CN116102493A - Amide compound and preparation method and application thereof - Google Patents

Amide compound and preparation method and application thereof Download PDF

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Publication number
CN116102493A
CN116102493A CN202111322038.7A CN202111322038A CN116102493A CN 116102493 A CN116102493 A CN 116102493A CN 202111322038 A CN202111322038 A CN 202111322038A CN 116102493 A CN116102493 A CN 116102493A
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amide compound
compound
compound according
difluoromethoxy
amide
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刘吉永
肖坦
李康明
丁福栋
胡乐天
周丽琪
吴明慧
相君成
赵廷廷
夏柱
吕亮
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Cac Nantong Chemical Co ltd
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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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides an amide compound, a preparation method and application thereof, wherein the amide compound has a structure shown in a formula I. The amide compound provided by the invention has high insecticidal activity and good quick-acting performance at a low dosage; and the effect is good at low dosage, the dosage of the medicine is reduced, the environment is protected, and the application prospect is wide.

Description

Amide compound and preparation method and application thereof
Technical Field
The invention belongs to the field of pesticides, and relates to an amide compound, and a preparation method and application thereof.
Background
In crop production such as agriculture and gardening, damage caused by pests and the like is still very remarkable. Because pests have resistance to the existing pesticides and the existing pesticides are not friendly to the environment, new pesticides with better activity, lower dosage and more friendly environment are always required to be developed.
The insecticidal activity of amide compounds has been reported. For example, CN1926094A discloses compounds KC1 (i.e., compound 2001 in CN 1926094A), KC2 (i.e., compound 2004 in CN 1926094A), KC3 (i.e., compound 2034 in CN 1926094A), KC4 (i.e., compound 2037 in CN 1926094A), and their insecticidal activity. These disclosed compounds have insecticidal activity, however, they are poor in insecticidal effect or poor in quick-acting property at low doses.
Figure BDA0003345862020000011
There remains a need in the art to actively develop new pesticides with high insecticidal activity that are fast-acting at low doses to meet agricultural as well as woody needs.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an amide compound, a preparation method and application thereof, wherein the amide compound has good insecticidal effect at low dosage, has good quick-acting property and low dosage, and is more beneficial to environmental protection.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an amide compound having a structure represented by formula I:
Figure BDA0003345862020000012
in the formula I, the compound (I),
q is selected from one of the following Q1, Q2, Q3 or Q4:
Figure BDA0003345862020000013
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C 1 -C 6 Alkyl, C 3 -C 8 Cycloalkyl, C 1 -C 6 Haloalkyl, C 3 -C 8 Halogenated cycloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylsulfinyl, C 1 -C 6 Haloalkyl sulfinyl, C 1 -C 6 Alkylsulfonyl or C 1 -C 6 A haloalkylsulfonyl group;
R 1 selected from halogen;
R 2 selected from difluoromethoxy;
W 1 and W is 2 Independently an oxygen atom or a sulfur atom.
The amide compound with the structure shown in the formula I can achieve better insecticidal activity at low dosage, has quick response, can exert insecticidal activity after one day of application, can achieve very high insecticidal activity within 3 days, and has good quick response; and the effect is good at low dosage, so that the damage to plants and human beings caused by overlarge drug concentration is reduced, and the drug residue generated during application is less, thereby being more beneficial to environmental protection.
In the present inventionAs a preferred embodiment, in formula I, Z 1 、Z 2 、Z 3 、Z 4 、Z 5 Each independently selected from hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylsulfinyl, trifluoromethylsulfonyl or trifluoromethylsulfonyl; r is R 1 Selected from chlorine, bromine or iodine; r is R 2 Selected from difluoromethoxy.
As a further preferable technical scheme of the invention, the amide compound is any one of compounds shown in the following table 1 with a general formula I.
TABLE 1
Figure BDA0003345862020000021
Figure BDA0003345862020000031
Figure BDA0003345862020000041
Figure BDA0003345862020000051
Figure BDA0003345862020000061
Figure BDA0003345862020000071
Figure BDA0003345862020000081
Figure BDA0003345862020000091
"H" represents a hydrogen atom, "O" represents an oxygen atom, "S" represents a sulfur atom, "F" represents a fluorine atom, "Cl" represents a chlorine atom, "Br" represents a bromine atom, "I" represents an iodine atom, and "OCF" represents a fluorine atom, a chlorine atom, a bromine atom, and a bromine atom 2 H' represents difluoromethoxy.
In the present invention, as a more preferable embodiment, in formula I, Z 1 、Z 2 、Z 3 、Z 4 、Z 5 Each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methanesulfonyl, or trifluoromethanesulfonyl; r is R 1 Selected from chlorine, bromine or iodine; r is R 2 Selected from difluoromethoxy; w (W) 1 And W is 2 Selected from oxygen.
In the present invention, as a particularly preferred embodiment, the amide compound is any one selected from the following compounds:
Figure BDA0003345862020000092
Figure BDA0003345862020000101
wherein the numbering of the compounds corresponds to the numbering of the compounds in table 1.
The alkyl group according to the present invention means an alkyl group in a straight-chain or branched form, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Haloalkyl refers to a group in which a hydrogen atom on the alkyl group is replaced with one or more halogen atoms. Alkoxy refers to a group having an oxygen atom attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, and the like. Haloalkoxy refers to a group in which a hydrogen atom on the alkoxy group is replaced with one or more halogen atoms. Halogen is F, cl, br or I.
The term "C" as used in the present invention 1 -C 6 Alkyl "refers to a straight or branched chain alkyl group having 1 to 6 carbon atoms and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, and the like. The term "C 1 -C 6 Alkoxy "refers to a straight or branched chain alkoxy group having 1 to 6 carbon atoms and includes, without limitation, methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy groups, and the like. "C 1 -C 6 Haloalkyl "refers to a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a halogen atom and includes, without limitation, trifluoromethyl, difluoromethyl, 1-trifluoroethyl, pentafluoroethyl, heptafluoroisopropyl and the like. "C 1 -C 6 Haloalkoxy "refers to a straight or branched chain alkoxy group of 1 to 6 carbon atoms substituted with a halogen atom and includes, without limitation, trifluoromethoxy, difluoromethoxy, 2-trifluoroethoxy, pentafluoroethoxy and the like. The term "C" as used in the present invention 3 -C 8 Cycloalkyl "refers to a cyclic alkyl group having 3 to 8 carbon atoms and includes, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The term "C" as used in the present invention 3 -C 8 Halocycloalkyl "refers to a cyclic alkyl group of 3 to 8 carbon atoms having a halogen substitution on the ring, including, without limitation, 1-chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl, and the like.
