CN117062800A - Aryl sulfide and preparation method and application thereof - Google Patents

Aryl sulfide and preparation method and application thereof Download PDF

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Publication number
CN117062800A
CN117062800A CN202280010782.XA CN202280010782A CN117062800A CN 117062800 A CN117062800 A CN 117062800A CN 202280010782 A CN202280010782 A CN 202280010782A CN 117062800 A CN117062800 A CN 117062800A
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haloalkyl
methyl
aryl sulfide
alkyl
formula
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Inventor
柳英帅
李宁
刘祥伟
李先江
刘瑞宾
刘保红
盛国柱
项效忠
陈瑜
冯睿杰
崔迎蕊
韩勤安
王杰
王世玲
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Shandong Kangqiao Bio Technology Co ltd
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Shandong Kangqiao Bio Technology Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P5/00—Nematocides
    • 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
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • 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
    • C07C317/36—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 atoms of the amino groups bound to hydrogen atoms or to carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • 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
    • C07C323/31—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom

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

Abstract

Discloses an aryl sulfide and a synthesis method and application thereof. The aryl sulfide is a compound with a structure shown as a formula I or agriculturally acceptable salt thereof. The aryl sulfide and the agriculturally acceptable salt thereof have excellent effects on various harmful organisms, particularly on spider mites represented by tetranychus cinnabarinus, tetranychus urticae, tetranychus citri, and the like, and can be used for controlling various harmful mites.

Description

Aryl sulfide and preparation method and application thereof
Cross Reference to Related Applications
The present application claims the benefit of chinese patent application 202110180116.8 filed on publication No. 2021, 02 and 07, the contents of which are incorporated herein by reference.
Technical Field
The application relates to the technical field of pesticides, in particular to an aryl sulfide, a preparation method and application thereof, an agricultural composition and a method for controlling invertebrate pests.
Background
JP201142611A discloses that compounds of the general formula:
wherein A is oxygen or sulfur, R 5 Is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted amino, nitrogen-containing heterocycle, and the like.
WO2018015852 (CN 109803956A) discloses compounds of the formula having acaricidal activity,
wherein R is 4 Represents hydrogen, formyl, C 1-6 Alkyl groups, etc.; r is R 5 、R 6 Identical or different and each represents hydrogen, halogen or C 1-6 Alkyl groups, etc.; r is R 7 、R 8 、R 9 、R 10 、R 11 The same or different and each represents hydrogen, halogen, etc.; x represents oxygen or sulfur.
CN111825585a discloses compounds of the general formula, having acaricidal activity,
however, the above compounds still have low killing activity in pest, particularly mite control, and particularly their mite killing activity is often unsatisfactory at low use rates, and the control effect on spider mites having acquired drug resistance is worse, so there is still an urgent need for new drugs with high efficiency and low toxicity and excellent killing effect on resistant mites in agricultural production.
Disclosure of Invention
The application aims to solve the technical problem that the existing compounds in the prior art have low killing activity in invertebrate pest (especially mite) control, and provides an aryl sulfide, a preparation method and application thereof, an agricultural composition and a method for controlling invertebrate pest.
The inventors of the present application have unexpectedly found that the substitution of hydrogen on nitrogen of the compound (aryl sulfide disclosed in CN111825585 a) previously disclosed by the inventors of the present application with a substituted acyl group, an alkyl group, a sulfonyl group or the like can exhibit a more efficient killing activity against invertebrate pests (particularly mites).
Accordingly, in order to achieve the above object, the first aspect of the present application provides an aryl sulfide compound having the structure shown in formula I or an agriculturally acceptable salt thereof,
wherein,
n is 0 or 1;
x, Y each independently is halogen, cyano, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or C 1 -C 3 Haloalkoxy groups;
R 1 is fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Haloalkoxy, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyloxy, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 Haloalkyl sulfonyl, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkylthio, C 2 -C 10 Alkenyloxycarbonyl, C 2 -C 10 Alkynyloxycarbonyl, C 1 -C 10 Alkylcarbonyl, aminocarbonyl, C 2 -C 10 Cyanoalkoxycarbonyl, C 1 -C 10 N-alkylcarbonyl, N-dimethylcarbonyl, N-dimethylthiocarbonyl, C 1 -C 10 N-alkylthio carbonyl, 2-oxo-propoxy carbonyl, C 1 -C 10 Alkylsulfinyl or C 1 -C 10 Haloalkyl sulfinyl;
R 2 、R 3 、R 4 、R 5 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Haloalkoxy, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyloxy, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkylthio, C 2 -C 10 Alkenyloxycarbonyl, C 1 -C 10 Alkylcarbonyl, aminocarbonyl, C 2 -C 10 Cyanoalkylcarbonyl, C 1 -C 10 N-alkylcarbonyl, N-dimethylcarbonyl, N-dimethylthiocarbonyl, C 1 -C 10 N-alkylthio carbonyl, 2-oxo-propoxy carbonyl；
R 6 Is C 1 -C 6 Haloalkyl, C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyl, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl or C 3 -C 6 An alkylene oxide group;
R 7 is C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 Haloalkyl sulfonyl, C 1 -C 10 Alkylcarbonyl or C 1 -C 10 Haloalkylcarbonyl groups.
