck with absorbent cotton, and the roots were immersed in clear water through the bottle cap.
  • a plastic insect bottle (3 ⁇ 2cm square holes on both sides and sealed with a fine mesh); placed in a plastic cup. Repeat 3 times for each treatment.
  • the 3 to 4-year-old brown planthopper nymphs raised from the indoor rice seedlings were gently picked up with a writing brush and placed on a seedling placed in a plastic cup, with 10 eggs per cup.
  • the plastic cup after the insect was placed in a 25 ° C worm room, light 16h / dark 8h.
  • the death of brown planthopper was investigated 120 h after the infestation and the mortality was calculated.
  • the 3rd instar larvae of Helicoverpa armigera were selected and the insecticidal effect test was carried out by using the leaf-fed feeding method.
  • the leaves of the leek that have not been exposed to the insecticide are made into a disc with a diameter of 1.5 mm by a puncher. These leaves are immersed in the solution of each compound for 30 s, and the leaf disc is placed on a blotting paper and air-dried onto the leaf disc. No obvious water spots.
  • Prepare the cleaned 24-well plate inject about 1ml of water agar medium into each well, and after solidification, place the leaf disc after the infusion on the medium of the 24-well plate, and then connect one cotton bollworm per hole.
  • the mortality rate of some compounds such as 1.1, 1.2, and 1.3 against cotton bollworm is above 80%.
  • the comparative compound KC1 (compound 1.3 in CN 104447688) and KC2 (compound 1.4 in CN 104447688) which are structurally closest to the compound of the present invention are selected for parallel determination of cotton bollworm, and the experimental results are obtained. See Table 4.