In the present invention, C before the specific group 1 -C 6 、C 3 -C 8 Etc. represent the number of carbon atoms contained in the group, e.g. C 1 -C 6 A group having 1, 2, 3, 4, 5 or 6 carbon atoms, C 3 -C 8 A group having 3, 4, 5, 6, 7 or 8 carbon atomsEtc., and so on.
In the present invention, "OCF" is used 2 H "represents difluoromethoxy group," H "represents hydrogen atom," F "represents fluorine atom," Cl "represents chlorine atom," Br "represents bromine atom," I "represents iodine atom," O "represents oxygen atom," S "represents sulfur atom," OMe "represents methoxy group," -CN "represents cyano," -NO 2 "means nitro.
The compounds of the general formula I according to the invention can be prepared by the process in which, unless otherwise indicated, the radicals are as defined above.
The preparation method 1 comprises the following steps:
the structure of the compound of the general formula I is as follows, and can be prepared by the following method:
Figure BDA0003345862020000111
wherein LG is selected from fluorine, chlorine, bromine, C 1 -C 12 Alkoxy, C 1 -C 12 Alkyloxyacyloxy or C 1 -C 12 An alkanoyloxy group; hal is selected from fluorine, chlorine, bromine or iodine; r is R 1 、R 2 、Q、W 1 、W 2 The definition of (a) is the same as above and will not be repeated here.
1- (i): the general formula compound II reacts with the general formula compound III to obtain the general formula compound IV.
Preferably, the molar ratio of the compound of formula II to the compound of formula III is from 0.5 to 2:1.
In the present invention, the reaction of step 1- (i) is carried out in the presence of a basic substance, which is an organic base and/or an inorganic base.
Preferably, the organic base is any one or a combination of at least two of triethylamine, N-diisopropylethylamine, pyridine, sodium methoxide or sodium ethoxide.
Preferably, the inorganic base is any one or a combination of at least two of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or sodium hydride.
Preferably, the solvent of the reaction of step 1- (i) is selected from any one or a combination of at least two of dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran, N-dimethylformamide or dimethyl sulfoxide.
Preferably, the reaction in step 1- (i) is carried out at a temperature of-10 ℃ or higher and not higher than the boiling point of the reaction solvent, for example, -10 ℃, 0 ℃, 10 ℃, 30 ℃, 50 ℃, 75 ℃, 90 ℃ or the like, or in a state of reflux, which is the boiling point of the solvent.
Preferably, the reaction time of step 1- (i) is from 0.5 to 48 hours.
1- (ii): hydrolyzing the compound IV to obtain a compound V.
The hydrolysis of step 1- (ii) is carried out in any one or a mixed solvent of at least two of water, methanol, ethanol, tetrahydrofuran or dioxane.
Preferably, the hydrolysis of step 1- (ii) is carried out in the presence of an alkaline substance, preferably lithium hydroxide, sodium hydroxide or potassium hydroxide.
Preferably, the basic substance is used in an amount of 1 to 5 times the molar amount of the compound of formula IV.
1- (iii): and carrying out substitution reaction on the compound V of the general formula to obtain the compound VI of the general formula.
In this step, the compound represented by the general formula VI is produced by reacting the compound V with a compound having an LG group such as thionyl chloride, oxalyl chloride or triphosgene by a known method.
1- (iv): reacting the compound VI with a compound VII to obtain a compound I.
Preferably, the molar ratio of the compound of formula VI to the compound of formula VII is from 0.5 to 2:1.
In the present invention, the reaction of step 1- (iv) is carried out in the presence of a basic substance, which is an organic base and/or an inorganic base.
Preferably, the organic base is any one or a combination of at least two of triethylamine, diisopropylethylamine, pyridine, piperidine, 4-N, N-dimethylaminopyridine, alkali metal alkoxide and lithium amide.
Preferably, the alkali metal alkoxide is sodium methoxide and/or sodium ethoxide. Preferably, the lithium amide is lithium diisopropylamide.
Preferably, the inorganic base is any one or a combination of at least two of alkali metal hydroxide, carbonate or phosphate.
Preferably, the alkali metal hydroxide is any one or a combination of at least two of lithium hydroxide, sodium hydroxide or potassium hydroxide. Preferably, the carbonate is any one or a combination of at least two of sodium bicarbonate, sodium carbonate or potassium carbonate. Preferably, the phosphate is dipotassium hydrogen phosphate and/or trisodium phosphate.
Preferably, the solvent of the reaction in step 1- (iv) is any one or a combination of at least two of halogenated hydrocarbons, aromatic hydrocarbons, chain or cyclic ethers, esters, ketones, nitriles or aprotic polar inert solvents.
Preferably, the halogenated hydrocarbon is any one or a combination of at least two of dichloromethane or chloroform. Preferably, the aromatic hydrocarbon is any one or a combination of at least two of toluene, xylene or chlorobenzene. Preferably, the chain or cyclic ether is any one or a combination of at least two of diethyl ether, tetrahydrofuran, dioxane or 1, 2-dimethoxyethane. Preferably, the ester is ethyl acetate. Preferably, the ketone is acetone. Preferably, the nitrile is acetonitrile nitrile. Preferably, the aprotic polar inert solvent is any one or a combination of at least two of 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone or N, N-dimethylacetamide.
Preferably, the temperature of the reaction in step 1- (iv) is-70 ℃ or higher and-50 ℃ or lower, for example, -10 ℃, 0 ℃, 45 ℃, 90 ℃, etc., or the reaction is carried out in a state of a solvent boiling point, i.e., reflux.
Preferably, the reaction of step 1- (iv) takes from 0.5 to 48 hours.
The preparation method 2 comprises the following steps:
the compounds of formula I of the present invention may be prepared as follows in another manner:
Figure BDA0003345862020000131
therein, Q, W 1 、W 2 、R 1 、R 2 The definitions of LG and Hal are the same as above and will not be described in detail here.
2- (i): the compound VIII of the general formula is subjected to substitution reaction to obtain the compound IX of the general formula
That is, in this step, the compound represented by the general formula IX having an LG group is produced by reacting the compound of the general formula VIII with thionyl chloride, oxalyl chloride, triphosgene or the like by a known method.
2- (ii): the compound of formula IX is reacted with the compound of formula VII to give the compound of formula X.
The compound represented by the general formula IX is reacted with the compound represented by the general formula VII under the same conditions as those described for 1- (iv), thereby producing the compound represented by the general formula X.
2- (iii): the compound X of the general formula is subjected to reduction reaction to obtain the compound XI of the general formula
The aromatic carboxylic acid amide derivative having a nitro group represented by the general formula X can be reduced to produce an aromatic carboxylic acid amide derivative having an amine group represented by the general formula XI.
