WO2017128942A1 - Pyrazole hydrazide compound and use thereof - Google Patents

Pyrazole hydrazide compound and use thereof Download PDF

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WO2017128942A1
WO2017128942A1 PCT/CN2017/070449 CN2017070449W WO2017128942A1 WO 2017128942 A1 WO2017128942 A1 WO 2017128942A1 CN 2017070449 W CN2017070449 W CN 2017070449W WO 2017128942 A1 WO2017128942 A1 WO 2017128942A1
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compound
formula
pyrazole
hydrazide compound
present
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PCT/CN2017/070449
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Chinese (zh)
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许良忠
吴华龙
王明慧
黄雪松
杨曦
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浙江博仕达作物科技有限公司
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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
    • 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
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
    • C07D231/16—Halogen atoms or nitro radicals

Definitions

  • the present invention claims the priority of the Chinese invention patent application CN 201610052389.3, and the application date is January 26, 2016.
  • the invention belongs to the field of agricultural insecticides, and in particular relates to a pyrazole hydrazide compound and a use thereof.
  • Bismuth hydrazide insecticides are insect growth regulators that control harmful insects by inhibiting eating, accelerating molting and reducing egg laying. They are characterized by strong systemic absorption, long-lasting effect, low toxicity and low pollution. Pests such as Lepidoptera, Coleoptera, and Diptera have excellent control effects. Tebufenozide (CK) is a representative product of this kind of insecticide. Its trade name "Miman” has good control effect on beet armyworm, Spodoptera litura and Chilo suppressalis, and has become a lepidopteran. Conventional insecticides such as pests.
  • the object of the present invention is to provide a pyrazole hydrazide compound with novel structure and comprehensive performance, which can be used for the control of harmful insects in agriculture or forestry.
  • R is selected from Cl or CH 3 .
  • the compounds of formula I according to the invention can be prepared by the process wherein the R groups are as defined above.
  • the compound of the formula II is reacted with triphosgene in toluene to obtain a compound of the formula III, and the compound of the formula III is reacted with t-butylhydrazine at 0 to 10 ° C to obtain a compound of the formula I.
  • the solvent used for the reaction is selected from the group consisting of dichloromethane, toluene, acetonitrile or Ethyl acetate or the like; a compound of the formula V is obtained by reacting a corresponding carboxylic acid with thionyl chloride in toluene; a compound of the formula IV is reacted with a compound of the formula V to obtain a target compound of the formula I, the solvent used for the reaction is selected from ethyl acetate. , acetonitrile, toluene or dichloromethane, the acid scavenger used is selected from triethylamine or sodium hydroxide or potassium hydroxide.
  • the specific preparation method is shown in the examples of the present invention.
  • Table 1 lists the structure and physical properties of the compounds of formula I.
  • the pyrazole ring is an important gene of a heterocyclic insecticide, and the pyrazole hydrazide compound of the present invention has unexpectedly high insecticidal activity compared with the known hydrazide insecticide (KC) (see Table). 2).
  • KC hydrazide insecticide
  • the compound of the invention has the characteristics of simple synthesis process, easy availability of raw materials, low control cost, high efficiency and low toxicity, and has the potential to create a new variety of commercial insecticides, and is of great significance for safeguarding China's food security and improving the international competitiveness of China's pesticide industry. .
  • the compound of the present invention when used for the purpose of preventing pests, it can be used alone or in combination with other insecticides to improve the comprehensive function of the product.
  • the present invention also encompasses pesticidal compositions having a compound of formula I as an active ingredient, which also includes agriculturally or forestry acceptable carriers.
  • composition of the present invention can be administered in the form of a preparation, and the compound of the formula I is dissolved or dispersed as an active ingredient in a carrier or a solvent, and a suitable surfactant is added to prepare an emulsifiable concentrate, a suspension, a microemulsion or a wettable powder or the like.
  • the cabbage leaves were punched into a 1 cm diameter leaf disc with a puncher, and a certain concentration of the test compound was sprayed on the front and back sides of each leaf disc with an Airbrush sprayer, and the spray amount was 0.5 mL.
  • 8 test insects were connected per treatment. 3 years old), repeated 3 times per treatment.
  • the cells were cultured at 24 ° C, relative humidity of 60-70%, and without light. After 96 hours, the number of viable insects was investigated and the mortality was calculated.
  • Compound KC is known to be compared in parallel, and the test results are shown in Table 2.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

Disclosed is a pyrazole hydrazide compound having the structure as shown in general formula I, wherein R is selected from Cl or CH3. The compound of general formula I has an excellent insecticidal effect against Lepidopteran pests, and can be used for controlling agricultural or forest pests.

