Patent Grant
11104648
The present invention relates to the field of agricultural insecticides and acaricides, and in particular to a pyrazole derivative.
Presently, due to long-term use of pesticides, pests and insects produce resistance, resulting in a significant increase in the use of pesticides and serious damage to the environment. Therefore, it is required to continuously discover high-efficiency new pesticides with new mechanism of action, for example, new pesticides with higher activity against insects and pests, bacteria or acarids. Among the existing acaricide pesticides, most of pesticides can only control one of the three stages of eggs, nymphs and adult mites. It will be of significance if we can research and develop acaricides that have control effects on three stages of acarids.
The PCT Patent Application WO 01/68589 discloses heterocyclic acrylonitrile ether compounds, and the following compounds 8-1, 8-2, 8-3 and 8-4 are disclosed on page 71 in the Description.
The pyrazole derivatives described herein are not disclosed in the prior art.
The present invention provides a pyrazole derivative having the following formula stru-1:
wherein:
R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C1-C20 alkyl, C1-C20 haloalkyl, C2-C20 alkenyl, C2-C20 haloalkenyl, C2-C20 alkynyl, C2-C20 haloalkynyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio, C1-C20 alkylsulfoxide, C1-C20 alkylsulfone, C1-C20 alkylsulfonate, C1-C20 alkyl carboxylic ester, C1-C20 alkyl acyl, C1-C20 haloalkyl acyl;
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C1-C20 alkyl, C1-C20 haloalkyl, C2-C20 alkenyl, C2-C2a haloalkenyl, C2-C20 alkynyl, C2-C20 haloalkynyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio, C1-C2 alkylsulfoxide, C1-C20 alkylsulfone, C1-C2 alkylsulfonate, C1-C20 alkyl carboxylic ester, C1-C20 alkyl acyl, C1-C20 haloalkyl acyl.
Preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile C1-C10 alkyl, C1-C10 haloalkyl, C2-C10 alkenyl, C2-C10 haloalkenyl, C2-C20 alkynyl, C2-C10 haloalkynyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, C1-C10 alkylsulfoxide, C1-C10 alkylsulfone, C1-C10 alkylsulfonate, C1-C10 alkyl carboxylic ester, C1-C10 alkyl acyl, C1-C10 haloalkyl acyl.
Further preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfoxide, C1-C6 alkylsulfone, C1-C6 alkylsulfonate, C1-C6 alkyl carboxylic ester, C1-C6 alkyl acyl, C1-C6 haloalkyl acyl.
Still further preferably, the substituents R, R2, R3, R4, R5 are independently selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, difluoroethoxy, methylthio, trifluoromethylthio, trifluoroethylthio, methylsulfonyl, methylsulfonate.
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C2-C20 alkenyl, C2-C20 haloalkenyl, C2-C20 alkynyl, C2-C20 haloalkynyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C2 haloalkylthio, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C2 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio and C1-C20 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano C1-C2 alkyl, C1-C2 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio and C1-C20 alkylsulfone.
Preferably, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C2-C10 alkenyl, C2-C10 haloalkenyl, C2-C10 alkynyl, C2-C10 haloalkynyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio and C1-C10 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio and C1-C10 alkylsulfone. The compound may be in the form of E, Z or a mixture of E and Z;
Further preferably, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio and C1-C6 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio and C1-C6 alkylsulfone.
Still further preferably, the substituent R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl, p-chlorophenyl, P-fluorophenyl.
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 alkoxymethylene.
Preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkoxymethylene.
Further preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxymethylene.
Still further preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxymethylene.
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, substituent R8 is selected from hydrogen, C1-C2 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxymethylene, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C20 alkyl, C1-C2 haloalkyl, C3-C2 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C2 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio and C1-C20 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one substituted pyridyl, pyrazolyl, thienyl, furyl or thiazolyl selected from the group consisting of hydrogen, halogen, nitro, cyano, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio and C1-C20 alkylsulfone.
Preferably, the substituent R8 is selected from hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxymethylene, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio and C1-C10 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio and C1-C10 alkylsulfone.
Further preferably, the substituent R8 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxymethylene, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio and C1-C6 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio and C1-C6 alkylsulfone.
Still further preferably, the substituent R8 is selected from hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, methoxymethylene, ethoxymethylene.
