Metadiamide compound and application thereof
阅读说明：本技术 一种间二酰胺类化合物及其应用 (Metadiamide compound and application thereof ) 是由 张立新 张静 汪杰 康卓 于 2020-04-02 设计创作，主要内容包括：本发明公开了一种间二酰胺类化合物及其应用,所述化合物结构如通式I所示：<Image he="123" wi="326" file="100004_DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式中各取代基的定义见说明书。通式I化合物结构新颖,具有优异的杀虫活性,在较低剂量下可有效防粘虫、甜菜夜蛾、小菜蛾、二化螟等害虫；通式I化合物还具有意想不到的高杀虫速效性,起效快,在施用1天后就可以达到较高的杀虫活性,在3天内就可以达到极高的杀虫活性,应用前景广阔。(The invention discloses a m-diamide compound and application thereof, wherein the structure of the compound is shown as a general formula I: the definition of each substituent group in the formula is shown in the specification. The compound in the general formula I has a novel structure and excellent insecticidal activity, and can effectively prevent pests such as armyworm, beet armyworm, diamond back moth, chilo suppressalis and the like under a lower dosage; the compound of the general formula I also has unexpected high quick insecticidal activity and quick response, takes effect quickly, can achieve higher insecticidal activity after being applied for 1 day, can achieve extremely high insecticidal activity within 3 days, and has wide application prospect.)
1. A compound of m-diamide, shown as general formula I:
in the formula:
R1、R2each independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6A haloalkoxy group;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C6Alkyl, but not selected from cyanomethyl;
R5selected from hydrogen, halogen, cyano, nitro, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio or C1-C6A haloalkylthio group; n =1, 2, 3, 4 or 5; when n is greater than 1, R5May be the same or different;
X1selected from halogen, cyano or C1-C6An alkoxy group;
X2、X3、X4each is independentIs selected from hydrogen, halogen, cyano or C1-C6An alkoxy group.
2. The compound of claim 1, wherein: in the general formula I, the compound is shown in the specification,
R1、R2each independently selected from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C4Alkyl, but not selected from cyanomethyl;
R5selected from hydrogen, halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio or C1-C4A haloalkylthio group; n =1, 2, 3 or 4; when n is greater than 1, R5May be the same or different;
X1selected from fluoro or methoxy;
X2、X3、X4each independently selected from hydrogen, fluoro or cyano.
3. The compound of claim 2, wherein: in the general formula I, the compound is shown in the specification,
R1、R2each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C4Alkyl, but not selected from cyanomethyl;
R5selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; n =1, 2 or 3; when n is largeAt 1, R5May be the same or different;
X1selected from fluorine;
X2、X3、X4each independently selected from hydrogen or fluorine.
4. A compound according to claim 3, characterized in that: in the general formula I, the compound is shown in the specification,
R1selected from halogens;
R2selected from halogen, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN、-CH2CH2CH2CH2CN、-CH(CH3)CN、-CH(CH2CH3)CN、-CH(CH2CH2CH3)CN、-C(CH3)(CH3) CN or-C (CH)3)(CH2CH3)CN；
R5Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; n =1, 2 or 3; when n is greater than 1, R5May be the same or different;
X1selected from fluorine;
X2、X3、X4selected from hydrogen.
5. The compound of claim 4, wherein: in the general formula I, the compound is shown in the specification,
R1selected from fluorine, chlorine, bromine or iodine;
R2selected from fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN；
R5Selected from hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy; n =1, 2 or 3; when n is greater than 1, R5May be the same or different;
X1selected from fluorine;
X2、X3、X4selected from hydrogen.
6. The compound of claim 5, wherein: in the general formula I, the compound is shown in the specification,
R1selected from fluorine, chlorine, bromine or iodine;
R2selected from fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN；
R5Selected from hydrogen, fluoro, chloro, bromo, cyano or trifluoromethyl; n =1, and R5Substitution at the 4-position of the phenyl group;
X1selected from fluorine;
X2、X3、X4selected from hydrogen.
7. The compound of claim 6, wherein: in the general formula I, the compound is shown in the specification,
R1selected from bromine, R2Selected from bromine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Is selected fromHydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from bromine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl,X1selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from bromine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen.
8. An intermediate compound for preparing the m-diamide compound according to any one of claims 1 to 7, which is represented by the general formula II:
in the formula:
R1、R2each independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6A haloalkoxy group;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C6Alkyl, but not selected from cyanomethyl;
X1selected from halogen, cyano or C1-C6An alkoxy group;
X2、X3、X4each independently selected from hydrogen, halogen, cyano or C1-C6An alkoxy group.
9. The use of the compounds of the general formula I according to claim 1 for the preparation of pesticides in the agricultural, forestry and hygiene sector.
10. An insecticidal composition characterized by: the composition contains the compound of the general formula I as claimed in claim 1 as an active component, and the weight percentage of the active component in the composition is 0.1-99%.
11. A method of controlling agricultural or forestry pests, comprising: applying an effective amount of the composition of claim 10 to a pest or its growth medium in need of control.
Technical Field
The invention belongs to the field of agricultural pesticides, and particularly relates to a novel m-diamide compound and application thereof.
Background
Patent CN102112437A discloses that compounds CK1 (compound No. 5-45) and CK2 (compound No. 5-108) have insecticidal activity.
WO2018194144A1 discloses compounds CK3 (compound No. 61) and CK4 (compound No. 64) having insecticidal activity.
Patent CN102119143A discloses compounds CK5 (compound No. 7-1104), CK6 (compound No. 7-1107), CK7 (compound No. 7-1574), CK8 (compound No. 7-1577), CK9 (compound No. 7-1595), CK10 (compound No. 7-1730) and the pesticidal activity of these compounds. CK7 is commercially available under the generic name Broflanilide.
The compounds disclosed therein have poor insecticidal effect at lower dosages or insufficient fast-acting properties, and it is difficult to meet the increasing requirements of use of insecticides in reality. There is still a need in the art to actively develop new insecticides with high insecticidal activity that can be rapidly effective at low doses to meet the needs of agriculture and other fields.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a novel structure of m-diamide compound to solve the technical problem that the prior art compound has poor insecticidal effect or has poor quick action at lower dosage. The compound of the invention can be used for preparing medicaments for controlling pests in agriculture and other fields.
The technical scheme of the invention is as follows:
a compound of m-diamide, shown as general formula I:
in the formula:
R1、R2each independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6A haloalkoxy group;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C6Alkyl, but not selected from cyanomethyl;
R5selected from hydrogen, halogen, cyano, nitro, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio or C1-C6A haloalkylthio group; n =1, 2, 3, 4 or 5; when n is greater than 1, R5May be the same or different;
X1selected from halogen, cyano or C1-C6An alkoxy group;
X2、X3、X4each independently selected from hydrogen, halogen, cyano or C1-C6An alkoxy group.
