CN110818596A - Semicarbazide compound and preparation and application thereof - Google Patents
Semicarbazide compound and preparation and application thereof Download PDFInfo
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- CN110818596A CN110818596A CN201911131124.2A CN201911131124A CN110818596A CN 110818596 A CN110818596 A CN 110818596A CN 201911131124 A CN201911131124 A CN 201911131124A CN 110818596 A CN110818596 A CN 110818596A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
Abstract
The invention discloses a substituted semicarbazide compound shown in a general formula I, a synthesis method thereof and application of the compound as an insecticide/acaricide. The definition of the substituent in the formula is shown in the specification. The compound has excellent acaricidal/insecticidal activity, has the activity of killing acarid eggs, young acarids and adult acarids, and has excellent control effect on green peach aphids, nematodes and diamondback moths.
Description
Technical Field
The invention belongs to the field of pesticide insecticides and acaricides, and particularly relates to a semicarbazide compound, and preparation and application thereof.
Background
Insect pests such as mites, spodoptera exigua, armyworms and aphids are serious problems commonly existing in current agricultural production, and various field crops including economic crops such as soybean, corn, peanut, cotton, purple flower, alfalfa, rice and tobacco crops need to be prevented from being damaged by pests such as the mites and the like. Furthermore, tomatoes, potatoes, sugar beets, carrots, peas, vegetables, fruits, nuts, ornamentals, seedbed crops such as apples, pears, apricots, citrus fruits and grapes also need to be protected from the above-mentioned pests.
The chemical structure of aromatic hydrazine has excellent bioactivity, and chemical abstracts 108(19) 163280d reports phenyl hydrazine carboxylic acid alkyl ester which can be used as acaricide; U.S. patent 4,725,302 reports substituted phenylhydrazines and phenyloxadiazolones useful as pesticides; european patent 0067471 reports 7-substituted-2, 3-dihydrobenzofurans useful as pesticides or intermediates of compounds; german abstracts 88-312695/44 reports arylhydrazines of trifluoroacetic acid having fungicidal, bactericidal, acaricidal and disinfectant activity, and chemical abstracts 105(17) 152686c reports a variety of phenylhydrazines having insecticidal and acaricidal activity.
Bifenazate is a representative compound of the aromatic hydrazine insecticide and acaricide, developed by the U.S. Unionil chemical company (see Chinese patent CN1075952), and has killing activity on both young mites and adult mites.
Since insects and mites are resistant to insecticidal and acaricidal agents after they are used for a certain period of time, new compounds having insecticidal/acaricidal activity are continuously invented. Meanwhile, with the increasing importance of people on the safety of farm and livestock products and the environmental protection, new insecticide/acaricide with high efficiency, low toxicity, environmental friendliness and lower use cost also needs to be continuously developed.
Disclosure of Invention
In order to meet the challenges of increasingly complex pest environments and evolving control requirements facing modern agricultural production, new pesticides with novel structures and excellent performance need to be continuously developed. The invention provides a semicarbazide compound which can be used as a pesticide to prevent and control various insect pests and mite pests of various crops in agriculture.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a semicarbazide compound is shown as a general formula I:
in the formula:
R1is selected from H; c1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl, each optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C2-C6Alkoxycarbonyl radical, C2-C6An alkylcarbonyl group; c3-C6Trialkylsilyl group, C1-C6An alkoxy group; c1-C6An alkylamino group; c2-C8A dialkylamino group; c3-C8Cycloalkylamino group, C2-C6Alkoxycarbonyl or C2-C6Alkylcarbonyl, or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6A haloalkynyl group; c3-C8Halocycloalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C6Dialkylamino radical, C3-C8CycloalkanesAmino group, C3-C6 (alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl));
x is selected from H; halogen; CN; NO2(ii) a A hydroxyl group; c1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl, each optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C2-C6Alkoxycarbonyl radical, C2-C6An alkylcarbonyl group; c3-C6Trialkylsilyl, or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6A haloalkynyl group; c3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkyl sulfide radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino group, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl)); c1-C6An alkoxy group; C1-C6an alkylamino group; c2-C6A dialkylamino group; c3-C8A cycloalkylamino group; c2-C6Alkoxycarbonyl or C2-C6An alkylcarbonyl group; or is phenyl, benzyl, a 5-or 6-membered heteroaromatic ring, or phenoxy, each optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Haloalkynyl group, C3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl groups);
R2selected from a) phenyl, lower phenylalkoxy, phenoxy, or benzyl, each optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Haloalkynyl group, C3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl groups); or b) a carbonylphenyl group optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Haloalkynyl group, C3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl).