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, substituent R9 is selected from hydrogen, halogen, nitro, C1-C2 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C2-C20 alkenyl, C2-C20 haloalkenyl, C2-C20 alkynyl, C2-C20 haloalkynyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio, C1-C20 alkylsulfone, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio and C1-C20 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C2 alkylthio, C1-C20 haloalkylthio and C1-C20 alkylsulfone.
Preferably, the substituent R9 is selected from hydrogen, halogen, nitro, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C2-C10 alkenyl, C2-C10 haloalkenyl, C2-C10 alkynyl, C2-C10 haloalkynyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, C1-C10 alkylsulfone, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio and C1-C10 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio and C1-C10 alkylsulfone.
Further preferably, the substituent R9 is selected from hydrogen, halogen, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfone, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio and C1-C6 alkylsulfone, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio and C1-C6 alkylsulfone.
Still further preferably, the substituent R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthiomethylene, phenyl, p-chlorophenyl, p-fluorophenyl, benzyl.
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, substituent L is selected from oxygen, sulfur, methylene, nitrogen.
Preferably, the substituent L is selected from oxygen, sulfur, methylene.
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, substituent Q is selected from oxygen, sulfur.
In the pyrazole derivatives represented by the formula stru-1 provided in the present invention, substituent R10 is selected from hydrogen, halogen, nitro, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C2-C20 alkenyl, C2-C20 haloalkenyl, C2-C20 alkynyl, C2-C20 haloalkynyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio, C1-C20 haloalkylthio, C1-C20 alkyl carboxylic ester, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C20 alkyl, C1-C20 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio and C1-C20 haloalkylthio, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C3-C20 cycloalkyl, C3-C20 halocycloalkyl, C1-C20 alkoxy, C1-C20 haloalkoxy, C1-C20 alkylthio and C1-C20 haloalkylthio.
Preferably, the substituent R10 is selected from hydrogen, halogen, nitro, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkenyl, C2-C10 haloalkenyl, C2-C10 alkynyl, C2-C10 haloalkynyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, C1-C10 alkyl carboxylic ester, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio and C1-C10 haloalkylthio, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C1-C10 alkoxy, C1-C20 haloalkoxy, C1-C10 alkylthio and C1-C10 haloalkylthio.
Further preferably, the substituent R10 is selected from hydrogen, halogen, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkyl carboxylic ester, phenyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio and C1-C6 haloalkylthio, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio and C1-C6 haloalkylthio.
Still further preferably, the substituent R10 is selected from hydrogen, fluorine, chlorine, nitro, C1-C6 alkyl, C3—C cycloalkyl, C3-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 methyl alkyl carboxylate. C1-C6 ethyl carboxylic acid ethyl ester, phenyl substituted by at least one of hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy, and methylthio, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy, and methylthio.
For the pyrazole derivatives represented by the formula stru-1 provided herein, as a preferred embodiment, in the formula stru-1:
R1, R2, R3, R4, R5 are independently selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, difluoroethoxy, methylthio, trifluoromethylthio, trifluoroethylthio, methylsulfonyl, methylsulfonate;
R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, p-chlorophenyl, p-fluorophenyl;
R7 is selected from hydrogen, halogen, nitro, nitrile, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxymethylene;
R8 is selected from methyl, ethyl;
R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthiomethylene, phenyl, p-chlorophenyl, p-fluorophenyl, benzyl:
L is selected from oxygen, sulfur, methylene:
Q is selected from oxygen, sulfur:
R10 is selected from hydrogen, fluorine, chlorine, nitro, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 methyl alkyl carboxylate. C1-C6, ethyl carboxylic acid ethyl ester, phenyl substituted by at least one of hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy, and methylthio, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy, and methylthio.
For the pyrazole derivatives represented by the formula stru-1 provided herein, as another preferred embodiment, in the formula stru-1:
R1, R2, R4, R5 are selected from hydrogen;
R3 is selected from t-butyl;
R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, p-chlorophenyl, p-fluorophenyl;
R7 is selected from hydrogen, halogen, nitro, nitrile, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxymethylene:
R8 is selected from methyl, ethyl;
R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthiomethylene, phenyl, p-chlorophenyl, p-fluorophenyl, benzyl:
L is selected from oxygen, sulfur, methylene:
Q is selected from oxygen, sulfur;
R10 is selected from hydrogen, fluorine, chlorine, nitro, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 methyl alkyl carboxylate, C1-C6 ethyl carboxylic acid ethyl ester, phenyl substituted by at least one of hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoroethoxy, and methylthio, pyridyl, pyrazolyl, thienyl, furyl or thiazolyl substituted by at least one of hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoroethoxy, and methylthio.