The reduction reaction may be carried out by a method using hydrogenation reaction or a method using a metal compound (such as stannous chloride) or a metal (zinc powder, iron powder, or the like).
The hydrogenation reaction can be carried out in a hydrogen atmosphere in the presence of a catalyst under normal pressure or under increased pressure in a suitable solvent. The catalyst used in the hydrogenation reaction may be a palladium catalyst such as palladium-carbon, a cobalt catalyst, a ruthenium catalyst, a platinum catalyst, or the like. The solvent may be an alcohol such as methanol or ethanol; aromatic hydrocarbons such as benzene and toluene; chain or cyclic ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate.
Preferably, the hydrogenation reaction is carried out at a pressure of 0.1 to 10MPa.
Preferably, the hydrogenation reaction is carried out at a temperature of-20 ℃ or higher and not higher than the boiling point of the reaction solvent, for example, -20 ℃, 0 ℃, 15 ℃, 45 ℃, 75 ℃, etc., or in a reflux state, which is the boiling point of the solvent.
Preferably, the hydrogenation reaction time is from 0.5 to 48 hours.
Preferably, the method using a metal compound or metal is performed in any one or a mixed solvent of at least two of methanol, ethanol, or ethyl acetate.
Preferably, the metal compound is stannous chloride, and the metal is any one or a combination of at least two of zinc powder and iron powder.
Preferably, the reaction temperature of the method using a metal compound or metal is-10 ℃ or higher and equal to or lower than the boiling point of the reaction solvent, for example, -10 ℃, 20 ℃, 45 ℃, 80 ℃, etc., or the reaction is carried out in a reflux state, which is the boiling point of the solvent.
Preferably, the reaction time of the method using a metal compound or metal is 0.5 to 48 hours.
2- (iv): the compound of formula XI reacts with the compound of formula III to obtain the compound of formula I.
The compound represented by the general formula XI and the compound represented by the general formula III are reacted under the same conditions as those described in step 1- (i), and the compound represented by the general formula XII is further produced.
In another aspect, the present invention also provides an intermediate for preparing the amide compound as described above, which has a structure represented by formula XI:
Figure BDA0003345862020000141
wherein W is 2 、R 1 And R is 2 Has the same defined range as in the compounds of the general formula I and is not described in detail here.
The preparation of the intermediate compounds of formula XI in the present invention is already described above for the preparation of formula I and will not be described in detail here.
In the present invention, representative compounds of the intermediate compounds of formula XI of the compounds of the present invention are shown in Table 2, but the intermediate compounds of the present invention are not limited to the compounds shown in Table 2.
TABLE 2
Figure BDA0003345862020000142
In another aspect, the present invention provides tautomers, enantiomers, diastereomers, or salts thereof, of the amide compounds described above.
In the present invention, the tautomer, enantiomer, diastereomer or salt thereof of the amide compound can exert the same effect as the amide compound, and the insecticidal effect and the quick-acting property are good at a low dose.
On the other hand, the invention provides application of the amide compound in preventing and controlling insect pests and nematodes in the fields of agriculture, forestry and gardening.
The amide compound of the invention is suitable for preventing and controlling various agricultural and horticultural insect pests, sanitary insect pests and nematodes which harm rice, corn, wheat, potato, fruit trees, vegetables, other crops, flowers and the like.
In the present invention, the pests include lepidoptera, coleoptera, hemiptera, thysanoptera, diptera, orthoptera, homoptera, isoptera, hymenoptera, tetranychus pests and nematodes, mosquitoes, flies, ants, and the like.
Preferably, the pests include, but are not limited to: cotton bollworms, plutella xylostella, asparagus caterpillar, prodenia litura, cabbage caterpillar, chilo suppressalis, tryporyza incertulas, borer, spodoptera frugiperda, cnaphalocrocis medinalis, thrips oryzae, frankliniella occidentalis, thrips cucullata, thrips fistulosa, jiang Jima, mangifer thrips, myzus persicae, cotton aphid, alfalfa aphid, apple yellow aphid, wheat aphid, flea beetle, stink bugs, brown planthopper, white-back planthopper, termite, mosquito and fly, and spider mites such as tetranychus cinnabarinus.
The compound of the invention has wide application range, and the applied plants or ranges mainly comprise the following categories: melon, fruit and vegetable, cucumber, luffa, watermelon, melon, pumpkin, melon, spinach, celery, cabbage, cucurbit, capsicum, eggplant, tomato, onion, ginger, garlic, leek, lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato and yam; cereal, wheat, barley, maize, rice, sorghum; fruit trees, apples, pears, bananas, oranges, grapes, litchis and mangoes; flowers, peony, rose and crane; oil crops, peanuts, soybeans, rape, sunflowers and sesame; sugar crops, beet and sugarcane; other crops such as strawberry, potato, sweet potato, tobacco and tea; gardening, forestry, home hygiene, public health areas, etc.; the above-listed plants or ranges have no limitation on the range of use of the amide-based compounds of the present invention.
In another aspect, the present invention provides an insecticidal composition comprising an active ingredient and an agropharmaceutically acceptable carrier, the active ingredient being an amide compound as described above.
The compositions of the present invention may be applied in the form of a formulation in which the compound of formula I is dissolved or dispersed as the active ingredient in a carrier or formulated so as to be more readily dispersible for use as an insecticide.
In the present invention, the pesticide composition may be prepared into wettable powder, suspension, emulsion in water, emulsion in oil, etc.
The pesticide composition can be used in the fields of agriculture, forestry, sanitation and the like.
Preferably, the pesticide composition comprises 1-99% by weight of the active ingredient, for example 1%, 10%, 20%, 35%, 55%, 75%, 95% or 99%.
Preferably, the agropharmaceutically acceptable carrier comprises a surfactant.
In the present invention, the surfactant is an ionic surfactant or a nonionic surfactant.
The surfactant includes an emulsifier, a dispersant, or a wetting agent. The emulsifier may be polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty ammonia, or commercially available emulsifier (Nongru 2201B, nongru 0203B, nongru 100#, nongru 500#, nongru 600#, nongru 600-2#, nongru 1601, nongru 2201, nongru NP-10, nongru NP-15, nongru 507#, nongru OX-635, nongru OX-622, nongru OX-653, nongru OX-667, ningru 36#, etc.). The dispersing agent comprises sodium lignin sulfonate, nekal, calcium lignin sulfonate, methyl naphthalene sulfonic acid formaldehyde condensate and the like. The wetting agent comprises sodium laurylsulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, etc.
Preferably, the agropharmaceutically acceptable carrier comprises a solid carrier and/or a liquid carrier.
