Classifications

• • 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
  • C07C323/01—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 halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
  • C07C323/09—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 halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• • 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
  • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
  • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
• • 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
  • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
  • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
  • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings

Definitions

• the invention belongs to the field of agricultural acaricides, in particular to a biphenyl compound and application thereof.
• R 1 and R 2 are each independently selected from hydrogen, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 2 -C 8 alkenyl, halo C 2 -C 8 alkenyl, C 2 a -C 8 alkynyl group, a halogenated C 2 -C 8 alkynyl group, a cyano C 1 -C 8 alkyl group or a cyano halogenated C 1 -C 8 alkyl group;
• n are each independently selected from 0, 1, or 2.
• R 1 and R 2 are each independently selected from halo C 1 -C 8 alkyl, halo C 2 -C 8 alkenyl, halo C 2 -C 8 alkynyl or cyano halo C 1 -C 8 alkane Further, R 1 and R 2 may also be the same selected from halogenated C 1 -C 8 alkyl, halogenated C 2 -C 8 alkenyl, halogenated C 2 -C 8 alkynyl or cyano halide C 1 -C 8 alkyl
• n are each independently selected from 0, 1, or 2.
• R 1 and R 2 are each independently selected from halo C 1 -C 3 alkyl, halo C 2 -C 6 alkenyl, halo C 2 -C 6 alkynyl or cyanohalogen C 1 -C 3 alkyl; further, R 1 and R 2 may also be the same selected from halo C 1 -C 3 alkyl, halo C 2 -C 6 alkenyl, halo C 2 -C 6 alkynyl Or a cyano halogenated C 1 -C 3 alkyl group;
• n are each independently selected from 0 or 1.
• n are each independently selected from 0 or 1.
• R 1 and R 2 are each independently selected from CH 2 CF 3 or CH 2 CHF 2 ; further, R 1 and R 2 may also be the same selected from CH 2 CF 3 or CH 2 CHF 2 ;
• n are each independently selected from 0 or 1.
• An acaricidal composition comprising a compound of the formula I and an agriculturally acceptable carrier; wherein the compound of the formula I is an active ingredient, the active component of the composition
• the weight percentage is from 0.1 to 99%.
• Alkyl straight-chain, branched or cyclic alkyl, such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl, hexyl isomers, and cyclopropyl, cyclopentyl , cyclohexyl or cyclopropylmethyl and the like.
• Haloalkyl a linear, branched or cyclic alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Difluoromethyl, trifluoromethyl, heptafluoroisopropyl, and the like.
• Alkenyl includes straight-chain or branched olefins such as vinyl, 1-propenyl, 2-propenyl and different butenyl, pentenyl and hexenyl isomers; alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
• Haloalkenyl an alkenyl group which may be substituted with at least one or more hydrogen atoms by a halogen atom.
• Alkynyl includes straight-chain or branched acetylenes such as ethynyl, 1-propynyl and different butynyl, pentynyl and hexynyl isomers; alkynyl groups also include groups composed of a plurality of triple bonds a group such as 2,5-hexadiynyl.
• Haloalkynyl an alkynyl group which may be substituted with at least one or more hydrogen atoms by a halogen atom.
• Cyanoalkyl CN-alkyl-, such as NCCH 2 -.
• Cyanohaloalkyl CN-haloalkyl-, such as NCCHBr-.
• the compounds of formula I may have different chirality structures, including central chiral, axial chiral or facial chiral structures, and different, due to different substitution patterns.
• the compound of the structure may exist in different forms of the enantiomer or the diastereomer; in addition, the compound represented by the formula I further includes various stereoisomers such as cis/trans isomer, which are to be protected by the present invention.
• the compounds of formula I are not limited by the various isomer structures described above.
• the invention also provides the use of a compound of the above formula I as an acaricide in the agricultural, forestry and sanitary fields.
• the invention further provides a acaricidal composition
• a acaricidal composition comprising a compound of the above formula I and an agriculturally acceptable carrier; wherein the compound of the formula I is an active ingredient, the combination
• the active ingredient is present in an amount of from 0.1 to 99% by weight.