In a second aspect, the present application provides a process for preparing an aryl sulfide, the process comprising:
contacting a compound shown in a formula II with a compound shown in a formula III to obtain a compound shown in a formula I,
R 7 -Q III
wherein, in formulas II and III, n, X, Y, R is concerned 1 、R 2 、R 3 、R 4 、R 5 、R 6 Or R is 7 Is the same as the definition given above; q is halogen, mesylate, benzenesulfonate, p-toluenesulfonate, triflate or substituted anhydride.
In a third aspect the present application provides the use of an aryl sulfide as described in the first aspect above for controlling invertebrate pests.
In a fourth aspect the present application provides an agricultural composition comprising at least one aryl sulfide as described in the first aspect above and at least one liquid or solid carrier.
In a fifth aspect the present application provides a method of controlling an invertebrate pest comprising applying a pesticidally effective amount of an aryl sulfide as described in the first aspect directly or indirectly to the invertebrate pest and/or a medium on which it is growing to be controlled.
Compared with the prior art, the application has at least the following advantages:
(1) The aryl sulfide provided by the application has excellent effects on various harmful organisms, particularly on spider mites represented by spider mites, citrus spider mites and the like;
(2) The aryl sulfide provided by the application has good characteristics in the application of protecting the important crops in agriculture and horticulture, domestic animals and other mites.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present application provides an aryl sulfide compound having the structure shown in formula I or an agriculturally acceptable salt thereof,
wherein,
n is 0 or 1;
x, Y each independently is halogen, cyano, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or C 1 -C 3 Haloalkoxy groups;
R 1 is fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Haloalkoxy, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyloxy, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 Haloalkyl sulfonyl, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkylthio, C 2 -C 10 Alkenyloxycarbonyl, C 2 -C 10 Alkynyloxycarbonyl, C 1 -C 10 Alkylcarbonyl, aminocarbonyl, C 2 -C 10 Cyanoalkoxycarbonyl, C 1 -C 10 N-alkylcarbonyl, N-dimethylcarbonyl, N-dimethylthiocarbonyl, C 1 -C 10 N-alkylthio carbonyl, 2-oxo-propoxy carbonyl, C 1 -C 10 Alkylsulfinyl or C 1 -C 10 Haloalkyl sulfinyl;
R 2 、R 3 、R 4 、R 5 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Haloalkoxy, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxy carbonylRadical, C 1 -C 10 Alkylsulfonyloxy, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkylthio, C 2 -C 10 Alkenyloxycarbonyl, C 1 -C 10 Alkylcarbonyl, aminocarbonyl, C 1 -C 10 N-alkylcarbonyl, N-dimethylcarbonyl, N-dimethylthiocarbonyl, C 1 -C 10 N-alkylthio carbonyl, 2-oxo-propoxy carbonyl;
R 6 is C 1 -C 6 Haloalkyl, C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyl, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl or C 3 -C 6 An alkylene oxide group;
R 7 is C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 Haloalkyl sulfonyl, C 1 -C 10 Alkylcarbonyl or C 1 -C 10 Haloalkylcarbonyl groups.
According to some embodiments of the application, n is 0 or 1; x is fluorine, chlorine or methyl; y is chlorine or methyl;
R 1 is C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Haloalkoxycarbonyl, C 2 -C 6 Alkenyloxycarbonyl, C 2 -C 6 Alkynyloxycarbonyl, C 2 -C 6 Cyanoalkoxycarbonyl, C 1 -C 6 Alkylthio, C 1 -C 6 Haloalkylthio, 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 2 、R 3 、R 4 、R 5 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy or C 1 -C 6 An alkoxycarbonyl group;
R 6 is C 1 -C 4 Haloalkyl or C 1 -C 4 An alkyl group;
R 7 is C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkylsulfonyl, C 1 -C 6 Haloalkyl sulfonyl, C 1 -C 6 Alkylcarbonyl or C 1 -C 6 Haloalkylcarbonyl groups.
According to some embodiments of the application, n is 0 or 1;
x is fluorine or methyl;
y is chlorine or methyl;
R 1 is C 1 -C 4 Alkoxycarbonyl group, C 1 -C 4 Haloalkoxycarbonyl, C 2 -C 4 Alkenyloxycarbonyl, C 2 -C 4 Alkynyloxycarbonyl or C 2 -C 6 Cyanoalkoxycarbonyl groups;
R 2 、R 4 and R is 5 Each independently is hydrogen;
R 3 hydrogen, fluorine, chlorine or cyano;
R 6 is C 1 -C 4 A haloalkyl group;
R 7 is C 1 -C 4 Alkyl, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Haloalkyl sulfonyl, C 1 -C 6 Alkylcarbonyl or C 1 -C 6 A haloalkylcarbonyl group; wherein the carbonyl group is attached to a nitrogen atom in formula I.
According to some embodiments of the application, n is 0 or 1; x is fluorine; y is chlorine or methyl;
R 1 is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, tert-butoxycarbonyl, fluoroethoxycarbonyl, difluoroethoxycarbonyl, trifluoroethoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl, pentafluoropropoxycarbonyl or cyanoethoxycarbonyl;
R 2 、R 4 and R is 5 Each independently is hydrogen;
R 3 hydrogen, fluorine, chlorine or cyano;
R 6 2, 2-trifluoroethyl;
R 7 is methyl, ethyl, chloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, pentafluoropropionyl, trichloroacetyl, methanesulfonyl, ethanesulfonyl or trifluoromethanesulfonyl.
