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WO2017067500A1 - Biphenyl compound and application thereof - Google Patents

Biphenyl compound and application thereof Download PDF

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Publication number
WO2017067500A1
WO2017067500A1 PCT/CN2016/102837 CN2016102837W WO2017067500A1 WO 2017067500 A1 WO2017067500 A1 WO 2017067500A1 CN 2016102837 W CN2016102837 W CN 2016102837W WO 2017067500 A1 WO2017067500 A1 WO 2017067500A1
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WO
WIPO (PCT)
Prior art keywords
compound
formula
halo
independently selected
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2016/102837
Other languages
French (fr)
Chinese (zh)
Inventor
张立新
张静
班兰凤
吴鸿飞
宋玉泉
于海波
李鹏
徐靖博
徐利保
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Sinochem Agrochemicals R&D Co Ltd
Original Assignee
Shenyang Sinochem Agrochemicals R&D Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to ES16856931T priority Critical patent/ES2908451T3/en
Priority to PL16856931T priority patent/PL3366672T3/en
Priority to RS20220230A priority patent/RS62983B9/en
Priority to LTEPPCT/CN2016/102837T priority patent/LT3366672T/en
Priority to EP16856931.7A priority patent/EP3366672B9/en
Priority to DK16856931.7T priority patent/DK3366672T3/en
Priority to BR112018008230-9A priority patent/BR112018008230B1/en
Priority to JP2018536328A priority patent/JP6666450B2/en
Application filed by Shenyang Sinochem Agrochemicals R&D Co Ltd filed Critical Shenyang Sinochem Agrochemicals R&D Co Ltd
Priority to CN201680059934.XA priority patent/CN108602768A/en
Priority to HRP20220483TT priority patent/HRP20220483T1/en
Publication of WO2017067500A1 publication Critical patent/WO2017067500A1/en
Priority to CONC2018/0003974A priority patent/CO2018003974A2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

The invention relates to the field of mite killers, and specifically, to a biphenyl compound and application thereof. The structure is expressed by formula I, and each substituent in the formula is defined in the specification. The formula I compound has favorable acaricidal activity, and can be used in preventing and treating all kinds of mite problems.

Description

一种联苯类化合物及其应用Biphenyl compound and application thereof 技术领域Technical field

本发明属农用杀螨剂领域，具体地涉及一种联苯类化合物及其应用。The invention belongs to the field of agricultural acaricides, in particular to a biphenyl compound and application thereof.

背景技术Background technique

具有联苯结构的化合物在药物领域中有着广泛的研究与应用。专利JP 2009023910A中公开了如下通式化合物，主要用作杀螨剂和杀虫剂。Compounds having a biphenyl structure have been extensively studied and applied in the pharmaceutical field. A compound of the general formula which is mainly used as an acaricide and an insecticide is disclosed in the patent JP 2009023910A.

Figure PCTCN2016102837-appb-000001
Figure PCTCN2016102837-appb-000001

现有技术中如本发明通式I所示的化合物未见报道。The compounds of the formula I according to the invention are not reported in the prior art.

发明内容Summary of the invention

本发明的目的在于提供一种在很小的剂量下就可以控制多种害螨的联苯类化合物，它可应用于农业、林业及卫生领域中防治害螨。It is an object of the present invention to provide a biphenyl compound which can control a variety of pests at a small dose, and which can be applied to the control of mites in agriculture, forestry and health.

本发明的技术方案如下：The technical solution of the present invention is as follows:

一种联苯类化合物，化合物如通式I所示：A biphenyl compound having the compound as shown in Formula I:

Figure PCTCN2016102837-appb-000002
Figure PCTCN2016102837-appb-000002

式中：In the formula:

R1、R2各自独立地选自氢、C1-C8烷基、卤代C1-C8烷基、C2-C8烯基、卤代C2-C8烯基、C2-C8炔基、卤代C2-C8炔基、氰基C1-C8烷基或氰基卤代C1-C8烷基；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;

m、n各自独立地选自0、1或2。m, n are each independently selected from 0, 1, or 2.

可选，通式I中Optional, in Formula I

R1、R2各自独立地选自卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基或氰基卤代C1-C8烷基；进一步地说，R1、R2还可相同的选自卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基或氰基卤代C1-C8烷基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

m、n各自独立地选自0、1或2。m, n are each independently selected from 0, 1, or 2.

进一步可选，R1与R2各自独立地选自卤代C1-C3烷基、卤代C2-C6烯基、卤代C2-C6炔基或氰基卤代C1-C3烷基；进一步地说，R1与R2还可相同的选自卤代C1-C3烷基、卤代C2-C6烯基、卤代C2-C6炔基或氰基卤代C1-C3烷基；Further optionally, 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;

m、n各自独立地选自0或1。 m, n are each independently selected from 0 or 1.

再进一步可选，通式I中Further optional, in Formula I

R1与R2各自独立地选自三氟甲基、CH2CF3、CH2CHF2、CH2CH2F或CH＝CF2；进一步地说，R1与R2还可相同的选自三氟甲基、CH2CF3、CH2CHF2、CH2CH2F或CH＝CF2；R 1 and R 2 are each independently selected from trifluoromethyl, CH 2 CF 3 , CH 2 CHF 2 , CH 2 CH 2 F or CH=CF 2 ; further, R 1 and R 2 may also be selected identically From trifluoromethyl, CH 2 CF 3 , CH 2 CHF 2 , CH 2 CH 2 F or CH=CF 2 ;

m、n各自独立地选自0或1。m, n are each independently selected from 0 or 1.

又进一步可选，通式I中Further optional, in formula I

R1与R2各自独立地选自CH2CF3或CH2CHF2；进一步地说，R1与R2还可相同的选自CH2CF3或CH2CHF2；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 ;

m、n各自独立地选自0或1。m, n are each independently selected from 0 or 1.

一种通式I所示化合物在农业、林业及卫生领域中用作杀螨剂的用途。Use of a compound of formula I as an acaricide in the agricultural, forestry and hygiene sectors.