The more preferred compounds of the present invention are: in the general formula I, the compound is shown in the specification,
R1、R2each independently selected from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C4Alkyl, but not selected from cyanomethyl;
R5selected from hydrogen, halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio or C1-C4A haloalkylthio group; n =1, 2, 3 or 4; when n is greater than 1, R5May be the same or different;
X1selected from fluoro or methoxy;
X2、X3、X4each independently selected from hydrogen, fluoro or cyano.
Further preferred compounds of the invention are: in the general formula I, the compound is shown in the specification,
R1、R2each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C4Alkyl, but not selected from cyanomethyl;
R5selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; n =1, 2 or 3; when n is greater than 1, R5May be the same or different;
X1selected from fluorine;
X2、X3、X4each is independentSelected from hydrogen or fluorine.
Further preferred compounds of the invention are: in the general formula I, the compound is shown in the specification,
R1selected from halogens;
R2selected from halogen, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN、-CH2CH2CH2CH2CN、-CH(CH3)CN、-CH(CH2CH3)CN、-CH(CH2CH2CH3)CN、-C(CH3)(CH3) CN or-C (CH)3)(CH2CH3)CN；
R5Selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, methyl, ethyl, propyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy or trifluoromethoxy; n =1, 2 or 3; when n is greater than 1, R5May be the same or different;
X1selected from fluorine;
X2、X3、X4selected from hydrogen.
Still further preferred compounds of the invention are: in the general formula I, the compound is shown in the specification,
R1selected from fluorine, chlorine, bromine or iodine;
R2selected from fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN；
R5Selected from hydrogen, fluoro, chloro, bromo, cyano, methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy; n =1, 2 or 3; when n is greater than 1, R5May be the same or different;
X1selected from fluorine;
X2、X3、X4selected from hydrogen.
Still further preferred compounds of the invention are: in the general formula I, the compound is shown in the specification,
R1selected from fluorine, chlorine, bromine or iodine;
R2selected from fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN；
R5Selected from hydrogen, fluoro, chloro, bromo, cyano or trifluoromethyl; n =1, and R5Substitution at the 4-position of the phenyl group;
X1selected from fluorine;
X2、X3、X4selected from hydrogen.
The most preferred compounds of the present invention are: in the general formula I, the compound is shown in the specification,
R1selected from bromine, R2Selected from bromine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from bromine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from bromine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CH2CH2CN，R5Selected from hydrogen, fluorine, cyano or trifluoromethyl, X1Selected from fluorine, X2、X3、X4Selected from hydrogen.
The invention also includes an intermediate compound useful in the preparation of a compound of formula I, as shown in formula II:
in the formula:
R1、R2each independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6A haloalkoxy group;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C6Alkyl, but not selected from cyanomethyl;
X1selected from halogen, cyano or C1-C6An alkoxy group;
X2、X3、X4each independently selected from hydrogen, halogen, cyano or C1-C6An alkoxy group.
The more preferred compounds of the present invention are: in the general formula II
R1、R2Each independently selected from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C4Alkyl, but not selected from cyanomethyl;
X1selected from fluoro or methoxy;
X2、X3、X4each independently selected from hydrogen, fluoro or cyano.
Further preferred compounds of the invention are: in the general formula II
R1、R2Each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4selected from cyano group C1-C4Alkyl, but not selected from cyanomethyl;
X1selected from fluorine;
X2、X3、X4each independently selected from hydrogen or fluorine.
Further preferred compounds of the invention are: in the general formula II
R1Selected from halogens;
R2selected from halogen, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN、-CH2CH2CH2CH2CN、-CH(CH3)CN、-CH(CH2CH3)CN、-CH(CH2CH2CH3)CN、-C(CH3)(CH3) CN or-C (CH)3)(CH2CH3)CN；
X1Selected from fluorine;
X2、X3、X4selected from hydrogen.
Still further preferred compounds of the invention are: in the general formula II
R1Selected from fluorine, chlorine, bromine or iodine;
R2selected from fluoro, chloro, bromo, iodo, trifluoromethyl, difluoromethoxy or trifluoromethoxy;
R3selected from heptafluoroisopropyl or nonafluoro-2-butyl;
R4is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN；
X1Selected from fluorine;
X2、X3、X4selected from hydrogen.
The most preferred compounds of the present invention are: in the general formula II
R1Selected from bromine, R2Selected from bromine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from heptafluoroisopropyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from bromine, R3Selected from the group consisting of nonafluoro-2-butyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from iodine, R3Selected from the group consisting of nonafluoro-2-butyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from bromine, R2Selected from trifluoromethyl, R3Selected from the group consisting of nonafluoro-2-butyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen; alternatively, the first and second electrodes may be,
R1selected from iodine, R2Selected from trifluoromethyl, R3Selected from the group consisting of nonafluoro-2-butyl, R4Is selected from-CH2CH2CN、-CH2CH2CH2CN or-CH2CH2CH2CH2CN，X1Selected from fluorine, X2、X3、X4Selected from hydrogen.
In the definitions of the compounds of the general formula given above, the terms used in the collection generally represent the following substituents:
halogen: refers to fluorine, chlorine, bromine or iodine.
Alkyl groups: straight-chain or branched alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers.
Halogenated alkyl groups: straight-chain or branched alkyl radicals in which the hydrogen atoms are partially or wholly replaced by halogen, e.g. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, heptafluoroisopropyl ()) Nonafluoro-2-butyl (C)
Alkoxy groups: straight or branched chain alkyl groups attached to the structure via an oxygen atom, such as methoxy, ethoxy, t-butoxy, and the like.
Haloalkoxy groups: the hydrogen atoms on the alkoxy groups may be partially or fully substituted with halogens, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.
Alkylthio group: straight or branched chain alkyl groups attached to the structure via a sulfur atom, such as methylthio, ethylthio, and the like.
Haloalkylthio: the hydrogen atoms on the alkylthio group may be partially or fully substituted with halogen, such as difluoromethylthio, trifluoroethylthio, and the like.
Cyanoalkyl group: straight-chain or branched alkyl groups in which the hydrogen atoms may be partially or completely replaced by cyano groups,
for example-CH2CH2CN、-CH2CH2CH2CN、-CH2CH2CH2CH2CN、-CH(CH3)CN、-CH(CH2CH3)CN、-CH(CH2CH2CH3)CN、-C(CH3)(CH3) CN or-C (CH)3)(CH2CH3)CN。
In the claims and the description, "n =1, and R5The "4 position" in "substitution at the 4 position of phenyl group means the position indicated by the number" 4 "in the following formula I.