For pyrazole derivatives represented by the formula stru-1 provided herein, as the most preferred embodiment, the pyrazole derivatives are selected from at least one of the compounds represented by the following structural formula:
For pyrazole derivatives represented by the above numbers, preferably, the compound is an E-pyrazole derivative, that is, E-isomer.
The pyrazole derivatives represented by the formula stru-1 provided herein comprise at least one selected from the group consisting of an E-type pyrazole derivative and a Z-type pyrazole derivative. When the pyrazole derivative comprises an E-type pyrazole derivative and a Z-type pyrazole derivative, the E-type pyrazole derivative and the Z-type pyrazole derivative may be present in any ratio.
For pyrazole derivatives represented by the formula stru-1 provided herein when substituents R1, R2, R4, and R5 are hydrogen and Q is oxygen, as an example, when the pyrazole derivative represented by the formula stru-1 is an E-type compound, the pyrazole derivative represented by the formula stru-1 may be a compound shown in Table 1.
For pyrazole derivatives represented by the formula stru-1 provided herein, when substituents R1, R2, R4, and R5 are hydrogen and Q is oxygen, as an example, when the pyrazole derivative represented by the formula stru-1 is a Z-type compound, the pyrazole derivative represented by the formula stru-1 may be a compound shown in Table 2.
Physical property data of part of compounds provided in the present invention are shown in Table 3 below
1H NMR (600 MHZ, CDCl3/TMS)
The present invention further provides the preparation method of a pyrazole derivative represented by the formula stru-1, the method comprising:
wherein X is selected from halogen.
In the preparation method provided herein, preferably, the base is at least one selected from an organic base and an inorganic base; further preferably, the base is at least one selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium hydroxide, sodium hydride, sodium alkoxide and potassium alkoxide.
In the preparation method provided herein, preferably, the acid is at least one selected from an organic acid and an inorganic acid; further preferably, the acid is at least one selected from hydrochloric acid, sulfuric acid and acetic acid.
In the preparation method provided herein, preferably, the solvent is at least one independently selected from a protic solvent and an aprotic solvent; further preferably, the solvent is at least one independently selected from acetone, methyl ethyl ketone, tetrahydrofuran, acetonitrile, N, N-dimethylformamide, toluene and chlorobenzene.
In the preparation method provided herein, the X is selected from a halogen; preferably, the X is selected from chlorine, bromine or iodine.
In the preparation method provided herein, the catalyst is at least one selected from potassium iodide, sodium iodide, and a phase transfer catalyst.
The present invention further provides an agricultural insecticide and an acaricide. The insecticide and acaricide contain a pyrazole derivative represented by the formula stru-1 with a mass percentage of 0.1˜99%. The insecticide and acaricide may further contain a carrier and an auxiliary agent commonly used in the industry in addition to the pyrazole derivative represented by the formula stru-1.
The pyrazole derivative represented by the formula stru-1 provided in the present invention is suitable for pest prevention and control, particularly suitable for prevention and control of at least one of adult mites, nymphs, mite eggs, aphids and planthoppers on crops. The pyrazole derivatives are very suitable for the prevention and control of animal pests in vine plants, fruits, horticulture, agriculture, animal health, forests, storage products and the fields of materials and health.
Preferably, the pyrazole derivatives are used for the prevention and control of at least one species of Isopoda, Diplopoda, Chilopoda, Symphyla, Thysanura, Collembola, Orthoptera, Blattaria, Dermaptera, Isoptera, Phthiraptera, Thysanoptera, Heteroptera. Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera, Arachnida and plant parasitic nematodes.
The Isopoda, for example, Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
The Diplopoda, for example, Blaniulus guttulatus.
The Chilopoda, for example, Geophilus carpophagus, Sutigera spp.
The Symphyla, for example, Scutigerella immaculate.
The Thysanura, for example, Lepisma saccharina.
The Collembola, for example, Onychiurus armatus.
The Orthoptera, for example, Acheta domestcus, Gryllotalpa spp., Locusta migratoria, Melanoplus spp., Schistocer cagregaria.
The Blattaria, for example, Blatta orientahs, Periplanet aamericana, Leucophae amaderae, Blattella germanica.
The Dermaptera, for example, Forficula auricularia.
The Isoptera, for example, Reticulitermes spp.
The Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., richodectes spp. and Damalinia spp.
The Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.
The Heteroptera, for example, Eurgaster spp., Dysdercus intermedius, Piesma quadrata, Cimexlectularius, Rhodnius prolixus, Triatoma spp.
The Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis jabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp. Phorodon humui, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvatalugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
The Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocrnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocap sapomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilap seudospretella, Cacoecia podana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
The Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hvpera postica, Dermestes spp., Togoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus bololeucus, Gibbium psylloides, Tribohum spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
The Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
The Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora vicina. Lucilia spp., Chrsomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Somoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyumi, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Lirionyza spp.
The Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp.
The Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Erio phyesribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia pratiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.
The plant parasitic nematodes, including, for example, Pratylenchus spp., Radopholus similis, Ditvlenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.
The sole FIGURE is a single crystal diffraction pattern of Compound 251.
The present invention is further described in combination with particular embodiments, but the present invention is not limited to these particular embodiments. Those skilled in the art should be aware that the present invention encompasses all alternatives, modifications, and equivalents that may be included within the scope of the appended claims.
154.1 g (1 mol) of intermediate A was added to a 1000 ml flask, then 500 ml of acetonitrile and 138 g of potassium carbonate were added, and then 1 mol of diethyl sulfate was added, and the system was stirred and heated to reflux until the reaction was finished in about 3 hr by thin-layer chromatography method. The system was filtered and the mother liquor was evaporated to dryness by a rotary evaporator, and the residue was distilled under a reduced pressure to give 140 g of intermediate B, with a yield of 77.0%.
18.2 g (0.1 mol) of intermediate B was added to a 100 ml flask, and 50 ml of dichloroethane and 138 g of potassium carbonate were added, and then 0.11 mol of sulfonyl chloride was added. The system was stirred and heated to reflux until the reaction was finished in about 2.5 hr by thin-layer chromatography method. The mother liquor was evaporated to dryness and the residue was used in the next reaction without treatment.
The intermediate D was prepared with reference to the method provided in JP2001342178A.
The intermediate D-1 was prepared with reference to the method provided in JP2001342178A.
The intermediate C-1 is prepared according to the same method as preparation of interemdicate C.
Conventional procedure; The substituted aldehyde and zinc chloride at the catalytic amount were uniformly stirred in a reactor, and the substituted acyl chloride was slowly added dropwise under a cooling state. After dropwise addition, the mixture was stirred continuously for 1-2 hr at a low temperature, and warmed up to continue reaction for 5 hr, and purified by distillation under a reduced pressure.
Preparation of Intermediate Chloromethyl Acetate:
50 g (0.6 mol) of acetyl chloride was added dropwise to a mixture of 85 g paraformaldehyde and 1.75 g zinc chloride after cooled to 0° C. The dropwise addition was finished in about 2 hr, and then the reaction system was allowed to warm to room temperature for reaction for 1 hr, and then heated to 90° C. to continue reaction for 10 hr, cooled, filtered to remove solid, and then 45 g of intermediate F-1 was obtained by reduced pressure distillation.
Conventional procedure: The chloro chloroformate was slowly added dropwise to the substituted alcohol and triethylamine solution under cooling state, after dropwise addition, the mixture was stirred continuously for 1-2 hr at a low temperature, and warmed up to continue reaction for 1 hr, filtered and the solvent was distilled off, and then purified by reduced pressure distillation to obtain the intermediate H.
Preparation of Intermediate H-1:
When cooled to 0° C., 71.5 g (0.5 mol) of 1-chloroethyl chloroformate was added dropwise to 40 g and 52.0 g of triethylamine in 250 ml of toluene solution. The dropwise addition was finished in about 2 hr, and then the reaction system was allowed to warm to room temperature for reaction for 1 hr, and then filtered to remove solid, to obtain 78.5 g of intermediate H-1 by reduced pressure distillation.
17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF when the system was cooled to −5° C., equimolar amount of solid sodium methoxide was added, and then equimolar amount of intermediate B was added dropwise while stirring. When the dropwise addition was finished in 2 hr, the mixture was stirred continuously for 1.5 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-1, which was used in the next reaction without purification.
17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF, when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate C was added dropwise while stirring. When the dropwise addition was finished in 2.5 hr, the mixture was stirred continuously for 2.0 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-2, which was used in the next reaction without purification.