In the present application, it is preferable that the aryl sulfide has the structure shown in table 1, but the compounds included in the derivative of the present application are by no means limited to these compounds. The compound numbers shown in table 1 are described below (table 1). In the present application, the aryl sulfide and the derivative thereof include E-type, Z-type or a mixture containing E-type and Z-type in an arbitrary ratio, depending on the kind of the substituent and the presence of the geometrical isomers of E-type and Z-type. In addition, in the compounds encompassed by the present application, there are cases where optical isomers are caused by having 1 or more asymmetric carbon atoms and asymmetric sulfur atoms, and the present application includes all optical isomers, racemates or diastereomers.
In table 1: the following expressions (e.g. Me, et, tBu, CF) 3 Ac) are as follows:
me: a methyl group; et: an ethyl group; tBu: a tertiary butyl group; CF (compact flash) 3 : trifluoromethyl; ac: acetyl.
TABLE 1
In the present application, the agriculturally acceptable salts, when hydroxyl, carboxyl, amino, or the like are present in the structure of the compound of the present application represented by formula I, refer to salts thereof with metals or organic bases or salts thereof with inorganic acids or organic acids, for example, potassium salts, sodium salts, magnesium salts, or calcium salts, and the like. Examples of the organic base include triethylamine and diisopropylamine, examples of the inorganic acid include hydrochloric acid, sulfuric acid and hydrobromic acid, and examples of the organic acid include formic acid, acetic acid, methanesulfonic acid, fumaric acid and maleic acid.
In a second aspect, the present application provides a process for preparing an aryl sulfide comprising contacting a compound of formula II with a compound of formula III to obtain a compound of formula I,
R 7 -Q III
wherein, in formulas II and III, n, X, Y, R is concerned 1 、R 2 、R 3 、R 4 、R 5 、R 6 Or R is 7 Is the same as the definition given above; q is halogen (which may be chlorine, bromine, iodine), mesylate, besylate, p-toluenesulfonate, triflate or substituted anhydride.
The application relates to the halogen, the methanesulfonate group and the benzenesulfonate groupThe p-toluenesulfonate group, trifluoromethanesulfonate group or substituted acid anhydride is not particularly limited as long as R can be provided to the compound represented by formula I 7 The group is just the one.
In the present application, R 7 Q may be methyl iodide, ethyl trifluoroacetate, trifluoroacetic anhydride, trifluoroacetyl chloride, ethyl difluoroacetate, difluoroacetic anhydride, ethyl trichloroacetate, trichloroacetic anhydride, methylsulfonyl chloride, ethylsulfonyl chloride, trifluoromethanesulfonyl anhydride.
According to some embodiments of the application, preferably, the contacting conditions include: the temperature is-20 ℃ to 210 ℃, preferably-10 ℃ to 150 ℃; the time is 1-50h, preferably 3-25h.
According to some embodiments of the application, the molar ratio of the compound of formula I to the compound of formula III may be 1: (1-5), preferably 1: (2-3).
According to some embodiments of the application, the contacting is preferably performed in the presence of a solvent, wherein the solvent is used in an amount of 5-30mL, preferably 10-20mL, relative to 1g of the compound of formula I.
Wherein the solvent is at least one selected from N, N-dimethylformamide, dichloromethane, acetonitrile, acetone, tetrahydrofuran, N-methylpyrrolidone, water, methanol, ethanol, dimethyl sulfoxide, toluene, 1, 2-dichloroethane, chloroform, xylene and ethyl acetate.
According to some embodiments of the application, the contacting is preferably performed in the presence of a base, wherein the amount of base is 1-5mol, preferably 2-3mol, relative to 1mol of the compound of formula I.
The base is at least one selected from triethylamine, diisopropylethylamine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine and 1, 8-diazabicyclo undec-7-ene.
In the present application, the post-treatment of the contact is preferably not particularly limited as long as the requirements of the present application can be satisfied, and for example, the following means may be used: adding an extraction solvent and water into the reaction liquid after contact, extracting and separating to obtain an organic phase, and discarding a water phase; the organic phase is dried and then subjected to column chromatography separation to obtain a purified product (a compound shown in a formula I). The extraction solvent is not particularly limited, and may be selected from dichloromethane and/or ethyl acetate, for example.
In the present application, the inventors have found that the compounds of formula I have unexpectedly high acaricidal activity, and therefore, the aryl sulfides of the present application can also be used in agriculture or other fields for the preparation of acaricides. In particular, the inventors of the present application have found that the compounds of formula I have high activity against the following invertebrate pests (the following list is for illustration of the application only and not for limitation): tetranychidae (such as Tetranychus cinnabarinus, panonychus citri, tetranychus urticae), eriobotryaceae, tetranychus urticae, aphididae (such as Aphis necator), nematode (such as root knot nematode, cyst nematode, short body nematode, aphis perfolia, and Aphis parades).
Accordingly, in a third aspect the present application provides the use of an aryl sulfide as described in the first aspect hereinbefore for controlling invertebrate pests.
According to some embodiments of the application, the invertebrate pest may be a mite pest and/or a nematode.
In the present application, preferably, the aryl sulfide can be used for protecting crops, livestock, etc. important in agriculture and horticulture from or against mites.
In the present application, for obtaining a desired effect, the amount of aryl sulfide used varies depending on various factors such as the compound used, the crop to be protected, the type of pest, the degree of infection, the method of application, the environment of application, the dosage form to be applied, and the like.
