CN116924952A - Sulfur-containing amide compound and preparation method and application thereof - Google Patents

Sulfur-containing amide compound and preparation method and application thereof Download PDF

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CN116924952A
CN116924952A CN202310432603.8A CN202310432603A CN116924952A CN 116924952 A CN116924952 A CN 116924952A CN 202310432603 A CN202310432603 A CN 202310432603A CN 116924952 A CN116924952 A CN 116924952A
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groups
compound
sulfur
hydrogen
containing amide
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刘吉永
丁福栋
刘民华
庄彩霞
刘祥威
周丽琪
邓远航
肖坦
龙欢媛
相君成
吕亮
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Cac Nantong Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/40—Y being a hydrogen or a carbon atom
    • C07C323/42—Y being a carbon atom of a six-membered aromatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00—Botany in general
    • A01G7/06—Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
    • C07C317/40—Y being a hydrogen or a carbon atom
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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  • Pest Control & Pesticides (AREA)
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  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Insects & Arthropods (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a sulfur-containing amide compound, a preparation method and application thereof, wherein the amide compound has a structure shown in a formula I. The sulfur-containing 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

Sulfur-containing amide compound and preparation method and application thereof
Technical Field
The invention belongs to the field of pesticides, and particularly relates to a sulfur-containing 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, CN101203484a discloses compound KC2 (i.e., compounds 1-425 in CN101203484 a) and its insecticidal activity. CN101367748A discloses compound KC3 (i.e. compound 203 in CN 101367748A), compound KC4 (i.e. compound 207 in CN 101367748A) and their insecticidal activity. . CN109497062a discloses amide compound KC1 (compound 62 in the invention) having cyclopropylmethyl group and insecticidal activity thereof against pests such as plutella xylostella, chilo suppressalis and the like, but the acaricidal activity of such compound is not disclosed in the invention.
There is still a need in the art to actively develop pesticides that have high insecticidal activity at low doses and a broader spectrum of insecticidal activity, which are environmentally safe, to meet the needs of agriculture and the woody industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a sulfur-containing amide compound and a preparation method and application thereof, in particular to an alkylthio, alkylsulfinyl and alkylsulfonyl-containing compound and a preparation method and application thereof, wherein the amide compound has good insecticidal effect at low dosage, good acaricidal activity and low dosage, not only reduces the medication cost, but also is more beneficial to environmental protection.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a sulfur-containing amide compound having a structure represented by formula I:
in the formula I, the compound (I),
q is selected from the group consisting of Q 1 、Q 2 、Q 3 Or Q 4 Is one of:
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 are independently selected from hydrogen, halogen atom, cyano, nitro and 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 C 3 -C 8 Cycloalkyl alkyl;
R 2 selected from hydrogen, fluorine or methoxy;
R 3 selected from C 1 -C 4 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 3 -C 8 Cycloalkyl, C 1 -C 4 Haloalkyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Haloalkynyl or C 3 -C 8 Halogenated cycloalkyl;
Y 1 selected from hydrogen, halogen atoms, C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group;
x are identical or different and are selected from hydrogen, halogen atoms, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy or cyano;
W 1 and W is 2 Independently an oxygen atom or a sulfur atom;
m represents an integer of 0 to 4;
n represents an integer of 0 to 2.
The sulfur-containing 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 invention, in the formula I, Z is as a preferable mode 1 、Z 2 、Z 3 、Z 4 、Z 5 Independently selected from hydrogen, halogen atom, cyano group, nitro group, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, t-butyl group, isobutyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-dimethylpropyl group, 1, 2-dimethylpropyl group, 2-dimethylpropyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, t-butoxy group, trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro-isopropyl group, difluoromethoxy group, trifluoromethoxy group, pentafluoroethoxy group, methylsulfinyl group, trifluoromethylsulfonyl group or trifluoromethylsulfonyl group; r is R 1 Selected from cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl; r is R 3 Selected from C 1 -C 4 Alkyl, C 3 -C 8 Cycloalkyl, C 1 -C 4 Haloalkyl or C 3 -C 8 Halogenated cycloalkyl; y is Y 1 Selected from halogen atoms; x are the same or different and are selected from hydrogen, halogen atoms or cyano groups.
As a further preferable embodiment of the present invention, the sulfur-containing amide compound is any one of the compounds shown in the following tables 1 to 4 having the general formula I.
TABLE 1
TABLE 2
TABLE 3 Table 3
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TABLE 4 Table 4
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"H" represents a hydrogen atom, "O" represents an oxygen atom, "S" represents a sulfur atom, "F" represents a fluorine atom, "and" O "represents a sulfur atom"Cl "represents chlorine atom," Br "represents bromine atom," I "represents iodine atom," Me "represents methyl," Et "represents ethyl," MeO "represents methoxy," n-Pr "represents n-propyl," I-Pr "represents isopropyl," t-Bu "represents tert-butyl," CH 2 CF 3 "represents 2, 2-trifluoroethyl.
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 cyclopropylmethyl or cyclobutylmethyl; r is R 2 Selected from fluorine; r is R 3 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or 2, 2-trifluoroethyl; y is Y 1 Selected from chlorine, bromine, iodine; x is the same or different and is selected from hydrogen, fluorine, chlorine, bromine or iodine; w (W) 1 And W is 2 Selected from oxygen.
In the present invention, as a particularly preferred embodiment, the sulfur-containing amide compound is any one selected from the following compounds:
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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, t-butyl, 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, 2-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 Groups representing the number of carbon atoms which may be 3, 4, 5, 6, 7 or 8, and the like.