  • the compound KC1 and the compound KC2 disclosed in the prior art are used in the killing process of cotton bollworm, at a concentration of less than 20 ppm, even at a concentration of 5 ppm, the cotton bollworm of the present invention.
  • the kill rate can also reach 70%, so the compounds of the present invention are more active than the compounds KC1 and KC2 of the prior art.

Abstract

公开了一种通式(I)的具有杀虫活性的吡唑酰胺类化合物苯甲酰胺类化合物以及可用于制备通式(I)化合物的中间体通式(II)，其中，R1选自卤素或CN，R2选自H、C1-C3烷基、C1-C3卤代烷基或C1-C5烷氧烷基，R3选自卤素或C1-C3卤烷基，R4选自卤素，R5选自H或卤素；通式(I)的化合物相比于现有技术中的化合物，在低浓度下具有更高的活性，缩减了化合物在农田中的使用量，减少了化合物在农田中的残留，保护环境。

Description

一种具有杀虫活性的吡唑酰胺类化合物及其应用 技术领域
本发明涉及杀虫剂领域，尤其涉及一种具有杀虫活性的苯甲酰胺类化合物及其应用。
背景技术
害虫对杀虫剂产生抗性的问题，常常是一个困扰人们的潜在问题，这也是为什么农药科研工作者一直寻求开发具有特殊作用机制的杀虫剂的最重要的原因之一。多年来农药科研工作者都在为发现特殊作用机制的杀虫剂而努力。由杜邦公司研发的邻甲酰氨基苯甲酰胺类化合物就是一类新型的以鱼尼丁受体为作用靶标的化合物，代表化合物氯虫酰胺(chlorantraniliprole，RynaxypyrTM)表现出了综合优异的杀虫活性和田间效果、对哺乳动物毒性低及环境相容性良好等评价结果。
专利CN 104447688中报道了一种2-苯甲酰胺基丙酰胺类化合物，其中化合物KC1、KC2结构式如下，对小菜蛾、粘虫和蚜虫具有较好的防效。
Figure PCTCN2018122724-appb-000001
在现有技术中，如本发明所示的苯甲酰胺类化合物及其杀虫活性 未见公开。
发明内容
本发明提供了一种结构新颖的、具有更高杀虫效果的苯甲酰胺类化合物，它可应用于虫害的防治。
本发明采用的技术方案如下：一种通式I的苯甲酰胺的化合物，
Figure PCTCN2018122724-appb-000002
通式I中：
R 1选自氯或CN；R 2选自H、C 1-C 3烷基、C 1-C 3卤代烷基或C 1-C 5烷氧烷基；R 3选自卤素或C 1-C 3卤烷基；R 4选自卤素；R 5选自H或卤素。其中部分通式I化合物的物理性能如图1所示；部分通式I化合物的进行核磁共振氢谱测试： 1HNMR：DMSO-d 6、300MHz所得的结果如图3所示。
本发明优选的化合物为，通式I中：
R 1选自氯或CN；R 2选自H、C 1-C 3烷基、CH 2OCH 3、CH 2OCH 2CH 3、CH 2CH 2OCH 3、CF 3、CH 2CH 2F、CH 2CHF 2、CH 2CF 3、CF 2CF 3或CF(CF 3) 2；R 3选自氯、溴或三氟甲基；R 4选自氯；R 5选自H或氯。
更优选的化合物为，通式I中：R 1选自氯；R 6为H或甲基；R 3选自氯或溴；R 4选自氯；R 5选自H。
本发明还包括直接用于制备通式I化合物的中间体，该中间体此前未见报道，结构如通式II所示：
Figure PCTCN2018122724-appb-000003
通式II中：
R 1选自卤素或CN；R 2选自H、C 1-C 3烷基、C 1-C 3卤代烷基或C 1-C 5烷氧烷基。其中部分通式II化合物的物理性能如图2所示。
本发明的典型制备方法如下，但是它决不在于以任何方式限制本发明的范围。
通式化合物I可以通过反应式1制备，其中取代基除特别指明外均如前所限定。
反应式1：
Figure PCTCN2018122724-appb-000004
在适宜的溶剂中，在有碱或无碱的情况下，通式II化合物与通式III化合物反应得到通式I化合物。
加入适量的碱类物质对反应有利，可以例举有机碱，如吡啶、三 乙胺、叔丁醇钾、4-二甲氨基吡啶或N-甲基吗啉等，以及无机碱，如氢化钠、碳酸氢钠、碳酸钠、碳酸钾、氢氧化钠等。该反应可在适合的惰性溶剂如四氢呋喃、乙腈、甲苯、二氯甲烷等中进行。