Further optional compounds, of formula I:
R1is selected from, C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, each optionally substituted with: (C)1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfidenesulfonyl radical, C1-C4Alkylsulfonyl radical, C2-C4Alkoxycarbonyl radical, C2-C4An alkylcarbonyl group; c3-C6Trialkylsilyl group, C1-C4An alkoxy group; c1-C4An alkylamino group; c2-C6A dialkylamino group; c3-C6Cycloalkylamino group, C2-C4Alkoxycarbonyl or C2-C4 alkylcarbonyl) or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4A haloalkynyl group; c3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino group, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl));
x is C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, each optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C2-C4Alkoxycarbonyl radical, C2-C4An alkylcarbonyl group; c3-C6Trialkylsilyl, or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4A haloalkynyl group; c3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino group, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C6Dialkylaminocarbonyl or C3-C6Trialkylsilyl)); c1-C4An alkoxy group; c1-C4An alkylamino group; c2-C6A dialkylamino group; c3-C6Cycloalkylamino group, C2-C4Alkoxycarbonyl or C2-C4An alkylcarbonyl group; or is phenyl, benzyl, a 5-or 6-membered heteroaromatic ring or phenoxy, each ring optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4Haloalkynyl group, C3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C4Alkoxy radicalCarbonyl group, C2-C4Alkylamino carbonyl radical, C2-C6Dialkylaminocarbonyl or C3-C6Trialkylsilyl groups);
R2is a) phenyl, lower phenylalkoxy, phenoxy, phenylalkyl; each of which is optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4Haloalkynyl group, C3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C4Alkylamino carbonyl radical, C3-C6Dialkylaminocarbonyl or C3-C6Trialkylsilyl); or b) a carbonylphenyl group, each optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4Haloalkynyl group, C3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl).
Still further alternative compounds, of formula I:
R1is selected from C1-C4Straight chain alkyl radical, C2-C6Straight chain alkenyl radical, C2-C6Straight chain alkynyl, C3、C5、C6Cycloalkyl, each optionally substituted with: (C)1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C2-C6Alkoxycarbonyl radical, C2-C6An alkylcarbonyl group; c3-C6Trialkylsilyl group, C1-C4An alkoxy group; c1-C4An alkylamino group; c2-C8A dialkylamino group; c3-C6Cycloalkylamino group, C2-C6Alkoxycarbonyl or C2-C6An alkylcarbonyl group; or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring being substituted with a plurality of identical or different groups each independently selected from: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5Or C6Cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4A straight chain haloalkynyl group; c3、C5Or C6Halocycloalkyl, halogen, CN, NO2，C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight-chain alkylamino radical, C2-C8Straight chain dioxaneAmino group, C3、C5Or C6Cycloalkylamino group, C3、C5Or C6(alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Straight-chain dialkylaminocarbonyl or C3-C6Linear trialkylsilyl));
x is selected from C1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5、C6Cycloalkyl, each optionally substituted with: (C)1-C4Straight-chain alkoxy radical, C1-C4Straight-chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C2-C6Straight chain alkoxycarbonyl, C2-C6A linear alkylcarbonyl group; c3-C6Linear trialkylsilyl, or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring optionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3-C6Straight-chain cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4A straight chain haloalkynyl group; c3-C6Straight-chain halocycloalkyl radical, C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C straight chain4Alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight-chain alkylamino radical, C2-C8Di-linear alkylamino, C3-C6Cycloalkylamino group, C3-C6(linear alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkoxyAlkylcarbonyl radical, C2-C6Straight-chain alkylaminocarbonyl radical, C3-C8Straight-chain dialkylaminocarbonyl or C3-C6Tri-linear alkylsilyl)); c1-C4A linear alkoxy group; c1-C4A straight-chain alkylamino group; c2-C8A di-linear alkylamino group; c3-C6Straight-chain cycloalkylamino radical, C2-C6Straight chain alkoxycarbonyl or C2-C6A linear alkylcarbonyl group; or is phenyl, benzyl, a 5-or 6-membered heteroaromatic ring or phenoxy, each optionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3-C6Straight-chain cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4Straight-chain haloalkynyl, C3-C6Straight-chain halocycloalkyl radical, C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight alkanethio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight chain alkylamino radical, C2-C8Di-linear alkylamino radical, C3-C6Cycloalkylamino, C3-C6(linear alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Di-linear alkylaminocarbonyl or C3-C6Tri-linear alkylsilyl);
R2is a) phenyl, lower phenylalkoxy, phenoxy, or phenylalkyl; each may be optionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5Or C6Cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4Straight-chain haloalkynyl, C3-C6Halocycloalkyl, halogen, CN, NO2，C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight chain alkylamino radical, C2-C8Straight-chain dialkylamino radical, C3、C5Or C6Cycloalkylamino, C3-C6(linear alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Di-linear alkylaminocarbonyl or C3-C6Tri-linear alkylsilyl); or b) a carbonylphenyl group, each optionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5Or C6Cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4Straight-chain haloalkynyl, C3、C5Or C6Halocycloalkyl radical, C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight chain alkylamino radical, C2-C8Di-linear alkylamino radical, C3、C5Or C6Cycloalkylamino, C3-C6(straight-chain alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Di-linear alkylaminocarbonyl or C3-C6TrialkylsilanesAnd (4) a base.