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:
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; l is selected from chlorine, bromine, iodine, C 1 -C 6 Alkyl sulfonate groups.
1- (i): the compound of the general formula III reacts with the compound of the general formula IV to obtain the compound of the general formula V.
In the present invention, the molar ratio of the compound of formula III to the compound of formula IV in step 1- (i) is 0.5-2:1, the reaction being carried out in the presence of a basic substance such as 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. The temperature of the reaction is equal to or higher than room temperature and equal to or lower than the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.
1- (ii): the compound of formula V reacts with the compound of formula VI to obtain the compound of formula VII.
In the present invention, the molar ratio of the compound of formula V to the compound of formula VI in step 1- (ii) is 0.5-2:1, and the reaction is carried out in the presence of a basic substance such as 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. The temperature of the reaction is more than or equal to minus 10 ℃ and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.
1- (iii): hydrolyzing the compound of formula VII to obtain the compound of formula VIII.
Step 1- (iii) the compound of the general formula VII is hydrolyzed in the presence of alkaline substances to prepare the compound of the general formula VIII. Preferably, the alkaline substance is 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 VII.
1- (iv): and carrying out substitution reaction on the compound of the general formula VIII to obtain the compound of the general formula II.
In this step, the compound represented by the general formula II is produced by reacting the compound of the general formula VIII with a compound having an LG group such as thionyl chloride, oxalyl chloride or triphosgene, etc., by a known method.
1- (v): reacting a compound of formula II with a compound of formula IX to give a compound of formula I
In the present invention, the molar ratio of the compound of formula II to the compound of formula IX is from 0.5 to 2:1, the reaction being 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.
The solvent for the reaction in the step 1- (v) is any one or a combination of at least two of halohydrocarbons, aromatic hydrocarbons, chain or cyclic ethers, esters, ketones, nitriles or aprotic polar inert solvents. The reaction temperature is-70 ℃ or higher and is less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 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:
2- (i): the compound of the general formula X is subjected to substitution reaction to obtain the compound of the general formula XI
That is, in this step, the compound represented by the general formula XI containing the LG group is produced by reacting the compound represented by the general formula X with thionyl chloride, oxalyl chloride, triphosgene or the like by a known method.
2- (ii): the compound of formula XI is reacted with a compound of formula IX to give a compound of formula XII.
The compound represented by the general formula XI was reacted with the compound represented by the general formula IX under the same conditions as those described for 1- (v), to thereby prepare the compound represented by the general formula XII.
2- (iii): the compound of the general formula XII is subjected to reduction reaction to obtain the compound of the general formula XIII
The aromatic carboxylic acid amide derivative having a nitro group represented by the general formula XII can be reduced to produce an aromatic carboxylic acid amide derivative having an amine group represented by the general formula XIII. 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 0.1-10MPa and a temperature of-20deg.C or higher and equal to or lower than the boiling point of the reaction solvent for 0.5-48 hours.
The method using a metal compound or a 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 is equal to or lower than the boiling point of the reaction 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 XIII is reacted with a compound of formula IV to give a compound of formula XIV.
The compound represented by the general formula XIII is reacted with the compound represented by the general formula IV under the same conditions as those described in step 1- (i), thereby producing the compound represented by the general formula XII.
2- (v): the compound of formula XIV is reacted with a compound of formula VI to give a compound of formula I.
The compound represented by the general formula XIV is reacted with the compound represented by the general formula VI under the same conditions as those described in step 1- (ii), thereby producing the compound represented by the general formula XII.
The preparation method comprises the following steps:
the compounds of formula I of the present invention can be prepared as follows:
3- (i): the compound of the general formula X is subjected to substitution reaction to obtain the compound of the general formula XI
The compound represented by the general formula X is reacted with the compound represented by the general formula XI under the same conditions as those described for 2- (i), thereby producing the compound represented by the general formula XI.
3- (ii): the compound of formula XI is reacted with a compound of formula IX to give a compound of formula XII.
The compound represented by the formula XI and the compound represented by the formula IX are reacted under the same conditions as those described for 1- (v), thereby producing the compound represented by the formula XII.
3- (iii): the compound of the general formula XII is subjected to reduction reaction to obtain the compound of the general formula XIII
The compound represented by the general formula XII is reacted with 2- (iii) under the same conditions as described above to thereby obtain a compound represented by the general formula XIII.
3- (iv): the compound of formula XIII is reacted with a compound of formula XV to give a compound of formula XIV.
In the present invention, the molar ratio of the compound of formula XIII to the compound of formula XV is from 0.5 to 2:1. Step 3- (iv) the reaction is carried out in the presence of an acidic substance and a reducing agent.
The acidic substance is organic acid and/or inorganic acid, and the reducing agent is borohydride. Preferably, the organic acid is any one or a combination of at least two of formic acid, acetic acid, trifluoroacetic acid or methanesulfonic acid. Preferably, the inorganic acid is any one or a combination of at least two of hydrochloric acid, phosphoric acid or sulfuric acid. The reducing agent is sodium borohydride, sodium cyanoborohydride or sodium triacetoxyborohydride.
The solvent for the reaction is selected from any one or a combination of at least two of dichloromethane, toluene, ethyl acetate, acetone, tetrahydrofuran, dioxane and N, N-dimethylformamide. The reaction temperature is not less than room temperature and not more than the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.
3- (v): the compound of formula XIV is reacted with a compound of formula VI to give a compound of formula I.
The compound represented by the general formula XIV is reacted with the compound represented by the general formula VI under the same conditions as those described in step 1- (ii), thereby producing the compound represented by the general formula I.