一种杀螨组合物，组合物中含有所述通式I所示化合物和农业上可接受的载体；以所述通式I所示化合物为活性组分，所述组合物中活性组分的重量百分含量为0.1-99％。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%.

上述给出的通式I化合物的定义中，汇集所用术语一般代表如下取代基：In the definitions of the compounds of formula I given above, the terms used in the collection generally refer to the following substituents:

烷基：直链、支链或环状烷基，例如甲基、乙基、正丙基、异丙基或不同的丁基、戊基、己基异构体，以及环丙基、环戊基、环己基或环丙基甲基等。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.

卤代烷基：直链、支链或环状烷基，在这些烷基上的氢原子可部分或全部被卤素所取代，例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、七氟异丙基等。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.

烯基：包括直链或支链烯类，例如乙烯基、1-丙烯基、2-丙烯基和不同的丁烯基、戊烯基和己烯基异构体；烯基还包括多烯类如1,2-丙二烯基和2,4-己二烯基。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.

卤代烯基：可被卤原子取代至少一个或多个氢原子的烯基。Haloalkenyl: an alkenyl group which may be substituted with at least one or more hydrogen atoms by a halogen atom.

炔基：包括直链或支链炔类，如乙炔基、1-丙炔基和不同的丁炔基、戊炔基和己炔基异构体；炔基还包括由多个三键组成的基团，例如2,5-己二炔基。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.

卤代炔基：可被卤原子取代至少一个或多个氢原子的炔基。Haloalkynyl: an alkynyl group which may be substituted with at least one or more hydrogen atoms by a halogen atom.

氰基烷基：CN-烷基-，例如NCCH2-。Cyanoalkyl: CN-alkyl-, such as NCCH 2 -.

氰基卤代烷基：CN-卤代烷基-，例如NCCHBr-。Cyanohaloalkyl: CN-haloalkyl-, such as NCCHBr-.

在本发明的化合物中，由于不同的取代方式，通式I化合物可以不同手征性(chirality)结构，包括中心型手征性、轴型手征性或面型手征性结构，且不同的结构的化合物可以以对映体或非对映体的不同形式存在；此外，所述通式I所示化合物还包括顺式/反式异构等各种立体异构体，本发明所要保护的通式I所示化合物并不受上述各类异构体结构限定。In the compounds of the present invention, 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.

本发明提供还提供了上述通式I所示化合物在农业、林业及卫生领域中用作杀螨剂的用途。The invention also provides the use of a compound of the above formula I as an acaricide in the agricultural, forestry and sanitary fields.

本发明又提供了一种杀螨组合物，所述组合物中含上述通式I所示化合物和农业上可接受的载体；以所述通式I所示化合物为活性组分，所述组合物中活性组分的重量百分含量为0.1-99％。所示组合物可包括各类异体结构的上述通式I所示的化合物。 The invention further provides 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.

表1中列出的具体化合物可以用来说明本发明，但并不限定本发明。The specific compounds listed in Table 1 can be used to illustrate the invention, but are not intended to limit the invention.

表1Table 1

Figure PCTCN2016102837-appb-000003
Figure PCTCN2016102837-appb-000003

编号Numbering R1 R 1 R2 R 2 mm nn 11 CH2CF3 CH 2 CF 3 CH2CF3 CH 2 CF 3 00 00 22 CH2CF3 CH 2 CF 3 CH2CF3 CH 2 CF 3 00 11 33 CH2CF3 CH 2 CF 3 CH2CF3 CH 2 CF 3 11 11 44 CH2CF3 CH 2 CF 3 CH2CF3 CH 2 CF 3 11 22 55 CF3 CF 3 CH2CF3 CH 2 CF 3 00 00 66 CF3 CF 3 CH2CF3 CH 2 CF 3 00 11 77 CF3 CF 3 CH2CF3 CH 2 CF 3 11 11 88 CH3 CH 3 CH2CF3 CH 2 CF 3 00 00 99 CH3 CH 3 CH2CF3 CH 2 CF 3 00 11 1010 CH3 CH 3 CH2CF3 CH 2 CF 3 11 11 1111 CH2CH3 CH 2 CH 3 CH2CF3 CH 2 CF 3 00 00 1212 CH2CH3 CH 2 CH 3 CH2CF3 CH 2 CF 3 00 11 1313 CH2CH3 CH 2 CH 3 CH2CF3 CH 2 CF 3 11 11 1414 环丙基甲基Cyclopropylmethyl CH2CF3 CH 2 CF 3 00 00 1515 环丙基甲基Cyclopropylmethyl CH2CF3 CH 2 CF 3 00 11 1616 环丙基甲基Cyclopropylmethyl CH2CF3 CH 2 CF 3 11 11 1717 CH2CH2CF3 CH 2 CH 2 CF 3 CH2CF3 CH 2 CF 3 00 00 1818 CH2CH2CF3 CH 2 CH 2 CF 3 CH2CF3 CH 2 CF 3 00 11 1919 CH2CH2CF3 CH 2 CH 2 CF 3 CH2CF3 CH 2 CF 3 11 11 2020 CH2CClF2 CH 2 CClF 2 CH2CF3 CH 2 CF 3 00 00 21twenty one CH2CClF2 CH 2 CClF 2 CH2CF3 CH 2 CF 3 00 11 22twenty two CH2CClF2 CH 2 CClF 2 CH2CF3 CH 2 CF 3 11 11 23twenty three CF2CHF2 CF 2 CHF 2 CH2CF3 CH 2 CF 3 00 00 24twenty four CF2CHF2 CF 2 CHF 2 CH2CF3 CH 2 CF 3 00 11 2525 CF2CHF2 CF 2 CHF 2 CH2CF3 CH 2 CF 3 11 11