In the definitions of the compounds of the general formula I given above, the terms used in the collection generally represent the following substituents:
halogen: fluorine, chlorine, bromine or iodine;
alkyl groups: a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl or tert-butyl;
cycloalkyl groups: substituted or unsubstituted cyclic alkyl groups, such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen, and the like;
halogenated alkyl groups: straight-chain or branched alkyl groups in which the hydrogen atoms may be partially or fully substituted by halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc.;
alkoxy groups: a linear or branched alkyl group attached to the structure via an oxygen atom linkage;
haloalkoxy groups: straight-chain or branched alkoxy groups, in which the hydrogen atoms may be partially or completely replaced by halogen. For example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like;
alkylamino group: one or two straight or branched chain alkyl groups attached to the structure via a nitrogen atom;
haloalkylamino group: a substituent formed by substituting a part or all of hydrogen atoms on the alkylamino group with halogen;
alkylthio group: a linear or branched alkyl group attached to the structure via a sulfur atom bond;
haloalkylthio: straight-chain or branched alkylthio groups in which the hydrogen atoms may be partially or fully substituted by halogen atoms. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like;
table 1 table 2 lists R1And X are commonly used substituents, but references to substituents in this patent should not be construed as being limited to the scope of tables 1 and 2.
TABLE 1
| R1 | R1 | R1 | R1 |
| -(CH2)2CH3 | -CH3 | -CH2CH(OCH3)2 | -CH2CHF2 |
| -CH(CH3)2 | -CH2CH3 | -CF3 | -COC(CH3)3 |
| -(CH2)3CH3 | -COCF3 | -CF2CF3 | -COCH2CF3 |
| -SOCF3 | -COCH3 | -CH2CF3 | -COCH(CH3)2 |
| -C(CH3)3 | -COCH3CH2 | -CH2CH2Br | -CH2CH2Cl |
| -CH2CCl3 | (CH2)6CH3 | CH2C(CH3)3 | -SOCH2CH2Cl |
| -SO2CH2CH3 | -SOCH3 | -SOCH2CF3 | CH2COCH3 |
| -CH2Ph-4-F | (CH2)7CH3 | -COPh-2-Cl | -CH2C(CH3)2CF3 |
| -COPh-4-F | -(CH2)5CH3 | -CH2Ph-2-Cl | CH2CH2C(CH3)3 |
| -CH2Ph-4-Cl | -(CH2)4CH3 | -CH2Ph-3-Cl | -CH(CH3)CH2CH3 |
| -COPh-4-Cl | -CH2Ph | -COPh-3-Cl | -CH(CH3)CH2CH(CH3)2 |
| -CH2Ph-4-C2H5 | -CH2Ph-4-CH3 | -COPh-4-Cl | -CH2Ph-2-CH3 |
TABLE 2
The compounds of the present invention are illustrated by the specific compounds formed in tables 3-6, but the compounds listed are not intended to limit the scope of the present invention.
TABLE 3
TABLE 4
TABLE 5
TABLE 6
The compounds of formula I of the present invention can be prepared according to the following two methods:
the first method comprises the following steps:
the compound in the general formula I can be prepared by directly condensing substituted phenylhydrazine compounds and isocyanates at a certain temperature in a suitable solvent within a certain reaction time.
In the above reaction formula, R1、R2X is as defined above;
in the above reaction, the solvent may be one or more of tetrahydrofuran, dichloromethane, chloroform, acetonitrile, toluene, xylene, benzene, acetone and butanone.
In the above reaction, the reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
And the second method comprises the following steps:
as shown in the reaction formula, the compound I with the general formula can be prepared by directly removing a molecule of alcohol from phenylhydrazine compounds and carbamates in a certain solvent at a certain reaction temperature for a certain time.
In the above reaction, the solvent may be one or more selected from tetrahydrofuran, dichloromethane, chloroform, acetonitrile, toluene, xylene, benzene, acetone or butanone.
In the above reaction, the reaction temperature may be between 25 ℃ and the boiling point temperature of the solvent, typically reflux temperature.
In the above reaction, the reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
The compounds of the invention may be provided in the form of a formulation. The compound of the general formula is used as an active component, and can be prepared into various preparation types according to a mode well known in the field, wherein the preparation types comprise missible oil, aqueous emulsion, microemulsion, soluble solution, dispersible oil suspending agent, ultra-low volume agent, suspending agent, granules, effervescent granules (or tablets), water dispersible granules, suspended seed coating agent, emulsifiable powder (or granules) agent and microcapsule suspending agent, and in any case, the selection of the preparation types depends on the physical, chemical and biological properties of the compound of the general formula.
The content of active ingredient in the preparation is between 0.1% and 99%, wherein 5-90% is preferred, and the optimal range of the content of active ingredient varies according to the type of preparation of the composition.
The preparation comprises the following components in percentage by weight: 0.1-99% of active component, 1-50% of surfactant and the balance of carrier.
The formulations of the compositions of the invention into finished preparations can be prepared by conventional processes, i.e. by mixing the active substance with a liquid carrier (solvent) or a solid carrier, and adding one or more surfactants such as emulsifiers, dispersants, wetting agents, binders, stabilizers and defoamers. Typically, the composition comprises at least one carrier and at least one surfactant. In each case, a homogeneous distribution of the active components of the compositions according to the invention should be ensured.
The aqua is prepared by mixing the raw medicine and the surfactant uniformly to form uniform and transparent liquid. Generally, the emulsion contains 5-30% of active components, 2-20% of emulsifying agents, 0-20% of other additives such as penetrating agents and the like, and the balance of water.