Preparation method 4:
the compounds of formula I of the present invention may be prepared as follows in another manner:
the compounds of the present invention with n=1 or 2 are prepared by oxidizing the compounds of the present invention with n=0.
4- (i): the compound of the general formula I-1 is oxidized to obtain the compound of the general formula I-2.
In the present invention, the reaction of step 4- (i) is an oxidation reaction by an oxidizing agent in the presence of a solvent such as an aliphatic halogenated hydrocarbon, an alcohol, acetic acid, water or a mixture thereof. Preferably, the oxidant is sodium periodate, hydrogen peroxide or m-chloroperoxybenzoic acid. Preferably, the molar ratio of the oxidizing agent to the compound of formula I-1 is from 1.0 to 2:0. Preferably, the temperature of the reaction in step 4- (i) is from-20 ℃ to 80 ℃. Preferably, the reaction of step 4- (i) takes a time in the range of 0.5 to 24 hours.
4- (ii): the compound of the general formula I-2 is oxidized to obtain the compound of the general formula I-3.
The compound represented by the general formula I-2 is reacted with 4- (I) under the same conditions as described above, thereby producing a compound represented by the general formula I-3.
4- (iii): the compound of the general formula I-1 is oxidized to obtain the compound of the general formula I-3.
The compound represented by the general formula I-1 is reacted with 4- (I) under similar conditions to those described above, thereby preparing a compound represented by the general formula I-3. Except that the molar ratio of the oxidizing agent to the compound of formula I-1 is 2.0-4:0.
In another aspect, the present invention also provides an intermediate for preparing the above-described sulfonamide compound, which has a structure represented by formula XIV:
therein X, W 2 、Y 1 、R 1 、R 2 、R 3 M and n have the same defined ranges as in the compounds of the general formula I and are not described here again.
The preparation of the intermediate compounds of formula XIV 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 XIV of the compounds of the present invention are shown in table 5, but the intermediate compounds of the present invention are not limited to the compounds shown in table 5.
TABLE 5
In another aspect, the present invention provides a tautomer, enantiomer, diastereomer, or salt thereof of a sulfur-containing amide compound as described above.
In the present invention, the tautomer, enantiomer, diastereomer or salt thereof of the sulfur-containing amide compound can exert the same action and effect as the amide compound, and the insecticidal effect and the quick-acting property are good at a low dosage.
In another aspect, the invention provides the use of the sulfur-containing amide compounds described above in the agricultural, forestry and horticultural arts for controlling insect pests and nematodes.
The sulfur 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 a sulfonamide-containing 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 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 a sulfonamide-containing 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 sulfur-containing 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 efficient 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 compound is subjected to nuclear magnetic hydrogen spectrum test characterization, corresponding samples are all dissolved in deuterated solvent, and hydrogen spectrum data are obtained by testing with a 400MHz nuclear magnetic resonance meter, wherein the chemical displacement unit is ppm (namely delta: 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 N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide (compound No. 187):
(1) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -2-fluoro-3-nitrobenzamide
To the reaction flask were successively added 2-fluoro-3-nitrobenzoic acid (1.43 g,7.73 mmol), toluene (20 mL), thionyl chloride (1.84 g,15.46 mmol), and the mixture was stirred under reflux for 2 hours and concentrated under reduced pressure to give 2-fluoro-3-nitrobenzoyl chloride. The acid chloride was added to 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-methylthioaniline (2.47 g,6.45 mmol), potassium iodide (0.43 g,2.58 mmol) and acetonitrile (30 mL), the reaction mixture was heated to 110℃and reacted for 3 hours, then cooled to room temperature, 200mL of ethyl acetate and 100mL of water were added, extraction and separation were carried out, 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=10:1) to give the objective product (3.09 g, yield 87%).
1 H NMR(CDCl 3 )：8.48-8.43(m,1H),8.29-8.23(m,1H),8.03(d,J＝11.6Hz,1H),7.69(s,1H),7.50(t,J＝8.0Hz,1H),7.41(s,1H),2.49(s,3H)。
(2) Synthesis of 3-amino-N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -2-fluorobenzamide
N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -2-fluoro-3-nitrobenzamide (3.04 g,5.51 mmol) was dissolved in THF (50 mL), acetic acid (1.78 mL), water (1.3 mL) and iron powder (1.23 g,22.04 mmol) were added in this order, and the mixture was heated to 80℃for reflux reaction for 4h. TLC monitored the reaction to completion, the reaction was filtered through celite, the filtrate was dried by spin-drying, water (50 mL) was added and extracted with ethyl acetate (100 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 2.44g of a tan solid in 85% yield.
1 H NMR(CDCl 3 ):8.11(d,J＝14.0Hz,1H),7.68(s,1H),7.53-7.47(m,1H),7.40(s,1H),7.11-7.06(m,1H),7.03-6.97(m,1H),3.76(s,2H),2.47(s,3H)。
(3) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ] -3- (cyclopropylmethylamino) -2-fluorobenzamide
3-amino-N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -2-fluorobenzamide (2.50 g,4.80 mmol) was dissolved in dichloroethane (30 mL), cyclopropylaldehyde (0.34 g,4.80 mmol), acetic acid (0.29 g,4.80 mmol) were added in this order, and stirred at room temperature for 30min, followed by sodium triacetoxyborohydride (1.02 g,4.80 mmol). TLC monitored the end of the reaction, the reaction was adjusted to pH 8 with saturated aqueous sodium bicarbonate, extracted with dichloromethane (50 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=30:1) to give a yellow solid (1.21 g, yield 44%).