Description

一种吡唑酰肼类化合物及其用途Pyrazol hydrazide compound and use thereof
本发明请求中国发明专利申请CN 201610052389.3为优先权，其申请日为2016年01月26日。The present invention claims the priority of the Chinese invention patent application CN 201610052389.3, and the application date is January 26, 2016.
技术领域Technical field
本发明属于农用杀虫剂领域，具体涉及一种吡唑酰肼类化合物及其用途。The invention belongs to the field of agricultural insecticides, and in particular relates to a pyrazole hydrazide compound and a use thereof.
背景技术Background technique
双酰肼类杀虫剂属于昆虫生长调节剂，通过抑制进食、加速蜕皮和减少产卵等方式防治有害昆虫，具有内吸性强、持效期长、低毒、低公害等特点，对常见鳞翅目、鞘翅目、双翅目等害虫有优良防效。虫酰肼(CK)是该类杀虫剂的代表性产品，其商品名“米满”对甜菜夜蛾、斜纹夜蛾及二化螟等具有较好的防治效果，已成为防治鳞翅目害虫等的常规杀虫剂。Bismuth hydrazide insecticides are insect growth regulators that control harmful insects by inhibiting eating, accelerating molting and reducing egg laying. They are characterized by strong systemic absorption, long-lasting effect, low toxicity and low pollution. Pests such as Lepidoptera, Coleoptera, and Diptera have excellent control effects. Tebufenozide (CK) is a representative product of this kind of insecticide. Its trade name "Miman" has good control effect on beet armyworm, Spodoptera litura and Chilo suppressalis, and has become a lepidopteran. Conventional insecticides such as pests.
Figure PCTCN2017070449-appb-000001
Figure PCTCN2017070449-appb-000001
上述公开的化合物(KC)虽与本发明化合物有一定相似之处，但在现有技术中，如本发明所述的吡唑酰肼类化合物(式I)未见公开。Although the compound (KC) disclosed above has some similarities with the compound of the present invention, in the prior art, the pyrazole hydrazide compound (Formula I) according to the present invention is not disclosed.
发明内容Summary of the invention
本发明的目的在于提供一种结构新颖、综合性能好的吡唑酰肼类化合物，可以用于农业或林业有害昆虫的防治。The object of the present invention is to provide a pyrazole hydrazide compound with novel structure and comprehensive performance, which can be used for the control of harmful insects in agriculture or forestry.
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种吡唑酰肼类化合物，结构如式I所示：A pyrazole hydrazide compound having the structure shown in Formula I:
Figure PCTCN2017070449-appb-000002
式中：R选自Cl或CH3。
Figure PCTCN2017070449-appb-000002
Wherein R is selected from Cl or CH 3 .
本发明式I化合物可由如下方法制备，反应式中R基团定义同前。 The compounds of formula I according to the invention can be prepared by the process wherein the R groups are as defined above.
Figure PCTCN2017070449-appb-000003
Figure PCTCN2017070449-appb-000003
式II化合物与三光气在甲苯中回流反应即得到式III化合物，式III化合物与叔丁基肼在0～10℃反应制得式I化合物，反应所用溶剂选自二氯甲烷、甲苯、乙腈或乙酸乙酯等；式V化合物由相应的羧酸与氯化亚砜在甲苯中回流反应制得；式IV化合物与式V化合物反应制得目标产物式I化合物，反应所用溶剂选自乙酸乙酯、乙腈、甲苯或二氯甲烷，所用缚酸剂选自三乙胺或氢氧化钠或氢氧化钾。具体制备方法见本发明实施例。The compound of the formula II is reacted with triphosgene in toluene to obtain a compound of the formula III, and the compound of the formula III is reacted with t-butylhydrazine at 0 to 10 ° C to obtain a compound of the formula I. The solvent used for the reaction is selected from the group consisting of dichloromethane, toluene, acetonitrile or Ethyl acetate or the like; a compound of the formula V is obtained by reacting a corresponding carboxylic acid with thionyl chloride in toluene; a compound of the formula IV is reacted with a compound of the formula V to obtain a target compound of the formula I, the solvent used for the reaction is selected from ethyl acetate. , acetonitrile, toluene or dichloromethane, the acid scavenger used is selected from triethylamine or sodium hydroxide or potassium hydroxide. The specific preparation method is shown in the examples of the present invention.
表1列出了式I化合物的结构及物理性质。Table 1 lists the structure and physical properties of the compounds of formula I.
表1式I化合物的结构及物理性质Table 1 Structure and physical properties of the compound of formula I
Figure PCTCN2017070449-appb-000004
