WO2018120880A1 - 一种具有醚键结构的杀虫化合物 - Google Patents

一种具有醚键结构的杀虫化合物 Download PDF

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WO2018120880A1
WO2018120880A1 PCT/CN2017/099398 CN2017099398W WO2018120880A1 WO 2018120880 A1 WO2018120880 A1 WO 2018120880A1 CN 2017099398 W CN2017099398 W CN 2017099398W WO 2018120880 A1 WO2018120880 A1 WO 2018120880A1
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insecticidal compound
compound
atom
insecticidal
group
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French (fr)
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戚明珠
周其奎
姜友法
沈阳
黄成美
吕杨
贾炜
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江苏扬农化工股份有限公司
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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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/04—Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/44—Halogenated unsaturated alcohols containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
    • C07C43/1747—Unsaturated ethers containing halogen containing six-membered aromatic rings containing six membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

Definitions

  • the invention relates to an insecticide, which is a kind of insecticidal compound having an ether bond structure, a preparation method thereof and application of pest control.
  • Pyrethroid compounds are a class of biomimetic synthetic insecticides that can be used in a variety of pests and have high insecticidal activity. Pyrethroid compounds have high efficiency, low toxicity to mammals, low residue and good environmental compatibility, and have been widely used in the field of pest control. However, pyrethroid insecticides with an ester bond structure are highly toxic to aquatic fish and arthropods. For example, the acute toxicity of cypermethrin to zebrafish 96hLC50 is less than 0.1a.i.mg/L, which is highly toxic.
  • the inventors of the present invention have improved the preparation of a class of tetrafluorophenyl structures disclosed in the patents of US 4,370,346 A and the like by the long-term study of pyrethroid insecticides.
  • Pyrethroids have proposed a new class of ether-containing insecticidal compounds, which are toxic to aquatic organisms such as zebrafish, which are in the range of moderate to high toxicity, and are superior to target pests such as rice planthopper.
  • target pests such as rice planthopper.
  • fenthrin The effect of fenthrin.
  • these compounds also have good control effects against mosquitoes, flies, cockroaches and other health pests.
  • One of the objects of the present invention is to provide an insecticidal compound containing an ether bond having a pyrethroid-like structure which is useful for insecticidal action.
  • Another object of the present invention is to provide a process for the preparation of the above compounds.
  • a third object of the present invention is to provide the use of said compound as an active ingredient of a pesticide.
  • R 1 is a methyl group, a halogen atom, a cyano group or a trifluoromethyl group
  • R 2 and R 3 are a H atom, a methyl group or an ethyl group
  • R 4 is a H atom, a methyl group or a methoxymethyl group.
  • the R 1 is a chlorine atom
  • R 2 and R 3 are a H atom
  • R 5 is a H atom
  • the R 1 is a cyano group
  • R 2 is a H atom
  • R 3 is a methyl group
  • R 4 is a methyl group
  • the R 1 is a trifluoromethyl group
  • R 2 and R 3 are a methyl group
  • R 4 is a methoxymethyl group
  • the present invention also provides a method for preparing an insecticidal compound containing an ether bond having a pyrethroid-like structure represented by Formula A: using an alcohol represented by Formula B and a tetrafluorobenzene halogenated product represented by Formula C as a raw material. The two are dissolved in an inert solvent such as DMF in the presence of NaH, and subjected to an etherification synthesis reaction at room temperature to prepare the ether-like insecticidal compound having a pyrethroid-like structure;
  • the molar ratio of the alcohol to the tetrafluorobenzene halide is 1:1;
  • the alcohol may be prepared by reduction of the corresponding chrysanthemic acid, or by gemalic acid chloride by Grignard reaction; the tetrafluorobenzene halogenated product is an existing compound.
  • each substituent in the formula is as defined above, and X is a halogen selected from fluorine, chlorine or bromine.
  • the compound of the formula A of the present invention has a double bond and a three-membered ring in the structure, and the groups to which they are attached are not completely identical, the corresponding ZE and cis and optical isomers are present, and the compounds of the present invention contain these specific stereoscopic forms.