The compounds of the present invention are shown in Table 1 in part and in Table 2 in part, but the present invention is by no means limited to these compounds.
In the general formula I, when X1=F, X2=X3=X4=H, R3=1, and R5When substituted at the 4-position of the phenyl group, formula I may be represented by formula i.a; r1, R2, R4, R5The substituents are shown in Table 1, and represent compounds numbered from 1 to 84.
TABLE 1
In the general formula II, when X1=F, X2=X3=X4= H and R3Where = heptafluoroisopropyl group, formula II may be represented by formula ii.a; r1, R2,R4The substituents are shown in Table 2, and represent compounds II.1-II.12.
TABLE 2
The compounds of the general formula I according to the invention can be prepared by the following process (where the radicals are as defined above, unless otherwise stated; LG = Cl or Br):
the method comprises the following steps:
compounds of the formula III and halides R4The compound of formula II is obtained by reacting LG in a suitable solvent at a temperature of from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours, the reaction being carried out in the presence of a base and a catalyst; the compound of the general formula I can be prepared by reacting the compound of the general formula II with the compound of the general formula IV in a proper solvent for 0.5 to 48 hours at the temperature of between-10 ℃ and the boiling point of the solventThe reaction may be carried out in the presence of a base and a catalyst. Suitable solvents in the above steps may be the same or different and are aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, and mixed solvents thereof. The bases in the above steps may be the same or different and are organic bases such as triethylamine, pyridine, DBU, 4-dimethylaminopyridine and the like, alkali metal hydrides such as sodium hydride, potassium hydride and the like, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like, alkaline earth metal hydroxides such as calcium hydroxide and the like, alkali metal carbonates such as sodium carbonate, potassium carbonate and the like, alkali metal bicarbonates such as sodium bicarbonate and the like, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide and the like. The catalyst in each step can be the same or different and is potassium iodide, sodium iodide, potassium fluoride, sodium fluoride, potassium bromide or sodium bromide, etc.
The method 2 comprises the following steps:
(1) preparation of Compounds of formula VI and VII
Compounds of the general formula V and halides R4The compounds of general formula VI can be obtained by reacting LG in a suitable solvent at a temperature of from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours, the reaction being carried out in the presence of a base; the compound of formula VI is reacted with the compound of formula IV in a suitable solvent at a temperature of from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to produce the compound of formula VII, which can be carried out in the presence of a base. In the above reaction, suitable solvents in the above steps may be the same or different and are aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketoneHalogenated hydrocarbons such as chloroform and dichloromethane, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, or mixed solvents thereof. The bases in the above steps may be the same or different and are organic bases such as triethylamine, pyridine, DBU, 4-dimethylaminopyridine and the like, alkali metal hydrides such as sodium hydride, potassium hydride and the like, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like, alkaline earth metal hydroxides such as calcium hydroxide and the like, alkali metal carbonates such as sodium carbonate, potassium carbonate and the like, alkali metal bicarbonates such as sodium bicarbonate and the like, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide and the like.
(2) Preparation of Compounds of formula VIII and Compounds of formula IX
Reacting the compound of the general formula VII in the presence of alkali at the temperature of between-10 ℃ and the boiling point of a solvent for 0.5 to 48 hours to obtain a compound of the general formula VIII; the suitable base may be lithium hydroxide, sodium hydroxide or potassium hydroxide, and the suitable solvent may be any one of water, methanol, ethanol, tetrahydrofuran or dioxane, or a mixed solvent of at least two thereof.
The compound of formula VIII is reacted with a halogenating agent such as thionyl chloride, oxalyl chloride, carbonyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, thionyl bromide, triphosgene, phosphorus tribromide or isopropyl chloroformate by a conventional method to obtain the compound of formula IX.
(3) Preparation of the Compounds of the formula I
Reacting a compound of formula IX with a compound of formula X in a suitable solvent at a temperature of from-70 ℃ to the boiling point of the solvent for 0.5 to 48 hours to obtain a compound of formula I, the reaction being carried out in the presence of a base; suitable solvents include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, or mixed solvents thereof, organic bases such as trimethylamine, triethylamine, diisopropylethylamine, tri-N-butylamine, pyridine, DBU and 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium hydrogen carbonate, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.
The method 3 comprises the following steps:
compounds of the formula XI with halides R4The compounds of formula I can be obtained by reacting LG in the presence of a suitable solvent, a suitable base, at a temperature of from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours. Suitable solvents include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, diethyl ether and 1, 2-dimethoxyethane, polar solvents such as water, acetonitrile, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, and mixed solvents thereof. Suitable bases include organic bases such as triethylamine, pyridine, DBU, and 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.
The compounds of the formula III, X and XI can be prepared by known methods, for example, see WO20110201687, WO2011093415, WO2005021488, WO2005073165, WO2006137395, JP2007099761, WO2008000438, WO2008074427, WO2008107091, WO2010013567, WO2010018714, WO2010090282, WO2010127926, WO2010127928, JP2011063549, WO2012020483, WO2012020484, WO2012077221, WO2012164698, WO2013050261, WO2014069665, WO2014067838, WO2014161848, WO2014161850, WO2015097091 or WO2015097094 and the like; compounds of formula IV, compounds of formula V and halides R4LG is generally commercially available and can be prepared by conventional methods.
The compounds of the general formula I according to the invention have an unexpectedly high insecticidal activity and can be used for controlling the following pests (the list of objects is intended to illustrate the invention and does not limit it in any way): lepidoptera pests such as diamondback moth, armyworm, beet armyworm, prodenia litura, tobacco budworm, cabbage looper, chilo suppressalis, tryporyza incertulas, cnaphalocrocis medinalis, corn borer, carposina cuneata, cotton bollworm, etc.; homoptera pests such as pea aphid, bean aphid, beet aphid, cotton aphid, apple aphid, peach aphid, corn aphid, whitefly, leafhopper, plant hopper, rice planthopper, mealybug, etc.; hemiptera pests such as corn long stinkbug, cotton net stinkbug, tomato plant stinkbug, rice green stinkbug, rice ailanthus and the like; thysanoptera pests such as thrips gossypii, thrips lucerne, thrips glycines, etc.; coleopteran pests such as potato beetle, click beetle, malignant leaf beetle, gray beetle, etc.; dipteran pests such as flies, mosquitoes, etc.; hymenopteran pests such as bees, ants, etc. The compound of the general formula I also has unexpected high quick insecticidal activity and quick response, takes effect quickly, can achieve high insecticidal activity after being applied for 1 day, and can achieve high insecticidal activity within 3 days. The preparation method of the compound of the general formula I is simple and efficient, is easy for large-scale industrial production, and has wide application prospect. Therefore, the technical scheme of the invention also comprises the application of the compound shown in the general formula I in preparing pesticide medicaments in agriculture or other fields.