1 H NMR(CDCl 3 )：8.10(d,J＝14.0Hz,1H),7.67(s,1H),7.43-7.37(m,2H),7.13(t,J＝8.0Hz,1H),6.91-6.85(m,1H),4.26(s,1H),3.04(d,J＝6.8Hz,2H),2.47(s,3H),1.19-1.11(m,1H),0.64-0.59(m,2H),0.32-0.27(m,2H)。
(4) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -3- (cyclopropylmethylamino) -2-fluorobenzamide (0.50 g,0.86 mmol) in toluene (5 mL) was added DIPEA (223 mg,1.73 mmol), benzoyl chloride (133 mg,0.95 mmol) in this order, and the mixture was reacted at 130℃for 4 hours. The reaction mixture was cooled to room temperature, water (10 mL) was then added thereto, ethyl acetate (50 mL) was added thereto to extract, and the organic phase was taken out, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=10:1) to give the objective product (0.50 g, yield 84%).
Compound 187 1 HNMR(CDCl 3 )：8.02(s,1H),7.89(d,J＝11.6Hz,1H),7.66(s,1H),7.52-7.46(m,1H),7.36(d,J＝14.8Hz,3H),7.28-7.18(m,4H),3.93-3.71(m,2H),2.46(s,3H),1.18-1.07(m,1H),0.55-0.44(m,2H),0.26-0.10(m,2H)。
Synthesis example 2
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylsulfinylphenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide (compound No. 190):
in N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ]]-3- [ N- (cyclopropylmethyl) -benzamide group]To a solution of 2-fluorobenzamide (0.43 g,0.63 mmol) in methylene chloride (10 mL) was added 3-chloroperoxybenzoic acid (98 mg,0.56 mmol), and the reaction mixture was reacted at-10-0℃for 1h. The reaction was then stirred at 25℃for 2h and monitored by TLC. Quenching the reaction solution with water, adding anhydrous K 2 CO 3 Ph=8, dichloromethane extraction, organic phase. Washing with saturated saline, drying with anhydrous sodium sulfate, concentrating under reduced pressure, and collecting residuePurification by column chromatography (PE: ea=5:1) afforded the desired product (0.30 g, 68% yield).
Compound 190 1 HNMR(CDCl 3 )：8.43(s,1H),8.24(s,1H),7.99(s,1H),7.98-7.92(m,1H),7.56(t,J＝6.4Hz,1H),7.39-7.26(m,4H),7.22(s,2H),3.93-3.66(m,2H),2.89(s,3H),1.16-1.05(m,1H),0.52-0.45(m,2H),0.25-0.09(m,2H)。
Synthesis example 3
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylsulfonylphenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide (compound No. 191):
in N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ]]-3- [ N- (cyclopropylmethyl) -benzamide group]To a solution of 2-fluorobenzamide (0.25 g,0.36 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (250 mg,1.08 mmol), and the mixture was heated to 80℃for 2 hours under reflux, monitored by TLC. Quenching the reaction solution with water, and obtaining anhydrous K 2 CO 3 Ph=8 was adjusted and extracted with dichloromethane and the organic phase was taken. After washing with saturated brine and drying over anhydrous sodium sulfate, concentration was performed under reduced pressure, and the residue was purified by column chromatography (PE: ea=3:1) to give the objective product (0.17 g, yield 64%).
Compound 191 1 H NMR(CDCl 3 )：8.90(s,1H),8.27(d,J＝1.8Hz,1H),8.18(d,J＝1.6Hz,1H),7.98(s,1H),7.54(t,J＝7.2Hz,1H),7.40–7.32(m,2H),7.30-7.20(m,4H),3.93-3.70(m,2H),2.99(s,3H),1.16-1.06(m,1H),0.51-0.47(m,2H),0.24-0.08(m,2H)。
Synthesis example 4
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamide ] -4-fluorobenzamide (Compound No. 434):
(1) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -4-fluoro-3-nitrobenzamide
4-fluoro-3-nitrobenzoic acid (2.30 g,12.43 mmol) and toluene (20 mL) were added sequentially to the reaction flask, thionyl chloride (2.95 g,24.86 mmol) was reacted under reflux with stirring for 2h, and concentrated under reduced pressure to give 4-fluoro-3-nitrobenzoyl chloride. The acid chloride was added to 2-bromo-4- (perfluoroisopropyl) -6-methylthioaniline (3.70 g,9.58 mmol), potassium iodide (0.76 g,4.60 mmol) and acetonitrile (50 mL), the reaction mixture was cooled to room temperature after heating to 110℃for 3 hours, 200mL of ethyl acetate and 100mL of water were added, the mixture was extracted and separated, 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=10:1) to give the desired product (4.85 g, yield 91%).
(2) Synthesis of 3-amino-N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -4-fluorobenzamide
N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -4-fluoro-3-nitrobenzamide (5.57 g,10.09 mmol) was dissolved in THF (100 mL), acetic acid (3.26 mL), water (1.01 mL) and iron powder (2.26 g,40.30 mmol) were added in this order, and the mixture was heated to 80℃for reflux reaction for 4h. TLC monitored the reaction to completion, the reaction was filtered through celite, the filtrate was dried by spin-drying, water (100 mL) was added and 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 4.41g of a white solid in 83% yield.