2626 CF2CHClFCF 2 CHClF CH2CF3 CH 2 CF 3 00 00 2727 CF2CHClFCF 2 CHClF CH2CF3 CH 2 CF 3 00 11 2828 CF2CHClFCF 2 CHClF CH2CF3 CH 2 CF 3 11 11 2929 CH2CF2CHF2 CH 2 CF 2 CHF 2 CH2CF3 CH 2 CF 3 00 00 3030 CH2CF2CHF2 CH 2 CF 2 CHF 2 CH2CF3 CH 2 CF 3 00 11 3131 CH2CF2CHF2 CH 2 CF 2 CHF 2 CH2CF3 CH 2 CF 3 11 11 3232 CH2CF2CF3 CH 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 00 3333 CH2CF2CF3 CH 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 11 3434 CH2CF2CF3 CH 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 11 11 3535 CF2CHFCF3 CF 2 CHFCF 3 CH2CF3 CH 2 CF 3 00 00 3636 CF2CHFCF3 CF 2 CHFCF 3 CH2CF3 CH 2 CF 3 00 11 3737 CF2CHFCF3 CF 2 CHFCF 3 CH2CF3 CH 2 CF 3 11 11 3838 CH2CF2CF2CF3 CH 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 00 3939 CH2CF2CF2CF3 CH 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 11 4040 CH2CF2CF2CF3 CH 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 11 11 4141 CH2CF2CF2CF2CF3 CH 2 CF 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 00 4242 CH2CF2CF2CF2CF3 CH 2 CF 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 11 4343 CH2CF2CF2CF2CF3 CH 2 CF 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 11 11 4444 CH2CF2CF2CF2CF2CF3 CH 2 CF 2 CF 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 00 4545 CH2CF2CF2CF2CF2CF3 CH 2 CF 2 CF 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 00 11 4646 CH2CF2CF2CF2CF2CF3 CH 2 CF 2 CF 2 CF 2 CF 2 CF 3 CH2CF3 CH 2 CF 3 11 11 4747 CH2CH2CH3 CH 2 CH 2 CH 3 CH2CF3 CH 2 CF 3 00 00 4848 CH2CH2CH3 CH 2 CH 2 CH 3 CH2CF3 CH 2 CF 3 00 11 4949 CH2CH2CH3 CH 2 CH 2 CH 3 CH2CF3 CH 2 CF 3 11 11 5050 3,4,4-三氟-3-丁烯-1-基3,4,4-trifluoro-3-buten-1-yl CH2CF3 CH 2 CF 3 00 00 5151 3,4,4-三氟-3-丁烯-1-基3,4,4-trifluoro-3-buten-1-yl CH2CF3 CH 2 CF 3 00 11 5252 3,4,4-三氟-3-丁烯-1-基3,4,4-trifluoro-3-buten-1-yl CH2CF3 CH 2 CF 3 11 11 5353 CH2CH2CH2CH3 CH 2 CH 2 CH 2 CH 3 CH2CF3 CH 2 CF 3 00 00 5454 CH2CH2CH2CH3 CH 2 CH 2 CH 2 CH 3 CH2CF3 CH 2 CF 3 00 11 5555 CH2CH2CH2CH3 CH 2 CH 2 CH 2 CH 3 CH2CF3 CH 2 CF 3 11 11 5656 CH2CHF2 CH 2 CHF 2 CH2CF3 CH 2 CF 3 00 00 5757 CH2CHF2 CH 2 CHF 2 CH2CF3 CH 2 CF 3 00 11 5858 CH2CHF2 CH 2 CHF 2 CH2CF3 CH 2 CF 3 11 11 5959 CH2CH2FCH 2 CH 2 F CH2CF3 CH 2 CF 3 00 00

6060 CH2CH2FCH 2 CH 2 F CH2CF3 CH 2 CF 3 00 11 6161 CH2CH2FCH 2 CH 2 F CH2CF3 CH 2 CF 3 11 11 6262 CH2CHF2 CH 2 CHF 2 CH2CHF2 CH 2 CHF 2 00 00 6363 CH2CHF2 CH 2 CHF 2 CH2CHF2 CH 2 CHF 2 00 11 6464 CH2CHF2 CH 2 CHF 2 CH2CHF2 CH 2 CHF 2 11 11

部分代表性化合物核磁氢谱(300MHz,CDCl3)数据如下：The nuclear hydrogen spectroscopy (300MHz, CDCl 3 ) data of some representative compounds are as follows:

化合物1:δ(ppm):2.53(s,6H),3.35(q,4H),7.08(m,2H),7.55(m,2H).Compound 1: δ (ppm): 2.53 (s, 6H), 3.35 (q, 4H), 7.08 (m, 2H), 7.55 (m, 2H).

化合物2:δ(ppm):2.45(s,3H),2.54(s,3H),3.34(q,2H),3.48(q,2H),7.07-7.12(m,2H),7.58(d,1H),7.99(d,1H).Compound 2: δ (ppm): 2.45 (s, 3H), 2.54 (s, 3H), 3.34 (q, 2H), 3.48 (q, 2H), 7.07-7.12 (m, 2H), 7.58 (d, 1H) ), 7.99 (d, 1H).

化合物3:δ(ppm):2.46(s,6H),3.97-4.08(m,4H),7.30-7.32(m,2H),7.93-7.95(m,2H).Compound 3: δ (ppm): 2.46 (s, 6H), 3.97-4.08 (m, 4H), 7.30-7.32 (m, 2H), 7.93-7.95 (m, 2H).

化合物62:δ(ppm):2.50(s,6H),3.05-3.20(m,4H),5.65-6.06(m,2H),7.04-7.07(m,2H),7.46-7.49(m,2H).Compound 62: δ (ppm): 2.50 (s, 6H), 3.05-3.20 (m, 4H), 5.65-6.06 (m, 2H), 7.04-7.07 (m, 2H), 7.46-7.49 (m, 2H) .