The missible oil is a uniform and transparent liquid formed by uniformly mixing a raw medicine, an organic solvent and a surfactant. Generally, the composition comprises 10-50% of active components, 2-20% of emulsifying agents, 0-20% of other additives such as penetrating agents and the like, and the balance of inert carriers.
Suspending agents are typically prepared by mixing the technical material, surfactant, anti-freeze, water and sanding with a sand mill to obtain a stable non-sedimenting flowable product. The suspending agent generally contains 5-75% of active components, 5-15% of dispersing agent, 4-10% of antifreezing agent, 0-10% of other additives such as defoaming agent, preservative, stabilizer, penetrating agent and thickening agent, and the balance of liquid carrier.
The water dispersible granule is usually obtained by mixing the original drug, the surfactant and the carrier, crushing to obtain a powder, kneading, and granulating. The granules are usually prepared into granules with 10-100 international standard meshes (1.676-0.152 mm), and can be prepared by extrusion, dipping or spray granulation. Generally, the water dispersible granule contains 5-75% of active ingredients, 5-20% of surface active agents such as a stabilizer, a wetting dispersant, a disintegrating agent and a binder, and the balance of an inert carrier.
The wettable powder is usually prepared by mixing raw pesticide, an auxiliary agent and a carrier, and crushing to obtain a powder, and usually contains 10-85% of an active component, 3-10% of a dispersing agent, 0-10% of other additives such as a penetrating agent or an adhesive and the balance of an inert carrier.
The emulsifiable powder (granule) is prepared by mixing active components, organic solvent and surfactant together to prepare uniform transparent oil phase, and then uniformly spraying the oil phase on a pre-crushed carrier, wherein the carrier usually contains 1-30% of the active components, 10-40% of emulsifier, wetting dispersant and 0-15% of organic solvent.
The aqueous emulsion is prepared by mixing the original medicine, the organic solvent and the surfactant uniformly to prepare an oil phase; mixing water and antifreeze agent together to prepare uniform transparent 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 1-60% of active components, 5-20% of emulsifier, 0-10% of other additives such as penetrating agent, and the balance of inert carrier.
Microemulsions are generally prepared by mixing the raw materials, organic solvents, surfactants, and water together to form a homogeneous, transparent liquid. Generally comprises 1-50% of active component, 10-40% of emulsifier, 2-10% of antifreeze, 0-10% of other additives such as penetrating agent and the balance of inert carrier.
The soluble agent is a uniform transparent liquid prepared by mixing active components, organic solvent and surfactant. Typically 1-50% active ingredient, 6-20% surfactant, 0-10% other additives such as penetrant, and the balance inert carrier.
The dispersible oil suspending agent is prepared by mixing an active component, a surfactant and an oil-based carrier, and then adding the mixture into a sand mill for sanding until the particle size is qualified, and generally contains 2-60% of the active component, 6-20% of an emulsifying agent, 0-10% of other additives such as a penetrating agent and the balance of an inert carrier.
The ultra-low volume agent is prepared by mixing active components, organic solvent and surfactant together and processing into a uniform transparent oil phase. Generally, the composition comprises 1-30% of active components, 2-15% of emulsifying agents, 0-10% of other additives such as penetrating agents and the balance of inert carriers.
Granules are generally prepared by mixing the active ingredient with the carrier, kneading, granulating, drying and coating. Typically, the composition contains 0.1-10% of active ingredient, 0-10% of other additives such as a binder, and the balance inert carrier.
Effervescent granules (or tablets) are usually prepared by mixing and crushing the active ingredients, the surfactant and the carrier, and then kneading and granulating (or tabletting). Generally, the effervescent tablet comprises 0.5-30% of active components, 2-15% of wetting dispersant, 5-10% of effervescent disintegrant, 0-10% of other additives such as binder, and the balance of inert carrier.
The suspended seed coating agent is prepared by mixing raw pesticide, surfactant, antifreezing agent, film-forming agent, water and the like, and sanding to obtain a stable non-deposition flowable product. The coating is characterized by generally comprising 5-75% of active components, 5-15% of dispersing agents, 4-10% of antifreezing agents, 1-15% of film forming agents, 0-10% of other additives such as defoaming agents, corrosion inhibitors, stabilizing agents, penetrating agents and thickening agents and the balance of liquid carriers.
The microcapsule suspending agent is prepared through mixing active component, surfactant and solvent, processing into emulsion, mixing with pre-prepared pre-polymer of urea-formaldehyde resin, regulating pH value with hydrochloric acid solution while stirring, capsulizing, curing, regulating pH value to 7 with 10% sodium hydroxide solution, adding water to replenish 100g, and stirring. The active ingredient is 2-45%, the dispersant is 5-15%, other additives such as wall materials, antifoaming agents, preservatives, stabilizers, penetrants and thickeners are 5-30%, and the balance is a liquid carrier.
The compositions of the invention may be formulated in finished formulations using (liquid or solid) carriers and various adjuvants well known to those skilled in the art.