(3) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ] -3- (cyclopropylmethylamino) -4-fluorobenzamide
3-amino-N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -4-fluorobenzamide (3.25 g,6.22 mmol) was dissolved in dichloroethane (30 mL), cyclopropylaldehyde (0.43 g,6.22 mmol), acetic acid (0.37 g,6.22 mmol) were added in this order, and stirred at room temperature for 30min, followed by sodium triacetoxyborohydride (1.31 g,6.22 mmol). TLC monitored the end of the reaction, the reaction was adjusted to pH 8 with saturated aqueous sodium bicarbonate, extracted with dichloromethane (100 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=30:1) to give a white solid (2.4 g, 67% yield).
(4) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ] -3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamide ] -4-fluorobenzamide
To a solution of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -3- (cyclopropylmethylamino) -4-fluorobenzamide (0.50 g,0.86 mmol) in toluene (5 mL) was added DIPEA (448 mg,3.40 mmol) and 2-fluoro-4-cyanobenzoyl chloride (238 mg,1.30 mmol) in this order, and the mixture was reacted at 130℃for 4 hours. The reaction mixture was cooled to room temperature, water (10 mL) was then added thereto, ethyl acetate (50 mL) was added thereto to extract, and the organic phase was taken out, 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 the objective product (0.43 g, yield 68%).
Compound 434 of 1 H NMR(CDCl 3 )：7.90–7.79(m,2H),7.68(s,1H),7.52(t,J＝7.2Hz,1H),7.43–7.34(m,3H),7.17–7.07(m,2H),3.92–3.72(m,2H),2.49(s,3H),1.11–1.02(m,1H),0.56-0.41(m,2H),0.26–0.14(m,2H)。
Synthesis example 5
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylsulfinylphenyl ] -3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamide ] -4-fluorobenzamide (compound No. 436):
in N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ]]-3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamide group]To a solution of 4-fluorobenzamide (0.43 g,0.59 mmol) in methylene chloride (10 mL) was added 3-chloroperoxybenzoic acid (124 mg,0.53 mmol), and the reaction mixture was reacted at-10-0℃for 1h. The reaction was then stirred at 25℃for 2h and monitored by TLC. Quenching the reaction solution with water, and obtaining anhydrous K 2 CO 3 Ph=8, dichloromethane extraction, organic phase. After washing with saturated brine and drying over anhydrous sodium sulfate, concentration was performed under reduced pressure, and the residue was purified by column chromatography (PE: ea=5:1) to give the objective product (0.31 g, yield 70%).
Compound 436 1 H NMR(CDCl 3 )：9.25(s,1H),8.04–7.97(m,3H),7.91(s,1H),7.56-7.49(m,1H),7.38-7.34(m,1H),7.16-7.05(m,2H),3.85-3.76(m,2H),2.91(s,3H),1.08–1.03(m,1H),0.54–0.47(m,2H),0.23-0.13(m,2H)。
Synthesis example 6
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methanesulfonylphenyl ] -3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamide ] -4-fluorobenzamide (compound No. 437):
in N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ]]-3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamide group]To a solution of 4-fluorobenzamide (0.18 g,0.24 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (170 mg,0.74 mmol), and the mixture was heated to 80℃for 2 hours under reflux, monitored by TLC. Quenching the reaction solution with water, and obtaining anhydrous K 2 CO 3 Ph=8 was adjusted and extracted with dichloromethane and the organic phase was taken. After washing with saturated brine and drying over anhydrous sodium sulfate, concentration was performed under reduced pressure, and the residue was purified by column chromatography (PE: ea=3:1) to give the objective product (0.15 g, yield 79%).
Compound 437 1 HNMR(CDCl 3 )：8.81(s,1H),8.26(s,1H),8.21(s,1H),8.09-8.06(m,1H),7.99(d,J＝8.0Hz,1H),7.96–7.88(m,2H),7.60–7.53(m,2H),7.44–7.37(m,2H),7.19-7.12(m,2H),3.94-3.69(m,2H),3.03(s,3H),1.10-1.03(m,1H),0.54-0.42(m,2H),0.24–0.16(m,2H)。
Synthesis example 7
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethylsulfanylphenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide (compound No. 196):
(1) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethylsulfanylphenyl ] -2-fluoro-3-nitrobenzamide
To the reaction flask were successively added 2-fluoro-3-nitrobenzoic acid (1.82 g,9.85 mmol), toluene (20 mL), thionyl chloride (2.34 g,19.70 mmol), and the mixture was stirred under reflux for 2 hours and concentrated under reduced pressure to give 2-fluoro-3-nitrobenzoyl chloride. The acid chloride was added to 2-bromo-4- (perfluoroisopropyl) -6-ethylthioaniline (3.04 g,7.60 mmol), potassium iodide (0.61 g,3.65 mmol) and acetonitrile (50 mL), the reaction mixture was cooled to room temperature after heating to 110℃for 3 hours, 200mL of ethyl acetate and 100mL of water were added, the mixture was extracted and separated, 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=10:1) to give the desired product (4.1 g, yield 95%).
(2) Synthesis of 3-amino-N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethylsulfanylphenyl ] -2-fluorobenzamide
N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethylsulfanylphenyl ] -2-fluoro-3-nitrobenzamide (4.30 g,7.50 mmol) was dissolved in THF (100 mL), acetic acid (2.46 mL), water (0.76 mL) and iron powder (1.70 g,30.30 mmol) were added in this order, and the mixture was heated to 80℃for reflux reaction for 4h. TLC monitored the reaction to completion, the reaction was filtered through celite, the filtrate was dried by spin-drying, water (100 mL) was added and 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 3.7g of a tan liquid in 92% yield.