  • the present invention also provides an application of an insecticide-containing insecticidal compound having a pyrethroid-like structure represented by Formula A for controlling sanitary pests or agricultural pests.
  • the sanitary pest is a mosquito, a fly, a locust or a cockroach.
  • the agricultural pest is rice planthopper or the like.
  • the insecticidal compound is prepared as an active ingredient into a conventional preparation for controlling a sanitary pest or an agricultural pest;
  • the conventional preparation includes the insecticidal compound itself, or includes the insecticidal compound and an inert carrier;
  • the weight of the insecticidal compound is 0.001 to 95% by weight based on the total weight of the conventional preparation
  • the conventional preparation can be prepared by the following method:
  • the insecticidal compound is used as an insecticide active ingredient for controlling pests, and the insecticidal compound can be combined with pyrethroid, propythrin, methrin, and lambda-cyhalothrin.
  • Other insecticides such as chlorpyrifos, avermectin, thiamethoxam, chlorantraniliprole, flubendiamide, etc. are used as an insecticidal active ingredient. It can be prepared into mosquito-repellent incense, electric liquid mosquito coil, electric mosquito-repellent incense film, aerosol or resin hanging piece suitable for volatilization at room temperature, filter paper ribbon, fan mosquito coil and other sanitary insecticide products.
  • the compounds of the invention are less toxic to aquatic organisms and have a better insecticidal effect on certain target pests.
  • Example 1 Compound 10 in Table 1 Z-trans-1-(1-[3-(2-chloro-vinyl)-2,2-dimethyl-cyclopropyl]-ethoxy)-2 Synthesis of 3,5,6-tetrafluorobenzene
  • Test Example 1 Determination of biological activity of rice planthopper
  • 0.01 g of the compound of the present invention, 10, 25 and ethylester were respectively taken; dissolved in 0.5 ml of DMF, and 0.2 ml of Tween 80 emulsifier was added thereto, and the mixture was uniformly stirred, and 100 ml of a pesticide solution having a concentration of 100 mg/L was added by deionization. Then, 8 ml of the mother liquid was taken, added to water containing 0.1% Tween 80, and diluted to 100 ml to obtain a test solution having a concentration of 8 mg/L. Further, the mixture was diluted with water containing 0.1% Tween 80, and a gradient of 6 concentrations of 4, 2, 1, 0.5, and 0.25 mg/L was obtained in a ratio of 2 times, and the test was carried out.
  • Test Example 2 Test for the control of cotton aphid
  • the control effect on the cotton aphid was evaluated by the contact method.
  • the experimental unit included a container with a small opening, and a cotton seedling plant growing for 6-7 days was placed inside. Pre-infection was carried out by placing 30-40 insects on a leaf cut from the cultured plants on the leaves of the test plants. When the leaves dried, the larvae moved to the experimental plants. The soil of the experimental unit is covered with a layer of sand.
  • 0.25 mg/L of the compound of the present invention 1 to 37 was placed in a manner similar to that of Test Example 1, and the test plants were sprayed 3 times, 1 ml each time, and the test unit was air-dried for 1 hour, and then a black sieved hole was placed thereon.
  • the lid was incubated for 6 days at room temperature of 20 degrees at a relative humidity of 50-70%, and the mortality of insects in each experimental unit was examined.
  • the test compounds except for the compounds 9 and 23, the remaining 35 compounds all obtained mortality of more than 80%.
  • the compound 33 of the present invention and tetrafluthrin were prepared into mosquito coils for efficacy test. 0.014 g of each of the pyrethroids was dissolved in 1 g of kerosene, and dropped into 35 g of blank mosquito scent to make 0.04% mosquito coil.