In the present application, it is preferred that for certain applications, such as agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers, etc. can be added to the acaricidal composition of the present application, whereby additional advantages and effects can be produced.
In a fourth aspect the present application provides an agricultural composition comprising at least one aryl sulfide as described in the first aspect above and at least one liquid or solid carrier. The liquid carrier or the solid carrier is not particularly limited as long as the requirements of the present application can be satisfied. In the case of a composition in liquid form, the concentration of the aryl sulfide in the composition may be in the range of 0.5 to 35mg/L.
In the present application, the liquid carrier may be one or more of water, various aromatic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, etc., such as toluene, xylene, acetone, cyclohexanone, xylene, benzene, cyclohexane, isopropanol, ethylene glycol, sorbitol, methanol, ethanol, butanol, dimethylformamide, N-methylpyrrolidone, decalin, engine oil, petroleum ether, cyclohexanone, methyl oleate, methylated soybean oil, etc.; solid carriers may include natural or synthetic clays and silicates, and solid carriers suitable for use in the powder formulation may include naturally occurring rock powders, chalk, quartz, clays, montmorillonite, silica white, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, china clay and synthetic ground minerals (such as finely divided silicic acid or alumina). Suitable particulate carriers may include crushed and graded natural rock such as calcite, marble, pumice, sepiolite and dolomite and synthetic particles made from powders of organic and inorganic materials.
In the present application, preferably, the composition may be applied in the form of a formulation. Wherein the compound of formula I is dissolved or dispersed as an active ingredient in a carrier or formulated for acaricidal use to facilitate dispersion. For example: the composition can be prepared into wettable powder, water dispersible granules, suspending agents, aqueous emulsion, water aqua or emulsifiable concentrates and the like. At least one liquid or solid carrier is added to the composition, and a suitable surfactant may also be added as needed. The surfactant may include dodecylbenzene sulfonate, fatty alcohol sulfate, tween, agricultural milk, sorbitol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, lignin sulfonate, alkyl naphthalene sulfonate, etc.
In a fifth aspect the present application provides a method of controlling an invertebrate pest comprising applying a pesticidally effective amount of an aryl sulfide as described in the first aspect directly or indirectly to the invertebrate pest and/or a medium on which it is growing to be controlled. Wherein, there is no particular limitation in the direct or indirect manner as long as the object of controlling the invertebrate pest can be achieved, for example, the direct manner may include directly contacting the substance containing the aryl sulfide component with the invertebrate pest (including directly eating the substance containing the aryl sulfide component by the invertebrate pest, directly contacting the invertebrate pest body surface with the substance containing the aryl sulfide component, etc.); an indirect means may include treating the locus where the invertebrate pest is to be located (its habitat or its breeding ground or the plant in which the invertebrate pest is to be grown, soil) with a substance containing an ingredient of the aryl sulfide or treating its food chain with a substance containing an ingredient of the aryl sulfide.
According to a preferred embodiment of the present application, the method comprises treating a plant grown by an invertebrate pest with a pesticidally effective amount of an aryl sulfide as described in the first aspect above.
In the present application, preferably, the invertebrate pest is a mite pest and/or a nematode. As previously mentioned, the acaridae pests may include, but are not limited to: tetranychidae (such as Tetranychus cinnabarinus, panonychus citri, tetranychus urticae), eriobotryaceae, tetranychus urticae, aphididae (such as Aphis necator), nematode (such as root knot nematode, cyst nematode, short body nematode, aphis perfolia, and Aphis parades).
In the present application, the plant is a plant of the phylum gymnosperm and/or phylum angiosperm, preferably at least one of the family rutaceae, the family solanaceae, the family cruciferae, the family leguminous and the family rosaceae.
In the present application, the pesticidally effective amount is not particularly limited and may mean, for example, a dosage of 8 g to 3 kg of the aryl sulfide per hectare, so as to provide sufficient control. Preferably, the pesticidally effective amount may be from 8 to 1000 grams per hectare, preferably from 15 to 300 grams per hectare.
It should be understood that various changes and modifications can be made within the scope of the application as defined in the appended claims.