Figure PCTCN2017070449-appb-000004
本发明的优点和积极效果：Advantages and positive effects of the present invention:
吡唑环是杂环类杀虫剂的重要基因，本发明的吡唑酰肼类化合物与已知的双酰肼杀虫剂(KC)相比，具有意想不到的高杀虫活性(见表2)。吡唑环的引入，不仅使本发明化合物在结构上具有新颖性，而且显著提高了杀虫活性，也为该类杀虫剂的抗药性治理提供了一种高效杀虫剂品种。本发明化合物具有合成工艺简单、原料易得、防治成本低、高效低毒等特点，具有创制商品化杀虫剂新品种的潜力，对保障我国粮食安全、提升我国农药工业国际竞争力具有重要意义。The pyrazole ring is an important gene of a heterocyclic insecticide, and the pyrazole hydrazide compound of the present invention has unexpectedly high insecticidal activity compared with the known hydrazide insecticide (KC) (see Table). 2). The introduction of the pyrazole ring not only makes the compound of the present invention novel in structure, but also significantly improves the insecticidal activity, and also provides a highly effective insecticide variety for the resistance treatment of the insecticide. The compound of the invention has the characteristics of simple synthesis process, easy availability of raw materials, low control cost, high efficiency and low toxicity, and has the potential to create a new variety of commercial insecticides, and is of great significance for safeguarding China's food security and improving the international competitiveness of China's pesticide industry. .
本发明化合物用于防制作物虫害用途时，根据需要可以单独使用，也可以与其它杀虫剂等组合使用，以提高产品的综合功能。When the compound of the present invention is used for the purpose of preventing pests, it can be used alone or in combination with other insecticides to improve the comprehensive function of the product.
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，该杀虫组合物中还包括农业或林业上可以接受的载体。The present invention also encompasses pesticidal compositions having a compound of formula I as an active ingredient, which also includes agriculturally or forestry acceptable carriers.
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或溶剂中，添加适当的表面活性剂配制成乳油、悬浮剂、微乳剂或可湿性粉剂等。The composition of the present invention can be administered in the form of a preparation, and the compound of the formula I is dissolved or dispersed as an active ingredient in a carrier or a solvent, and a suitable surfactant is added to prepare an emulsifiable concentrate, a suspension, a microemulsion or a wettable powder or the like.
应该明确的是，本发明权利要求所限定的范围内，可进行各种变换和改动。It is to be understood that various modifications and changes can be made within the scope of the invention as defined by the appended claims.
具体实施方式detailed description
下列合成实例及生测试验结果可用来进一步说明本发明，但不意味着限制本发明。The following synthetic examples and bioassay results are used to further illustrate the invention, but are not intended to limit the invention.
合成实例 Synthesis example
实例1、化合物Ia的制备Example 1. Preparation of Compound I a
(1)1-甲基-3-乙基-4-氯-5-吡啶甲酰氯的合成(1) Synthesis of 1-methyl-3-ethyl-4-chloro-5-pyridinecarbonyl chloride
Figure PCTCN2017070449-appb-000005
Figure PCTCN2017070449-appb-000005
向250mL反应瓶中加入30.0g(0.156mol)式II化合物和60mL二氯乙烷，搅拌下滴加由23.0g(0.078mol)三光气(即固体光气)和60mL二氯乙烷组成的混合液，溶毕，升温回流反应6h，降温，脱除溶剂，得35g油状化合物III。To a 250 mL reaction flask was added 30.0 g (0.156 mol) of the compound of formula II and 60 mL of dichloroethane, and a mixture of 23.0 g (0.078 mol) of triphosgene (ie solid phosgene) and 60 mL of dichloroethane was added dropwise with stirring. After the solution was dissolved, the mixture was heated under reflux for 6 h, cooled, and the solvent was removed to give 35 g of Compound III.
(2)N-(1-甲基-3-乙基-4-氯-5-吡啶甲酰基)-N'-叔丁基肼的合成(2) Synthesis of N-(1-methyl-3-ethyl-4-chloro-5-pyridinecarbonyl)-N'-tert-butylfluorene
Figure PCTCN2017070449-appb-000006
Figure PCTCN2017070449-appb-000006