反应完全后，按照普通方法将含有预期产物的反应混合物进行分离处理，必要时通过重结晶、柱色谱等进行纯化，由此可以得到预期产物。这些方法在文献中有较多的记载，例如J.Org.Chem.32,3069(1967)等。
通式II化合物可以通过反应式2制备，其中取代基除特别指明外均如前所限定。
反应式2：
Figure PCTCN2018122724-appb-000005
通式IV化合物与双氧水，在碱性条件下反应得到通式III化合物。碱选自氢氧化钠、氢氧化钾等。反应可在适合的惰性溶剂如四氢呋喃、乙腈、甲苯、二氯甲烷等中进行。反应完全后，按照普通方法将含有预期产物的反应混合物进行分离处理，必要时通过重结晶、柱色谱等进行纯化，由此可以得到预期产物。
通式IV化合物可以由反应式3来制备，其中取代基除特别指明外均如前所限定。
反应式3：
Figure PCTCN2018122724-appb-000006
通式V代表的化合物采用已知通用的方法制备(例如Organic Syntheses,9,32(1929).)，通过市售的酰氯化试剂如氯化亚砜、草酰氯等，很容易得到通式V化合物。
通式VII或VII’代表的化合物部分市售，部分采用已知通用的方法制备，例如J.Am.Chem.Soc.,75,4841-4842(1953)、Chemical Communications,48(50),6253-6255(2012)等。
(1)通式V→通式VI
由通式V化合物和通式IV化合物反应获得通式VI化合物，可以采用已知方法加以制备，例如J.Am.Chem.Soc.,135(12),4628-4631(2013)等。
(2)通式VI→通式II
典型的方法包括在金属催化剂如Pd/C、氧化铂或Ni的存在下，在羟基溶剂如乙醇、甲醇、异丙醇中加氢还原(例如Chinese Journal of Chemical Engineering,24(9),1195-1200(2016))。也可以用金属如锌粉、铁粉，在酸的催化下来还原制备，这些方法在文献中有较多的记载，例如WO 2010042699、染料工业,37(4):16-18(2000)等。
在有机分子中，用给电子的甲基或其它烷基取代氢或卤原子后，可以改变分子的脂溶性，通过核磁数据分析可知，本发明中由于甲基 的引入，导致了分子在空间排布上发生了变化。分子的脂溶性与分子在植物、昆虫等生物体内的疏导性密切相关；分子空间结构的变化对分子与靶标的结合能力也会产生影响，这两点对药效的发挥起着重要的作用。分子脂溶性和空间结构的变化对生物活性分子疏导性能以及与靶标结合能力的影响是不可预知的，需要大量的创造性劳动才能获知。
现已发现，同已知的苯甲酰胺类化合物相比，本发明通式I所示的化合物具有意想不到的高杀虫活性，因此，本发明还包括了通式I化合物用于控制虫害的用途。
本发明还包括以通式I化合物作为活性组分的杀虫组合物。该杀虫组合物中活性组分的重量百分含量在1-99％之间。该杀虫组合物中还包括农业、林业、卫生上可接受的载体。
本发明的组合物可以制剂的形式施用。通式I化合物作为活性组分溶解或分散于载体中或配制成制剂以便作为杀虫剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油。在这些组合物中，至少加入一种液体或固体载体，并且当需要时可以加入适当的表面活性剂。
本发明的技术方案还包括防治虫害的方法：将本发明的杀虫组合物施于所述的害虫或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克。
对于某些应用，例如在农业上可在本发明的杀虫组合物中加入一种或多种其它的杀菌剂、杀虫剂、除草剂、植物生长调节剂或肥料等， 由此可产生附加的优点和效果。
本发明的优点在于：本发明公开的两种化合物，其中通式I的化合物相比于现有技术，其在针对斜纹夜蛾、小绿叶蝉、花蓟马、褐飞虱、棉铃虫这类害虫具有较高的杀虫活性，甚在40ppm以下都具有较好的杀虫效果，对比现有技术中类似的化合物，缩减了化合物在农田中的使用量，减少了化合物在农田中的残留，保护环境。
通式II的化合物是合成通式I化合物的中间体，采用本发明的方法合成的通式I和通式II的化合物；解决了现有技术中类似化合物合成不方便的问题，适用于工业上应用，缩减企业的生产成本。