Owing to their positive properties, the abovementioned compounds can be used advantageously for protecting crops, livestock and breeding animals of agricultural and horticultural importance, as well as the environment in which humans are often located, against pests.
The amount of the compound used to achieve the desired effect will vary depending on factors such as the compound used, the crop to be protected, the type of pest, the extent of infection, the climatic conditions, the method of application, the dosage form employed, and the like.
A dose of 5 g to 5 kg of compound per hectare provides adequate control.
The invention also comprises the pesticide with the compound of the general formula I as the active component. The weight percentage of the active components in the pesticide is between 0.1 and 99 percent. The pesticide also comprises carriers and auxiliary agents which are acceptable in agriculture, forestry and sanitation.
The insecticides of the present invention can be applied in the form of formulations. The compounds of the general formula I are dissolved or dispersed as active ingredients in carriers and/or adjuvants or formulated so as to be easier to disperse for insecticidal use.
The compound of the general formula I is used as an active component, and can be prepared into various preparation types according to a known mode in the field, wherein the preparation types comprise water aqua, soluble liquid agent, missible oil, microemulsion, aqueous emulsion, suspending agent, suspended seed coating agent, dispersible oil suspending agent, ultra-low volume agent, powder, wettable powder, soluble powder, emulsifiable powder, granules, water dispersible granules, soluble granules, emulsifiable granules, dry suspending agent, effervescent granules, floating granules, tablets, soluble tablets, effervescent tablets, microcapsule powder and microcapsule suspending agent, and the selection of the preparation types depends on the physical, chemical and biological characteristics of the compound of the general formula I under any condition.
The insecticidal formulations of the compounds of formula I of the present invention can be prepared by conventional processing methods, i.e., by mixing the active substance with a liquid or solid carrier and then adding one or more surfactants such as emulsifiers, dispersants, wetting agents, thickeners, stabilizers, defoamers, and the like. Typically, the composition comprises at least one carrier and at least one surfactant. In each case, a homogeneous distribution of the active ingredients of the compositions according to the invention should be ensured.
The water aqua is prepared by uniformly mixing the compound of the general formula I, a surfactant and water to form uniform and transparent liquid. Generally, the composition comprises 5-50% of active ingredients, 5-20% of emulsifiers, 0-10% of other additives such as penetrants, and the balance of water.
The soluble liquid is prepared by uniformly mixing the compound of the general formula I, a surfactant and a non-aqueous polar solvent to form uniform and transparent liquid. The soluble liquid agent usually contains 5-60% of active ingredients, 5-20% of emulsifier, 0-10% of other additives such as penetrating agent, and the balance of liquid carrier.
The missible oil is formed by uniformly mixing the compound shown in the general formula I, a surfactant and an organic solvent to form a homogeneous oily liquid. The emulsifiable concentrate generally contains 1-70% of active ingredients, 5-20% of emulsifiers, 0-10% of other additives such as penetrants, stabilizers and the balance of liquid carriers.
The microemulsion is prepared by uniformly mixing the compound of the general formula I, a surfactant, water and an organic solvent to form uniform and transparent liquid. The microemulsion usually contains 1-50% of active ingredients, 5-30% of emulsifiers, 2-10% of antifreeze, 0-10% of other additives such as penetrating agents and stabilizers, and the balance of liquid carriers.
The water emulsion is prepared by uniformly mixing a compound shown in a general formula I, a surfactant and an organic solvent to prepare an oil phase; mixing water and antifreeze agent together to obtain water phase. And (3) shearing the oil phase at a high speed by using a high-shear emulsifying machine, and slowly adding the water phase into the oil phase to obtain the uniformly dispersed emulsion in water. Generally, the composition comprises 5-50% of active ingredients, 5-20% of emulsifiers, 2-5% of antifreeze and the balance of liquid carrier.
The suspending agent is prepared by uniformly mixing the compound shown in the general formula I, a dispersing agent, a wetting agent, an antifreezing agent and water, and then sanding the mixture by a sand mill to obtain stable non-deposition flowable liquid. The suspending agent generally contains 5-50% of active ingredients, 2-10% of dispersing agents, 2-5% of wetting agents, 2-5% of antifreezing agents, 0-10% of other additives such as defoaming agents, thickening agents, preservatives and the balance of liquid carriers.
The suspension seed coating agent is prepared by uniformly mixing the compound shown in the general formula I, a dispersing agent, a wetting agent, a film forming agent and water, and then sanding the mixture by a sand mill to obtain stable non-deposition flowable liquid. The suspended seed coating agent usually contains 1-50% of active ingredients, 2-10% of dispersing agents, 2-5% of wetting agents, 2-5% of antifreezing agents, 2-10% of film forming agents, 0-10% of other additives such as defoaming agents, thickening agents, preservatives, warning colors and the balance of liquid carriers.
The dispersible oil suspending agent is prepared by uniformly mixing the compound of the general formula I, the surfactant and the oil-based carrier, and then sanding the mixture by a sand mill to obtain stable non-deposition flowable liquid. The dispersible oil suspension agent usually contains 5-50% of active ingredients, 5-30% of surfactant, 0-10% of other additives such as thickening agent and stabilizer, and the balance of liquid carrier.
The ultra-low volume agent is prepared by uniformly mixing the compound shown in the general formula I, a surfactant and an organic solvent and processing the mixture into a uniform transparent oil phase. Generally, the composition comprises 1-30% of active ingredients, 5-30% of emulsifiers, 0-10% of other additives such as stabilizers, and the balance liquid carrier.
The powder is prepared by mixing the compound of the general formula I, an auxiliary agent and a carrier and crushing the mixture. The powder typically contains 5-85% active ingredient, 5-10% dispersant, 0-10% other additives such as stabilizers, and the balance solid carrier.
Wettable powder is prepared by mixing a compound shown in a general formula I, a dispersing agent, a wetting agent and a carrier and crushing the mixture to obtain powder. The wettable powder usually contains 5-85% of active ingredients, 5-10% of dispersing agents, 1-10% of wetting agents, 0-10% of other additives such as stabilizers, and the balance of solid carriers.
The soluble powder is prepared by mixing the compound of the general formula I, a dispersing agent, a wetting agent and a carrier and crushing the mixture to obtain powder. The soluble powder generally contains 5-80% of active ingredients, 5-10% of dispersing agents, 1-10% of wetting agents, 0-10% of other additives such as stabilizers, and the balance of solid carriers.
