WO2018120881A1 - Composé d'éther insecticide ayant une structure similaire à un pyréthroïde - Google Patents

Composé d'éther insecticide ayant une structure similaire à un pyréthroïde Download PDF

Info

Publication number
WO2018120881A1
WO2018120881A1 PCT/CN2017/099413 CN2017099413W WO2018120881A1 WO 2018120881 A1 WO2018120881 A1 WO 2018120881A1 CN 2017099413 W CN2017099413 W CN 2017099413W WO 2018120881 A1 WO2018120881 A1 WO 2018120881A1
Authority
WO
WIPO (PCT)
Prior art keywords
ether
compound
insecticidal compound
insecticidal
atom
Prior art date
Application number
PCT/CN2017/099413
Other languages
English (en)
Chinese (zh)
Inventor
姜友法
黄成美
沈阳
吕杨
贾炜
Original Assignee
江苏扬农化工股份有限公司
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 江苏扬农化工股份有限公司 filed Critical 江苏扬农化工股份有限公司
Publication of WO2018120881A1 publication Critical patent/WO2018120881A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers

Definitions

  • the invention relates to an insecticide, which is a kind of ether insecticidal compound having a pyrethroid-like 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 ether insecticidal compound having a pyrethroid-like structure which is useful for insecticidal purposes.
  • 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 and R 2 are a methyl group, a halogen atom or a trifluoromethyl group
  • R 3 and R 4 are a H atom, a methyl group or an ethyl group
  • R 5 is a H atom, a methyl group or a methoxymethyl group.
  • R 1 and R 2 are a chlorine atom
  • R 3 is a H atom
  • R 4 is a methyl group
  • R 5 is a methoxymethyl group
  • R 1 and R 2 are fluorine atoms
  • R 3 and R 4 are H atoms
  • R 5 is H
  • the compound has the following structure.
  • the R 1 is a chlorine atom
  • R 2 is a trifluoromethyl group
  • R 4 is a methyl group
  • R 5 is a methyl group
  • the compound has the following structure.
  • the present invention also provides a method for preparing an ether insecticidal compound 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, It is dissolved in an inert solvent such as DMF in the presence of NaH, and is 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 ether-like 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 ether 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 ether-based insecticidal compound itself, or includes the ether-based insecticidal compound and an inert carrier;
  • the weight of the ether 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 ether insecticidal compound is used as an insecticide active ingredient for controlling pests, and the ether insecticidal compound can be combined with pyrethroid, propythrin, methrin, and high-efficiency chlorine.
  • Other insecticides such as cypermethrin, 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 9 trans-1-(1-[3-(2,2-dichloro-vinyl)-2,2-dimethyl-cyclopropyl]-ethoxymethyl in Table 1 Synthesis of -2,3,5,6-tetrafluoro-4-methoxymethyl-benzene
  • Example 2 Table compound 10 1-methyl-1-(1-[3-(2,2-dichloro-vinyl)-2,2-dimethyl-cyclopropyl]-ethoxymethyl )-2,3,5,6-tetrafluoro-4-methoxymethyl-benzene
  • Example 5 Compound 2 in Table 1 trans-1-(1-[3-(2,2-difluoro-vinyl)-2,2-dimethyl-cyclopropyl]-ethoxy)- Synthesis of 2,3,5,6-tetrafluorobenzene
  • Test Example 1 for determination of biological activity of rice planthopper
  • 0.01 g of the compound of the present invention 9, 12 and ethylester were separately taken; dissolved in 0.5 ml of DMF, 0.2 ml of Tween 80 emulsifier was added, and the mixture was stirred uniformly, and 100 ml of the insecticide mother liquid 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 for the control test 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 17 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. Among the test compounds, except for the compound 7, the remaining 16 compounds all obtained mortality of more than 80%.
  • the compound 10 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 10 of the present invention is nearly 1.8 times more effective against mosquitoes than tetrafluthrin.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un composé d'éther insecticide ayant une structure similaire à un pyréthroïde. La formule structurale du composé est représentée par la formule A, dans laquelle R1 et R2 représentent un méthyle, un atome d'halogène ou un trifluorométhyle, R3 et R4 représentent un atome H, un méthyle ou un éthyle, et R5 représente un atome H, un méthyle ou un méthoxyméthyle. Par comparaison avec un insecticide pyréthroïde classique, le composé de la présente invention est moins toxique pour les organismes aquatiques, et a un meilleur effet insecticide sur un certain nuisible cible.
PCT/CN2017/099413 2016-12-30 2017-08-29 Composé d'éther insecticide ayant une structure similaire à un pyréthroïde WO2018120881A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201611254086.6A CN108264452A (zh) 2016-12-30 2016-12-30 一种具有类似拟除虫菊酯结构的醚类杀虫化合物
CN201611254086.6 2016-12-30