  • Pipette 20 female Culex pipiens pallens put them into a closed drum test device, take a piece of tested mosquito coils, put them on the mosquito-repellent incense rack, ignite the mosquito-repellent incense, remove the mosquito-repellent incense after 1min, record at intervals The number of test mosquitoes knocked down, after 20 minutes, all the test mosquitoes were transferred to a clean insect cage, and the number of dead mosquitoes was checked after 24 hours. The results are shown in the table below: it is shown that the compound 33 of the present invention is nearly 1.8 times more effective against mosquitoes than tetrafluthrin.

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Abstract

本发明提供一种具有醚键结构的杀虫化合物，该化合物的结构式如式A所示；其中R1为甲基、卤素原子、氰基或三氟甲基；R2、R3为H原子、甲基或乙基；R4为H原子、甲基或甲氧基甲基。相对于传统的拟除虫菊酯杀虫剂，本发明化合物对水生生物的毒性较低，且对某些特定靶标害虫具有更好的杀虫效果。

Description

一种具有醚键结构的杀虫化合物 技术领域
本发明涉及一种杀虫剂，为一类具有醚键结构的杀虫化合物，以及其制备方法和害虫防治上的应用。
背景技术
拟除虫菊酯类化合物是一类仿生合成的杀虫剂，可以用于多种害虫，并且具有较高的杀虫活性。拟除虫菊酯类化合物具有高效、对哺乳动物低毒、低残留、环境兼容性好的特点，在害虫的防治领域得到了广泛的应用。然而具有酯键结构的拟除虫菊酯杀虫剂均具有对水生鱼类，节肢动物等高毒性的特点。例如氯氰菊酯对斑马鱼的96hLC50急性毒性小于0.1a.i.mg/L,为剧毒。
上世纪日本三井东压化学公司开发了醚菊酯Ethofenprox，有别于传统拟除虫菊酯，该化合物中没有酯键，取而代之的是醚键。这种结构上的变化减低了对鱼类的毒性，达到中等至高毒，从而可以用于防治一些水稻田害虫如稻飞虱等。但是其药效相对于高效氯氟氰菊酯、氯氰菊酯等含酯键的菊酯还是不尽人意。
本技术发明人经过对拟除虫菊酯类杀虫剂的长期研究，改进了四氟苯菊酯、氯氟醚菊酯以及ICI公司在US4370346A等专利中公开的一类含四氟苯基结构的拟除虫菊酯，提出了一类全新结构的含醚键杀虫化合物，对斑马鱼等水生生物的毒性均在中等毒至高毒的可接受范围内，同时获得了对稻飞虱这样的靶标害虫优于醚菊酯的防效。另外这类化合物对蚊、蝇、蜚蠊等卫生害虫也有很好的防效。
发明内容
本发明的目的之一是提供一种具有类似拟除虫菊酯结构的含有醚键的杀虫化合物，该化合物可用于杀虫。
本发明的目的之二是提供一种所述的化合物的制备方法。
本发明的目的之三是提供一种所述的化合物作为杀虫剂活性成分的应用。
为了实现上述发明目的，本发明采用如下技术方案：
一种具有类似拟除虫菊酯结构的含有醚键的杀虫化合物，其结构如式A所示：
Figure PCTCN2017099398-appb-000001
其中R1为甲基、卤素原子、氰基或三氟甲基；R2、R3为H原子、甲基或乙基；R4为H原子、甲基或甲氧基甲基。
上述技术方案中，所述的R1为氯原子，R2、R3为H原子，R5为H原子时，该化合物为如下式结构
Figure PCTCN2017099398-appb-000002
上述技术方案中，所述的R1为氰基，R2为H原子，R3为甲基，R4为甲基时，该化合物为如下式结构
Figure PCTCN2017099398-appb-000003