化合物63:δ(ppm):2.42(s,3H),2.46(s,3H),3.31-3.64(m,4H),5.90-6.70(m,2H),7.22(d,1H),7.28(d,1H),7.60(d,1H),7.83(d,1H).Compound 63: δ (ppm): 2.42 (s, 3H), 2.46 (s, 3H), 3.31-3.64 (m, 4H), 5.90-6.70 (m, 2H), 7.22 (d, 1H), 7.28 (d) , 1H), 7.60 (d, 1H), 7.83 (d, 1H).

本发明的通式I化合物可按照以下方法制备，除另有注明外，式中各基团的定义同前。The compounds of the formula I according to the invention can be prepared according to the following procedure, the meaning of each group in the formula being the same as before, unless otherwise stated.

方法一(用于制备R1＝R2且m＝n＝0的通式I化合物，下式中R＝R1＝R2)：Method 1 (for the preparation of a compound of formula I wherein R 1 =R 2 and m=n=0, where R = R 1 = R 2 ):

Figure PCTCN2016102837-appb-000004
Figure PCTCN2016102837-appb-000004

中间体II与适宜的卤代试剂在适宜的溶剂中、适宜的碱存在下，温度从0℃到溶剂沸点下反应0.5-48小时制得通式III化合物。适宜的卤代试剂可选自碘甲烷、碘乙烷、三氟碘乙烷、溴代环丙烷、氯乙腈、溴乙烯、3-溴丙炔、三氟甲基碘、三氟碘乙烷、二溴乙腈、2-溴-1,1-二氟乙烯、二溴乙炔等。适宜的溶剂可选自水、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙腈、四氢呋喃、二氧六环、DMF或DMSO等。适宜的碱可选自氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、碳酸氢钠、三乙胺、吡啶、甲醇钠、乙醇钠、氢化钠、叔丁醇钾或叔丁醇钠等。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.

通式III化合物与亚硝酸钠、一种或多种酸、碘化钾反应制得通式IV化合物。酸可以是无机酸或有机酸，例如盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸或甲磺酸等。反应溶剂可选自水、氯仿、二氯甲烷、四氯化碳、己烷、苯、甲苯、乙酸乙酯、DMF、四氢呋喃或二氧六环等。反应通常在0-100℃的温度进行。反应时间通常在0.5-48小时。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.

通式IV化合物与联硼酸频哪醇酯在适宜的溶剂中、适宜的碱、适宜的钯催化剂存在下，温度从-10℃到溶剂沸点下反应0.5-48小时制得通式I-1化合物。适宜的溶剂可选自 水、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙腈、四氢呋喃、二氧六环、DMF或DMSO等。适宜的碱包括碱金属如锂、钠或钾的氢化物如氢化钠、氢化钾，碱金属如锂、钠或钾的氢氧化物如氢氧化钠、氢氧化钾，还可以是碱金属锂、钠、钾或铯的碳酸盐如碳酸钠、碳酸铯，也可以是有机碱如三乙胺、叔丁醇钠或叔丁醇钾等。适宜的钯催化剂可选自四(三苯基膦)钯、[1,1’-双(二苯基膦基)二茂铁]二氯化钯等。某些情况下，还可以加入适宜的配体如1,1’-双(二苯基膦基)二茂铁、三苯基膦、三叔丁基膦等。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. In some cases, a suitable ligand such as 1,1'-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-tert-butylphosphine or the like may also be added.

方法二(用于制备m＝n＝0的通式I化合物，R1、R2可相等或不等)：Method 2 (for the preparation of a compound of formula I wherein m = n = 0, R 1 , R 2 may be equal or unequal):

Figure PCTCN2016102837-appb-000005
Figure PCTCN2016102837-appb-000005

中间体II与亚硝酸钠、一种或多种酸、碘化钾反应制得中间体V。酸可以是无机酸或有机酸，例如盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸或甲磺酸等。反应溶剂可选自水、氯仿、二氯甲烷、四氯化碳、己烷、苯、甲苯、乙酸乙酯、DMF、四氢呋喃或二氧六环等。反应通常在0-100℃的温度进行。反应时间通常在0.5-48小时。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.

中间体V与联硼酸频哪醇酯在适宜的溶剂中、适宜的碱、适宜的钯催化剂存在下，温度从-10℃到溶剂沸点下反应0.5-48小时制得中间体VI。适宜的溶剂可选自水、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙腈、四氢呋喃、二氧六环、DMF或DMSO等。适宜的碱包括碱金属如锂、钠或钾的氢化物如氢化钠、氢化钾，碱金属如锂、钠或钾的氢氧化物如氢氧化钠、氢氧化钾，还可以是碱金属锂、钠、钾或铯的碳酸盐如碳酸钠、碳酸铯，也可以是有机碱如三乙胺、叔丁醇钠或叔丁醇钾等。适宜的钯催化剂可选自四(三苯基膦)钯、[1,1’-双(二苯基膦基)二茂铁]二氯化钯等。某些情况下，还可以加入适宜的配体如1,1’-双(二苯基膦基)二茂铁、三苯基膦、三叔丁基膦等。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. In some cases, a suitable ligand such as 1,1'-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-tert-butylphosphine or the like may also be added.

中间体VI与适宜的卤代试剂在适宜的溶剂中、适宜的碱存在下，通过一步可制得通式I-2化合物；而后由通式I-2化合物进一步反应可制得通式I-3化合物。适宜的卤代试剂可选自碘甲烷、碘乙烷、三氟碘乙烷、溴代环丙烷、氯乙腈、溴乙烯、3-溴丙炔、三氟甲基碘、三氟碘乙烷、二溴乙腈、2-溴-1,1-二氟乙烯、二溴乙炔等。适宜的溶剂可选自水、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙腈、四氢呋喃、二氧六环、DMF或DMSO等。适宜的碱可选自氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、碳酸氢钠、三乙 胺、吡啶、甲醇钠、乙醇钠、氢化钠、叔丁醇钾或叔丁醇钠等。反应通常在0℃到溶剂沸点下进行。反应时间通常在0.5-48小时。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.