The surfactant varieties related in the formula of the insecticidal preparation are reported in a plurality of monographs related to the processing of surfactants and pesticide formulations. For example, surfactant science and applications, a major edition of Jiangqinghui, and the like, the Chinese petrochemical press, 2009; special surfactant, kingdom of Wangbei, China weaving release; "agricultural chemical formulation processing technology", Master catalog of Liu Walsh, chemical industry Press, 1998; "New surfactants", edited by Sunzhi et al, chemical industry Press 2003; handbook of chemical products, edited by Huanghong Weekly, chemical industry Press, 2005; gemini surfactant research and application, Tang-Gong Law, Liu Zhong Yun, Hu Xiao Dong Shu, chemical industry Press, 2011; preparation and application of functional surfactant, edited by the master of the army, chemical industry press, 2009; sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ., Co., Inc., New York, 1964.
Suitable surfactants in the insecticidal and acaricidal preparation of the present invention may be emulsifiers, dispersants or wetting agents; may be non-ionic or ionic. The anionic surfactant comprises sulfonates, sulfates, carboxylates, phosphates, succinates, lignosulfonates, acrylamide acrylic acid copolymers and the like, and the nonionic surfactant comprises fatty alcohol polyoxyethylene ether, alkylphenol ethoxylates, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ether, acid alcohol ester and polyoxyethylene ether thereof, fatty amide and polyoxyethylene ether thereof, alkanolamide and polyoxyethylene ether thereof, polyoxyethylene polyoxypropylene ether block copolymer, sodium alkyl naphthalene sulfonate fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether and the like. For example: sodium salt or calcium salt of lignosulfonic acid, polyoxyethylene (n20) phenethylphenol ether oleate, alkyl aryl polyoxyethylene polyoxypropylene ether, tristyrylphenol polyoxyethylene (n20) ether phosphorylated triethanolamine salt, Nongru 0201B, Nongru 0203B, Nongru 100#, Nongru 507#, Nongru AEO-3, Nongru T-20, Nongru T-80, Nongru T-85, Nongru S-80, Nongru 500#, Nongru 600#, Nongru 700#, Nongru 1601#, Nongru NP-7, Nongru NP-10, Nongru NP-15, Nongru OX-2681, Nongru OX-8686, Nongru OX-690, Nongru 2201#, Nongru PICO-LOE, Nongru PICO-LE1, Nongru LME-2, Nongru LME-4, Nongru LME-5, Nongru LEW-0, Nongru LEW-5, Agricultural emulsion LEW-50, sodium salt of alkyl naphthalene sulfonic acid polycondensate, polycarboxylate dispersant GY-D800, polycarboxylate dispersant GY-D04, polycarboxylate dispersant GY-D02, sodium naphthalene sulfonate formaldehyde condensate, sodium naphthol sulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene polyoxypropylene ether, styrene maleic anhydride, methyl naphthalene sulfonic acid formaldehyde condensate, alkyl-diethylene glycol ether-sodium sulfonate, N-methyl-oleoyl-taurate, detergent LS, methylene naphthalene sulfonic acid sodium salt, oleic acid methyl aminoethyl sulfonic acid sodium salt, dispersant SP-28F, dispersant SP-SC 909 3, Darun dispersant D909S, alkylaryl polyoxyethylene ether, dodecyl polyoxyethylene ether phosphate, alkyl naphthalene sulfonate formaldehyde condensate (NNO), alkylphenol polyoxyethylene ether formaldehyde condensate, dibutyl naphthalene sulfonic acid formaldehyde condensate, Dispersant PICO-SWP1, dispersant PICO-SWP2, dispersant PICO-SWP3, dispersant PICO-SF1, dispersant PICO-SF2, dispersant PICO-SF3, dispersant PICO-LO1, agricultural milk PICO-LE2, dispersant SP-OF3468, dispersant SP-OF3472, dispersant SP-2728, dispersant SP-SC3, dispersant SP-SC29, dispersant SupergilMNS/90, dispersant SK-20TX, dispersant SK-25CH, dispersant Soprophor FD, dispersant PICO-LPQ, Morwet EFW, wetting agent IgepBC/10, wetting agent GEROPONL-WET/P, Rhodasurf 860/P, SP-SC 3266, wetting agent PICO-SW-2, wetting agent PICO-SW3, wetting agent sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene ether, polyoxyethylene alkyl phenol based ether condensate, Alkyl succinic acid sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, calcium dodecyl benzene sulfonate and the like.
By adding one or more other bactericides and/or insecticides and acaricides to the composition, the composition can have broader-spectrum activity than the compound of the general formula I alone. In addition, other bactericides can have synergistic effect on the bactericidal/insecticidal and acaricidal activity of the compound shown in the general formula I, and the compound shown in the general formula I can also be mixed with other bactericides/insecticidal and acaricidal agents, the content of active ingredients in the mixture is wide in variation range, the content of the active ingredients in the mixture is generally 1-95%, and the content of the active ingredients in the mixture is preferably 5-60%.
The specific implementation mode is as follows:
first, preparation example
Example 1: synthesis of Compound 1
Reaction type
Wherein, the synthesis process of the 2, 5-dichloro-4-trifluoromethoxy isocyanate can be prepared by condensing corresponding amino with phosgene, diphosgene or triphosgene by referring to common tolueneisocyanate.