上述技术方案中，所述的R1为三氟甲基，R2、R3为甲基，R4为甲氧基甲基时，该化合物为如下式结构
Figure PCTCN2017099398-appb-000004
本发明还提供一种式A所示的具有类似拟除虫菊酯结构的含有醚键的杀虫化合物的制备方法：以式B所示的醇、式C所示的四氟苯卤代物作为原料，二者在NaH存在的条件下溶于DMF等惰性溶剂中，在室温条件下进行醚化合成反应制备成所述的具有类似拟除虫菊酯结构的醚类杀虫化合物；
所述的醇和四氟苯卤代物的摩尔比为1：1；
所述的醇为
Figure PCTCN2017099398-appb-000005
所述的四氟苯卤代物为
Figure PCTCN2017099398-appb-000006
所述的醇可由相应的菊酸酯还原制备，或者由菊酸酰氯经格氏反应，还原制备；所述的四氟苯卤代物为现有化合物。
本发明，式中各取代基定义同上，X为选自氟、氯、溴的卤素。
因为本发明式A的化合物结构中有双键和三元环，且其相连的基团不完全一样，因此存在相应的ZE和顺反及旋光异构体，本发明所述的化合物包含这些特定立体结构的单一异构体或其混合物。
通过以上方法制备的本发明式A化合物列于表1中。
表1
Figure PCTCN2017099398-appb-000007
Figure PCTCN2017099398-appb-000008
备注：构型中空白为不区分的混式。
本发明还提供一种式A所示的具有类似拟除虫菊酯结构的含有醚键的杀虫化合物在防治卫生害虫或者农业害虫方面的应用。
上述技术方案中，所述的卫生害虫为蚊、蝇、蠹虫或蜚蠊等。
上述技术方案中，所述的农业害虫为稻飞虱等。
上述技术方案中，所述的杀虫化合物作为有效成分制备成常规制剂从而用于防治卫生害虫或者农业害虫；
所述的杀虫化合物作为有效成分制备成常规制剂时，常规制剂包括所述的杀虫化合物本身，或者包括所述的杀虫化合物和惰性载体；
所述的常规制剂包括所述的杀虫化合物和惰性载体时，杀虫化合物的重量占常规制剂总重量的0.001～95％；
所述的常规制剂可以通过下列方法制备所述常规制剂：
①将本发明杀虫化合物与液体和/或气体载体混合，并且任选加入制剂用表面活性剂及其它辅剂；
②将本发明杀虫化合物与粉状固体载体混合，并且任选加入制剂用表面活性剂及其它辅剂；或
③用本发明杀虫化合物浸渍成形的固体载体；或将本发明化合物与粉状固体载体混合，并且任选加入制剂用表面活性剂及其它辅剂，并将得到的混合物成形。
上述技术方案中，所述的杀虫化合物作为防治害虫的杀虫剂活性成分的应用中，所述杀虫化合物可以和丙烯菊酯、丙炔菊酯、胺菊酯、高效氯氟氰菊酯、毒死蜱、阿维菌素、噻虫嗪、氯虫苯甲酰胺、氟虫酰胺等其它杀虫剂作为杀虫有效成分复配使用。可以制备成蚊香、电热液体蚊香、电蚊香片、气雾剂或适合在常温下挥发使用的树脂挂片、滤纸飘带、风扇蚊香等多种卫生杀虫制品。
相对于传统的拟除虫菊酯杀虫剂，本发明化合物对水生生物的毒性较低，且对某些特定靶标害虫具有更好的杀虫效果。
具体实施方式
下面用实施例的形式详细解释本发明的技术方案和效果，但本发明并不限于以下实施例。以下％含量未经特殊说明均指质量分数。
实施例1：表格1中化合物10 Z-反式-1-(1-[3-(2-氯-乙烯基)-2,2-二甲基-环丙基]-乙氧基)-2,3,5,6-四氟苯的合成
Figure PCTCN2017099398-appb-000009
1)Z-反式-[3-(2-氯乙烯基)-2,2-二甲基-环丙基]-1-醇的合成：
在250ml四口烧瓶中加入25g Z-反式的一氯菊酸甲酯(获取可参见CN200710044542.9)，55g甲醇。在25℃，分批加入9.7g硼氢化钠，投毕，反应一小时。用15％盐酸调pH到5-6，减压脱去甲醇，加入100g水，用3*50mL氯仿萃取，合并有机相，水洗至中性后，脱溶收深棕色油状液体Z-反式-[3-(2-氯乙烯基)-2,2-二甲基-环丙基]-1-醇18g，收率87％。
2)1-氯甲基-2,3,5,6-四氟苯的合成：
在带有搅拌的1000ml四口烧瓶中加入64g 2,3,5,6-四氟苯甲醇，400g二氯乙烷，催化量DMF，在常温滴加82.4g氯化亚砜。滴毕，回流两小时，减压脱溶得62g目标产物，收率90％。
3)Z-反式-1-(1-[3-(2-氯-乙烯基)-2,2-二甲基-环丙基]-乙氧基)-2,3,5,6-四氟苯的合成(即本 发明表格化合物10)