附图说明
图1为本发明的部分通式I化合物的物理性能；
图2为本发明的部分通式II化合物的物理性能；
图3为部分通式I化合物的进行核磁共振氢谱测试。
具体实施方式
下面结合具体实施方式对本发明作进一步详细的描述，但不意味着限制本发明。
除非另外说明，在说明书和权利要求中使用的以下术语具有下面讨论的含义：“烷基”表示饱和的脂烃基，包括直链和支链形式，例如甲基、乙基、丙基、异丙基等。“卤代烷基”表示烷基被一个或多个卤原子取代的基团，如氯乙基、三氟甲基等。“烷氧烷基”表示烷基末端连有氧原子的基团，例如甲氧甲基、甲氧乙基、乙氧甲基等。
实施例1
化合物1.1：N-(2-N-((1-氨基-2-甲基-1-酰丙-2-基)-甲酰基)-4-氯-6-甲基苯基)-1-(3-氯吡啶-2-基)-3-溴-1H-吡唑-5-甲酰胺的合成
(1)、2-硝基-3-甲基苯甲酰氯的合成
Figure PCTCN2018122724-appb-000007
将10.0g(0.055mol)的2-硝基-3-甲基苯甲酸、200ml的二氯乙烷、23.8g(0.2mol)的氯化亚砜和1滴DMF依次加入至250ml的单口烧瓶中，升温至回流反应，反应3h后，加压脱溶，得11.0g棕色液体，收率100％。不做进一步后处理，直接用于下一步。
(2)、N-(1-氰基异丙基)-3-甲基-2-硝基苯甲酰胺的合成
Figure PCTCN2018122724-appb-000008
将6.0g(0.05mol)的2-甲基-2-(甲胺基)丙腈盐酸盐、20ml的四氢呋喃、20ml水和8.4g(0.1mol)NaHCO 3依次加入至250ml的四口烧瓶中，-10℃下滴加含10g(0.05mol)2-硝基-3-甲基苯甲酰氯的20ml四氢呋喃溶液，滴毕后，继续在-10℃下搅拌反应2h。向反应液中加入50ml水后，用20ml×3的乙酸乙酯萃取，合并有机相，有机相依次用饱和氯化钠水溶液洗涤，无水硫酸钠干燥，减压脱溶，得6.0g棕色固体，收率48.2％。
(3)、N-(1-氰基异丙基)-3-甲基-2-氨基苯甲酰胺的合成
Figure PCTCN2018122724-appb-000009
依次将20ml水、2.2g(0.04mol)的还原Fe粉和1ml的30％盐酸加入至100ml的四口烧瓶中，缓慢加热至80℃，再在80℃下搅拌30min后，分批分次加入2.5g(0.01mol)的N-(1-氰基异丙基)-3-甲基-2-硝基苯甲酰胺，温度一直保持不超过80℃，加毕后，继续在80℃下搅拌反应，HPLC追踪至反应结束。反应液降至室温后，加入1.6g的氢氧化钠后，抽滤，滤饼用热水洗涤，收集的滤液用2×100ml的乙酸乙酯萃取，有机相经水、饱和碳酸钠溶液和饱和食盐水洗涤后，用无水硫酸钠干燥，减压脱溶，得1.4g棕色固体，收率63.1％。
(4)、N-(1-氰基异丙基)-2-氨基-3-甲基-5-氯苯甲酰胺的合成
Figure PCTCN2018122724-appb-000010
依次将1.5g(6.9mmol)的N-(1-氰基异丙基)-3-甲基-2-氨基苯甲酰胺、1.4g(10.3mmol)N-氯代丁二酰亚胺和20ml的DMF加入至100ml的四口烧瓶中，室温下搅拌反应，HPLC追踪至反应结束。将反应液倒入100ml水中，用20ml×3的乙酸乙酯萃取，合并有机相，有机相依次用饱和氯化钠水溶液、水洗涤，无水硫酸钠干燥，减压脱溶，粗品经过柱(石油醚：乙酸乙酯＝5:1)得1.4g白色固体，收率80.1％。
(5)、N-(1-氨基-2-甲基-1-酰丙-2-基)-2-氨基-3-甲基-5-氯苯 甲酰胺的合成
Figure PCTCN2018122724-appb-000011
冰浴下，依次将1g(4.0mmol)的N-(1-氰基异丙基)-2-氨基-3-甲基-5-氯苯甲酰胺、10ml的四氢呋喃、含有0.24g(6.0mmol)氢氧化钠的5ml水溶液以及2g(18mmol)30％的双氧水加入至100ml的单口烧瓶中，自然升至室温搅拌反应，HPLC追踪至反应结束。将反应液减压脱溶，得到棕黄色固体，用10ml×2四氢呋喃洗涤，过滤，收集滤液，减压脱溶，粗品经过柱(石油醚：乙酸乙酯＝1:1)得0.39g白色固体，收率40.1％。