方法三(用于制备m、n＝0、1或2的通式I化合物(但m、n不同时为0))：Method 3 (for the preparation of m, n = 0, 1 or 2 of the compound of formula I (but m and n are not 0 at all)):

Figure PCTCN2016102837-appb-000006
Figure PCTCN2016102837-appb-000006

通式I-1～3化合物与合适的氧化剂反应可制得相应的亚砜或砜，即通式I-4化合物。合适的氧化剂可为间氯过氧苯甲酸、双氧水或(偏)高碘酸钠等。反应溶剂主要选自水、甲醇、乙醇、乙醚、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、DMF、四氢呋喃或二氧六环等。反应通常在0-100℃的温度进行，优选在20-40℃进行。反应时间通常在10分钟-48小时。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.

上述制备方法中所涉及的原料及中间体来源如下：The sources of raw materials and intermediates involved in the above preparation methods are as follows:

中间体II可以按公知方法制备，例如参照WO2010100189、US2012053052、JP2012519662、EP2403837或CN102341376等报道的方法制得。The intermediate II can be produced by a known method, for example, by the methods reported in WO2010100189, US2012053052, JP2012519662, EP2403837 or CN102341376.

卤代试剂、亚硝酸钠、无机或有机酸、碘化钾、联硼酸频哪醇酯、钯催化剂、配体、氧化试剂及其它常规原料和试剂通常有市售，也可按照常规方法自制。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.

由于本发明的联苯类化合物具有意想不到的高杀螨活性，因此本发明还包括通式I化合物用于控制害螨的用途。尤其是，通式I化合物对下列科的重要品种有活性：叶螨科(二斑叶螨、朱砂叶螨、苹果全爪螨、柑橘全爪螨等)、瘿螨科、跗线螨科等。Since the biphenyl compounds of the present invention have unexpectedly high acaricidal activity, the present invention also encompasses the use of the compounds of formula I for the control of mites. In particular, 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.

由于其积极的特性，上述化合物可有利地用于保护农业和园艺业重要的作物、家畜和种畜，以及人类常去的环境免于有害螨虫的伤害。Due to their positive properties, 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.

为获得理想效果，化合物的用量因各种因素而改变，例如所用化合物、预保护的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型。To achieve the desired effect, 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.

每公顷10克-5千克的化合物剂量能提供充分的防治。A dose of 10 grams to 5 kilograms of compound per hectare provides adequate control.

本发明的另一目的还涉及通过施用通式I化合物，防治农业和园艺业重要的作物和/或家畜和种畜和/或人类常去的环境中的害螨的方法。尤其是，化合物的用量在每公顷10克-5千克内变化。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. In particular, the amount of the compound varies from 10 g to 5 kg per hectare.

为了实际应用于农业，使用含一种或多种通式I化合物的组合物通常是有益的。For practical application in agriculture, it is generally advantageous to use a composition comprising one or more compounds of formula I.

因此，本发明的另外一种技术方案还包括一种杀螨组合物，含有作为活性组分的通式I化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为0.1-99％。Accordingly, another embodiment of the present invention further comprises 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%.

组合物的使用形式可以是干粉、可湿性粉剂、乳油、微乳剂、糊剂、颗粒剂、溶液、悬浮剂等，组合物类型的选择取决于具体的应用。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.

组合物是以已知方式制备的，例如任选在表面活性剂的存在下，通过用溶剂介质和/ 或固体稀释剂稀释或溶解活性物质。The 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.

可用的固体稀释剂或载体可以是二氧化硅、高岭土、膨润土、滑石、硅藻土、白云石、碳酸钙、氧化镁、白垩、粘土、合成硅酸盐、硅镁土、海泡石等。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.

除水以外，可用的液体稀释剂是芳族有机溶剂(二甲苯或烷基苯的混合物、氯苯等)、石蜡(石油馏分)、醇类(甲醇、丙醇、丁醇、辛醇、甘油)、酯类(乙酸乙酯、乙酸异丁酯等)、酮类(环己酮、丙酮、苯乙酮、异佛尔酮、乙基戊基酮等)、酰胺类(N,N-二甲基甲酰胺、N-甲基吡咯烷酮等)。In addition to water, 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.).

可用的表面活性剂是烷基磺酸盐、烷基芳基磺酸盐、聚氧乙烯烷基酚、山梨醇的聚氧乙烯酯、木质素磺酸盐等的钠、钙、三乙基胺或三乙醇胺盐。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.

组合物还可含特殊的添加剂用于特定的目的，例如粘合剂如阿拉伯胶、聚乙烯醇、聚乙烯吡咯烷酮等。The compositions may also contain special additives for specific purposes such as binders such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone and the like.

上述组合物中活性成分的浓度可根据活性成分、其使用目的、环境条件和采用的制剂类型而在较宽范围内改变。通常，活性成分的浓度范围是1-90％，优选5-50％。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%.

具体实施方式detailed description

以下具体实施例用来进一步说明本发明，但本发明绝非限于这些例子。(除另有注明外，所用原料均有市售)The following specific examples are intended to further illustrate the invention, but the invention is in no way limited to these examples. (All materials used are commercially available unless otherwise stated)

合成实施例Synthesis example

实施例1：化合物1的制备Example 1: Preparation of Compound 1

Figure PCTCN2016102837-appb-000007
Figure PCTCN2016102837-appb-000007

1.1中间体IV-1的制备1.1 Preparation of intermediate IV-1

称取3-(2,2,2-三氟乙硫基)-4-甲基-6-氟苯胺(中间体III-1，可参照WO2010100189、US2012053052、JP2012519662、EP2403837或CN102341376等报道的方法制得)10.00克(41.80mmol)置于500毫升三口瓶中，加入60毫升浓盐酸，降温至0-5℃，搅拌反应30分钟。向其中缓慢滴加亚硝酸钠3.46克(50.15mmol)的100毫升水溶液，在此过程中，维持反应温度不超过0-5℃。滴加完毕后，继续搅拌反应1小时。3-(2,2,2-Trifluoroethylthio)-4-methyl-6-fluoroaniline (Intermediate III-1) can be weighed by the method reported in WO2010100189, US2012053052, JP2012519662, EP2403837 or CN102341376. 10.00 g (41.80 mmol) was placed in a 500 ml three-necked flask, 60 ml of concentrated hydrochloric acid was added, the temperature was lowered to 0-5 ° C, and the reaction was stirred for 30 minutes. A solution of 3.46 g (50.15 mmol) of sodium nitrite in 100 ml of water was slowly added dropwise thereto, during which the reaction temperature was maintained at not more than 0 to 5 °C. After the dropwise addition was completed, the reaction was further stirred for 1 hour.