In order to better understand the technical solutions of the present application, the following description will clearly and completely describe the technical solutions of the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
Preparation examples:
preparation example 1
Preparation of methyl 2- ((N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 35)
Methyl 2- ((((2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) amino) methyl) benzoate (0.5 g,1.29 mmol) was added to a round bottom flask, methylene chloride (10 mL) and triethylamine (0.26 g,2.58 mmol) were added in sequence, then acetyl chloride (0.15 g,1.935 mmol) was added dropwise, after stirring the reaction solution at room temperature for 4 hours, methylene chloride (30 mL) and water (50 mL) were added, the organic phase after extraction and separation was added to anhydrous sodium sulfate (5 g) to dry, concentrated to dryness under reduced pressure, and silica gel column chromatography was purified to give 0.36g of white solid;
1 H-NMR(400MHz,CDCl 3 ):δ＝7.79(d,J＝8.0Hz,1H),7.44-7.50(m,2H),7.27-7.31(m,1H),7.07(d,J＝7.6Hz,1H),6.99(d,J＝10.4Hz,1H),5.59(d,J＝10.8Hz,1H),5.04(d,J＝15.2Hz,1H),3.75(s,3H),3.10-3.19(m,2H),2.42(s,3H),1.91(s,3H)；
MS(m/z,ESI):452.3(m+Na)。
preparation example 2
Preparation of methyl 2- ((2-chloro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 37)
Prepared according to the method described in preparation example 1;
1 H-NMR(400MHz,CDCl 3 ):δ＝7.81(d,J＝7.6Hz,1H),7.47(d,J＝3.6Hz,2H),7.30-7.34(m,1H),7.07(d,J＝7.6Hz,1H),7.01(d,J＝10.4Hz,1H),5.67(d,J＝14.8Hz,1H),5.02(d,J＝15.2Hz,1H),3.86(d,J＝8.0Hz,2H),3.75(s,3H),3.07-3.21(m,2H),2.44(s,3H)；
MS(m/z,ESI):464.3(m+H)。
preparation example 3
Preparation of methyl 2- ((N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) isobutyramide) methyl) benzoate (Compound 1877)
Prepared according to the method described in preparation example 1;
1 H-NMR(400MHz,CDCl 3 ):δ＝7.70(d,J＝7.6Hz,1H),7.36(s,2H),7.22(s,1H),6.92(d,J＝8.8Hz,2H),5.59(d,J＝14.8Hz,1H),4.84(d,J＝15.2Hz,1H),3.69(s,3H),2.96-3.10(m,2H),2.31-2.34(m,4H),0.99(t,J＝7.2Hz,6H)；
MS(m/z,ESI):458.3(m+H),480.3(m+Na)。
preparation example 4
Preparation of methyl 2- ((2-chloro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) propanamido) methyl) benzoate (Compound 57)
Prepared according to the method described in preparation example 1;
1 H-NMR(400MHz,CDCl 3 ):δ＝7.83(d,J＝7.2Hz,1H),7.47(s,2H),7.32(s,1H),7.16(d,J＝6.8Hz,1H),7.01(d,J＝10.8Hz,1H),5.72(d,J＝15.2Hz,1H),4.93(d,J＝14.8Hz,1H),4.15(d,J＝6.0Hz,1H),3.77(s,3H),3.05-3.21(m,2H),2.43(s,3H),1.60-1.64(m,3H)；
MS(m/z,ESI):478.2(m+H),500.2(m+Na).
preparation example 5
Preparation of methyl 2- ((N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) propanamido) methyl) benzoate (Compound 53)
Prepared according to the method described in preparation example 1;
1 H-NMR(400MHz,CDCl 3 ):δ＝7.78(d,J＝7.6Hz,1H),7.46-7.48(m,2H),7.29-7.31(m,1H),6.97-7.03(m,2H),5.62(d,J＝14.8Hz,1H),5.00(d,J＝14.8Hz,1H),3.74(s,3H),3.08-3.16(m,2H),2.42(s,3H),2.08(q,J＝6.8Hz,2H),1.09(t,J＝6.8Hz,3H)；
MS(m/z,ESI):444.2(m+H),466.2(m+Na)。
preparation example 6
Preparation of methyl 2- ((N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) benzamide) methyl benzoate (Compound 1845)
Prepared as described in preparation example 1.
1 H-NMR(400MHz,CDCl 3 ):δ＝7.84(d,J＝8.0Hz,1H),7.61(d,J＝7.6Hz,1H),7.50(t,J＝7.2Hz,1H),7.32-7.35(m,3H),7.17-7.21(m,3H),6.95(d,J＝6.4Hz,1H),6.79(d,J＝10.8Hz,1H),5.76(s,1H),5.26(s,1H),3.81(s,3H),2.91(s,2H),2.31(s,3H)；
MS(m/z,ESI):514.3(m+Na)。
Preparation example 7
Preparation of methyl 2- (((2, 2-trifluoro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 45)
Methyl 2- ((((2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) amino) methyl benzoate (2.5 g,6.45 mmol) was added to a round bottom flask, methylene chloride (15 mL) and potassium carbonate (1.34 g,9.68 mmol) were added sequentially, trifluoroacetic anhydride (1.63 g,7.74 mmol) was slowly added dropwise at room temperature, the reaction was continued to be stirred at room temperature for 3.5 hours, methylene chloride (20 mL) and water (50 mL) were added to the reaction solution, the extract was separated, the aqueous phase was again added to 20mL methylene chloride for extraction, the organic phases were combined after separation, anhydrous sodium sulfate (5 g) was added for drying, and concentrated to dryness under reduced pressure, and column chromatography was purified to give a white solid of 2.65g.