Preferably, the solid support comprises natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicate such as talc; magnesium aluminum silicate such as kaolinite, kaolin, montmorillonite and mica; white carbon black, calcium carbonate and light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine. The liquid carrier includes water and an organic solvent, which can also be used as an adjuvant or an anti-freezing additive when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, methylene chloride, etc.; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, propylene glycol, cyclohexanol, and the like; and their ethers and esters; also ketones, such as acetone, cyclohexanone, dimethylformamide and N-methylpyrrolidone.
The active ingredient may be mixed with the liquid carrier and/or the solid carrier during formulation of the pesticide composition, with the addition of surfactants (e.g., emulsifiers, dispersants, stabilizers, wetting agents), and optionally other adjuvants (e.g., binders, defoamers, oxidants, etc.).
In another aspect, the present invention provides a method of controlling pests, the method comprising: an effective amount of an amide compound or pesticide composition as described above is applied to the pest or medium in need of control or growth thereof.
Preferably, the effective dose is 7.5-1000g, e.g. 7.5g, 50g, 100g, 180g, 250g, 350g, 450g, 600g, 800g or 1000g per hectare, preferably 15-600g per hectare.
The composition of the present invention may be applied to the pests or their growing media in the form of a formulation. The compounds of the general formula I are dissolved or dispersed as active ingredients in carriers or formulated into preparations for easier dispersion when used as pesticides. For example: these chemicals may be formulated into various liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules or capsules.
For certain applications, such as agriculture, one or more other pesticides, fungicides, herbicides, plant growth regulators or fertilizers, etc. may be added to the pesticidal compositions of the present invention, thereby producing additional advantages and effects.
Compared with the prior art, the invention has the following beneficial effects:
The amide compound has remarkable effects on controlling pests in the fields of agriculture, forestry, diseases and insect pests, nematodes and sanitation, can achieve good insecticidal effect under low dosage, has quick response, can exert insecticidal activity after one day of application, can achieve very high insecticidal activity within 3 days, has good quick-acting property, can be applied under low dosage, reduces the damage of excessive drug concentration to plants and human beings, ensures that less drug residue is generated during application, is more beneficial to environmental protection, and has simple and high-efficiency preparation method, easy mass production and wide application prospect.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. As in the examples and the invention, not particularly illustrated: the corresponding samples of the compound, which were characterized by nuclear magnetic hydrogen spectrum testing, were all dissolved in deuterated dimethyl sulfoxide (DMSO-d 6 ) In the above, hydrogen spectrum data were obtained by testing with a 400MHz nmr, and the chemical shift unit was ppm (i.e., δ: ppm); the eluent for column chromatography purification is petroleum ether (PE for short) according to the following formula: the ethyl acetate (EA for short) is prepared by volume ratio.
Synthetic examples
Synthesis example 1
Preparation of 6-benzoylamino-N- [ 2-chloro-6- (difluoromethoxy) -4- (perfluoroprop-2-yl) phenyl ] pyridinecarboxamide (compound No. 1):
(1) Synthesis of N- [ 2-chloro-6- (difluoromethoxy) -4- (perfluoroprop-2-yl) phenyl ] -6-nitropyridine carboxamide
Figure BDA0003345862020000161
6-nitropyridine-2-carboxylic acid (1.86 g,9.96 mmol), toluene (20 mL), thionyl chloride (5.92 g,49.8 mmol) were added sequentially to the reaction flask, and the mixture was stirred at 120℃for 2 hours and concentrated under reduced pressure to give 6-nitro-2-pyridine formyl chloride.
2-chloro-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxy aniline (3.00 g,8.3 mmol) and potassium iodide (0.66 g,4.00 mmol) were added to an acetonitrile (35 mL) solution of 6-nitro-2-pyridine formyl chloride, and after heating to 99℃for 2 hours, TLC monitored the progress of the reaction. The reaction solution was cooled to room temperature, ethyl acetate (70 mL) and water (70 mL) were added to extract, and the organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=9:1) to give a reddish brown solid (2.94 g, yield 69.34%).
1 H NMR:10.65(s,1H),8.62–8.57(m,1H),8.56–8.53(m,1H),8.51(d,J＝7.60Hz,1H),7.82(s,1H),7.52(s,1H),7.39(t,J＝72.0Hz,1H).
(2) Synthesis of 6-amino-N- [ 2-chloro-6- (difluoromethoxy) -4- (perfluoroprop-2-yl) phenyl ] pyridinecarboxamide
Figure BDA0003345862020000162
N- [ 2-chloro-6- (difluoromethoxy) -4- (perfluoroprop-2-yl) phenyl ] -6-nitropyridine carboxamide (2.86 g,5.59 mmol) was dissolved in a mixed solvent of ethanol (30 mL) and water (30 mL), iron powder (3.12 g,55.89 mmol) and ammonium chloride (2.99 g,55.89 mmol) were added with stirring, and after heating to 99℃for 2 hours, TLC monitored the progress of the reaction. The reaction solution was cooled to room temperature, filtered and the mother liquor was dried by spinning. Ethyl acetate (70 mL), water (70 mL) were added to extract, the organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=6:1) to give a yellow solid (2.53 g, yield 93.70%).
1 H NMR:10.05(s,1H),7.79(d,J＝1.6Hz,1H),7.60(dd,J＝8.4,7.2Hz,1H),7.49(s,1H),7.34(t,J＝72.0Hz,1H),7.28–7.23(m,1H),6.81–6.67(m,1H),6.23(s,2H).
(3) Synthesis of 6-benzoylamino-N- [ 2-chloro-6- (difluoromethoxy) -4- (perfluoroprop-2-yl) phenyl ] pyridinecarboxamide
Figure BDA0003345862020000163
Benzoic acid (0.06 g,0.50 mmol), toluene (8 mL), thionyl chloride (0.30 g,2.5 mmol) were added sequentially to the reaction flask, and the mixture was stirred at 120℃for 2 hours and concentrated under reduced pressure to give benzoyl chloride.
6-amino-N- [ 2-chloro-6- (difluoromethoxy) -4- (perfluoroprop-2-yl) phenyl ] pyridinecarboxamide (0.2 g,0.42 mmol) and potassium iodide (0.03 g,0.20 mmol) were added to a solution of benzoyl chloride in acetonitrile (4 mL), and after heating to 99℃for 2 hours, TLC monitored the progress of the reaction. The reaction solution was cooled to room temperature, ethyl acetate (20 mL), water (20 mL) and the organic layer was then extracted, separated, and the residue was purified by column chromatography (PE: ea=4:1) to give a white solid (0.29 g, yield 95.69%).