向该重氮盐溶液中缓慢滴加碘化钾13.88克(83.61mmol)的100毫升水溶液，在此过程中，维持反应温度不超过0-5℃。撤去冰浴，室温下继续搅拌反应3小时。TLC监测反应完毕后，加入300毫升乙酸乙酯稀释，有机层依次用200毫升水、200毫升饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，粗品柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:30)纯化，得油状物8.79克。To the diazonium salt solution, 13.88 g (83.61 mmol) of a 100 ml aqueous solution of potassium iodide was slowly added dropwise, during which the reaction temperature was maintained at not more than 0 to 5 °C. The ice bath was removed and the reaction was stirred at room temperature for 3 hours. After the reaction was completed by TLC, the mixture was diluted with ethyl acetate (300 ml), and the organic layer was washed with 200 ml of water and 200 ml of brine, dried over anhydrous magnesium sulfate, filtered, It was purified by ethyl acetate and petroleum ether in a volume ratio of 1:30 to give 8.79 g of an oil.

1.2、化合物1的制备1.2, Preparation of Compound 1

称取中间体IV-1 5.00克(14.28mmol)，联硼酸频哪醇酯5.44克(21.42mmol)， 碳酸铯9.32克(28.60mmol)，[1,1’-双(二苯基膦基)二茂铁]二氯化钯0.06克，1,1’-双(二苯基膦基)二茂铁0.04克，加入100毫升1,4-二氧六环，3毫升水。加热回流3小时。TLC监测反应完毕后，加入200毫升乙酸乙酯稀释，有机层依次用100毫升水、100毫升饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，粗品柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:30)纯化，得白色固体4.79克(熔点:59-60℃)。Weighing intermediate IV-1 5.00 g (14.28 mmol), bisboronic acid pinacol ester 5.44 g (21.42 mmol), 9.32 g (28.60 mmol) of cesium carbonate, 0.06 g of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocene 0.04 g, add 100 ml of 1,4-dioxane, 3 ml of water. Heat to reflux for 3 hours. After the reaction was completed by TLC, the mixture was diluted with ethyl acetate (200 ml), and the organic layer was washed with 100 ml of water and 100 ml of brine, dried over anhydrous magnesium sulfate, filtered, Purification of ethyl acetate and petroleum ether in a volume ratio of 1:30) gave 4.79 g (yield: 59-60 ° C) as a white solid.

核磁数据如下：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.53(s,6H),3.35(q,4H),7.08(m,2H),7.55(m,2H)。LC-MS(m/z):446.9(m+1)。The nuclear magnetic data are as follows: 1 H NMR (300 MHz, internal standard TMS, solvent CDCl 3 ) δ (ppm): 2.53 (s, 6H), 3.35 (q, 4H), 7.08 (m, 2H), 7.55 (m, 2H) . LC-MS (m/z): 446.9 (m-1).

实施例2：化合物2和3的制备Example 2: Preparation of Compounds 2 and 3

Figure PCTCN2016102837-appb-000008
Figure PCTCN2016102837-appb-000008

将2.00克(4.48mmol)化合物1溶于20毫升氯仿中，降温至0-5℃。在此温度下，分三次加入0.98克(4.68mmol，85％纯度)间氯过氧苯甲酸。将反应混合物在0-5℃温度下搅拌2小时。TLC监测反应完毕后，反应液依次用硫代硫酸钠水溶液和碳酸氢钠水溶液洗涤并用无水硫酸镁干燥、过滤、减压脱溶，粗品柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:6～1:3)纯化后分别得到1.21克化合物2(白色固体)和0.70克化合物3(白色固体)。核磁及质谱数据如下：2.00 g (4.48 mmol) of compound 1 was dissolved in 20 ml of chloroform and cooled to 0-5 °C. At this temperature, 0.98 g (4.68 mmol, 85% purity) of m-chloroperoxybenzoic acid was added in three portions. The reaction mixture was stirred at a temperature of 0 to 5 ° C for 2 hours. After the reaction was completed by TLC, the reaction mixture was washed successively with aqueous sodium thiosulfate and aqueous sodium hydrogen carbonate and dried over anhydrous magnesium sulfate, filtered, and evaporated. The volume ratio was 1:6 to 1:3. After purification, 1.21 g of Compound 2 (white solid) and 0.70 g of Compound 3 (white solid) were obtained, respectively. The nuclear magnetic and mass spectrometry data are as follows:

化合物2：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.45(s,3H),2.54(s,3H),3.34(q,2H),3.48(q,2H),7.07-7.12(m,2H),7.58(d,1H),7.99(d,1H)。LC-MS(m/z):463.0(m+1)。Compound 2: 1 H NMR (300MHz, internal standard TMS, solvent CDCl 3) δ (ppm): 2.45 (s, 3H), 2.54 (s, 3H), 3.34 (q, 2H), 3.48 (q, 2H), 7.07-7.12 (m, 2H), 7.58 (d, 1H), 7.99 (d, 1H). LC-MS (m/z): 46.

化合物3：1H NMR(300MHz，内标TMS，溶剂DMSO)δ(ppm):2.46(s,6H),3.97-4.08(m,4H),7.30-7.32(m,2H),7.93-7.95(m,2H)。LC-MS(m/z):479.0(m+1)。Compound 3: 1 H NMR (300MHz, internal standard TMS, solvent DMSO) δ (ppm): 2.46 (s, 6H), 3.97-4.08 (m, 4H), 7.30-7.32 (m, 2H), 7.93-7.95 ( m, 2H). LC-MS (m/z): 479.0 (m-1).