向250mL反应瓶中分别加入100mL甲苯、24.8g(0.2mol)叔丁基肼盐酸盐，搅拌下滴加20g40％NaOH溶液(0.2mol)，控制温度0～5℃，滴加由化合物III与30mL甲苯组成的混合液，同时滴加15.6g40％NaOH溶液(0.156mol)；滴毕，室温搅拌1h，旋蒸出甲苯，抽滤，水洗，抽干，烘干得白色固体化合物IV32.6g，两步总收率81.0％。To a 250 mL reaction flask, 100 mL of toluene and 24.8 g (0.2 mol) of t-butyl hydrazine hydrochloride were added, and 20 g of a 40% NaOH solution (0.2 mol) was added dropwise with stirring. The temperature was controlled at 0 to 5 ° C, and the compound III was added dropwise. A mixture of 30 mL of toluene was added dropwise with 15.6 g of a 40% NaOH solution (0.156 mol); after completion, the mixture was stirred at room temperature for 1 h, and toluene was distilled off, suction filtered, washed with water, dried, and dried to give a white solid compound IV 32.6 g. The total yield in two steps was 81.0%.
(3)本发明化合物Ia的制备(3) Preparation of the compound I a of the present invention
Figure PCTCN2017070449-appb-000007
Figure PCTCN2017070449-appb-000007
向250mL反应瓶中，分别加入25.8g(0.1mol)化合物IV，100mL乙酸乙酯和12.0g三乙胺(0.12mol)，搅拌下滴加由16.8g(0.1mol)和30mL乙酸乙酯组成的混合液，滴毕，20～40℃反应2h，蒸出乙酸乙酯，加水100mL，搅拌溶解生成的三乙胺盐酸盐，抽滤，水洗两次，抽干，烘干，得33.9g白色固体，收率87％。25.8 g (0.1 mol) of Compound IV, 100 mL of ethyl acetate and 12.0 g of triethylamine (0.12 mol) were added to a 250 mL reaction flask, and 16.8 g (0.1 mol) and 30 mL of ethyl acetate were added dropwise with stirring. The mixture was diluted, and reacted at 20-40 ° C for 2 h. Ethyl acetate was distilled off, 100 mL of water was added, and the resulting triethylamine hydrochloride was stirred and stirred, filtered, washed twice, dried and dried to give 33.9 g of white. Solid, yield 87%.
1HNMR(500MHz，DMSO-d6),δ(ppm)数据如下： 1 H NMR (500 MHz, DMSO-d 6 ), δ (ppm) data are as follows:
化合物Ia：1.089-1.119(t，3H)，1.486(s，9H)，2.226(s，6H)，2.415-2.440(m，2H)，3.088(s，3H)，7.019-7.048(d，3H)，10.902(s，1H)。Compound I a : 1.089-1.119 (t, 3H), 1.486 (s, 9H), 2.226 (s, 6H), 2.415-2.440 (m, 2H), 3.088 (s, 3H), 7.019-7.048 (d, 3H) ), 10.902 (s, 1H).
实例2、化合物Ib的制备Example 2, Preparation of Compound I b
按照上述化合物Ia的制备方法，用3，5-二氯苯甲酰氯代替3，5-二甲基苯甲酰氯，用同样方法制得化合物Ib。According to the above preparation method of the compound I a , 3,5-dichlorobenzoyl chloride was used instead of 3,5-dimethylbenzoyl chloride, and the compound I b was obtained in the same manner.
1HNMR(500MHz，DMSO-d6),δ(ppm)数据如下： 1 H NMR (500 MHz, DMSO-d 6 ), δ (ppm) data are as follows:
化合物Ib：：1.130-1.136(t，3H)，1.489(s，9H)，2.728-2.887(m，5H)，7.404-7.437 (d，2H)，7.692(s，1H)，11.018(s，1H)。Compound I b ::1.130-1.136(t,3H), 1.489(s,9H), 2.728-2.887(m,5H),7.404-7.437 (d,2H), 7.692(s,1H),11.018(s, 1H).
生物活性测定Biological activity assay
实例3杀虫活性测定Example 3 Determination of insecticidal activity
1.杀甜菜夜蛾活性测定：1. Determination of the activity of killing beet armyworm:
将甘蓝叶片用打孔器打成直径1cm的叶碟，用Airbrush喷雾器处理一定浓度的测试化合物在每叶碟的正反面喷雾，喷雾量为0.5mL，阴干后每处理接入8头试虫(3龄)，每处理3次重复。处理后放入24℃、相对湿度60-70％、无光照的室内培养，96h后调查存活虫数，计算死亡率。已知化合物KC进行平行比较，试验结果见表2。The cabbage leaves were punched into a 1 cm diameter leaf disc with a puncher, and a certain concentration of the test compound was sprayed on the front and back sides of each leaf disc with an Airbrush sprayer, and the spray amount was 0.5 mL. After the dry operation, 8 test insects were connected per treatment. 3 years old), repeated 3 times per treatment. After the treatment, the cells were cultured at 24 ° C, relative humidity of 60-70%, and without light. After 96 hours, the number of viable insects was investigated and the mortality was calculated. Compound KC is known to be compared in parallel, and the test results are shown in Table 2.
表2杀甜菜夜蛾试验结果Table 2 Test results of killing beet armyworm
Figure PCTCN2017070449-appb-000008
Figure PCTCN2017070449-appb-000008
由表2结果说明，本发明化合物I对甜菜夜蛾杀灭率显著高于已知化合物虫酰肼(KC)。 From the results of Table 2, the killing rate of the compound I of the present invention against Spodoptera exigua was significantly higher than that of the known compound tebufenozide (KC).