The synthesis of compound 1 was synthesized according to the following procedure: dissolving 35.2g (0.1mol) of 2, 5-dichloro-4-trifluoro methoxy isocyanate in 200g of dichloromethane solution, dropwise adding 21.4g (0.1mol) of dichloromethane (150g) solution of 2-methoxy-5-phenyl hydrazine under stirring, reacting at 0-40 ℃ for 5-100 minutes, wherein the optional temperature is 25-30 ℃, the optional reaction is 40-60 minutes, desolventizing can be carried out, and recrystallizing with ethanol to obtain the white powder compound.
Other compounds of formula I can be prepared by the preparation method provided by the invention, and the nuclear magnetic data of part of the compounds are shown in Table-7.
TABLE 7
Example 2: synthesis of Compound 91
The reaction formula is as follows:
among these, 3-methoxy-2-methylbenzoyl isocyanate was synthesized according to the synthesis method provided in the example of CN108912013A, in which only some of the groups were changed.
The synthesis of the compound was synthesized according to the following procedure: dissolving 19.1g (0.1mol) of 3-methoxy-2-methylbenzoyl isocyanate in 200g of dichloromethane solution, dropwise adding 21.4g (0.1mol) of dichloromethane (150g) solution of 2-methoxy-5-phenyl phenylhydrazine under stirring, reacting at 0-40 ℃ for 5-100 minutes, wherein the optional temperature is 25-30 ℃, the optional reaction is 40-60 minutes, desolventizing can be carried out, and recrystallizing with ethanol to obtain a white powder compound.
Nuclear magnetic data of the compoundHNMR(400MH,DMSO)δ7.1-7.9(m,9H),2.34,δ 3.72(s,3H)δ2.34(s,3H)。
Other compounds of general formula (I) can be prepared by the preparation method provided by the invention, and the nuclear magnetic data of part of the compounds are shown in Table-8.
TABLE 8
Second, determination of biological Activity
The following examples relate to the pesticidal use of the compounds of the present invention. In all of these examples, a stock solution of 3000ppm of the compound was prepared by dissolving 0.3g of the test compound in 10ml of acetone and adding 90ml of distilled water dropwise with an ethoxylate of sorbitan monolaurate, or a similar suitable wetting agent. In each of the examples described below, this stock solution was used and a specific dilution was prepared. In all tests discussed below, which included the compounds of the invention for treatment, all were repeated with a control in which no active compound was provided to compare the calculated percent control.
Example 3: adult mite killing and mite egg/young mite killing test (test object: Tetranychus cinnabarinus)
One day before treatment, the tree pest sticking glue is coated on each leaf of two cowpea primary leaves to form a 8 shape, each pot is provided with two plants, in each 8 shape, a ring closer to a plant stem is designed to be used for a mite killing ovum/young mite killing test, and a ring farther away from the stem is designed to be used for a mature mite killing test.
The day before treatment, several adult mites (Tetranychus urticae koch) were transferred to the ovicide ring and female mites were allowed to lay eggs until one hour before treatment. Plants were treated with spray rinsing with 1000ppm solution diluted from 3000ppm stock solution.
One day after treatment, approximately 25 adult mites of the group moved to the adult mite killing ring. Five days later, the loops were observed for live mites which remained on the leaves. The percentage control was evaluated on the basis of the number of live mites present on the control plants.
The eggs hatched in the acaricidal eggs/larvicidal rings and the surviving larvicides were observed nine days after the treatment, and the percentage of control was evaluated based on the number of hatched eggs and surviving larvicides on the control plants. When the treatment is effective against eggs, the control is designated as ovicidal (O) and when the treatment is effective against young mites, the control is designated as larvicidal (L).
The test results of the adult mite-killing (MI) and mite-killing egg/larvicide Mite (MIOLV) tests of the test samples and the control agents are shown in table 9.
TABLE 9
Mi-miticidal agents
MIOVL-miticide/larvicide
Example 4: panonychus test
Orchard citrus trees infested with panonychus ulmi (Pannychu citri) were spray treated with a dilute emulsion spray of the compound. With compounds No. 2,3, 4, 6, 7, 8, 9, 10, 91, 92, 94, 95 and 97, a control rate of greater than 75% can be achieved at a dosage of 150ppm of active ingredient where appropriate.
Example 5: nematode test
The determination method comprises the following steps: the corn leaves were cut into 2cm long sections, and the pressure of airbrush spray treatment was 10psi (about 0.7kg/cm2), and the amount of the spray was 0.5ml per section. After drying in the shade, 10 test insects of 2 years old were inoculated into each treatment, and the treatment was repeated 3 times. After treatment, the treated seeds are placed into an observation room at the temperature of 25 ℃ and the relative humidity of 60-70% for culture, the number of the survived insects is investigated after 72 hours, and the mortality is calculated.
The results of the nematode kill of the armyworm for the test samples and the control agents are shown in Table 10.
Example 6: myzus test
The determination method comprises the following steps: a culture dish with the diameter of 6cm is taken, a layer of filter paper is covered on the bottom of the culture dish, and a proper amount of tap water is dripped for moisturizing. And (3) shearing cabbage leaves with proper size (the diameter is about 3cm) and 15-30 heads of aphids from the cabbage plants for culturing the myzus persicae, removing the aphids with the wing aphids and the front sides of the leaves, and placing the leaves in a culture dish with the back sides upward. The airbrush spray treatment was carried out at a pressure of 10psi (approx. 0.7kg/cm2) and a liquid spray volume of 0.5ml, with 3 repetitions of the treatment. And (3) after treatment, placing the treated mixture into an observation room with the temperature of 25 ℃ and the relative humidity of 60-70% for culture, investigating the number of the survival insects after 48 hours, and calculating the mortality.