• the compositions shown may comprise a variety of compounds of the above formula I in a heterostructure.
• R 1 R 2 m n 1 CH 2 CF 3 CH 2 CF 3 0 0 2 CH 2 CF 3 CH 2 CF 3 0 1 3 CH 2 CF 3 CH 2 CF 3 1 1 4 CH 2 CF 3 CH 2 CF 3 1 2 5 CF 3 CH 2 CF 3 0 0 6 CF 3 CH 2 CF 3 0 1 7 CF 3 CH 2 CF 3 1 1 8 CH 3 CH 2 CF 3 0 0 9 CH 3 CH 2 CF 3 0 1 10 CH 3 CH 2 CF 3 1 1 11 CH 2 CH 3 CH 2 CF 3 0 0 12 CH 2 CH 3 CH 2 CF 3 0 1 13 CH 2 CH 3 CH 2 CF 3 1 1 14 Cyclopropylmethyl CH 2 CF 3 0 0 15 Cyclopropylmethyl CH 2 CF 3 0 1 16 Cyclopropylmethyl CH 2 CF 3 1 1 17 CH 2 CH 2 CF 3 CH 2 CF 3 0 0 18 CH 2 CH 2 CF 3 CH 2 CF 3 0 1 19 CH 2 CH 2
• the compound of the formula III can be obtained by reacting the intermediate II with a suitable halogenating reagent in a suitable solvent in the presence of a suitable base at a temperature from 0 ° C to the boiling point of the solvent for 0.5 to 48 hours.
• suitable halogenating agents may be selected from the group consisting of methyl iodide, ethyl iodide, trifluoroiodoethane, bromocyclopropane, chloroacetonitrile, vinyl bromide, 3-bromopropyne, trifluoromethyl iodide, trifluoroiodoethane, Dibromoacetonitrile, 2-bromo-1,1-difluoroethylene, dibromoacetylene, and the like.
• Suitable solvents may be selected from the group consisting of water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane, DMF or DMSO.
• Suitable bases may be selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium t-butoxide or sodium t-butoxide.
• the compound of formula III is reacted with sodium nitrite, one or more acids, potassium iodide to produce a compound of formula IV.
• the acid may be an inorganic or organic acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid or methanesulfonic acid.
• the reaction solvent may be selected from the group consisting of water, chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane.
• the reaction is usually carried out at a temperature of from 0 to 100 °C.
• the reaction time is usually from 0.5 to 48 hours.
• the compound of the formula IV is obtained by reacting a compound of the formula IV with a pinacol borate in a suitable solvent in the presence of a suitable base, a suitable palladium catalyst, at a temperature from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
• suitable solvents can be selected from Water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane, DMF or DMSO.
• Suitable bases include alkali metal such as lithium, sodium or potassium hydrides such as sodium hydride, potassium hydride, alkali metal such as lithium, sodium or potassium hydroxides such as sodium hydroxide, potassium hydroxide, and also alkali metal lithium,
• the carbonate of sodium, potassium or cesium such as sodium carbonate or cesium carbonate may also be an organic base such as triethylamine, sodium t-butoxide or potassium t-butoxide.
• a suitable palladium catalyst may be selected from the group consisting of tetrakis(triphenylphosphine)palladium, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, and the like.
• a suitable ligand such as 1,1'-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-tert-butylphosphine or the like may also be added.
• Intermediate II is reacted with sodium nitrite, one or more acids, and potassium iodide to produce Intermediate V.
• the acid may be an inorganic or organic acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid or methanesulfonic acid.
• the reaction solvent may be selected from the group consisting of water, chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane.
• the reaction is usually carried out at a temperature of from 0 to 100 °C.
• the reaction time is usually from 0.5 to 48 hours.
• Intermediate VI is prepared by reacting intermediate V with diboronic acid pinacol ester in a suitable solvent, in the presence of a suitable base, a suitable palladium catalyst, at a temperature from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
• suitable solvents may be selected from the group consisting of water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane, DMF or DMSO.