(3) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (ethylthio) phenyl ] -3- (cyclopropylmethylamino) -2-fluorobenzamide
3-amino-N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethylsulfanylphenyl ] -2-fluorobenzamide (4.07 g,7.59 mmol) was dissolved in dichloroethane (30 mL), cyclopropylaldehyde (0.53 g,7.59 mmol), acetic acid (0.45 g,7.59 mmol) were added in this order, and stirred at room temperature for 30min, and sodium triacetoxyborohydride (1.60 g,7.59 mmol) was added. TLC monitored the end of the reaction, the reaction was adjusted to pH 8 with saturated aqueous sodium bicarbonate, extracted with dichloromethane (50 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=30:1) to give a tan liquid (2.5 g, yield 55%).
(4) Synthesis of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (ethylthio) phenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethylsulfanylphenyl ] -3- (cyclopropylmethylamino) -2-fluorobenzamide (0.49 g,0.83 mmol) in toluene (5 mL) was added DIPEA (214 mg,1.66 mmol) and benzoyl chloride (128 mg,0.91 mmol) in this order, and the mixture was reacted at 130℃for 4 hours. The reaction mixture was cooled to room temperature, water (10 mL) was then added thereto, ethyl acetate (50 mL) was added thereto to extract, and the organic phase was taken out, 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 the objective product (0.50 g, yield 88%).
Compound 196 1 H NMR(CDCl 3 )：8.02(s,1H),7.94(d,J＝12.8Hz,1H),7.67(s,1H),7.53-7.44(m,2H),7.39-7.30(m,2H),7.27-7.13(m,4H),3.92-3.68(m,2H),2.92(q,J＝7.2Hz,2H),1.31(t,J＝7.2Hz,3H),1.17-1.03(m,1H),0.54-0.43(m,2H),0.27–0.08(m,2H).
Synthesis example 8
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethylsulfinylphenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide (compound No. 197):
in N- [ 2-bromo-4- (perfluoroisopropyl) -6- (ethylthio) phenyl ]]-3- [ N- (cyclopropylmethyl) -benzamide group]To a solution of 2-fluorobenzamide (0.37 g,0.53 mmol) in methylene chloride (10 mL) was added 3-chloroperoxybenzoic acid (110 mg,0.47 mmol), and the reaction mixture was reacted at-10-0℃for 1h. The reaction was then stirred at 25℃for 2h and monitored by TLC. Quenching the reaction solution with water, and obtaining anhydrous K 2 CO 3 Ph=8 was adjusted and extracted with dichloromethane and the organic phase was taken. After washing with saturated brine and drying over anhydrous sodium sulfate, concentration was performed under reduced pressure, and the residue was purified by column chromatography (PE: ea=5:1) to give the objective product (0.32 g, yield 85%).
Compound 197 1 H NMR(CDCl 3 )：8.35(s,1H),8.12(s,1H),8.00(s,1H),7.97-7.90(m,1H),7.55(t,J＝6.4Hz,1H),7.40–7.28(m,4H),7.24-7.10(m,2H),3.93–3.68(m,2H),3.20–3.05(m,1H),2.80–2.69(m,1H),1.27–1.23(m,3H),1.17–1.04(m,1H),0.51-0.45(m,2H),0.23-0.05(m,2H).
Synthesis example 9
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-ethanesulfonylphenyl ] -3- [ N- (cyclopropylmethyl) -benzamide ] -2-fluorobenzamide (compound number 198):
in N- [ 2-bromo-4- (perfluoroisopropyl) -6- (ethylthio) phenyl ]]-3- [ N- (cyclopropylmethyl) -benzamide group]To a solution of 2-fluorobenzamide (0.21 g,0.29 mmol) in dichloromethane (10 mL) was added 3-chloroperoxybenzoic acid (204 mg,0.88 mmol), and the mixture was heated to 80℃for 2 hours under reflux, monitored by TLC. Quenching the reaction solution with water, and obtaining anhydrous K 2 CO 3 Ph=8 was adjusted and extracted with dichloromethane and the organic phase was taken. After washing with saturated brine and drying over anhydrous sodium sulfate, concentration was performed under reduced pressure, and the residue was purified by column chromatography (PE: ea=3:1) to give the objective product (0.13 g, yield 60%).
Compound 198 1 HNMR(CDCl 3 )：9.03(s,1H),8.21(s,1H),8.18(s,1H),8.00-7.92(m,1H),7.55-7.48(m,1H),7.38-7.31(m,2H),7.28-7.19(m,4H),3.91-3.71(m,2H),3.09-2.97(m,2H),1.18(t,J＝7.2Hz,3H),1.14-1.06(m,1H),0.51-0.45(m,2H),0.21-0.07(m,2H).
Synthesis example 10
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ] -3- [ N- (cyclopropylmethyl) -nicotinamide ] -4-fluorobenzamide (compound No. 444):
to a solution of N- [ 2-bromo-4- (perfluoroisopropyl) -6- (methylthio) phenyl ] -3- (cyclopropylmethylamino) -4-fluorobenzamide (0.50 g,0.87 mmol) in toluene (5 mL) was added N, N-diisopropylethylamine (0.22 g,1.73 mmol), nicotinyl chloride (0.14 g,0.92 mmol) and the reaction was completed at 130℃for 3 hours, followed by TLC monitoring. The reaction mixture was cooled to room temperature, water (10 mL) and ethyl acetate (50 mL) were added to the reaction solution, the organic phase was extracted, and after washing with saturated brine and drying over anhydrous sodium sulfate, the organic phase was concentrated under reduced pressure, and the residue was purified by column chromatography (PE: ea=3:1) to give the objective product (332 mg, yield 56.02%).