1 H-NMR(400MHz,CDCl 3 ):δ＝7.84(d,J＝8.0Hz,1H),7.47(t,J＝7.2Hz,1H),7.34-7.39(m,2H),6.94-7.01(m,2H),5.74(d,J＝14.4Hz,1H),5.00(d,J＝14.4Hz,1H),3.75(s,3H),2.98-3.15(m,2H),2.43(s,3H)；
MS(m/z,ESI):484.2(m+H),506.2(m+Na)。
Preparation example 8
Preparation of methyl 2- ((2, 2-difluoro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 43)
Prepared according to the method described in preparation example 7;
1 H NMR(400MHz,CDCl 3 ):δ＝7.84(t,J＝8.5Hz,1H),7.46(dd,J＝17.9,9.1Hz,2H),7.42–7.32(m,1H),7.01(d,J＝9.9Hz,2H),5.87–5.58(m,2H),5.02(dd,J＝14.3,9.4Hz,1H),3.76(t,J＝7.1Hz,3H),3.11(dt,J＝24.0,7.5Hz,2H),2.44(d,J＝9.9Hz,3H)；
MS(m/z,ESI):466.1(m+H),488.1(m+Na)。
preparation example 9
Preparation of methyl 2- ((2, 2-trichloro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 47)
Prepared according to the method described in preparation example 7;
1 H NMR(400MHz,CDCl 3 ):δ＝7.84(d,J＝7.7Hz,1H),7.46(dd,J＝13.7,6.7Hz,2H),7.34(t,J＝8.2Hz,1H),7.09(d,J＝6.6Hz,1H),6.95(d,J＝10.5Hz,1H),5.84(s,1H),4.92(s,1H),3.77(s,3H),3.04(s,2H),2.37(d,J＝38.1Hz,3H)；
MS(m/z,ESI):532.1(m+H),556.0(m+Na)。
preparation example 10
Preparation of methyl (2-fluoro-4-methyl-5- (2, 2-trifluoroethyl) thiophenyl) (methyl) amino) benzoate (Compound 1)
Methyl 2- ((((2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) amino) benzoate (1 g,2.58 mmol) was added to a 50mL round bottom flask, DMF (10 mL) was added, then potassium carbonate (0.72 g,5.22 mmol) and methyl iodide (0.732 g,5.16 mmol) were added sequentially, the reaction was heated to 42℃and stirred for 24 hours, 50mL ethyl acetate and 100mL water were added to the reaction solution, 50mL ethyl acetate was again added to the aqueous phase after separation by extraction, the organic phases were combined after separation by extraction, and 100mL water was added in two portions to wash the separated organic phases, dried over anhydrous sodium sulfate (5 g), and concentrated to dryness under reduced pressure to give 180mg of a pale yellow oily liquid by column chromatography;
1 H NMR(400MHz,CDCl3)δ＝8.00–7.66(m,1H),7.57(s,1H),7.46(d,J＝6.3Hz,1H),7.38–7.01(m,1H),7.06(d,J＝8.6Hz,1H),6.87(d,J＝13.3Hz,1H),4.64(s,2H),3.91(dd,J＝51.8,23.7Hz,3H),3.45–2.98(m,2H),2.80(s,3H),2.59–2.13(m,3H)；
MS(m/z,ESI):402.1(m+H)，424.1(m+Na)。
preparation example 11
Preparation of methyl 2- ((ethyl (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) amino) methyl) benzoate (Compound 3)
Prepared according to the method described in preparation example 10;
1 H NMR(400MHz,CDCl 3 ):δ＝7.83(d,J＝7.7Hz,1H),7.52(d,J＝7.7Hz,1H),7.42(t,J＝7.6Hz,1H),7.29(d,J＝7.6Hz,1H),7.00(d,J＝8.8Hz,1H),6.86(d,J＝13.4Hz,1H),4.65(s,2H),3.87(d,J＝0.6Hz,3H),3.36–2.97(m,4H),2.35(s,3H),1.08(t,J＝7.0Hz,3H)；
MS(m/z,ESI):416.4(m+H)。
preparation example 12
Preparation of 2- ((2-fluoro-4-methyl-5- (2, 2-trifluoroethylthio) phenyl) - (propyl) amino) methylbenzoate (Compound 5)
Prepared according to the method described in preparation example 10;
1 H-NMR(400MHz,CDCl 3 ):δ＝7.76(d,J＝7.6Hz,1H),7.43(d,J＝7.6Hz,1H),7.30-7.35(m,1H),7.20-7.22(m,1H),6.90(d,J＝8.8Hz,1H),6.77(d,J＝13.6Hz,1H),4.60(s,2H),3.82(s,3H),3.01-3.09(m,4H),2.27(s,3H),1.44-1.50(m,2H),0.78(t,J＝7.2Hz,3H)；
MS(m/z,ESI):430.3(m+H)。
preparation example 13
Preparation of ethyl 2- ((2, 2-trifluoro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 103)
Prepared as described in preparation example 7 as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.84(d,J＝7.7Hz,1H),7.47(t,J＝7.5Hz,1H),7.36(dd,J＝17.2,8.2Hz,2H),6.97(dd,J＝13.1,8.9Hz,2H),5.74(d,J＝14.4Hz,1H),5.02(d,J＝14.4Hz,1H),4.41–4.01(m,2H),3.07(tdd,J＝15.4,9.6,6.0Hz,2H),2.42(s,3H),1.32(t,J＝7.1Hz,3H).
MS(m/z,ESI):520.1(m+Na)。
preparation example 14
Preparation of methyl 5-fluoro-2- (((2, 2-trifluoro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 1511)
Prepared as described in preparation example 7 as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.54(dd,J＝9.2,2.8Hz,1H),7.41(dd,J＝8.5,5.4Hz,1H),7.24–7.10(m,1H),7.00(dd,J＝8.7,6.0Hz,2H),5.62(d,J＝14.4Hz,1H),5.07(d,J＝14.5Hz,1H),3.75(s,3H),3.34–3.01(m,2H),2.45(s,3H)。
preparation example 15
Preparation of trifluoroethyl 2- (((2, 2-trifluoro-N- (2-fluoro-4-methyl-5- ((2, 2-trifluoroethyl) thio) phenyl) acetamido) methyl) benzoate (Compound 393)
Prepared as described in preparation example 7 as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.92(d,J＝7.8Hz,1H),7.55(t,J＝7.1Hz,1H),7.51–7.36(m,2H),7.07–6.95(m,2H),5.68(d,J＝14.7Hz,1H),5.07(d,J＝14.7Hz,1H),4.55(pd,J＝9.1,4.2Hz,2H),3.25–2.93(m,2H),2.41(d,J＝14.6Hz,3H).