• Suitable bases include alkali metal such as lithium, sodium or potassium hydrides such as sodium hydride, potassium hydride, alkali metal such as lithium, sodium or potassium hydroxides such as sodium hydroxide, potassium hydroxide, and also alkali metal lithium,
• the carbonate of sodium, potassium or cesium such as sodium carbonate or cesium carbonate may also be an organic base such as triethylamine, sodium t-butoxide or potassium t-butoxide.
• a suitable palladium catalyst may be selected from the group consisting of tetrakis(triphenylphosphine)palladium, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, and the like.
• a suitable ligand such as 1,1'-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-tert-butylphosphine or the like may also be added.
• the compound of the formula I-2 can be obtained in one step from the intermediate VI in a suitable solvent in the presence of a suitable base; then the compound of the formula I-2 can be further reacted to give the formula I- 3 compounds.
• Suitable halogenating agents may be selected from the group consisting of methyl iodide, ethyl iodide, trifluoroiodoethane, bromocyclopropane, chloroacetonitrile, vinyl bromide, 3-bromopropyne, trifluoromethyl iodide, trifluoroiodoethane, Dibromoacetonitrile, 2-bromo-1,1-difluoroethylene, dibromoacetylene, and the like.
• Suitable solvents may be selected from the group consisting of water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane, DMF or DMSO.
• Suitable bases may be selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and triethyl ethane. Amine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium t-butoxide or sodium t-butoxide.
• the reaction is usually carried out at a temperature of from 0 ° C to the boiling point of the solvent.
• the reaction time is usually from 0.5 to 48 hours.
• the compound of formula I-1 to 3 can be reacted with a suitable oxidizing agent to produce the corresponding sulfoxide or sulfone, i.e., a compound of formula 1-4.
• a suitable oxidizing agent may be m-chloroperoxybenzoic acid, hydrogen peroxide or (meta) sodium periodate.
• the reaction solvent is mainly selected from the group consisting of water, methanol, ethanol, diethyl ether, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane.
• the reaction is usually carried out at a temperature of from 0 to 100 ° C, preferably at from 20 to 40 ° C.
• the reaction time is usually from 10 minutes to 48 hours.
• the intermediate II can be produced by a known method, for example, by the methods reported in WO2010100189, US2012053052, JP2012519662, EP2403837 or CN102341376.
• Halogen reagents sodium nitrite, inorganic or organic acids, potassium iodide, diboronic acid pinacol esters, palladium catalysts, ligands, oxidizing agents and other conventional starting materials and reagents are generally commercially available or can be prepared according to conventional methods.
• the present invention also encompasses the use of the compounds of formula I for the control of mites.
• the compound of the formula I is active against important species of the following families: the leaf family (two-spotted leafhopper, the cinnabar leafhopper, the apple whole-clawed scorpion, the citrus full-clawed scorpion, etc.), the scorpionidae, the scorpionidae, and the like.
• the above compounds can be advantageously used to protect crops, livestock and stocks important in agriculture and horticulture, as well as the environment frequented by humans from harmful mites.
• the amount of the compound varies depending on various factors such as the compound used, the pre-protected crop, the type of pest, the degree of infection, the climatic conditions, the method of administration, and the dosage form employed.
• a dose of 10 grams to 5 kilograms of compound per hectare provides adequate control.
• a further object of the invention also relates to a method for controlling pests in agricultural and horticultural industries and/or pests in livestock and/or livestock and/or humans, often by applying the compounds of formula I.
• the amount of the compound varies from 10 g to 5 kg per hectare.
• composition comprising one or more compounds of formula I.
• another embodiment of the present invention further comprises a acaricidal composition
• a acaricidal composition comprising as an active ingredient a compound of formula I and an agriculturally acceptable carrier, wherein the active ingredient is present in an amount of 0.1 by weight. -99%.
• the composition may be used in the form of a dry powder, a wettable powder, an emulsifiable concentrate, a microemulsion, a paste, a granule, a solution, a suspending agent, etc., and the choice of the type of the composition depends on the particular application.
• composition is prepared in a known manner, for example, optionally in the presence of a surfactant, by using a solvent medium and / Or dilute or dissolve the active substance with a solid diluent.
• Useful solid diluents or carriers can be silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, chalk, clay, synthetic silicates, attapulgite, sepiolite, and the like.