在250mL的四口瓶中加入30g无水DMF，在氮气保护下，加入1.5gNaH。将8g Z-反式-[3-(2-氯乙烯基)-2,2-二甲基-环丙基]-1-醇溶于20gDMF中，然后在18℃滴加到含有NaH的DMF溶液中，滴毕，搅拌1小时。将10g 1-氯甲基-2,3,5,6-四氟苯溶于30gDMF中，在5℃条件下，滴加到前述溶液中。滴毕，升温至室温搅拌4小时。加入200g水淬灭反应，用3*50mL乙酸乙酯萃取水相，合并有机相后水洗至中性，脱溶柱层析后得10.3g淡黄油状物，收率64.3％，含量98.3％。
该化合物即为本发明表格化合物10：Z-反式-1-(1-[3-(2-氯-乙烯基)-2,2-二甲基-环丙基]-乙氧基)-2,3,5,6-四氟苯，分子式：C15H15OF4Cl,分子量322.73，质谱分子离子峰M＝322。500兆核磁共振氢谱(1H(ppm)CDCl3)：6.57(m,1H)；5.92(d,1H)；5.45(t,1H)；0.87(t,1H)；0.51(t,1H)；4.67(s,2H)；3.32(s,2H)；1.11(s,6H).
实施例2：表格化合物25 Z-1-(1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-乙氧基甲基)-2,3,5,6-四氟-4-甲基苯的合成
Figure PCTCN2017099398-appb-000010
1)Z-1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-乙基酮的合成
在1000ml四口烧瓶中加入150g Z-3-(2-氰基-乙烯基)-2,2-二甲基-环丙酰氯(单氰基菊酸酰氯,获得可参见CN201010002678.5)，无水四氢呋喃，降温至10℃。在该温度下缓慢滴加225g甲基氯化镁格氏试剂的四氢呋喃溶液(折算镁为0.75mol)。滴毕，在该温度下保温8小时。待反应结束，加入200mL水搅拌，分液，水层用3*200mL乙酸乙酯萃取。有机相用水洗至中性，减压脱溶得150g粗品。柱层析得无色油状的Z-1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-乙基酮63g，收率42％。
2)Z-1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-1-乙醇的合成
在四口烧瓶中加入25g第一步中得到的乙基酮、50g甲醇。在25℃，分批加入9.5g硼氢化钠，投毕，反应一小时。用15％盐酸调pH到5-6，减压脱去甲醇，加入200g水，用3*50mL氯仿萃取，合并有机相，水洗至中性后，脱溶收油状液体Z-1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-1-乙醇23.2g,收率93％。
3)Z-1-(1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-乙氧基甲基)-2,3,5,6-四氟-4-甲基苯(化合物25)的合成
在250mL的四口瓶中加入30g无水DMF，在氮气保护下，加入1.5gNaH。将7.7g Z-1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-1-乙醇溶于20gDMF中，然后在18℃滴加到含有NaH的DMF溶液中，滴毕，搅拌1小时。将10.6g 1-氯甲基-2,3,5,6-四氟-4-甲基苯溶于30gDMF中，在5℃条件下，滴加到前述溶液中。滴毕，升温至室温搅拌4小时。加入200g水淬灭反应，用3*50mL乙酸乙酯萃取水相，合并有机相后水洗至中性，脱溶柱层析后得10.5g淡黄油状物，收率64.7％，含量98.1％。
该化合物即为本发明表格化合物25：Z-1-(1-[3-(2-氰基-乙烯基)-2,2-二甲基-环丙基]-乙氧基甲基)-2,3,5,6-四氟-4-甲基苯，分子式：C18H19NOF4,分子量327.32，质谱分子离子峰M＝327。500兆核磁共振氢谱(1H(ppm)CDCl3)：3.05(m,1H)；5.11(d,1H)；5.87(t,1H)；0.87(t,1H)；0.51(t,1H)；4.63(s,2H)；2.32(s,3H)；1.22(d,3H)；1.11(s,6H).