MS(m/z,ESI):574.15(m+Na)。
preparation example 16
Preparation of methyl 2- ((N- (4-chloro-2-fluoro-5- ((2, 2-trifluoroethyl) thio) phenyl) -2, 2-trifluoroacetamido) methyl) benzoate (Compound 799)
1 H NMR(400MHz,CDCl 3 )δ7.86(d,J＝7.8Hz,1H),7.50(t,J＝7.5Hz,1H),7.39(dd,J＝13.1,7.0Hz,2H),7.25(d,J＝8.0Hz,1H),7.08(d,J＝7.6Hz,1H),5.68(d,J＝14.4Hz,1H),5.07(d,J＝14.3Hz,1H),3.76(s,3H),3.24(q,J＝9.5Hz,2H).
MS(m/z,ESI):526.08(m+Na)。
Preparation example 17
Preparation of ethyl methyl 2- ((N- (4-chloro-2-fluoro-5- ((2, 2-trifluoroethyl) thio) phenyl) -2, 2-trifluoroacetamido) methyl) benzoate (Compound 857)
Prepared as described in preparation example 7 as a white solid;
1 H NMR(400MHz,CDCl 3 )δ7.86(d,J＝7.9Hz,1H),7.50(t,J＝7.5Hz,1H),7.45–7.35(m,2H),7.25(d,J＝10.2Hz,1H),7.08(d,J＝7.6Hz,1H),5.69(d,J＝14.4Hz,1H),5.09(d,J＝14.3Hz,1H),4.29–4.04(m,2H),3.23(tt,J＝9.5,4.7Hz,2H),1.32(t,J＝7.1Hz,3H).
MS(m/z,ESI):540.01(m+Na)。
formulation example 1:
preparation of 20% Compound 45 emulsifiable concentrate preparation
Dissolving 20 parts by weight of a compound 45 in 24 parts by weight of N-methylpyrrolidone, then adding 12 parts by weight of 500# (calcium dodecyl benzene sulfonate) and 6 parts by weight of 33# (trityl phenol polyoxyethylene ether) respectively, stirring uniformly, adding 7.2 parts by weight of methyl oleate 680, continuously stirring uniformly, adding methyl naphthalene to fill the rest to 100 parts by weight, and stirring uniformly to obtain a 20% compound 45 emulsifiable concentrate preparation.
Use example 1
Tetranychus cinnabarinus activity test
The test compound was dissolved in acetone and diluted to the desired concentration with 0.1 wt% aqueous tween 80, with an acetone content of no more than 5 wt%.
The kidney bean seedlings growing to two leaves are removed, the number of the leaves is investigated after the two leaves are inoculated with tetranychus cinnabarinus, the whole plant of spraying treatment is carried out by using a handheld sprayer, each treatment is repeated for 3 times (the application amount of the preparation is about 0.5 g), the treated seedlings are observed in a constant temperature observation room, the number of live mites is investigated after 72 hours, and the death rate is calculated. The experiment was repeated 3 times, and the number of spider mites inoculated each time was 50-150.
Mortality = (number of vaccinations-number of live insects after drug)/(number of vaccinations x 100%).
In this test, the following compounds showed a mortality rate of more than 90% at 25ppm (25 mg/L):
1，3，5，37，43，45，47，57，103，393,799,857，1511。
in this test, the following compounds showed a mortality rate of more than 90% at 6.25ppm (6.25 mg/L):
1，43，45，47，103，393,799,857，1511。
in this test, the following compounds showed a mortality rate of more than 80% at 1.56ppm (1.56 mg/L):
45，103，393,799,857，1511。
according to the above method, compounds 45, 103 were selected for a parallel test against mites (tetranychus cinnabarinus) with compound 53 disclosed in CN111825585a, the test results are shown in table 2 below:
TABLE 2
The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Within the scope of the technical idea of the application, a number of simple variants of the technical solution of the application are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the application, all falling within the scope of protection of the application.

Claims (10)

  1. An aryl sulfide is characterized in that the aryl sulfide is a compound with a structure shown as a formula I or agriculturally acceptable salt thereof,
    wherein,
    n is 0 or 1;
    x, Y each independently is halogen, cyano, C 1 -C 3 Alkyl, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or C 1 -C 3 Haloalkoxy groups;
    R 1 is fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Haloalkoxy, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyloxy, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 Haloalkyl sulfonyl, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkylthio, C 2 -C 10 Alkenyloxycarbonyl, C 2 -C 10 Alkynyloxycarbonyl, C 1 -C 10 Alkylcarbonyl, aminocarbonyl, C 2 -C 10 Cyanoalkoxycarbonyl, C 1 -C 10 N-alkylcarbonyl, N-dimethylcarbonyl, N-dimethylthiocarbonyl, C 1 -C 10 N-alkylthio carbonyl, 2-oxo-propoxy carbonyl, C 1 -C 10 Alkylsulfinyl or C 1 -C 10 Haloalkyl sulfinyl;
    R 2 、R 3 、R 4 、R 5 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Haloalkoxy, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyloxy, C 1 -C 10 Alkylthio, C 1 -C 10 Haloalkylthio, C 2 -C 10 Alkenyloxycarbonyl, C 1 -C 10 Alkylcarbonyl, aminocarbonyl, C 1 -C 10 N-alkylcarbonyl, N-dimethylcarbonyl, N-dimethylthiocarbonyl, C 1 -C 10 N-alkylthio carbonyl, 2-oxo-propoxy carbonyl;
    R 6 is C 1 -C 6 Haloalkyl, C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyl, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl or C 3 -C 6 An alkylene oxide group;
    R 7 is C 1 -C 10 Alkyl, C 1 -C 10 Haloalkyl, C 1 -C 10 Alkoxycarbonyl group, C 1 -C 10 Haloalkoxycarbonyl, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 Haloalkyl sulfonyl, C 1 -C 10 Alkylcarbonyl or C 1 -C 10 Haloalkylcarbonyl groups.