Emulsifiable powder a compound of the general formula I, a surfactant, and an organic solvent are mixed to prepare a uniform transparent oil phase, and then the oil phase is uniformly sprayed on a carrier which has been previously pulverized. The emulsifiable powder generally contains 5-50% of active ingredients, 5-30% of emulsifiers, 5-10% of wetting dispersants, 0-15% of organic solvents and the balance of solid carriers.
The granules are prepared by mixing the compound of the general formula I, an auxiliary agent and a carrier, and then kneading, granulating, drying and coating. Granules typically contain 0.5-20% active ingredient, 0.1-10% binder, 0-10% other additives such as stabilizers, and the balance solid carrier.
The water dispersible granule is prepared by mixing the compound shown in the general formula I, a dispersing agent, a wetting agent, a disintegrating agent and a carrier, and then kneading, granulating and drying. The water dispersible granule generally contains 5-85% of active ingredients, 1-10% of dispersing agents, 1-10% of wetting agents, 0.1-10% of binders, 0-10% of other additives such as disintegrating agents and stabilizing agents, and the balance of solid carriers.
The soluble granule is prepared by mixing the compound shown in the general formula I, a dispersing agent, a wetting agent, a disintegrating agent and a carrier, and then kneading, granulating and drying. The soluble granule usually contains 5-85% of active ingredients, 1-10% of dispersing agents, 1-10% of wetting agents, 0.1-10% of binders, 0-10% of other additives such as disintegrants and stabilizers, and the balance of solid carriers.
The emulsifiable granule is prepared by mixing the compound of the general formula I, a surfactant and an organic solvent to prepare a uniform transparent oil phase, then uniformly spraying the oil phase on a carrier which is smashed in advance, kneading, granulating and drying. The emulsifiable granules usually contain 5-50% of active ingredients, 5-30% of emulsifiers, 5-10% of wetting dispersants, 0-15% of organic solvents, 0-10% of other additives such as disintegrants, stabilizers, binders and the balance of solid carriers.
The dry suspending agent is prepared by uniformly mixing the compound shown in the general formula I, a dispersing agent, a wetting agent, a carrier and water, sanding by a sand mill, and then performing spray drying. The dry suspending agent usually contains 5-80% of active ingredients, 2-20% of dispersing agents, 2-10% of wetting agents, 0-10% of other additives such as defoaming agents, thickening agents and the balance of solid carriers.
The effervescent granule is prepared by mixing the compound of the general formula I, a wetting dispersant, an effervescent disintegrant and a carrier, and then kneading and granulating. The effervescent granule usually contains 0.5-30% of active ingredients, 2-20% of wetting dispersant, 2-20% of effervescent disintegrant, 0-10% of other additives such as stabilizer, binder and the balance of solid carrier.
The floating granule is prepared by mixing the compound shown in the general formula I, a wetting dispersant, floating beads and a carrier, and then kneading and granulating. The floating granules usually contain 0.5-30% of active ingredients, 2-20% of wetting dispersants, 5-20% of floating beads, 0-10% of other additives such as stabilizers, binders, disintegrants, and the balance of solid carriers.
The tablet is prepared by mixing the compound of formula I, dispersant, wetting agent, disintegrant and carrier, kneading, tabletting, and drying. The tablet usually contains 5-50% of active ingredients, 1-10% of dispersing agents, 1-10% of wetting agents, 0.1-10% of binders, 0-10% of other additives such as disintegrating agents and stabilizing agents, and the balance of solid carriers.
The soluble tablet is prepared by mixing the compound of the general formula I, a dispersing agent, a wetting agent, a disintegrating agent and a carrier, and then kneading, tabletting and drying. The soluble tablet usually contains 5-50% of active ingredients, 1-10% of dispersing agents, 1-10% of wetting agents, 0.1-10% of binders, 0-10% of other additives such as disintegrating agents and stabilizing agents, and the balance of solid carriers.
The effervescent tablet is prepared by mixing the compound of formula I, wetting dispersant, effervescent disintegrant and carrier, kneading, and tabletting. The effervescent tablet generally contains 0.5-30% of active ingredients, 2-20% of wetting dispersant, 2-20% of effervescent disintegrant, 0-10% of other additives such as stabilizer, binder and the balance of solid carrier.
Dissolving the compound shown in the general formula I in a solvent, adding an emulsifier and a wall material into the solvent, and uniformly stirring to obtain an oil phase; adding a dispersant into water to obtain a water phase; adding the oil phase into the water phase under high speed stirring to form oil-in-water emulsion; adding curing agent into the emulsion under stirring, heating and keeping the temperature to form a capsule, and then filtering and drying. The microcapsule powder usually contains 0.5-30% of active ingredients, 2-10% of emulsifiers, 2-10% of wetting dispersants, 5-30% of other additives such as wall materials, antifoaming agents, curing agents, stabilizers, and the balance of solid carriers.
Dissolving the compound shown in the general formula I in a solvent by using the microcapsule suspending agent, adding an emulsifier and a wall material into the solvent, and uniformly stirring to obtain an oil phase; adding a dispersant into water to obtain a water phase; adding the oil phase into the water phase under high speed stirring to form oil-in-water emulsion; adding curing agent into the emulsion under stirring, heating and keeping the temperature to form a capsule, thus forming the microcapsule suspending agent. The microcapsule suspension usually contains 0.5-30% of active ingredients, 2-10% of emulsifiers, 2-10% of wetting dispersants, 5-30% of other additives such as wall materials, antifoaming agents, preservatives, thickeners, curing agents, stabilizers, and the balance of liquid carriers.
The pesticidal formulations of the compounds of the general formula I according to the invention can be formulated using (liquid or solid) carriers and various adjuvants known to the person skilled in the art. Examples include, but are not limited to, the following classes of materials.
Suitable surfactants in the insecticidal formulations of the compounds of the general formula I according to the invention may be emulsifiers, dispersants or wetting agents; may be one or more of non-ionic or ionic. The ionic surfactant is selected from sulfonates, sulfates, carboxylates, phosphates, succinates, lignosulfonates, acrylamide acrylic acid copolymers, etc. The nonionic surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ether, acid alcohol ester and polyoxyethylene ether thereof, alkyl polyglycol ether, alkylphenyl polyglycol ether, fatty amide and polyoxyethylene ether thereof, alkanolamide and polyoxyethylene ether thereof, polyoxyethylene polyoxypropylene ether block copolymer, alkyl sodium naphthalene sulfonate fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, etc.