• useful liquid diluents are aromatic organic solvents (mixtures of xylene or alkylbenzenes, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol, butanol, octanol, glycerol). ), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides (N, N-II) Methylformamide, N-methylpyrrolidone, etc.).
• Usable surfactants are sodium, calcium, triethylamines such as alkyl sulfonates, alkyl aryl sulfonates, polyoxyethylene alkyl phenols, polyoxyethylene esters of sorbitol, lignosulfonates, and the like. Or triethanolamine salt.
• compositions may also contain special additives for specific purposes such as binders such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone and the like.
• the concentration of the active ingredient in the above composition may vary within a wide range depending on the active ingredient, its intended use, environmental conditions, and the type of preparation employed. Generally, the concentration of the active ingredient ranges from 1 to 90%, preferably from 5 to 50%.
• R 1 and R 2 of the formula I of the present invention are the same can be prepared by referring to the above examples. Specifically, these compounds can be obtained by substituting the reagents in the course of the reaction according to the above-mentioned preparation method of the compound of the above formula I.
• the compound of the formula I of the present invention in which R 1 and R 2 are different can be obtained by the synthesis of the above-mentioned compound of the above formula I, and the synthesis can be carried out by using different suitable halogenating agents.
• the test compound dissolve it with acetone or dimethyl sulfoxide, and use 0.1% Tween 80 solution to configure 50 ml of the solution to be tested at the desired concentration.
• the content of acetone or dimethyl sulfoxide in the solution is not More than 10%.
• the compounds of the present invention were tested for acaricidal activity by using a plurality of halogenated alkyl compounds having the same R 1 and R 2 as the examples, and the results of some tests are shown in Table 2.
• Table 2 Activity data on saplings of A. cinnafolia (mortality, %)
• Table 4 Activity data on the eggs of T. cinnabarinus (incubation inhibition rate, %)
• the test agent (the compound obtained in the above example) was weighed and dissolved in a small amount of acetone, and the serial concentration was adjusted with water containing 0.1% Tween 80. Each concentration was one treatment, and each treatment was repeated 3 times, and water was additionally set as a blank control. Put 10 ml of the drug solution into the test tube, take two leaves of true bean seedlings, wash the roots of the soil, and immerse the roots of the bean seedlings in different treatment liquids. After fully absorbing for 24 hours, transfer the cinnabar leaves directly into the moon. 30-50 heads were then placed in an observation room at 25 ⁇ 1 ° C. After 72 hours, the number of dead and alive sputum was investigated, and the mortality of each treatment was compared to determine whether the compound had root absorption and systemic activity.
• the test structure is shown in Table 5.
• Table 5 Suction activity data of compound 1 root absorption on T. cinnabarinus (mortality, %)
• the citrus whole scorpion scorpion scorpion, juvenile scorpion, and scorpion egg were present, and the ratio of licking eggs was 1:1.2.
• the weather was fine on the day of application, the average temperature was 24 °C, and the weather was fine for 3 days after application.
• the number of insect populations was investigated before application, and the samples were investigated once every day, 3 days, 7 days, 14 days, 22 days, and 28 days after application.
• 2 trees were surveyed in each plot. According to the east, west, south, north and middle orientations of the canopy, the full number of active states on the 5 leaves were investigated in each direction. 50 leaves were investigated in each plot, and the mouth was calculated according to the following formula. Decrease rate and corrective effect:
• Mouth reduction rate (%) [(the average number of leaves before application - the average number of leaves after application) / the number of leaves before application] ⁇ 100

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
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• 2015
  • 2015-10-23 CN CN201510696452.2A patent/CN105541682B/zh active Active
• 2016
  • 2016-10-21 BR BR112018008230-9A patent/BR112018008230B1/pt active IP Right Grant
  • 2016-10-21 CN CN201680059934.XA patent/CN108602768A/zh active Pending
  • 2016-10-21 WO PCT/CN2016/102837 patent/WO2017067500A1/zh active Application Filing
• 2018
  • 2018-04-13 CO CONC2018/0003974A patent/CO2018003974A2/es unknown

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