1 H NMR：10.63(s,1H),10.30(s,1H),8.40(d,J＝8.0Hz,1H),8.05(d,J＝7.2Hz,2H),7.96–7.95(m,1H),7.94–7.93(m,1H),7.88(d,J＝7.2Hz,1H),7.84(s,1H),7.57(s,1H),7.54(s,1H),7.50(s,1H),7.40(t,J＝72.0Hz,1H).
Some of the compounds in Table 3 were prepared by a similar method to that in Synthesis example 1, and the nuclear magnetic data of some of the compounds synthesized by Synthesis example 1 are shown in Table 3 below.
TABLE 3 Table 3
Figure BDA0003345862020000171
Synthesis example 2
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -6- (4-cyano-2-methylbenzamide) pyridine amide (Compound No. 123):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -6-nitropyridine amide
Figure BDA0003345862020000172
6-nitropicolinic acid (3.36 g,20.00 mmol) and toluene (15 mL) were added sequentially to the flask, thionyl chloride (8.57 g,72.0 mmol) was reacted under reflux with stirring for 2h, and concentrated under reduced pressure to give 6-nitrobenzoyl chloride. 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxy aniline (6.77 g,16.67 mmol), potassium iodide (1.38 g,8.34 mmol) and 30mL acetonitrile were added to 6-nitrobenzoyl chloride, the reaction solution was cooled to room temperature after reacting for 4 hours at 84℃and 80mL of ethyl acetate and 40mL of water were added, extraction and separation were performed, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue was purified by column chromatography (PE: EA=6:1) to give the objective product (8.20 g, yield 88.5%).
1 H NMR：10.66(s,1H),8.62～8.57(m,1H),8.56～8.47(m,2H),7.92(s,1H),7.55(s,1H),7.38(t,J＝72.8Hz,1H).
(2) Synthesis of 6-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] pyridine amide
Figure BDA0003345862020000181
N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -6-nitropyridine amide (11.2 g,20 mmol) was dissolved in ethanol (40 mL) and water (40 mL), followed by addition of ammonium chloride (10.70 g,200 mmol) and iron powder (11.17 g,200 mmol), and heated under reflux for 5h. TLC monitored the end of the reaction, the reaction solution was desolventized under reduced pressure to remove ethanol, followed by suction filtration, addition of 80mL of ethyl acetate, 40mL of water, extraction, separation of the liquid, washing of the organic layer with saturated brine, drying over anhydrous sodium sulfate, concentration under reduced pressure, purification of the residue by column chromatography (PE: EA=4:1) gave the desired product (9.10 g, yield 86.5%).
1 H NMR：10.20(s,1H),7.89(s,1H),7.53(s,1H),7.32(t,J＝72.0Hz,1H),7.03–6.89(m,2H),6.80(t,J＝6.8Hz,1H),5.39(s,2H)。
(3) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -6- (4-cyano-2-methylbenzamide) pyridine amide
Figure BDA0003345862020000182
To a solution of 6-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] pyridine amide (0.17 g,0.32 mmol) in acetonitrile (5 mL) was added potassium iodide (27 mg,0.16 mmol), 2-methyl-4-cyanobenzoyl chloride (70 mg,0.39 mmol) and the mixture was reacted at 80℃for 4 hours. The reaction mixture was cooled to room temperature, diluted with 40mL of ethyl acetate, washed successively with 2M hydrochloric acid (5 mL), saturated aqueous sodium hydrogencarbonate (30 mL) and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=3:1) to give the objective product (0.15 g, yield 69.4%).
Compound 123 1 H NMR：11.11(s,1H),10.04(s,1H),8.40(s,1H),8.15(t,J＝8.0Hz,1H),7.92(s,1H),7.90(d,J＝7.2Hz,1H),7.85(s,1H),7.81(d,J＝8.0Hz,1H),7.73(d,J＝8.0Hz,1H),7.56(s,1H),7.38(t,J＝72.8Hz,1H)
Some of the compounds in Table 4 were prepared by a similar method to that in Synthesis example 2, and the nuclear magnetic data of some of the compounds synthesized by Synthesis example 2 are shown in Table 4 below.
TABLE 4 Table 4
Figure BDA0003345862020000183
Figure BDA0003345862020000191
Synthesis example 3
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -6- [ 5-fluoro-picolinamido ] -picolinamide (compound No. 167:
Figure BDA0003345862020000192
to a solution of 6-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] pyridine carboxamide (0.17 g,0.32 mmol) in acetonitrile (5 mL) was added 5-fluoropyridine formyl chloride (62 mg,0.39 mmol), potassium iodide (27 mg,0.16 mmol) and reacted at 85℃for 2 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, diluted with 20mL of ethyl acetate, washed with saturated aqueous sodium hydrogencarbonate (30 mL) and saturated brine in this order, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=4:1) to give the desired product (0.19 g, yield 90.10%).
Compound 167 1 H NMR：10.80(s,1H),10.31(s,1H),8.60–8.53(m,1H),8.36–8.30(m,1H),8.23–8.15(m,2H),7.94–7.91(m,2H),7.61–7.56(m,2H),7.37(t,J＝72.8Hz,1H).
The partial compounds in table 5 were prepared by a similar method to that in synthesis example 3, and the nuclear magnetic data of the partial compounds synthesized by reference to synthesis example 3 are given in table 5 below.
TABLE 5
Figure BDA0003345862020000201
Synthesis example 4
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -6-nicotinamide pyridinamide (Compound No. 142):
Figure BDA0003345862020000202
in 6-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl]To a solution of picolinamide (0.18 g,0.34 mmol) in acetonitrile (5 mL) was added potassium iodide (28.4 mg,0.17 mmol) and nicotinyl chloride (58.1 mg,0.41 mmol) in this order, and the mixture was reacted at 80℃for 4 hours. The reaction mixture was cooled to room temperature, diluted with 40mL of ethyl acetate, washed successively with 2M hydrochloric acid (5 mL), saturated aqueous sodium hydrogencarbonate (30 mL) and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=2:1) to give the objective product (0.21 g, yield 96.73%). Compound 142 1 H NMR：10.99(s,1H),10.20(s,1H),9.19(d,J＝1.6Hz,1H),8.81(dd,J＝4.8,1.6Hz,1H),8.41～8.36(m,2H),8.16(t,J＝8.0Hz,1H),7.94(d,J＝1.6Hz,1H),7.91(dd,J＝7.6,0.8Hz,1H),7.63～7.59(m,1H),7.57(s,1H),7.39(t,J＝72.8Hz,1H).
The partial compounds in table 6 were prepared by a similar method to that in synthesis example 4, and the nuclear magnetic data of the partial compounds synthesized by reference to synthesis example 4 are given in table 6 below.