实施例3表格化合物33 E-反式-1-甲基-1-(1-[3-(2-三氟甲基-乙烯基)-2,2-二甲基-环丙基]-乙氧基甲基)-2,3,5,6-四氟-4-甲氧基甲基-苯的合成
在250mL的四口瓶中加入30g无水DMF，在氮气保护下，加入1.5gNaH。将9.8g E-反式-1-甲基-1-(1-[3-(2-三氟甲基-乙烯基)-2,2-二甲基-环丙基]-1-乙醇(可由CN200810167598.8中的菊酸酰氯参照上述方法格氏反应还原制备)溶于20gDMF中，然后在18℃滴加到含有NaH的DMF溶液中，滴毕，搅拌1小时。将12.1g 1-氯甲基-2,3,5,6-四氟-4-甲氧基甲基苯溶于30gDMF中，在5℃条件下，滴加到前述溶液中。滴毕，升温至室温搅拌4小时。加入200g水淬灭反应，用3*50mL乙酸乙酯萃取水相，合并有机相后水洗至中性，脱溶柱层析后得16.2g深黄油状物，收率79.7％，含量98.2％。
该化合物即为本发明表格化合物33：E-反式-1-甲基-1-(1-[3-(2-三氟甲基-乙烯基)-2,2-二甲基-环丙基]-乙氧基甲基)-2,3,5,6-四氟-4-甲氧基甲基-苯，分子式：C20H23O2F7,分子量428.38，质谱分子离子峰M＝428。500兆核磁共振氢谱(1H(ppm)CDCl3)：5.70(d,1H)；5.97(t,1H)； 0.87(t,1H)；0.51(t,1H)；4.63(s,2H)；4.61(s,2H)；3.22(S,3H)；1.26(s,6H)；1.11(s,6H).
测试实施例1 对稻飞虱的生物活性测定
稻飞虱取田间采集的在室内以稻苗培养的饲养多代的3龄若虫。
分别取0.01g本发明表格化合物10、25、醚菊酯；用0.5mlDMF溶解，加0.2ml吐温80乳化剂，搅拌均匀，加去离子补足100ml配置成浓度100mg/L的杀虫剂母液。再取8ml母液，加入到含0.1％吐温80的水中，稀释至100ml，得到8mg/L浓度的供试液。再用含0.1％吐温80的水逐次稀释，按2倍比例得到4、2、1、0.5、0.25mg/L的6个浓度的梯度，进行试验。
选取二叶一芯稻苗15株，在供试药液中浸渍30秒后取出自然晾干，用湿脱脂棉包住根部保湿，外包保鲜膜，至于玻璃试管(200*30mm)中，每浓度4次重复。然后用毛笔接入用乙醚轻度麻醉的稻飞虱3龄若虫，每管15正负2头，管口用白纱布扎紧。处理完毕，至于观察室内。
数据统计与分析方法参见NY/T 1154.11-2008农药室内生测测定试验准则，结果如下表
供试药剂 回归方程 LC50mg/L
本发明化合物10 y＝1.2648+3.5101x 11.59
本发明化合物25 y＝1.2541+3.3919x 12.72
醚菊酯 y＝0.5938+2.3519x 74.72
测试实施例2 对棉蚜的防治测试
通过接触法评价对棉蚜的防治效果，实验单元包括一小开口的容器，内部放有生长6-7天的棉苗植株。用从培养植株上割下的一片叶子上的30-40头昆虫放置在供试植株叶片上进行预侵染。当叶片变干后，幼虫移向实验植株。实验单元的土壤上覆盖一层沙。
按类似测试实施例1中的方法配置本发明化合物1～37的0.25mg/L药液，对试验植株喷雾3次，每次1ml，实验单元风干1小时，然后上面放置一个黑色带筛孔的盖子，在20度室温，相对湿度50-70％下室内培养6天，检测每个实验单元中的昆虫死亡率。供试化合物中，除化合物9和23以外，其余的35种化合物都得到了80％以上的死亡率。