The surfactant can be selected from one or more of the surfactants shown, such as: sodium or calcium lignosulfonate, polyoxyethylene (n20) phenethylphenol ether oleate, alkylaryl polyoxyethylene polyoxypropylene ether, tristyrylphenol polyoxyethylene (n20) ether phosphorylated triethanolamine salt, Nongru 0201B, Nongru 0203B, Nongru 100 #, Nongru 600#, Nongru 700#, Nongru 1601#, Nongru AEO-3, Nongru AEO-5, Nongru AEO-7, Nongru T-20, Nongru T-80, Nongru T-85, Nongru S-80, Nongru S-85, Nongru NP-7, Nongru NP-10, Nongru NP-15, Nongru OX-2681, Nongru OX-8686, Nongru OX-690, Nongru 2201#, polycarboxylate dispersant GY-D800, polycarboxylate dispersant GY-D04, polycarboxylate dispersant GY-D02, alkyl naphthalene sulfonate condensate (NNO), Naphthol sulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene polyoxypropylene ether, styrene maleic anhydride, methyl naphthalene sulfonic acid formaldehyde condensate, castor oil ethylene oxide adduct, alkylphenol polyoxyethylene polyoxypropylene ether, alkyl-diethylene glycol ether-sodium sulfonate, N-methyl-oleoyl-sodium taurate, detergent LS, sodium methylene naphthalene sulfonate, sodium methyl aminoethyl sulfonate oleate, dispersant SP-28F, dispersant SP-SC3, Darun dispersant D909S, alkylaryl polyoxyethylene ether, dodecyl polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether formaldehyde condensate, sodium dibutyl naphthalene sulfonate (nekal BX), dibutyl naphthalene sulfonic acid formaldehyde condensate, dispersant SD-811, dispersant SD815, dispersant SK-24, dispersant SK-20TX, dispersant SK-5218, and the like, Dispersant SK-33H, dispersant SK-10LX, dispersant SK-551, dispersant Atlox4913, dispersant EL-20, dispersant EL-40, dispersant EL-90, dispersant YUS-NV1203, dispersant YUS-NV1420, dispersant YUS-WG4, dispersant YUS-TG285, dispersant YUS-1, dispersant YUS-110, dispersant YUS-EP60P, dispersant YUS-CH1100, dispersant SP-OF3468, dispersant SP-OF 34OF 72, dispersant SP-2728, dispersant SP-SC29, dispersant Supergil MNS/90, dispersant Soprophor FD, dispersant YUS-FS1, dispersant YUS-PQ100, dispersant YUS-WG5, YUS-D935, octylphenol polyoxyethylene ether sulfate, Morwet EFW, Igepatal BC/10, wetting agent PORONL-WET/P100, Wetting agents Rhodasurf 860/p, wetting agents SP-SC3266, wetting agents PICO-SW2, wetting agents PICO-SW3, wetting agents YUS-LXC, wetting agents YUS-204, sodium alkyl alcohol polyoxyethylene ether sulfate, alkyl phenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl succinic acid sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, calcium dodecyl benzene sulfonate and the like.
Suitable liquid carriers in the insecticidal preparation of the compound with the general formula I can be one or more of water, organic solvent and oily medium. Suitable organic solvents are selected from aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols and their ethers and esters, ketones and the like, such as benzene, xylene, toluene, alkylbenzene, alkylnaphthalene, chlorinated benzene, vinyl chloride, trichloroethane, methylene chloride, chloroform, carbon tetrachloride, polychlorinated ethane, petroleum fractions, cyclohexane, methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, glycerol, sorbitol, benzyl alcohol, furfuryl alcohol, cyclohexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-pyrrolidone, tributyl phosphate, dimethylformamide, dimethyl sulfoxide and the like. Suitable oily media are selected from soybean oil, methyl oleate, light mineral oil, liquid paraffin, kerosene, turpentine oil and the like.
Suitable solid carriers for the pesticidal formulations of the compounds of formula I according to the invention include natural or synthetic. May be selected from, but is not limited to, clays, rock powders, chalk, quartz, clays, montmorillonite, sodium sulfate, silica, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, attapulgite, precipitated calcium carbonate, china clay, montmorillonite, magnesium aluminum silicate, activated clay, white carbon black, ammonium sulfate, coumarone resins, perphosphates, alumina, calcite, marble, pumice, and the like, suitable particulate carriers include crushed and graded natural rocks such as sepiolite and dolomite and synthetic particles made from organic and inorganic powders.
Suitable binders, thickeners include synthetic or natural water soluble polymers. Selected from, but not limited to, carboxymethyl alcohol, polyvinyl acetate, xanthan gum, gelatin, gum arabic, polyvinylpyrrolidone, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, phenolic resin, shellac, methyl cellulose, soluble starch, carboxymethyl cellulose, sodium alginate, etc., and is added to the formulation in the form of powder, granule, or latex.
Suitable antifoaming agents may be selected from, but are not limited to, antifoaming agents SAG1522, silicones, C8-10 fatty alcohols, phosphates, esters,
C10-20 saturated fatty acids (such as capric acid) and amides.
Suitable antifreeze agents can be selected from, but are not limited to, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, ethylene glycol butyl ether acetate, urea, and the like.
Suitable penetrants can be selected from, but are not limited to, silicones, penetrants T, penetrants JFC, and the like.
Suitable film forming agents include natural products and modifications thereof and synthetic polymers. May be selected from, but is not limited to, sodium carboxymethyl starch, soluble starch, phosphorylated starch, oxidized starch, chitosan and its derivatives, polypropylene graft copolymer, xanthan gum, sodium alginate, agar, gelatin, gum arabic, polyethylene glycol, polyvinyl alcohol, polyvinyl acetate, polyacrylamide, polyvinyl pyrrolidone, polyacrylic acid, and the like.
Suitable preservatives can be selected from, but are not limited to, sodium benzoate, kathon, potassium sorbate, and the like.
Suitable disintegrants can be selected from, but are not limited to, sodium carboxymethyl starch, sodium cross-linked carboxymethyl cellulose, modified starch, cross-linked polyvinylpyrrolidone, ammonium sulfate, sodium chloride, ammonium chloride, and the like.
The effervescent disintegrant may be an acidic component and/or a basic component, wherein the acidic component may be selected from organic acids, inorganic acids, for example
Such as: tartaric acid, citric acid, salicylic acid, phosphoric acid, and the like; the alkaline component may be selected from basic carbonates, for example: sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, and the like.
Suitable warning colors may be selected from, but are not limited to, inorganic pigments such as iron oxide, titanium oxide, or prussian blue; organic dyes such as alizarine, acid scarlet G, basic rhodamine, azo dyes, metal phthalocyanines, and the like.