TABLE 6
Figure BDA0003345862020000203
Figure BDA0003345862020000211
Synthesis example 5
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -6-isonicotinamide pyridine amide (Compound No. 146):
Figure BDA0003345862020000212
In 6-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl]To a solution of picolinamide (0.18 g,0.34 mmol) in acetonitrile (5 mL) was added potassium iodide (28.4 mg,0.17 mmol) followed by isonicotinyl chloride (58.1 mg,0.41 mmol) and reacted at 80℃for 4 hours. The reaction mixture was cooled to room temperature, diluted with 40mL of ethyl acetate, washed successively with 2M hydrochloric acid (5 mL), saturated aqueous sodium hydrogencarbonate (30 mL) and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=2:1) to give the objective product (0.16 g, yield 74.09%). Compound 146 1 H NMR：11.03(s,1H),10.20(s,1H),8.83(dd,J＝4.4,1.6Hz,2H),8.38(dd,J＝8.4,0.8Hz,1H),8.26～8.11(m,1H),7.96～7.90(m,4H),7.57(s,1H),7.39(t,J＝72.8Hz,1H).
The partial compounds in table 7 were prepared by a similar method to that in synthesis example 5, and the nuclear magnetic data of the partial compounds synthesized by reference to synthesis example 5 are given in table 7 below.
TABLE 7
Figure BDA0003345862020000213
Synthesis example 6
Preparation of N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6- [4- (methylsulfonyl) -benzamide ] pyridine amide (Compound No. 193):
(1) Synthesis of N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6-nitropyridine amide
Figure BDA0003345862020000214
6-nitro-2-pyridinecarboxylic acid (3.60 g,21.41 mmol), toluene (30 mL), thionyl chloride (10.19 g,85.66 mmol) were added sequentially to the reaction flask, and the mixture was stirred under reflux for 2 hours and concentrated under reduced pressure to give 6-nitropyridine acid chloride. Acetonitrile (80 mL), potassium iodide (1.17 g,7.06 mmol), 2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) aniline (8.00 g,17.76 mmol) were added to 6-nitropyridine acyl chloride, the temperature was raised to 90℃for 2 hours, the reaction solution was cooled to room temperature, 100mL of ethyl acetate and 50mL of water were added, extraction and separation were performed, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue was purified by column chromatography (PE: EA=5:1) to give the desired product (10.0 g, yield 93.90%).
1 H NMR:10.61(s,1H),8.60(dd,J＝7.6,1.2Hz,1H),8.57-8.47(m,2H),8.03(s,1H),7.53(s,1H),7.33(t,J＝72.6Hz,1H).
(2) Synthesis of 6-amino-N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6-nitropyridine amide
Figure BDA0003345862020000221
N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6-nitropyridine amide (10.0 g,16.58 mmol) was dissolved in ethanol (100 mL), concentrated hydrochloric acid (10 mL) and stannous chloride dihydrate (16.83 g,74.61 mmol) were added sequentially, and the mixture was heated under reflux for 3h. TLC monitored the reaction to completion, the reaction was evaporated to near dryness under reduced pressure, the pH of the residue was adjusted to 12 with 10% aqueous sodium hydroxide solution, extracted with ethyl acetate (200 mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=5:1) to give 8.42g of yellow oil in 84.21% yield.
1 H NMR：9.98(s,1H),7.98(d,J＝4.0Hz,1H),7.66-7.56(m,1H),7.50(s,1H),7.27(t J＝72.6Hz,1H),7.26(dd,J＝7.2,0.8Hz,1H),6.81-6.66(m,1H),6.23(s,2H).
(3) Synthesis of N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6- [4- (methylsulfonyl) -benzamide ] pyridine amide
Figure BDA0003345862020000222
To a solution of 6-amino-N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6-nitropyridine amide (0.2 g,0.35 mmol) in acetonitrile (5 mL) was added potassium iodide (23.17 mg,0.14 mmol) and 4- (methylsulfonyl) benzoyl chloride (91.56 mg,0.42 mmol) in this order, followed by reaction at 90℃for 2 hours. TLC monitored the end of the reaction, the reaction solution was evaporated to near dryness under reduced pressure and cooled to room temperature, diluted with 20mL of ethyl acetate, washed successively with saturated aqueous sodium hydrogencarbonate (20 mL) and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: EA=4:1) to give the objective product (0.16 g, yield 60.70%).
Compound 193 1 H NMR：11.01(s,1H),10.15(s,1H),8.41(d,J＝8.4Hz,1H),8.26(d,J＝1.6Hz,1H),8.25(d,J＝1.6Hz,1H),8.19-8.14(m,1H),8.13(d,J＝1.6Hz,1H),8.11(s,1H),8.05(s,1H),7.92(dd,J＝7.6,0.8Hz,1H),7.55(s,1H),7.35(t,J＝72.6Hz,1H),3.31(s,3H)。
The partial compounds in table 8 were prepared by a similar method to that in synthesis example 6, and the nuclear magnetic data of the partial compounds synthesized by reference to synthesis example 6 are given in table 8 below.
TABLE 8
Figure BDA0003345862020000223
Figure BDA0003345862020000231
Synthesis example 7
Preparation of N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6- (nicotinamide) pyridine amide (Compound No. 230):
Figure BDA0003345862020000232
to a solution of 6-amino-N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6-nitropyridine amide (0.2 g,0.35 mmol) in acetonitrile (5 mL) was added potassium iodide (23.17 mg,0.14 mmol), nicotinyl chloride (59.27 mg,0.42 mmol) in this order, and the mixture was reacted at 90℃for 2 hours. TLC monitored the end of the reaction, the reaction solution was evaporated to near dryness under reduced pressure and cooled to room temperature, diluted with 20mL of ethyl acetate, washed successively with saturated aqueous sodium hydrogencarbonate (20 mL) and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: EA=4:1) to give the objective product (0.21 g, yield 88.31%).
Compound 230 1 H NMR：10.99(s,1H),10.14(s,1H),9.19(d,J＝1.6Hz,1H),8.80(dd,J＝4.8,1.6Hz,1H),8.41-8.36(m,2H),8.16(t,J＝8.0Hz,1H),8.05(d,J＝1.2Hz,1H),7.92(dd,J＝7.6,0.8Hz,1H),7.62-7.59(m,1H),7.55(s,1H),7.32(t,J＝72.6Hz,1H)。
The partial compounds in table 9 were prepared by a similar method to that in synthesis example 7, and the nuclear magnetic data of the partial compounds synthesized by reference to synthesis example 7 are given in table 9 below.