参照以上实施例还可以制备获得本发明通式I中R1与R2相同的其它化合物。具体是按照上述通式I化合物制备方法一中记载，将反应过程中试剂进行替换进而可获得这些化合物。本发明通式I中R1与R2不同的化合物，可按照上述通式I化合物制备方法二中记载，采用不同的适宜卤代试剂进行合成可获得这些化合物。Other compounds in which 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.

生物活性测定Biological activity assay

实施例3温室杀螨活性测定Example 3 Determination of Greenhouse Killing Activity

采用上述获得通式I化合物进行温室杀螨活性测定，具体：The above formula I is used to obtain the greenhouse acaricidal activity assay, specifically:

根据待测化合物的溶解性，用丙酮或二甲基亚砜溶解，并用0.1％的吐温80溶液配置所需浓度的待测溶液50毫升，丙酮或二甲基亚砜在溶液中的含量不超过10％。According to the solubility of 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%.

3.1对朱砂叶螨成螨活性测定3.1 Determination of the activity of cinnabarin

取两片真叶菜豆苗，接种朱砂叶螨成螨并调查基数后，用手持喷雾器进行整株喷雾处理，每处理3次重复，处理后置于标准观察室，72小时后调查存活螨数，计算死亡率。Take two pieces of true leafy bean sprouts, inoculate the cinnabar leaf mites into a mites and investigate the base number, then spray the whole plant with a hand-held sprayer, repeat 3 times each time, put it in the standard observation room after treatment, investigate the survival number after 72 hours, calculate the death rate.

根据上述方法，对以多个R1和R2为相同的卤代烷基化合物作为实施例，本发明化合物进行了杀螨活性测定，部分试验结果见表2。 According to the above method, 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.

表2：对朱砂叶螨成螨活性数据(死亡率，％)Table 2: Activity data on saplings of A. cinnafolia (mortality, %)

Figure PCTCN2016102837-appb-000009
Figure PCTCN2016102837-appb-000009

注:“/”表示未进行测试。Note: “/” means that no test has been performed.

由上述表格中可见本发明所述化合物具有杀螨生物活性，现以上述表2中化合物1进一步对杀螨活性进行检测，具体如下：It can be seen from the above table that the compound of the present invention has acaricidal activity, and the acaricidal activity is further tested by the compound 1 in Table 2 above, as follows:

3.2对朱砂叶螨若螨活性测定3.2 Determination of the activity of cinnabarin

取两片真叶盆栽菜豆苗，然后将健康朱砂叶螨雌成螨10头接到叶片上，24小时后去除成螨，对螨卵继续进行培养，10天后进入若螨调查基数后进行喷雾处理，每处理3次重复，处理后置于标准观察室，72小时后调查存活螨数，计算死亡率。Take two pieces of true leaf potted bean sprouts, and then connect the healthy cinnabar leaves to the leaves, and then remove them into the leaves. After 24 hours, the eggs are removed and the eggs are continuously cultured. After 10 days, they are sprayed into the base of the investigation. Each treatment was repeated 3 times, and the treatment was placed in a standard observation room. After 72 hours, the number of survival was investigated and the mortality was calculated.

按上述方法，将本发明高活性化合物1与商品化产品95％哒螨灵原药进行朱砂叶螨若满活性的平行测定，试验结果见表3。According to the above method, the highly active compound 1 of the present invention and the commercialized product 95% of the original drug were tested in parallel for the activity of the cinnabar, and the test results are shown in Table 3.

表3:杀朱砂叶螨若螨活性数据(死亡率,％)Table 3: Activity data of killing cinnabar leaves (mortality, %)

Figure PCTCN2016102837-appb-000010
Figure PCTCN2016102837-appb-000010

3.3对朱砂叶螨螨卵活性测定3.3 Determination of egg activity of T. cinnabarinus

取两片真叶盆栽菜豆苗，去除一片真叶，然后将健康朱砂叶螨雌成螨10头接到叶片上，24小时后去除成螨，调查卵数后进行喷雾处理，每处理3次重复。5天后待空白对照卵全部孵化，调查各处理未孵化卵数，计算孵化抑制率。Take two pieces of true leaf potted bean sprouts, remove one true leaf, and then connect the healthy cinnabar leaves to the head of the scorpion, and then remove the sputum into the leaves. After 24 hours, the mites are removed. The number of eggs is investigated and sprayed, and each treatment is repeated three times. . After 5 days, all the blank control eggs were hatched, and the number of unhatched eggs in each treatment was investigated to calculate the hatching inhibition rate.

按上述方法，将上述实施例获得的化合物1与商品化产品98％螺螨酯原药进行杀朱砂叶螨螨卵活性的平行测定，试验结果见表4。According to the above method, the compound 1 obtained in the above examples and the 98% snail ester of the commercial product were tested for the parallel activity of the eggs of the genus Corydalis, and the test results are shown in Table 4.

表4:对朱砂叶螨螨卵活性数据(孵化抑制率,％)Table 4: Activity data on the eggs of T. cinnabarinus (incubation inhibition rate, %)

Figure PCTCN2016102837-appb-000011
Figure PCTCN2016102837-appb-000011

3.4根部吸收对朱砂叶螨内吸活性的测定3.4 Determination of systemic absorption of T. cinnabarinus by root absorption

供试药剂(上述实施例获得化合物)称量并用少量丙酮溶解后，用含有0.1％吐温80的水配置系列浓度，每浓度为一个处理，每处理3次重复，另设清水为空白对照。将10毫升药液装入试管中，取两片真叶的菜豆苗，洗净根部泥土，将菜豆苗根部浸渍于不同处理的药液中，充分吸收24小时后，直接转接朱砂叶螨成螨月30-50头，然后置于25±1℃的观察室中培养，72小时后调查死活螨数，比较各处理成螨死亡率，确定化合物是否具有根部吸收内吸活性，试验结构见表5。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.