Claims (3)

  1. 一种吡唑酰肼类化合物，结构如通式I所示：A pyrazole hydrazide compound having the structure shown in Formula I:
    Figure PCTCN2017070449-appb-100001
    式中：R选自Cl或CH3。
    Figure PCTCN2017070449-appb-100001
    Wherein R is selected from Cl or CH 3 .
  2. 按照权利要求1所述的一种吡唑酰肼类化合物的用途，其特征在于式I化合物单一使用或与另外的生物活性化合物组合使用，可用于农业或林业上鳞翅目害虫的防治。Use of a pyrazole hydrazide compound according to claim 1, characterized in that the compound of the formula I is used singly or in combination with another biologically active compound and can be used for the control of lepidopteran pests in agriculture or forestry.
  3. 一种杀虫组合物，含有权利要求1所述的通式I化合物为活性组分和农业或林业上可接受的载体。 A pesticidal composition comprising the compound of formula I according to claim 1 as an active ingredient and an agriculturally or forestry acceptable carrier.
PCT/CN2017/070449 2016-01-26 2017-01-06 Pyrazole hydrazide compound and use thereof WO2017128942A1 (en)

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CN110256361A (en) * 2019-05-08 2019-09-20 湖南人文科技学院 A kind of bishydrazide compounds and preparation method thereof of the structure fragment of ketone containing phenyl pyrimidine

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CN105777639A (en) * 2016-01-26 2016-07-20 浙江博仕达作物科技有限公司 Pyrazole hydrazide compound and use thereof

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