(6)、化合物1.1：N-(2-N-((1-氨基-2-甲基-1-酰丙-2-基)-甲酰基)-4-氯-6-甲基苯基)-1-(3-氯吡啶-2-基)-3-溴-1H-吡唑-5-甲酰胺的合成
Figure PCTCN2018122724-appb-000012
将0.27g(1mmol)的N-(1-氨基-2-甲基-1-酰丙-2-基)-2-氨基-3-甲基-5-氯苯甲酰胺、10ml的乙腈、0.1g(1mmol)的三乙胺和0.32g(1mmol)2-(3-氯-吡啶-2-基)-5-溴-2H-吡唑-3-碳酰氯(按照WO 02/070483方法制得)依次加入至50ml的单口烧瓶中， 室温搅拌，HPLC追踪至反应结束。将反应液倒入50ml水中，二氯甲烷3×20ml萃取，有机相依次用饱和碳酸钠、饱和氯化钠水溶液和水洗涤，无水硫酸钠干燥，减压脱溶，粗产品通过柱色谱提纯(洗脱剂：乙酸乙酯：石油醚＝3:1)，得0.23g白色固体，收率41.2％。
实施例2
化合物1.3：N-甲基-N-(2-N-((1-氨基-2-甲基-1-酰丙-2-基)-甲酰基)-4-氯-6-甲基苯基)-1-(3-氯吡啶-2-基)-3-溴-1H-吡唑-5-甲酰胺的合成
(1)、2-甲基-2-(甲胺基)丙腈的合成
Figure PCTCN2018122724-appb-000013
将8.5g(0.1mol)的丙酮氰醇加入至50ml的四口烧瓶中，室温下缓慢通入3.1g(0.1mol)的甲胺气体，通毕后，继续在室温下搅拌反应5h后，用10ml×3二氯甲烷萃取，合并有机相，无水硫酸钠干燥，减压脱溶，得6.18g无色透明液体，收率63.0％。
(2)、2-硝基-3-甲基苯甲酰氯的合成
Figure PCTCN2018122724-appb-000014
将5.4g(0.03mol)的2-硝基-3-甲基苯甲酸、100ml的二氯乙烷、23.8g(0.2mol)的氯化亚砜和1滴DMF依次加入至250ml的单口烧瓶中，升温至回流反应，反应3h后，加压脱溶，得5.7g棕色液体，收率95.2％。不做进一步后处理，直接用于下一步。
(3)、N-(1-氰基异丙基)-N-甲基-3-甲基-2-硝基苯甲酰胺的合成
Figure PCTCN2018122724-appb-000015
将4.0g(0.03mol)的2-甲基-2-(甲胺基)丙腈盐酸盐、10ml的四氢呋喃、10ml水和5.1g(0.06mol)NaHCO 3依次加入至250ml的四口烧瓶中，-10℃下滴加含5.7g 2-硝基-3-甲基苯甲酰氯的20ml四氢呋喃溶液，滴毕后，继续在-10℃下搅拌反应2h。向反应液中加入50ml水后，用20ml×3的乙酸乙酯萃取，合并有机相，有机相依次用饱和氯化钠水溶液洗涤，无水硫酸钠干燥，减压脱溶，得4.4g棕色固体，收率56.5％。
(4)、N-(1-氰基异丙基)-N-甲基-3-甲基-2-氨基苯甲酰胺的合成
Figure PCTCN2018122724-appb-000016
依次将20ml水、2.2g(0.04mol)的还原Fe粉和1ml的30％盐酸加入至100ml的四口烧瓶中，缓慢加热至80℃，再在80℃下搅拌30min后，分批分次加入2.6g(0.01mol)的N-(1-氰基异丙基)-N-甲基-3-甲基-2-硝基苯甲酰胺，温度一直保持不超过80℃，加毕后，继续在80℃下搅拌反应，HPLC追踪至反应结束。反应液降至室温后，加入1.6g的氢氧化钠后，抽滤，滤饼用热水洗涤，收集的滤液用2×100ml的乙酸乙酯萃取，有机相经水、饱和碳酸钠溶液和饱和食盐水洗涤后，用无水硫酸钠干燥，减压脱溶，得1.68g棕色固体，收率71.3％。
(5)、N-(1-氰基异丙基)-N-甲基-2-氨基-3-甲基-5-氯苯甲酰胺的合成
Figure PCTCN2018122724-appb-000017
依次将1.6g(6.9mmol)的N-(1-氰基异丙基)-N-甲基-3-甲基-2-氨基苯甲酰胺、1.4g(10.3mmol)N-氯代丁二酰亚胺和20ml的DMF加入至100ml的四口烧瓶中，室温下搅拌反应，HPLC追踪至反应结束。将反应液倒入100ml水中，用20ml×3的乙酸乙酯萃取，合并有机相，有机相依次用饱和氯化钠水溶液、水洗涤，无水硫酸钠干燥，减压脱溶，得1.52g淡黄色色固体，收率83.1％。
(6)、N-(1-氨基-2-甲基-1-酰丙-2-基)-N-甲基-2-氨基-3-甲基-5-氯苯甲酰胺的合成