17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of methyl tert-butyl ether, when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate D was added dropwise while stirring. When the dropwise addition was finished in 3.0 hr, the mixture was stirred continuously for 2.0 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the methyl tert-butyl ether was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-3, which was used in the next reaction without purification.
17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF, when the system was cooled to −5° C., equimolar amount of solid sodium methoxide was added, and then equimolar amount of intermediate M was added dropwise while stirring. When the dropwise addition was finished in 2 hr, the mixture was stirred continuously for 1.5 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-1, which was used in the next reaction without purification.
17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate C was added dropwise while stirring. When the dropwise addition was finished in 2.5 hr, the mixture was stirred continuously for 2.0 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-5, which was used in the next reaction without purification.
17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of THF, when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate D-1 was added dropwise while stirring. When the dropwise addition was finished in 3.0 hr, the mixture was stirred continuously for 2.0 hr. and then warmed up to room temperature to continue stirring for 2 hr, after reaction, MTBE was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-3, which was used in the next reaction without purification.
(1) Preparation of Target Compound 226
0.31 g (0.001 mol) of intermediate TA-1 and 0.12 g (0.0011 mol) of intermediate F-1, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 7 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.32 g of product, with a yield of 84%.
(2) Preparation of Target Compound 251
31 g (0.1 mol) of intermediate TA-1 and 13 g (0.11 mol) of intermediate F-2, 15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 10 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 35.1 g of product, with a yield of 89%.
(3) Preparation of Target Compound 259
0.31 g (0.001 mol) of intermediate TA-1 and 0.13 g (0.0011 mol) of intermediate F-3, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 12 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.28 g of product, with a yield of 66%.
(4) Preparation of Target Compound 326
0.34 g (0.001 mol) of intermediate TA-2 and 0.13 g (0.0011 mol) of intermediate F-2, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 N, N-Dimethylformamide, heated to 70° C. to react for 4 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate the solvent under a reduced pressure. The residue was purified by column chromatography to obtain 0.24 g of product, with a yield of 56%.
(5) Preparation of Target Compound 401
0.32 g (0.001 mol) of intermediate TA-2 and 0.13 g (0.0011 mol) of intermediate F-2, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 11 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate the solvent under a reduced pressure. The residue was purified by column chromatography to obtain 0.29 g of product, with a yield of 71%.
(6) Preparation of Target Compound 105
0.33 g (0.001 mol) of intermediate TA-5 and 0.18 g (0.0011 mol) of intermediate F-4, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 11 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.25 g of product, with a yield of 55%.
(7) Preparation of Target Compound 4
0.295 g (0.1 mol) of intermediate TA-4 and 0.15 g (0.11 mol) of intermediate F-6, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 5 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.31 g of product, with a yield of 78%.
(8) Preparation of Target Compound 91
0.33 g (0.1 mol) of intermediate TA-5 and 0.18 g (0.11 mol) of intermediate F-4, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 11 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.25 g of product, with a yield of 55%.
(9) Preparation of Target Compound 548
0.31 g (0.001 mol) of intermediate TA-1 and 0.16 g (0.0011 mol) of intermediate H-1, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 6 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.33 g of product, with a yield of 78%.
(10) Preparation of Target Compound 739
0.34 g (0.001 mol) of intermediate TA-2 and 0.13 g (0.0011 mol) of intermediate H-2, 0.15 potassium carbonate and a catalytic amount of sodium iodide were added to 25 N, N-Dimethylformamide, heated to 70° C. to react for 5 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate the solvent under a reduced pressure. The residue was purified by column chromatography to obtain 0.28 g of product, with a yield of 65%.
(11) Preparation of Target Compound 835
0.31 g (0.001 mol) of intermediate TA-6 and 0.13 g of intermediate H-3, 0.15 potassium carbonate and a catalytic amount of sodium iodide were added to 25 ml of THF, heated to reflux for 10 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.25 g of product, with a yield of 61%.
Reagents were prepared according to a mass ratio in the following embodiments.
The compound 251 was fully mixed with other components, to obtain 30% suspension. The 30% suspension could be diluted with water to obtain diluent at any concentration.
Phosphorous acid was dissolved in toluene, then the compound 548 and ethoxylated triglyceride were added to obtain a transparent solution, i.e. 30% emulsion.
The compound 91, sodium dodecylnaphthalene sulfonate, sodium lignosulfonate and diatomite were mixed together, and pulverized in a pulverizer until particles reached the standard, to obtain 60% wettable powder.