TABLE 9
Figure BDA0003345862020000233
Synthesis example 8
Preparation of N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6- (isonicotinamide) pyridine amide (Compound No. 233):
Figure BDA0003345862020000241
to a solution of 6-amino-N- [2- (difluoromethoxy) -6-iodo-4- (1, 2, 3-heptafluoroprop-2-yl) phenyl ] -6-nitropyridine amide (0.2 g,0.35 mmol) in acetonitrile (5 mL) was added potassium iodide (23.17 mg,0.14 mmol), isonicotinyl chloride (59.27 mg,0.42 mmol) and the mixture was reacted at 90℃for 2 hours. TLC monitored the end of the reaction, the reaction solution was evaporated to near dryness under reduced pressure and cooled to room temperature, diluted with 20mL of ethyl acetate, washed successively with saturated aqueous sodium hydrogencarbonate (20 mL) and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: EA=4:1) to give the objective product (0.14 g, yield 59.15%).
Compound 233 1 H NMR：11.03(s,1H),10.14(s,1H),8.83(d,J＝6.0Hz,2H),8.39(dd,J＝8.4,0.8Hz,1H),8.17(t,J＝8.0Hz,1H),8.04(d,J＝1.2Hz,1H),7.94-7.92(m,3H),7.55(s,1H),7.34(t,J＝72.6Hz,1H)。
Some of the compounds in Table 10 were prepared in a similar manner as in Synthesis example 8, and the nuclear magnetic data of some of the compounds synthesized in Synthesis example 8 are shown in Table 10 below.
Table 10
Figure BDA0003345862020000242
Other compounds of formula I of the present invention may be synthesized by reference to the methods described above.
Formulation example 1
In this example, a formulation was prepared using compound 1 of the present invention as a representative compound, specifically as follows:
30 parts by weight of the compound 1 of the present invention, 15 parts by weight of polyoxyethylene styrylphenyl ether, 10 parts by weight of phosphorous acid, and 45 parts by weight of xylene were uniformly mixed to obtain an emulsifiable concentrate of the compound 1 of the present invention having a concentration of 30%.
Formulation example 2
In this example, a formulation was prepared using the present compound 86 as a representative compound, specifically as follows:
20 parts by weight of the compound 86 of the present invention, 2 parts by weight of sodium dodecyl sulfate, 2 parts by weight of dialkyl sulfosuccinate, 1 part by weight of sodium salt of a formaldehyde condensate of beta-naphthalene sulfonic acid, 75 parts by weight of diatomaceous earth were uniformly stirred and mixed to obtain 20% wettable powder of the compound 86 of the present invention.
Formulation example 3
In this example, a formulation was prepared using the present compound 156 as a representative compound, as follows:
30 parts by weight of the compound 156 of the present invention, 10 parts by weight of ethylene glycol, 6 parts by weight of nonylphenol polyethylene glycol ether, 10 parts by weight of sodium lignin sulfonate, 10 parts by weight of carboxymethyl cellulose, 1 part by weight of a silicone oil aqueous solution, and water were supplemented to 100 parts by weight to obtain a 30% suspension of the compound 156 of the present invention.
Biological Activity test examples
A variety of pests were tested using the compounds of the present invention obtained as described above. As in the examples and the invention, not particularly illustrated: the sample preparation method is to weigh 10mg of the original drug of the sample to be detected, dissolve the original drug with 1mL of DMF to prepare 10000ppm of mother liquor, and dilute the mother liquor to the required concentration with 0.05% Tween-80 water for activity test. Mortality is the mortality rate that leads to pest death at the compound test concentration, and the formula is mortality rate (%) = dead number/total number of insects 100.
Test of insecticidal Activity of the Compounds of example 1 against armyworm
Activity testing was performed using a corn steep seedling feeding method. And cutting off the overground part of the fresh corn seedlings planted indoors, wherein the overground part is about 10cm for standby. Soaking corn seedling in the liquid medicine for 10s, airing in shade, cutting into 3-5 cm leaf segments, placing in culture dishes, and placing 3 leaf segments in each dish. 10 larvae of myxoplasma 3 years are inoculated into each dish, and the process is repeated for 3 times. Placing in an illumination incubator at 25 ℃, and culturing by illumination of 14hL to 10 hD. The number of dead insects was investigated 1, 2 and 3 days after the drug, and the mortality was calculated.
The mortality of the compounds 1, 6, 39, 61, 63, 69, 85, 86, 90, 91, 101, 107, 110, 123, 129, 142, 146, 152, 153, 182 and 239 of the invention on myxoma after 3 days of medicine is more than or equal to 90% at the concentration of 1 ppm.
According to the above method, selected compounds 61, 69, 85, 86, 90, 123, 129, 153, 182 and KC1, KC2 were tested in parallel for the insecticidal activity of myxoworm, respectively, to compare the insecticidal activity with the insecticidal quick-acting property. The test results are shown in Table 11.
Table 11: comparison of insecticidal Activity and quick-acting Properties of Compounds 61 and the like of the present invention with KC1 and KC2 against myxoworm
Figure BDA0003345862020000251
As can be seen from Table 11, the compounds of the present invention have better quick-acting properties and high insecticidal activity at lower doses than the existing compounds.
Measurement example 2Indoor bioactivity of compound on tetranychus cinnabarinus
Cutting off single leaf of broad bean with stem, inserting into penicillin bottle filled with 20mL clear water, and inoculating about 20 adult mites of Tetranychus cinnabarinus on each leaf. After 24 hours, the mite-forming base was checked and more than 15 mites were selected for the test. Immersing the single leaf with the mites into the liquid medicine for 10s, taking out, airing, placing in a viewing chamber for culturing at 20-26 ℃ under the illumination of 14hL to 10hD and the humidity of 40-60%. The number of dead mites was investigated 3d after the drug, and the mortality was calculated.
The test results were as follows:
the mortality of the compounds 6, 39, 60, 61, 69, 85, 86, 91, 101, 106, 110, 123, 129, 133, 135, 136, 142, 146, 152, 155, 156, 160, 161, 162, 182, 193, 215, 218, 221, 223, 224, 230, 233, 239, 242, 243, 247, 248, 249 of the invention after the use for tetranychus cinnabarinus is more than or equal to 90 percent in 3 days at the concentration of 100 ppm.
The mortality of the compounds 39, 86, 101, 123, 129, 133, 136, 146, 156, 162, 193, 215, 218, 221, 224, 233 and 243 of the invention on tetranychus cinnabarinus after the medicament is 3 days is more than or equal to 90 percent when the concentration is 10 ppm.
According to the above method, the selected compounds 39, 86, 123, 129, 136, 146, 218, 224, 243 and KC1, KC2 were assayed in parallel for tetranychus cinnabarinus activity. The test results are shown in Table 12.