Synthesis example 11
Preparation of N- [ 2-bromo-4- (perfluoroisopropyl) -6-methylthiophenyl ] -3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamide ] -2-fluorobenzamide (Compound No. 278):
3- [ N- (cyclopropylmethyl) -2-fluoro-4-cyanobenzamido ] -2-fluorobenzoic acid (1.10 g,3.09 mmol), toluene (11 mL), thionyl chloride (1.10 g,12.36 mmol) were added sequentially to the reaction flask, the reaction was stirred at 120℃for 2 hours, toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (3 mL) for use.
2-bromo-4-perfluoroisopropyl-6-methylthioaniline (1.19 g,3.09 mmol), DIPEA (0.80 g,6.17 mmol) and DMAP (76 mg, 620. Mu. Mol) were sequentially added to a reaction flask, and the acid chloride solution prepared in the above step was slowly added at room temperature and reacted at 110℃for 2 to 3 hours. TLC monitored the reaction to completion, water (40 mL) was added to the reaction solution to quench the reaction, the separated solution was extracted with ethyl acetate (60 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=4:1) to give the desired product (0.50 g, yield 33.25%) as a yellow liquid.
Compound 278 1 HNMR(CDCl 3 )：8.07(t,J＝7.2Hz,1H),7.81(d,J＝13.6Hz,1H),7.68(s,1H),7.54(q,J＝9.2,8.0Hz,2H),7.37(dd,J＝8.0,1.3Hz,2H),7.26(s,2H),7.16(dd,J＝8.8,1.2Hz,1H),3.83(d,J＝7.2Hz,2H),2.50(s,3H),1.09(dt,J＝12.0,6.1Hz,1H),0.58–0.49(m,2H),0.32–0.15(m,2H).
The partial compounds in tables 6 and 7 were prepared by the similar method as in synthesis examples 1 to 11, and the nuclear magnetic data of the partial compounds synthesized by the synthesis examples 1 to 11 are given in tables 6 and 7 below.
TABLE 6
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TABLE 7
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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 2 of the present invention as a representative compound, specifically as follows:
30 parts by weight of the compound 2 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 2 of the present invention having a concentration of 30%.
Formulation example 2
In this example, a formulation was prepared using compound 187 of the present invention as a representative compound, as follows:
20 parts by weight of compound 187 according to 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 compound 187 according to the present invention.
Formulation example 3
In this example, a formulation was prepared using the present compound 350 as a representative compound, as follows:
30 parts by weight of the compound 350 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 350 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 1mLDMF, prepare 10000ppm mother liquor, dilute the mother liquor to the required concentration with 0.05% Tween-80 water, and perform 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 rate of the compound 190, 191, 278, 287, 292, 360 and 381 of the invention on armyworm after 3 days of medicine is more than or equal to 80% at the concentration of 1 ppm. The mortality of control compounds KC2, KC3, KC4 to myxoplasma was 0% at a concentration of 1ppm at 3 days post-drug. The activity of the compounds of the invention is significantly better than that of the control compounds.
Test of insecticidal Activity of the Compound of example 2 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 mortality rate of the compounds 187, 190, 191, 222, 228, 229, 278, 287, 236, 239, 240, 286, 401 and 464 of the invention on plutella xylostella is more than or equal to 90% after 3 days of medicine at the concentration of 1 ppm. The mortality of the control compounds KC2, KC3 and KC4 to plutella xylostella at a concentration of 1ppm was 0% 3 days after the administration. The activity of the compounds of the invention is significantly better than that of the control compounds.
Test of indoor biological Activity of the Compounds of example 3 against 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 mortality rate of the compounds 63, 260, 263, 266, 416, 417, 421 and 422 of the invention to tetranychus cinnabarinus is more than or equal to 80% in 3 days after the administration at the concentration of 100 ppm.
The mortality rate of the compound 260, 263, 417 and 421 of the invention to tetranychus cinnabarinus is more than or equal to 80% in 3 days after the medicine is taken at the concentration of 10 ppm.
According to the method, the selected compounds 260, 263, 417, 421 and KC1, KC2, KC3, KC4 are subjected to parallel measurement of the insecticidal activity of Tetranychus cinnabarinus. The test results are shown in Table 8.
TABLE 8 comparison of insecticidal Activity of Compounds 260 and the like of the present invention against Tetranychus cinnabarinus with control Compounds
As can be seen from Table 8, the compound of the present invention has not only a greatly improved insecticidal activity but also an advantage that a very good insecticidal effect can be exhibited even after a substantial reduction in the dosage.
Testing of Compounds of example 4 for indoor biological Activity against brown planthoppers
Soaking all rice seedlings in the medicinal liquid for 10s, taking out, and airing on absorbent paper until no water is exposed. Placing a piece of filter paper at the bottom of the plastic cup for paving, adding 1mL of water for wetting (sucking out excessive clear water); 15-30 brown planthopper nymphs are inoculated into the plastic cup. Then placing the dried rice seedlings in a plastic cup, and placing the roots of the dried rice seedlings downwards by contacting with filter paper; sealing the fresh-keeping film at the cup opening, puncturing holes, ventilating, placing in an observation chamber for culture, wherein the temperature is 20-26 ℃, the illumination is 14hL:10hD, and the humidity is 40-60%. The number of dead insects was investigated 3d after the drug and the mortality was calculated.
The mortality rate of the compounds 196, 202, 269, 295, 305, 308, 309, 337, 338, 339, 392, 393, 401, 409, 423, 426, 438, 445, 447, 448, 464, 472, 474 and 476 of the invention on brown planthoppers 3 days after the medicine is more than or equal to 80 percent at the concentration of 400 ppm.