The suitable wall material comprises one or more of natural polymer material, semi-synthetic polymer material and fully synthetic polymer material. The natural polymer material can be selected from but not limited to gelatin, acacia, agar, alginate, chitosan, fibrin, zein, etc.; the semi-synthetic polymer material can be selected from but not limited to methyl (ethyl) cellulose, carboxymethyl cellulose (sodium), cellulose acetate and esters and partial glyceride thereof; the fully synthetic polymeric material may be selected from, but is not limited to, polyacrylic resins, urea-formaldehyde resins, polyamides, polyesters, polymethyl methacrylates, polyureas, polyurethanes, and the like.
Suitable curing agents include one or more of polyols, polyamines. The polyhydric alcohol can be selected from, but is not limited to, ethylene glycol, glycerol, 1, 2-propanediol, 1, 4-butanediol, diethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, and the like; the polyamine can be selected from, but is not limited to, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine, isophoronediamine, and the like.
The following are examples of formulation preparations:
microcapsule suspending agent: 5 parts of active compound, 5 parts of No. 600, 10 parts of dimethylbenzene and 1 part of diphenylmethane diisocyanate are uniformly stirred to prepare an oil phase, then the oil phase is added into a water phase consisting of 1 part of ethylenediamine, 5 parts of glycerol, 3 parts of Atlox4913, 2 parts of EFW, 1 part of SAG1522 and the balance of water, and the 5% active compound microcapsule suspending agent can be prepared by high-speed stirring, curing and heat preservation.
And (3) missible oil: and adding 10 parts of active compound, 5 parts of 0201B, 7 parts of 0203B and solvent naphtha 150 to 100%, stirring and mixing uniformly, and heating and dissolving by using a hot water bath if necessary to obtain 10% active compound emulsifiable solution.
Emulsion in water: adding 15 parts of active compound, 8 parts of T-20, 4 parts of agricultural emulsion S-85, 5 parts of tributyl phosphate and 5 parts of solvent oil 200 into a mixing kettle, stirring and mixing to dissolve the active compound into a uniform oil phase, and adding the balance of water (to make up to 100%) into the oil phase under high-speed stirring to obtain the 15% active compound aqueous emulsion with good dispersibility.
Dispersible oil suspending agent: adding 25 parts OF active compound, 6 parts OF dispersant SP-OF3468, 6 parts OF dispersant SP-OF3472, 2 parts OF agricultural emulsifier 1601#, 2 parts OF organic bentonite and methyl oleate to 100% in a mixing tank in sequence, mixing, performing coarse grinding and homogenization by high shear, pumping into a sand mill for fine grinding, detecting the particle size OF the ground material by a particle size distribution instrument, and filtering when the particle size meets the standard requirement, thus obtaining the 25% active compound dispersible oil suspending agent.
Water dispersible granules: adding 60 parts of active compound, 2 parts of Morwet EFW, 4 parts of dispersing agent D425, 4 parts of alkyl naphthalene sulfonate formaldehyde condensate, 10 parts of soluble starch, 8 parts of ammonium sulfate and diatomite which are complemented to 100 percent together, mixing and crushing, adding water and kneading, and adding into a granulator with a screen with a certain specification for granulation. Then drying and screening (according to the range of a screen) are carried out, thus obtaining the 60 percent active compound water dispersible granule.
Wettable powder: 50 parts of active compound, 3 parts of sodium dodecyl sulfate, 4 parts of sodium salt of alkyl naphthalene sulfonic acid polycondensate, 4 parts of methylene naphthalene sodium sulfonate, 4 parts of sodium lignosulfonate, 5 parts of white carbon black and diatomite are fully mixed until the mixture is 100 percent, and the mixture is crushed by a superfine crusher to obtain 50 percent active compound wettable powder.
Microemulsion: 10 parts of active compound, 6 parts of agricultural emulsion 0201B, 2 parts of NP-15, 8 parts of YUS-A51G, 5 parts of methanol,
5 parts of cyclohexanone are added together to dissolve the cyclohexanone into a uniform oil phase, the balance is complemented to 100 percent by water, and the water phase is added into the oil phase or the oil phase is added into the water phase under high-speed stirring to form the microemulsion of the 10 percent active compound with good dispersibility.
Soluble agent: the active compound 10 parts, tristyrylphenol polyoxyethylene (N20) ether phosphorylated triethanolamine salt 6 parts, agricultural emulsion T-20 3 parts, agricultural emulsion 0201B 2 parts, N-methylpyrrolidone 3 parts and cyclohexanone are complemented to 100 percent and are uniformly mixed, and if necessary, the mixture is heated and dissolved by a hot water bath to obtain the active compound soluble agent 10 percent.
Emulsifiable powder: adding 15 parts of active compound, 2 parts of agricultural emulsion 1601#, 3 parts of agricultural emulsion 500#, 5 parts of agricultural emulsion 0201B, 5 parts of N-methyl pyrrolidone and 5 parts of Armid FMPC into a mixing kettle, stirring and mixing uniformly, heating and dissolving by using a hot water bath if necessary, uniformly spraying the oil base on a mixture consisting of 20 parts of white carbon black and bentonite and supplementing to 100% under the stirring condition, and crushing by using an ultrafine crusher to obtain 15% active compound emulsifiable powder.
Suspending agent: adding 20 parts of active compound, 2 parts of dispersant 4913, 2 parts of wetting agent TXC, 2 parts of agricultural emulsifier 1601#, 2 parts of white carbon black, 0.2 part of xanthan gum, 1 part of SAG1522, 5 parts of ethylene glycol and water to 100% in a mixing tank in sequence for mixing, performing coarse crushing and homogenization by high shear, pumping into a sand mill for fine grinding, detecting the particle size of the sand-ground material by a particle size distribution instrument, and filtering when the particle size reaches the standard requirement to obtain the 20% active compound suspending agent.
Dry suspending agent: adding 50 parts of active compound, 20 parts of sodium lignosulfonate, 2 parts of wetting agent TXC, 2 parts of white carbon black and kaolin to 100% in sequence, mixing with water, performing coarse crushing and homogenization by high shear, pumping into a sand mill for fine grinding, detecting the particle size of the sand-milled material by a particle size distribution instrument, performing spray granulation, and drying to obtain the 50% active compound dry suspending agent.
Ultra-low volume agent: adding 10 parts of active compound, 5 parts of Armid FMPC, 2 parts of Nongru 0201B, 1 part of S-80 and solvent oil to 100% of the total amount, adding into a mixing kettle, stirring and mixing uniformly, and heating and dissolving by using a hot water bath if necessary to obtain the 10% active compound ultralow volume agent.