测试实施例3：
将本发明的化合物33和四氟苯菊酯制备成蚊香进行药效测试。各取菊酯0.014g溶于1g煤油，点滴至35g空白蚊香坯制成0.04％蚊香。用吸蚊管吸取20头雌性致乏库蚊，放入密闭圆桶测试装置，任取被测试蚊香一段，放至蚊香架上，点燃蚊香计时，1min后移走蚊香，每隔一段时间记录被击倒的试蚊数，20min后将全部供试蚊转移至清洁的养虫笼中，24hr后检查死试蚊数。结果见下表：表明本发明化合物33对蚊虫的药效超过四氟苯菊酯近1.8倍。
蚊香类型 浓度(m/m) KT50(min) 24小时死亡率
本发明化合物33 0.04％ 4.3 100％
四氟苯菊酯 0.04％ 7.2 100％

Claims (10)

  1. 一种具有醚键结构的杀虫化合物，其特征在于，其结构如式A所示：
    Figure PCTCN2017099398-appb-100001
    其中R1为甲基、卤素原子、氰基或三氟甲基；R2、R3为H原子，甲基或乙基；R4为H原子、甲基或甲氧基甲基。
  2. 根据权利要求1所述的杀虫化合物，其特征在于：所述的R1为氯原子，R2、R3为H原子，R5为H原子时，该化合物为如下式结构
    Figure PCTCN2017099398-appb-100002
  3. 根据权利要求1所述的杀虫化合物，其特征在于：所述的R1为氰基，R2为H原子，R3为甲基，R4为甲基时，该化合物为如下式结构
    Figure PCTCN2017099398-appb-100003
  4. 根据权利要求1所述的杀虫化合物，其特征在于：所述的R1为三氟甲基，R2、R3为甲基，R4为甲氧基甲基时，该化合物为如下式结构
    Figure PCTCN2017099398-appb-100004
  5. 一种权利要求1-4任一项所述的杀虫化合物的制备方法，其特征在于，包括以下步骤：以式B所示的醇、式C所示的四氟苯卤代物作为原料，二者在NaH存在的条件下溶于DMF等惰性溶剂中，在室温条件下进行醚化合成反应制备成所述的具有类似拟除虫菊酯结构的醚类杀虫化合物；所述的醇和四氟苯卤代物的摩尔比为1：1；
    Figure PCTCN2017099398-appb-100005
  6. 一种权利要求1-4任一项所述的杀虫化合物在防治卫生害虫或者农业害虫方面的应用。
  7. 根据权利要求6所述的应用，其特征在于，所述的卫生害虫为蚊、蝇、蠹虫或蜚蠊；所述的农业害虫为稻飞虱。
  8. 根据权利要求6所述的应用，其特征在于，所述的杀虫化合物作为有效成分制备成常规制剂从而用于防治卫生害虫或者农业害虫。
  9. 根据权利要求8所述的应用，其特征在于，所述的杀虫化合物作为有效成分制备成常规制剂时，常规制剂包括所述的杀虫化合物本身，或者包括所述的杀虫化合物和惰性载体。
  10. 根据权利要求9所述的应用，其特征在于，所述的常规制剂包括所述的杀虫化合物和惰性载体时，杀虫化合物的重量占常规制剂总重量的0.001～95％。
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