The mortality rate of the compounds 305, 309, 337, 447, 448, 464 and 476 of the invention to brown planthoppers after the medicine is 3 days is more than or equal to 80 percent at the concentration of 100 ppm.
The insecticidal activity of brown planthoppers was determined in parallel with KC1, KC2, KC3, KC4 by selecting compounds 305, 309, 337, 447, 448, 464, 476 according to the above method. The test results are shown in Table 9.
TABLE 9 comparison of insecticidal Activity of Compound 305, etc. of the invention against brown planthopper with control Compound
As can be seen from Table 9, the compound of the present invention has not only a greatly improved insecticidal activity but also an advantage that a very good insecticidal effect can be exhibited even after a substantial reduction in the dosage.
The present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e., the present invention should not be construed as being 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. The sulfur-containing amide compound is characterized in that the amide compound has a structure shown in the following formula I:
in the formula I, the compound (I),
q is selected from the group consisting of Q 1 、Q 2 、Q 3 Or Q 4 Is one of:
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 are independently selected from hydrogen, halogen atom, cyano, nitro and 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 C 3 -C 8 Cycloalkyl alkyl;
R 2 selected from hydrogen, fluorine or methoxy;
R 3 selected from C 1 -C 4 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 3 -C 8 Cycloalkyl, C 1 -C 4 Haloalkyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Haloalkynyl or C 3 -C 8 Halogenated cycloalkyl;
Y 1 selected from hydrogen, halogen atoms, C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group;
x are identical or different and are selected from hydrogen, halogen atoms, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy or cyano;
W 1 and W is 2 Independently an oxygen atom or a sulfur atom;
m represents an integer of 0 to 4;
n represents an integer of 0 to 2.
2. The sulfur-containing amide compound of claim 1, wherein in formula I,
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 independently selected from the group consisting of hydrogen, halogen atoms, cyano groups, nitro groups, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, cyclopropyl groups, n-butyl groups, t-butyl groups, isobutyl groups, n-pentyl groups, 1-methylbutyl groups, 2-methylbutyl groups, 3-methylbutyl groups, 1-dimethylpropyl groups, 1, 2-dimethylpropyl groups, 2-dimethylpropyl groups, methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, t-butoxy groups, trifluoromethyl groups, pentafluoroethyl groups, heptafluoro-n-propyl groups, heptafluoroisopropyl groups, difluoromethoxy groups, trifluoromethoxy groups, pentafluoroethoxy groups, methylsulfinyl groups, trifluoromethylsulfinyl groups, methyl groups Sulfonyl or trifluoromethanesulfonyl; r is R 1 Selected from cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl; r is R 3 Selected from C 1 -C 4 Alkyl, C 3 -C 8 Cycloalkyl, C 1 -C 4 Haloalkyl or C 3 -C 8 Halogenated cycloalkyl; y is Y 1 Selected from halogen atoms; x are the same or different and are selected from hydrogen, halogen atoms or cyano groups.
3. The sulfur-containing amide compound of claim 1, wherein 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 cyclopropylmethyl or cyclobutylmethyl; r is R 2 Selected from fluorine; r is R 3 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or 2, 2-trifluoroethyl; y is Y 1 Selected from chlorine, bromine, iodine; x is the same or different and is selected from hydrogen, fluorine, chlorine, bromine or iodine; w (W) 1 And W is 2 Selected from oxygen.
4. A sulfur-containing amide-based compound according to any one of claims 1 to 3, wherein the amide-based compound is any one selected from the group consisting of:
5. the tautomer, enantiomer, diastereomer or salt thereof of a sulfur-containing amide-based compound according to any one of claims 1 to 4.
6. An intermediate compound for preparing the sulfur-containing amide compound according to any one of claims 1 to 5, which has a structure represented by the following formula XIV:
in formula XIV, R 1 Selected from C 3 -C 8 Cycloalkyl alkyl; r is R 2 Selected from hydrogen, fluorine or methoxy; r is R 3 Selected from C 1 -C 4 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 3 -C 8 Cycloalkyl, C 1 -C 4 Haloalkyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 Haloalkynyl or C 3 -C 8 Halogenated cycloalkyl; y is Y 1 Selected from hydrogen, halogen atoms, C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group; x are identical or different and are selected from hydrogen, halogen atoms, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy, C 1 -C 3 Haloalkoxy or cyano; w (W) 2 Is an oxygen atom or a sulfur atom; m represents an integer of 0 to 4; n represents an integer of 0 to 2.
7. Use of the sulfur-containing amide compounds according to any of claims 1 to 4 or of the tautomers, enantiomers, diastereomers of the sulfur-containing amide compounds according to claim 5 or of their salts for controlling plant pests.
8. An insecticidal composition comprising an active ingredient and an agropharmaceutically acceptable carrier, the active ingredient being a sulfur-containing amide compound according to any one of claims 1 to 4 or a tautomer, enantiomer, diastereomer or salt thereof of a sulfur-containing amide compound according to claim 5.
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 the sulfur-containing amide compound of any one of claims 1 to 4 or the tautomer, enantiomer, diastereomer or salt thereof of the sulfur-containing amide compound of claim 5 or the pesticidal composition of claim 8 or 9 to a pest or a medium in need of control of growth thereof;
preferably, the effective dose is 7.5-1000g per hectare, preferably 15-600g per hectare.
CN202310432603.8A 2022-04-21 2023-04-21 Sulfur-containing amide compound and preparation method and application thereof Pending CN116924952A (en)

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