Figure PCTCN2018122724-appb-000018
冰浴下，依次将0.80g(3.0mmol)的N-(1-氰基异丙基)-N-甲基-2-氨基-3-甲基-5-氯苯甲酰胺、10ml的四氢呋喃、含有0.35g(6.0mmol)氢氧化钾的5ml水溶液以及2g(18mmol)30％的双氧水加入至100ml的单口烧瓶中，自然升至室温搅拌反应，HPLC追踪至反应结束。将反应液减压脱溶，得到棕黄色固体，用10ml×2四氢呋喃洗涤，过滤，收集滤液，减压脱溶，粗品经过柱(石油醚：乙酸乙酯＝1:1)得0.31g白色固体，收率36.7％。
(7)、N-甲基-N-(2-N-((1-氨基-2-甲基-1-酰丙-2-基)-甲酰基)-4-氯-6-甲基苯基)-1-(3-氯吡啶-2-基)-3-溴-1H-吡唑-5-甲酰胺的合成
Figure PCTCN2018122724-appb-000019
将0.30g(1mmol)的N-(1-氨基-2-甲基-1-酰丙-2-基)-N-甲基-2-氨基-3-甲基-5-氯苯甲酰胺、10ml的乙腈、0.079g(1mmol)的吡啶和0.32g(1mmol)2-(3-氯-吡啶-2-基)-5-溴-2H-吡唑-3-碳酰氯(按照WO 02/070483方法制得)依次加入至50ml的单口烧瓶中，室温搅拌，HPLC追踪至反应结束。将反应液倒入50ml水中，二氯甲烷3×20ml萃取，有机相依次用饱和碳酸钠、饱和氯化钠水溶液和水洗涤，无水硫酸钠干燥，减压脱溶，粗产品通过柱色谱提纯(洗脱剂：乙酸乙酯：石油醚＝3:1)，得0.24g白色固体，收率42.8％。
其余化合物均可采用上述方法合成。
生物活性测定
供试药剂均用丙酮∶N`N`—二甲基甲酰胺等比混合液溶解成1000mg/L的溶液。在各药剂溶液中加入1％的吐温-80作乳化剂。然后将这些溶液用1％吐温-20水溶液稀释成所需浓度试验溶液。以含 1％吐温-20的水溶液作对照处理。
实施例3：对斜纹夜蛾的杀虫效果
选择3龄斜纹夜蛾幼虫，采用浸叶饲喂法进行杀虫效果测试。将未接触过杀虫剂的苞菜叶片用剪刀制成40mm左右见方的叶碟，这些叶碟在各化合物溶液中浸渍30s，将叶碟置于吸水纸上，风干至叶碟上无明显水渍。将浸药后的叶碟置于培养皿中(7cm)，每培养皿放3个叶碟。从室内甘蓝苗上饲养的3龄斜纹夜蛾幼虫用毛笔轻轻挑取置于培养皿的叶碟上，每培养皿接虫10～15头。接虫后盖培养皿盖，放于25℃养虫室内，光照16h/黑暗8h。调查5d的死亡虫数，计算死亡率。
药液浓度为40ppm时，部分化合物如1.1对斜纹夜蛾的防治效果较好，达到80％以上。
实施例4：对小绿叶蝉的杀虫效果
剪取桃树上叶片(带叶柄)，叶片上有小绿叶蝉2～4龄若虫10头以上(大龄若虫用尖针剔除)，将带虫叶片在各药剂试验溶液中浸渍20s后取出，用脱脂棉包裹叶柄，将叶片侧向放在垫有滤纸的培养皿中，利用滤纸吸干叶片表面水分，再盖上培养皿盖；每处理重复3次。处理后将培养皿放于25℃光照、16h/黑暗8h养虫温箱中。接虫后72h调查小绿叶蝉死亡情况，计算死亡率。
药液浓度为40ppm时，部分化合物如1.1和1.3对小绿叶蝉的防治效果较好，达到80％以上。
实施例5：对花蓟马的杀虫效果
在直径6cm的玻璃培养皿底，铺一张同样直径的滤纸，用移液器吸取l mL药液均匀滴于滤纸上，待丙酮挥发后，用毛笔将木棉花中的花蓟马若虫移入培养皿中的滤纸上；0.5～1h后待虫身沾满药剂后放入长3cm的木棉花的花瓣，并盖上培养皿盖。每处理重复3次。接虫后的培养皿放于25℃养虫室内，光照16h/黑暗8h。接虫后72h调查花蓟马死亡，计算死亡率。
药液浓度为60ppm时，部分化合物如1.1对花蓟马的防治效果较好，达到80％以上。
实施例6：对褐飞虱的杀虫效果
60d秧龄的秧苗洗去根部泥土，剪去叶片，风干后在各药剂试验溶液中浸渍30s后取出，放在吸水纸上风干，用脱脂棉包裹根颈部，根部通过瓶盖浸入清水中，地上部处于塑料养虫瓶中(两侧有3×2cm方孔并用细网封口)；放到塑料杯中。每处理重复3次。从室内稻苗上饲养的3～4龄褐飞虱若虫用毛笔轻轻挑取置于塑料杯中的秧苗上，每杯接虫10头。接虫后的塑料杯放于25℃养虫室内，光照16h/黑暗8h。接虫后120h调查褐飞虱死亡情况，计算死亡率。
药液浓度为40ppm时，部分化合物如1.1、1.2对褐飞虱的防治效果较好，达到80％以上。