According to the solubility of the test compound, the crude drug was dissolved in N N-dimethylformamide, and then prepared into a test solution of the desired concentration with 1‰ Tween 80 aqueous solution. The content of N. N-dimethylformamide in the solution should not exceed 10%.
Spray method. The broad bean leaves with petioles were cut and inserted into a bottle with water. A certain number of female mites were placed, 24h later, adult mites were removed, and spray treatment was performed in 24 h. The experiment was repeated three times, and a blank control was set, and placed to an observation room (26±2° C., humidity 70%˜80%, 16h light per day) for culture. When the blank control group was incubated, the results were investigated. The non-incubated ones were used as death for investigation.
According to the above method, the activity assay found that the ovicidal activity was equal to or higher than 90% at the concentration of 5 mg/L for the compounds 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835-838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468; while the ovicidal activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO 01/68589 was less than 30% at a concentration of 5 mg/L.
According to the above method, the activity assay found that the ovicidal activity was equal to or higher than 90% at the concentration of 2 mg/L for the compounds 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969; while the ovicidal activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 was 0% at a concentration of 2 mg/L.
According to the above method, parallel determination of ovicidal activity was performed for the compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 of the present invention and the compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589. The results were shown in Table 4.
According to the solubility of the test compound, the crude drug was dissolved in N, N-dimethlfornamide, and then prepared into a test solution of the desired concentration with 1‰ Tween 80 aqueous solution. The content of N,N-dimethylformamide in the solution should not exceed 10%.
Two euphylla bean seedlings were taken, after inoculated with adult Tetranychus cinnabarinus and the base number was investigated, whole plants were sprayed with a hand-held sprayer. The experiment was repeated three times for each treatment, after treatment, placed in a standard observation room after treatment, to investigate the survival number of mites in 48 hand calculate the death rate.
According to the above method, the activity assay found that the adult mite-killing activity was equal to or higher than 90% at the concentration of 2.5 mg/L for the compounds 1-17, 26-72, 76-92 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835-838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468; while the adult mite-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO 01/68589 was less than 80% at a concentration of 2.5 mg/L.
According to the above method, the activity assay found that the adult mite-killing activity was equal to or higher than 90% at the concentration of 1.25 mg/L for the compounds 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969; while the adult mite-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO 01/68589 was less than 50% at a concentration of 1.25 mg/L.
According to the above method, parallel determination of adult mite-killing activity was performed for the compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 of the present invention and the compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589. The results were shown in Table 5.
According to the solubility of the test compound, the crude drug was dissolved in N, N-dimethylformamide, and then prepared into a test solution of the desired concentration with 1‰ Tween 80 aqueous solution. The content of N,N-dimethylformamide in the solution should not exceed 10%.
The broad bean leaves with petioles were cut and inserted into a small bottle with water. A certain number of brightly colored, active female adult mites were placed, 24h later, adult mites were removed, and leaves with insufficient eggs were removed. When eggs were hatched and grew into nymphs, spray treatment was performed. The experiment was repeated three times, and a blank control was set, and placed to an observation room (26±2° C., humidity 70%˜80%, 16h light per day) for culture. 48 h later, the results were investigated. The nymphs were gently touched during investigation, and if no response, they were regarded as deaths.
According to the above method, the activity assay found that the nymph-killing activity was equal to or higher than 95% at the concentration of 2.5 mg/L for the compounds 1-17 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483, 486, 488, 489, 490, 492, 494, 499 500 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835-838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468, while the nymph-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 was less than 80% at a concentration of 2.5 mg/L.
According to the above method, the activity assay found that the nymph-killing activity was equal to or higher than 90% at the concentration of 2 mg/L for the compounds 230, 234. 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969 while the nymph-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 was less than 30% at a concentration of 0.5 mg/L.
According to the above method, parallel determination of nymph-killing activity was performed for the compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 of the present invention and the compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589. The results were shown in Table 6.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2018/087840 | 5/22/2018 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2019/222912 | 11/28/2019 | WO | A |
| Number | Date | Country |
|---|---|---|
| WO-0168580 | Sep 2001 | WO |
| WO 200168589 | Sep 2001 | WO |
| Entry |
|---|
| A machine generated English translation of WO 2001/68589 A1 (Sep. 20, 2001), Yagihara et al. (Year: 2001). |
| Number | Date | Country | |
|---|---|---|---|
| 20200339515 A1 | Oct 2020 | US |