Publications (1)

Publication Number Publication Date
WO2018120881A1 true WO2018120881A1 (fr) 2018-07-05

Family

ID=62707774

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/099413 WO2018120881A1 (fr) 2016-12-30 2017-08-29 Composé d'éther insecticide ayant une structure similaire à un pyréthroïde

Country Status (2)

Country Link
CN (1) CN108264452A (fr)
WO (1) WO2018120881A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109384669A (zh) * 2018-12-26 2019-02-26 江苏扬农化工股份有限公司 一种拟除虫菊酯化合物及其合成方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370346A (en) * 1979-12-21 1983-01-25 Imperial Chemical Industries Plc Halogenated esters
US4904677A (en) * 1985-12-23 1990-02-27 Imperial Chemical Industries Plc Certain phenoxy- or benzyl substituted pyridylmethyloxy-alkenes having insecticidal properties
WO2009132526A1 (fr) * 2008-04-29 2009-11-05 江苏扬农化工股份有限公司 Composé pyréthroïde optiquement actif et son procédé de fabrication et son utilisation
WO2014079928A1 (fr) * 2012-11-23 2014-05-30 Bayer Cropscience Ag Utilisation d'un composé comprenant un fragment de polyfluorobenzyle contre des nuisibles résistants aux insecticides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370346A (en) * 1979-12-21 1983-01-25 Imperial Chemical Industries Plc Halogenated esters
US4904677A (en) * 1985-12-23 1990-02-27 Imperial Chemical Industries Plc Certain phenoxy- or benzyl substituted pyridylmethyloxy-alkenes having insecticidal properties
WO2009132526A1 (fr) * 2008-04-29 2009-11-05 江苏扬农化工股份有限公司 Composé pyréthroïde optiquement actif et son procédé de fabrication et son utilisation
WO2014079928A1 (fr) * 2012-11-23 2014-05-30 Bayer Cropscience Ag Utilisation d'un composé comprenant un fragment de polyfluorobenzyle contre des nuisibles résistants aux insecticides

Also Published As

Publication number Publication date
CN108264452A (zh) 2018-07-10

Similar Documents

Publication Publication Date Title
DE2826864C2 (fr)
DE2547534C2 (de) Cyclopropancarbonsäureester, Verfahren zu deren Herstellung und deren Verwendung
CN103524422A (zh) 苯并咪唑衍生物及其制备方法和用途
WO2018120881A1 (fr) Composé d'éther insecticide ayant une structure similaire à un pyréthroïde
WO2018120880A1 (fr) Composé insecticide ayant une structure de liaison éther
JPS6157820B2 (fr)
JPH0751525B2 (ja) ジフルオロハロメトキシフエニル誘導体およびそれを含有する殺虫、殺ダニ剤
DE2554634A1 (de) Cyclopropancarbonsaeureester, verfahren zu ihrer herstellung und diese verbindungen enthaltende insekticide und acaricide
JPS58148805A (ja) Ｎ−メチルカルバメ−ト類のｎ−オキサリル誘導体類、それらの製造法、およびそれらの害虫駆除剤としての使用
JP2011219419A (ja) 光学活性（＋）−１−［２，４−ジメチル−５−（２，２，２−トリフルオロエチルスルフィニル）フェニル］−３−（トリフルオロメチル）−１ｈ−１，２，４−トリアゾール及び有害生物防除剤
JPS6310944B2 (fr)
JPS6134410B2 (fr)
JPS60115545A (ja) 炭化水素系化合物を有効成分とする殺虫剤
JPS59196803A (ja) 新規２−フエニルプロピルエ−テル誘導体を含有する殺虫、殺ダニ剤及びその製造法
KR800001637B1 (ko) 카르복실산 에스테르의 제조 방법
JPH0543536A (ja) 新規アミジン誘導体、及びこれを含有する殺虫、殺ダニ剤
DE2943394A1 (de) Carbonsaeureester, verfahren zu ihrer herstellung und diese ester enthaltende insektizide und/oder akarizide mittel
JPS6141903B2 (fr)
DK159306B (da) 6-phenoxypyrid-2-ylmethyl-estere af cyklopropancarboxylsyrer, insekticide midler med indhold heraf samt fremgangsmaade til insektbekaempelse
JPH0211589B2 (fr)
JPS58121246A (ja) 置換ベンジルエステル及びこれを有効成分とする殺虫剤
JPS5932459B2 (ja) シクロプロパンカルボン酸エステル，その製造法およびそれを有効成分とする低魚毒性殺虫剤
JPS63170386A (ja) 有機ケイ素系芳香族アルカン誘導体及びその製造方法
JPS6253497B2 (fr)
JPS6011495A (ja) オキシム誘導体および殺虫・殺ダニ組成物

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: 17886143

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17886143

Country of ref document: EP

Kind code of ref document: A1