Suspension seed coating agent: 10 parts of active compound, 2 parts of dispersing agent FS3000, 2 parts of wetting agent TXC, 2 parts of SK-92FS1, 2 parts of white carbon black, 0.2 part of xanthan gum, 10 parts of 10% polyvinyl alcohol solution, 0.2 part of basic rose essence, 1 part of SAG1522, 5 parts of ethylene glycol and water are added into a mixing tank to be mixed in sequence when the total weight of the mixture is up to 100%, the mixture is subjected to coarse crushing and homogenization through high shear, then the mixture is pumped into a sand mill to be finely ground, the particle size of the sanded material is detected through a particle size distribution instrument, and the 10% active compound suspension seed coating agent can be obtained through filtration when the particle size reaches the standard requirement.
Powder preparation: and (3) fully mixing 30 parts of active compound, 5 parts of sodium methylene naphthalene sulfonate, 6 parts of sodium lignin sulfonate, 8 parts of white carbon black and diatomite to 100%, and crushing by a superfine crusher to obtain 30% active compound powder.
Soluble powder: fully mixing 50 parts of active compound, 3 parts of sodium dodecyl sulfate, 4 parts of sodium salt of alkyl naphthalene sulfonic acid polycondensate, 4 parts of EFW, 5 parts of hydroxypropyl cellulose and ammonium sulfate until the mixture is 100 percent, and crushing the mixture by a superfine crusher to obtain soluble powder of the active compound with the concentration of 50 percent.
And (3) tablet preparation: 10 parts of active compound, 2 parts of sodium methyl naphthalene sulfonate formaldehyde condensate and 1 part of dodecyl sulfuric acid
Sodium, 15 parts of soluble starch, 8 parts of sodium sulfate, 5 parts of white carbon black and diatomite are fully mixed until the mixture is 100 percent, and the mixture is superfined
Pulverizing with a pulverizer, and tabletting to obtain 10% active compound tablet.
Granules: adding 10 parts of active compound, 3 parts of sodium methyl naphthalene sulfonate formaldehyde condensate, 2 parts of sodium salt of alkyl naphthalene sulfonic acid polycondensate, 10 parts of sodium sulfate and diatomite to 100%, mixing and crushing, adding water, kneading, and adding into a granulator with a screen of a certain specification for granulation. Then drying and screening (according to the range of a screen) are carried out, thus obtaining the active compound granules with 10 percent.
Effervescent granules: the 20% active compound effervescent granule is prepared by fully mixing 20 parts of active compound, 4 parts of sodium salt of alkyl naphthalene sulfonic acid polycondensate, 2 parts of methyl naphthalene sulfonic acid sodium formaldehyde condensate, 2 parts of sodium dodecyl sulfate, 20 parts of soluble starch, 15 parts of sodium citrate, 15 parts of sodium bicarbonate, 10 parts of sodium sulfate and diatomite to 100%, crushing by a superfine crusher, kneading and granulating.
Emulsifiable granules: adding 20 parts of active compound, 1 part of agricultural emulsion EL-40, 3 parts of OX-2681, 4 parts of agricultural emulsion 0201B, 2 parts of agricultural emulsion 700#, 3 parts of N-methyl pyrrolidone and 3 parts of Armid FMPC into a mixing kettle, stirring and mixing uniformly, heating and dissolving by using a hot water bath if necessary, uniformly spraying the oil base on a mixture consisting of 25 parts of white carbon black and light calcium carbonate to 100% under the stirring condition, crushing by using an ultrafine crusher, adding water for kneading, and adding into a granulator provided with a screen mesh with a certain specification for granulation. Then drying and screening (according to the range of a screen) are carried out, thus obtaining the emulsifiable granules of 20 percent of active compound.
Soluble tablet preparation: the active compound soluble tablet with the content of 20 percent is obtained by fully mixing 20 parts of active compound, 3 parts of wetting agent TXC, 4 parts of sodium salt of alkyl naphthalene sulfonic acid polycondensate, 4 parts of EFW, 5 parts of hydroxypropyl cellulose and ammonium sulfate until the mixture is completed to 100 percent, crushing the mixture by an ultrafine crusher and tabletting the crushed mixture.
Microcapsule granule: adding 600 ml of 0.5% polyvinyl alcohol aqueous solution into a 1000 ml plastic (with a baffle) bottle, adding 40 parts of active compound, 9 g of ethylene oxide propylene oxide block copolymer, 6 g of epoxidized soybean oil, 3 g of diphenylmethane-4, 4-diisocyanate, 1.5 g of ethylenediamine, 5 g of sodium carbonate and 150 ml of water into a tetrafluoroethylene stirrer under high-speed stirring, after the addition of the active compound is finished, continuing stirring at a slow speed for 1 hour, standing for 1 hour, filtering, and drying in vacuum to obtain the 40% active compound microcapsule granules.
Effervescent tablets: and (2) complementing 10 parts of active compound, 4 parts of sodium lignosulphonate, 4 parts of NNO, 2 parts of sodium dodecyl sulfate, 20 parts of soluble starch, 20 parts of sodium citrate, 20 parts of sodium bicarbonate, 10 parts of sodium sulfate and calcined kaolin to 100%, fully mixing, crushing by using a superfine crusher, kneading, and tabletting to obtain the 10% active compound effervescent tablet.
Floating granules: and (2) fully mixing 15 parts of active compound, 4 parts of D425, 2 parts of EFW, 2 parts of sodium dodecyl sulfate, 20 parts of corn starch, 20 parts of floating bead, 5 parts of white carbon black, 10 parts of sodium sulfate and diatomite to 100%, crushing by using a superfine crusher, kneading, and granulating to obtain the 15% active compound floating granule.
Soluble granules: and fully mixing 30 parts of active compound, 3 parts of wetting agent TXC, 4 parts of sodium salt of alkyl naphthalene sulfonic acid polycondensate, 4 parts of sodium dodecyl sulfate, 5 parts of carboxymethyl cellulose, 5 parts of glucose and ammonium sulfate until the mixture is 100 percent, crushing by a superfine crusher, kneading and granulating to obtain the 30 percent active compound soluble granule.
The insecticidal preparation of the compound of the general formula I can be diluted by a user or directly sprayed with water before use, and can also be directly used.
The technical scheme of the invention also comprises a method for preventing and controlling pests, which comprises the following steps: the insecticide of the present invention is applied to the pests or their growth medium. Preferably, an effective amount of 10 to 1000 grams per hectare is generally selected, with an effective amount of 10 to 500 grams per hectare being preferred.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Detailed Description
The following specific examples are intended to further illustrate the invention, but the invention is by no means limited to these examples. (all materials are commercially available unless otherwise noted)
Synthetic examples
The compounds represented by the general formula I and the intermediate general formula II of the invention can be prepared respectively by adopting different raw material compounds according to the synthetic route described above, and are further described as follows:
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