The results of the myzus persicae test, the test sample and the control agent are shown in table 10.
Example 7: diamondback moth assay
The determination method comprises the following steps: cabbage leaves were punched into a 2 cm-diameter disk by a punch, airbrush was sprayed under a pressure of 10psi (approximately 0.7kg/cm2), and the amount of the sprayed liquid was 0.5ml per disk. After drying in the shade, 10 test insects of 2 years old are inoculated in each treatment, and the treatment is repeated for 3 times. After treatment, the mixture is placed into an observation room with the temperature of 25 ℃ and the relative humidity of 60-70% for culture, the number of the survival insects is investigated after 72 hours, and the death rate is calculated.
The results of the test samples and the control agent plutella xylostella are shown in table 10.
Watch 10
Claims (8)
1. A semicarbazide compound has insecticidal/acaricidal activity, and is characterized in that: the compound has a structural general formula I:
in the formula:
R1is selected from H; c1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl, each optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C2-C6Alkoxycarbonyl radical, C2-C6An alkylcarbonyl group; c3-C6Trialkylsilyl group, C1-C6An alkoxy group; c1-C6An alkylamino group; c2-C8A dialkylamino group; c3-C8Cycloalkylamino group, C2-C6Alkoxy radicalCarbonyl or C2-C6Alkylcarbonyl, or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6A haloalkynyl group; c3-C8Halocycloalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C6Dialkylamino radical, C3-C8Cycloalkylamino group, C3-C6 (alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl));
x is selected from H; halogen; CN; NO2(ii) a A hydroxyl group; c1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl, each optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C2-C6Alkoxycarbonyl radical, C2-C6An alkylcarbonyl group; c3-C6Trialkylsilyl, or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6A haloalkynyl group; c3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino group, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl)); c1-C6An alkoxy group; c1-C6An alkylamino group; c2-C6A dialkylamino group; c3-C8A cycloalkylamino group; c2-C6Alkoxycarbonyl or C2-C6An alkylcarbonyl group; or is phenyl, benzyl, a 5-or 6-membered heteroaromatic ring, or phenoxy, each optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Haloalkynyl group, C3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl radicalsOr C3-C6Trialkylsilyl groups);
R2selected from a) phenyl, lower phenylalkoxy, phenoxy, or benzyl, each optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Haloalkynyl group, C3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl groups); or b) a carbonylphenyl group optionally substituted with: (C)1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Haloalkynyl group, C3-C8Halocycloalkyl, halogen, CN, NO2，C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylamino radical, C2-C8Dialkylamino radical, C3-C8Cycloalkylamino, C3-C8(alkyl) cycloalkylamino, C2-C6Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl).
2. Semicarbazide-based compound according to claim 1, characterized in that: in the general formula I, the compound is shown in the specification,
R1is selected from, C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, each optionally substituted with: (C)1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C2-C4Alkoxycarbonyl radical, C2-C4An alkylcarbonyl group; c3-C6Trialkylsilyl group, C1-C4An alkoxy group; c1-C4An alkylamino group; c2-C6A dialkylamino group; c3-C6Cycloalkylamino group, C2-C4Alkoxycarbonyl or C2-C4 alkylcarbonyl) or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4A haloalkynyl group; c3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino group, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl));
x is C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, each optionally substituted with: (halogen, CN, NO)2Hydroxy, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C2-C4Alkoxycarbonyl radical, C2-C4An alkylcarbonyl group; c3-C6Trialkylsilyl, or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4A haloalkynyl group; c3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino group, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C6Dialkylaminocarbonyl or C3-C6Trialkylsilyl)); c1-C4An alkoxy group; c1-C4An alkylamino group; c2-C6A dialkylamino group; c3-C6Cycloalkylamino group, C2-C4Alkoxycarbonyl or C2-C4An alkylcarbonyl group; or a phenyl group, or a salt thereof,benzyl, a 5-or 6-membered heteroaromatic ring or a phenoxy group, each ring optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4Haloalkynyl group, C3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C4Alkoxycarbonyl radical, C2-C4Alkylamino carbonyl radical, C2-C6Dialkylaminocarbonyl or C3-C6Trialkylsilyl groups); r2Is a) phenyl, lower phenylalkoxy, phenoxy, phenylalkyl; each of which is optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4Haloalkynyl group, C3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C4Alkylamino carbonyl radical, C3-C6Dialkylaminocarbonyl or C3-C6Trialkylsilyl groups); or b) a carbonylphenyl group, each optionally substituted with: (C)1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C2-C4Haloalkenyl group, C2-C4Haloalkynyl group, C3-C6Halocycloalkyl radical, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C3-C6(alkyl) cycloalkylamino, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl radical, C2-C6Alkylamino carbonyl radical, C3-C8Dialkylaminocarbonyl or C3-C6Trialkylsilyl).