表5:化合物1根部吸收对朱砂叶螨成螨内吸活性数据(死亡率,％)Table 5: Suction activity data of compound 1 root absorption on T. cinnabarinus (mortality, %)

Figure PCTCN2016102837-appb-000012
Figure PCTCN2016102837-appb-000012

实施例4：田间小区验证试验Example 4: Field plot verification test

防治柑桔全爪螨田间小区试验(中国江西)Field trial of citrus whole claw cockroach (Jiangxi, China)

试验设在江西赣州2年生沙糖柑桔园进行，砧木为枳，株行距1.50×2.50米，平均株高1.45米，冠幅1.30米。每小区2株树，重复4次，随机区组排列。上述实施例获得化合物1(10％悬浮剂)设100mg/L,50mg/L and 25mg/L三个剂量，螺螨酯(29％悬浮剂)设50mg/L一个剂量，哒螨灵(20％乳油)设100mg/L一个剂量。采用“MATABI”超级16型背负式喷雾器均匀喷雾，喷液量每株约2L。于5月中旬施药1次，此时柑桔全爪螨成螨、幼若螨、螨卵均存在，螨卵个数比为1:1.2。施药当天天气晴好，平均气温24℃，施药后3天均为晴好天气。施药前调查虫口基数，施药后1天、3天、7天、14天、22天和28天各调查一次。调查时每小区调查2株树，按树冠东、西、南、北和中五个方位，各个方位调查5张叶片上的活动态满数，每小区调查50张叶片，根据下式计算螨口减退率及校正防效：The experiment was carried out in the 2 year old sand sugar citrus orchard in Zhangzhou, Jiangxi Province. The rootstock was 枳, the plant spacing was 1.50×2.50 meters, the average plant height was 1.45 meters, and the crown width was 1.30 meters. Two trees per plot were repeated 4 times and arranged in random blocks. In the above examples, Compound 1 (10% suspension) was obtained at 100 mg/L, 50 mg/L and 25 mg/L, and spironolactone (29% suspension) was administered at a dose of 50 mg/L. Epoxy oil) set a dose of 100mg / L. Spray evenly with the “MATABI” Super 16 Knapsack Sprayer, with a spray volume of approximately 2L per plant. It was applied once in mid-May. At this time, 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. At the time of the survey, 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:

螨口减退率(％)＝【(施药前叶均螨数-施药后叶均螨数)/施药前叶均螨数】×100Mouth reduction rate (%) = [(the average number of leaves before application - the average number of leaves after application) / the number of leaves before application] × 100

校正防效(％)＝【(处理区螨口减退率-未处理区螨口减退率)/(100-未处理区螨口减退率)】×100Correction effect (%) = [(treatment area mouth drop rate - untreated area mouth drop rate) / (100 - untreated area mouth drop rate)] × 100

化合1防治柑桔全爪螨田间小区试验(江西赣州)的试验结果见表6。The test results of Compound 1 for controlling the citrus full-claw field field (Jinxi, Jiangxi) are shown in Table 6.

表6Table 6

Figure PCTCN2016102837-appb-000013
Figure PCTCN2016102837-appb-000013

按照上述记载的内容制备获得的本发明通式I所示的其他化合物均具有相应的防治活性的作用。 Other compounds of the formula I of the present invention prepared according to the above description have the corresponding antibacterial activity.

Claims (6)

一种联苯类化合物，其特征在于：化合物如通式I所示：A biphenyl compound characterized in that the compound is as shown in Formula I:
Figure PCTCN2016102837-appb-100001
Figure PCTCN2016102837-appb-100001
 式中：In the formula: R1、R2各自独立地选自氢、C1-C8烷基、卤代C1-C8烷基、C2-C8烯基、卤代C2-C8烯基、C2-C8炔基、卤代C2-C8炔基、氰基C1-C8烷基或氰基卤代C1-C8烷基；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; m、n各自独立地选自0、1或2。m, n are each independently selected from 0, 1, or 2. 根据权利要求1所述的化合物，其特征在于：通式I中A compound according to claim 1 wherein: R1、R2各自独立地选自卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基或氰基卤代C1-C8烷基；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 base; m、n各自独立地选自0、1或2。m, n are each independently selected from 0, 1, or 2. 根据权利要求2所述的化合物，其特征在于：通式I中The compound according to claim 2, wherein in the formula I R1与R2各自独立地选自卤代C1-C3烷基、卤代C2-C6烯基、卤代C2-C6炔基或氰基卤代C1-C3烷基；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 cyano halo C 1 -C 3 alkane base; m、n各自独立地选自0或1。m, n are each independently selected from 0 or 1. 根据权利要求3所述的化合物，其特征在于：通式I中The compound according to claim 3, wherein R1与R2各自独立地选自三氟甲基、CH2CF3、CH2CHF2、CH2CH2F或CH＝CF2；R 1 and R 2 are each independently selected from the group consisting of trifluoromethyl, CH 2 CF 3 , CH 2 CHF 2 , CH 2 CH 2 F or CH=CF 2 ; m、n各自独立地选自0或1。m, n are each independently selected from 0 or 1. 一种按照权利要求1-4所述任意一项通式I所示化合物在农业、林业及卫生领域中用作杀螨剂的用途。Use of a compound of formula I according to any of claims 1-4 as an acaricide in the agricultural, forestry and sanitary fields. 一种杀螨组合物，其特征在于：组合物中含有权利要求1-4所述任意一项所述通式I所示化合物和农业上可接受的载体；以所述通式I所示化合物为活性组分，所述组合物中活性组分的重量百分含量为0.1-99％。 An acaricidal composition, characterized in that the composition comprises a compound of the formula I according to any one of claims 1 to 4 and an agriculturally acceptable carrier; As active ingredient, the active ingredient is present in the composition in an amount of from 0.1 to 99% by weight.
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