TABLE 12 comparison of the Activity of Compound 39 and the like of the present invention against Tetranychus cinnabarinus with KC1, KC2
Figure BDA0003345862020000261
As can be seen from table 12, the compounds of the present invention have the advantage of exerting better insecticidal effects at lower doses than the existing compounds.
Measurement example 3Insecticidal activity of compound against plutella xylostella
Activity testing was performed using a leaf dipping dish feeding method. Immersing leaf discs in the liquid medicine for 10s, airing, placing the leaf discs in culture dishes, 4 discs in each dish, and placing filter paper in the culture dishes for moisturizing. And (5) inoculating 10 heads of plutella xylostella insects on each dish, and repeating for 3 times. Placing in an illumination incubator at 25 ℃, and culturing by illumination of 14hL to 10 hD. The death rate was calculated by investigating the number of plutella xylostella dead insects 1, 2 and 3 days after the administration.
The test results were as follows:
the mortality rate of the compounds 6, 61, 63, 68, 69, 85, 86, 90, 101, 110, 129, 152, 153, 155, 156, 160, 161, 162, 182, 193, 202, 218, 224, 239, 242, 243, 247, 248, 249 on plutella xylostella is more than or equal to 90% in 3 days after the drug is at the concentration of 1 ppm.
According to the above method, the selected compounds 86, 90, 153, 202, 218, 243, 248 were subjected to parallel measurement and quick-acting comparison of the insecticidal activity of plutella xylostella with KC1, KC 2. The test results are shown in Table 13.
TABLE 13 comparison of insecticidal Activity and quick-acting Properties of Compound 86 and the like of the present invention with KC1 and KC2 against plutella xylostella
Figure BDA0003345862020000262
As can be seen from Table 13, the compounds of the present invention have better quick-acting properties and high insecticidal activity at lower doses than the existing compounds.
Test example 4Insecticidal activity of compounds against Aphis Medicago
Preparation of 3-day-old Ruo aphid: the broad bean single leaf with stem is cut and inserted into a penicillin bottle (the capacity is 20 mL) filled with clean water. And 5, inoculating the Aphis medicata to each single leaf to form an Aphis medicata, and covering a plastic cup with a pricked hole. And removing the grown aphids after 24 hours. Before the test, the cardinality is investigated, and single leaves with the number of aphids being more than 15 are selected for the test.
The insect immersing method comprises the following steps: soaking single leaf of Aphis citrifolia in the medicinal liquid for 10s, taking out, air drying, and repeating for 3 times. Placing on a culture rack of an observation chamber, covering a plastic cup with a hole, and culturing at 20-25deg.C under the illumination of 14 hL:10hD. The death rate was calculated by investigating the number of dead and alive insects after 3 days.
The death rate of the compound 85, 142, 146, 152, 153, 182, 230, 239 to the Aphis medicago sativa is more than or equal to 80% 3 days after the drug is taken at the concentration of 100 ppm.
The death rate of the compound 142 to the alfalfa aphid is more than or equal to 90 percent 3 days after the compound is used at the concentration of 10 ppm.
According to the method, the insecticidal activity of the alfalfa aphids is measured in parallel by selecting the compounds 142, 230 and 239 and KC1 and KC 2. The test results are shown in Table 14.
TABLE 14 comparison of insecticidal Activity of Compounds 142 and the like of the invention with KC1, KC2 against Aphis Medicago
Medicament Concentration of Mortality (%), 3 days after drug administration
142 100ppm 100.00
230 100ppm 100.00
239 100ppm 100.00
KC1 100ppm 0.00
KC2 100ppm 0.00
As can be seen from table 14, the compounds of the present invention have the advantage of exerting better insecticidal effects at lower doses than the existing compounds.
The present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e., it is not meant to be limited to the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. An amide compound is characterized by having a structure shown in the following formula I:
Figure FDA0003345862010000011
in the formula I, the compound (I),
q is selected from one of the following Q1, Q2, Q3 or Q4:
Figure FDA0003345862010000012
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C 1 -C 6 Alkyl, C 3 -C 8 Cycloalkyl, C 1 -C 6 Haloalkyl, C 3 -C 8 Halogenated cycloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylsulfinyl, C 1 -C 6 Haloalkyl sulfinyl, C 1 -C 6 Alkylsulfonyl or C 1 -C 6 A haloalkylsulfonyl group;
R 1 selected from halogen;
R 2 selected from difluoromethoxy;
W 1 and W is 2 Independently an oxygen atom or a sulfur atom.
2. The amide compound according to claim 1, wherein in the formula I,
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 each independently selected from hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylsulfinyl, trifluoromethylsulfonyl or trifluoromethylsulfonyl; r is R 1 Selected from chlorine, bromine or iodine; r is R 2 Selected from difluoromethoxy.
3. The amide compound according to claim 1, wherein in the formula I,
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methanesulfonyl, or trifluoromethanesulfonyl; r is R 1 Selected from chlorine, bromine or iodine; r is R 2 Selected from difluoromethoxy; w (W) 1 And W is 2 Selected from oxygen.
4. An amide compound according to any one of claims 1 to 3, wherein the amide compound is any one selected from the group consisting of:
Figure FDA0003345862010000013
Figure FDA0003345862010000021
5. the tautomer, enantiomer, diastereomer or salt thereof of an amide-based compound according to any one of claims 1 to 4.
6. An intermediate compound for preparing the amide compound according to any one of claims 1 to 5, which has a structure represented by the following formula XI:
Figure FDA0003345862010000022
in formula XI, R 1 Selected from halogen; r is R 2 Selected from difluoromethoxy.
7. Use of an amide compound according to any one of claims 1-4 or a tautomer, enantiomer, diastereomer or salt thereof of an amide compound according to claim 5 for controlling plant pests.
8. An insecticidal composition comprising an active ingredient which is an amide compound according to any one of claims 1 to 4 or a tautomer, enantiomer, diastereomer or salt thereof of an amide compound according to claim 5 and an agropharmaceutically acceptable carrier.
9. A pesticide composition according to claim 8, wherein the pesticide composition contains 1 to 99% by weight of active ingredient.
10. A method of controlling pests, the method comprising: applying an effective dose of an amide compound according to any one of claims 1 to 4 or a tautomer, enantiomer, diastereomer or salt thereof of an amide compound according to claim 5 or an insecticidal composition according to claim 8 or 9 to a medium in need of control of pests or their growth;
preferably, the effective dose is 7.5-1000g per hectare, preferably 15-600g per hectare.
CN202111322038.7A 2021-11-09 2021-11-09 Amide compound and preparation method and application thereof Pending CN116102493A (en)

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