3. Semicarbazide-based compound according to claim 2, characterized in that: in the general formula I, the compound is shown in the specification,
R1is selected from C1-C4Straight chain alkyl radical, C2-C6Straight chain alkenyl radical, C2-C6Straight chain alkynyl, C3、C5、C6Cycloalkyl, each optionally substituted with: (C)1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C2-C6Alkoxycarbonyl radical, C2-C6An alkylcarbonyl group; c3-C6Trialkylsilyl group, C1-C4An alkoxy group; c1-C4An alkylamino group; c2-C8A dialkylamino group; c3-C6Cycloalkylamino group, C2-C6Alkoxycarbonyl or C2-C6An alkylcarbonyl group; or phenyl, phenoxy or a 5-or 6-membered heteroaromatic ring, each ring being substituted with a plurality of identical or different groups each independently selected from: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5Or C6Cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4A straight chain haloalkynyl group; c3、C5Or C6Halocycloalkyl, halogen, CN, NO2，C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight-chain alkylamino radical, C2-C8Straight-chain dialkylamino, C3、C5Or C6Cycloalkylamino group, C3、C5Or C6(alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Straight-chain dialkylaminocarbonyl or C3-C6Linear trialkylsilyl));
x is selected from C1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5、C6Cycloalkyl, each optionally substituted with: (C)1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C2-C6Straight chain alkoxycarbonyl, C2-C6A linear alkylcarbonyl group; c3-C6Linear trialkylsilyl, or phenyl, phenoxy or 5-or 6-membered heteroaromatic rings, each ring being able to containOptionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3-C6Straight-chain cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4A straight chain haloalkynyl group; c3-C6Straight-chain halocycloalkyl radical, C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C straight chain4Alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight-chain alkylamino radical, C2-C8Di-linear alkylamino, C3-C6Cycloalkylamino group, C3-C6(straight-chain alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Straight-chain dialkylaminocarbonyl or C3-C6Tri-linear alkylsilyl)); c1-C4A linear alkoxy group; c1-C4A straight-chain alkylamino group; c2-C8A di-linear alkylamino group; c3-C6Straight-chain cycloalkylamino radical, C2-C6Straight chain alkoxycarbonyl or C2-C6A linear alkylcarbonyl group; or is phenyl, benzyl, a 5-or 6-membered heteroaromatic ring or phenoxy, each optionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3-C6Straight-chain cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4Straight-chain haloalkynyl, C3-C6Straight-chain halocycloalkyl radical, C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight chain alkylamino radical, C2-C8Di-linear alkylamino radical, C3-C6Cycloalkylamino, C3-C6(linear alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Di-linear alkylaminocarbonyl or C3-C6Tri-linear alkylsilyl);
R2is a) phenyl, lower phenylalkoxy, phenoxy, or phenylalkyl; each of which is optionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5Or C6Cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4Straight-chain haloalkynyl, C3-C6Halocycloalkyl, halogen, CN, NO2，C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight chain alkylamino radical, C2-C8Straight-chain dialkylamino radical, C3、C5Or C6Cycloalkylamino, C3-C6(linear alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Di-linear alkylaminocarbonyl or C3-C6Tri-linear alkylsilyl); or b) a carbonylphenyl group, each optionally substituted with: (C)1-C4Straight chain alkyl radical, C2-C4Straight chain alkenyl radical, C2-C4Straight chain alkynyl, C3、C5Or C6Cycloalkyl radical, C1-C4Straight chain haloalkyl, C2-C4Straight-chain haloalkenyl, C2-C4Straight-chain haloalkynyl, C3、C5Or C6Halocycloalkyl radical, C1-C4Straight-chain alkoxy radical, C1-C4Straight chain haloalkoxy, C1-C4Straight chain alkylthio radical, C1-C4Straight chain alkylsulfinyl, C1-C4Linear alkylsulfonyl radical, C1-C4Straight chain alkylamino radical, C2-C8Di-linear alkylamino radical, C3、C5Or C6Cycloalkylamino, C3-C6(linear alkyl) cycloalkylamino, C2-C4Straight chain alkylcarbonyl group, C2-C6Straight chain alkyloxycarbonyl, C2-C6Straight chain alkylaminocarbonyl radical, C3-C8Di-linear alkylaminocarbonyl or C3-C6A trialkylsilyl group.
4. A preparation composition containing the compound of the general formula I is used for killing mites and insects in plant protection.
5. The formulation composition of claim 4, wherein: the weight percentage of the compound of the general formula I in the preparation composition is 0.1-99%.
6. The formulation composition of claim 5, wherein the formulation is an aqueous solution, an emulsifiable concentrate, a suspension, a water dispersible granule, a wettable powder, an emulsifiable powder, an aqueous emulsion, a microemulsion, a soluble solution, an oil dispersible suspension, an ultra-low volume agent, a granule, an effervescent granule, a suspended seed coating, or a microcapsule suspension.
7. A process for the preparation of a compound of formula I, characterized in that: the compound is prepared by directly condensing substituted phenylhydrazine compounds and isocyanates in a proper solvent at a certain temperature within a certain reaction time.
8. A process for the preparation of a compound of formula I, characterized in that: the compound is prepared by dissolving substituted phenylhydrazine compounds and carbamates in a specific agent, and directly removing a molecule of alcohol at a certain reaction temperature within a certain time.
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