实施例7：对棉铃虫的杀虫效果
选择3龄棉铃虫幼虫，采用浸叶饲喂法进行杀虫效果测试。自于未接触过杀虫剂的苞菜叶片用打孔器制成直径1.5mm的叶碟，这些叶碟在各化合物溶液中浸渍30s，将叶碟置于吸水纸上，风干至叶碟上无明显水渍。准备好洗净的24孔板，在每孔中注入1ml左右的水琼脂培养基，凝固后将浸药后的叶碟置于24孔板的培养基上，然后每孔接入1头棉铃虫3龄幼虫，接虫后盖24孔板盖，放于25℃养虫室内，光照16h/黑暗8h。调查3d的死亡虫数，计算死亡率。
部分测试结果如下：
药液浓度为40ppm时，部分化合物如1.1、1.2、1.3对棉铃虫的死亡率在80％以上。
按照以上方法，选取现有技术中结构上与本发明化合物最为接近的对比化合物KC1(CN 104447688中的化合物1.3)和KC2(CN 104447688中的化合物1.4)，进行杀棉铃虫的平行测定，实验结果见表4。
表4.本发明化合物1.1和1.2与已知化合物KC1和KC2杀棉铃虫的活性平行比较(死亡率，％)
Figure PCTCN2018122724-appb-000020
从上表可知：现有技术中公开的化合物KC1和化合物KC2在应用于棉铃虫的杀灭过程中，在低于20ppm的浓度下，甚至是在 5ppm的浓度下，本发明的对于棉铃虫的杀灭率还能达到70％，因此对比现有技术中的化合物KC1和KC2，本发明的化合物的活性更高。

Claims (8)

  1. 一种通式Ⅰ的具有杀虫活性的吡唑酰胺类化合物，
    Figure PCTCN2018122724-appb-100001
    其中:
    R 1选自氯或CN；
    R 2选自H、C 1-C 3烷基、C 1-C 3卤代烷基或C 1-C 5烷氧烷基；
    R 3选自卤素或C 1-C 3卤烷基；
    R 4选自卤素；
    R 5选自H或卤素。
  2. 根据权利要求1所述的具有杀虫活性的吡唑酰胺类化合物，其特征在于，优选通式I的化合物：
    R 1选自氯或CN；
    R 2选自H、C 1-C 3烷基、CH 2OCH 3、CH 2OCH 2CH 3、CH 2CH 2OCH 3、CF 3、CH 2CH 2F、CH 2CHF 2、CH 2CF 3、CF 2CF 3或CF(CF 3) 2；
    R 3选自氯、溴或三氟甲基；
    R 4选自氯；
    R 5选自H或氯。
  3. 根据权利要求1所述的具有杀虫活性的吡唑酰胺类化合物，其特 征在于，优选通式I的化合物：
    R 1选自氯；
    R 2选自H或甲基；
    R 3选自氯或溴；
    R 4选自氯；
    R 5选自H。
  4. 一种制备权利要求1所述的通式I的具有杀虫活性的吡唑酰胺类化合物的中间体，如通式II所示：
    Figure PCTCN2018122724-appb-100002
    式中:
    R 1选自氯或CN；
    R 2选自H、C 1-C 3烷基、C 1-C 3卤代烷基或C 1-C 5烷氧烷基。
  5. 一种如权利要求1所述的通式I化合物的制备方法，所述的方法如下：
    将通式II的化合物与通式Ⅲ的化合物反应得到通式I化合物，反应式如下：
    Figure PCTCN2018122724-appb-100003
    其中：
    R 1选自氯或CN；
    R 2选自H、C 1-C 3烷基、C 1-C 3卤代烷基或C 1-C 5烷氧烷基；
    R 3选自卤素或C 1-C 3卤烷基；
    R 4选自卤素；
    R 5选自H或卤素。
  6. 根据权利要求1或2或3所述的通式I的化合物用于制备杀虫剂控制虫害的应用。
  7. 一种杀虫组合物，含有权利要求1所述的通式I化合物和农业、林业、卫生上可接受的载体，组合物中活性组分的重量百分含量为0.1～99.5％。
  8. 一种控制虫害的方法，其特征在于：将权利要求7所述的杀虫组合物以10g/hm 2～1000g/hm 2的有效剂量施放于害虫或者害虫的生长介质上。
PCT/CN2018/122724 2017-12-29 2018-12-21 一种具有杀虫活性的吡唑酰胺类化合物及其应用 WO2019128872A1 (zh)

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