  2. The aryl sulfide of claim 1, wherein n is 0 or 1;
    x is fluorine, chlorine or methyl;
    y is chlorine or methyl;
    R 1 is C 1 -C 6 Alkoxycarbonyl group, C 1 -C 6 Haloalkoxycarbonyl, C 2 -C 6 Alkenyloxycarbonyl, C 2 -C 6 Alkynyloxycarbonyl, C 2- C 6 Cyanoalkoxycarbonyl, C 1 -C 6 Alkylthio, C 1 -C 6 Haloalkylthio, 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 2 、R 3 、R 4 、R 5 each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy or C 1 -C 6 An alkoxycarbonyl group;
    R 6 is C 1 -C 4 Haloalkyl or C 1 -C 4 An alkyl group;
    R 7 is C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkylsulfonyl, C 1 -C 6 Haloalkyl sulfonyl, C 1 -C 6 Alkylcarbonyl or C 1 -C 6 Haloalkylcarbonyl groups.
  3. The aryl sulfide of claim 1 or 2, wherein n is 0 or 1;
    x is fluorine or methyl;
    y is chlorine or methyl;
    R 1 is C 1 -C 4 Alkoxycarbonyl group, C 1 -C 4 Haloalkoxycarbonyl, C 2 -C 4 Alkenyloxycarbonyl, C 2 -C 4 Alkynyloxycarbonyl or C 2- C 6 Cyanoalkoxycarbonyl groups;
    R 2 、R 4 and R is 5 Each independently is hydrogen;
    R 3 hydrogen, fluorine, chlorine or cyano;
    R 6 is C 1 -C 4 A haloalkyl group;
    R 7 is C 1 -C 4 Alkyl, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Haloalkyl sulfonyl, C 1 -C 6 Alkylcarbonyl or C 1 -C 6 A haloalkylcarbonyl group; wherein the carbonyl group is attached to a nitrogen atom in formula I;
    preferably, n is 0 or 1;
    x is fluorine;
    y is chlorine or methyl;
    R 1 is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, tert-butoxycarbonyl, fluoroethoxycarbonyl, difluoroethoxycarbonyl, trifluoroethoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl, pentafluoropropoxycarbonyl or cyanoethoxycarbonyl;
    R 2 、R 4 and R is 5 Each independently is hydrogen;
    R 3 hydrogen, fluorine, chlorine or cyano;
    R 6 2, 2-trifluoroethyl;
    R 7 is methyl, ethyl, chloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, pentafluoropropionyl, trichloroacetyl, methanesulfonyl, ethanesulfonyl or trifluoromethanesulfonyl.
  4. A process for preparing an aryl sulfide comprising:
    contacting a compound shown in a formula II with a compound shown in a formula III to obtain a compound shown in a formula I,
    R 7 -Q III
    wherein, in formulas II and III, n, X, Y, R is concerned 1 、R 2 、R 3 、R 4 、R 5 、R 6 Or R is 7 Is as defined in any one of claims 1 to 3; q is halogen, mesylate, benzenesulfonate, p-toluenesulfonate, triflate or substituted anhydride.
  5. The method of claim 4, wherein the contacting conditions comprise: the temperature is-20 ℃ to 210 ℃, preferably-10 ℃ to 150 ℃; the time is 1-50h, preferably 3-25h;
    and/or the molar ratio of the compound shown in the formula I to the compound shown in the formula III is 1: (1-5), preferably 1: (2-3);
    and/or the contacting is carried out in the presence of a solvent, preferably in an amount of 5-30mL, preferably 10-20mL, relative to 1g of the compound of formula I;
    wherein the solvent is at least one selected from N, N-dimethylformamide, dichloromethane, acetonitrile, acetone, tetrahydrofuran, N-methylpyrrolidone, water, methanol, ethanol, dimethyl sulfoxide, toluene, 1, 2-dichloroethane, chloroform, xylene and ethyl acetate;
    and/or the contacting is carried out in the presence of a base, preferably in an amount of 1 to 5mol, preferably 2 to 3mol, relative to 1mol of the compound of formula I;
    wherein the base is selected from at least one of triethylamine, diisopropylethylamine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine and 1, 8-diazabicyclo undec-7-ene.
  6. Use of an aryl sulfide according to any one of claims 1 to 3 for controlling invertebrate pests.
  7. The use according to claim 6, wherein the invertebrate pest is a mite pest and/or a nematode.
  8. An agricultural composition comprising at least one aryl sulfide of any one of claims 1-3 and at least one liquid or solid carrier.
  9. A method for controlling an invertebrate pest comprising applying a pesticidally effective amount of an aryl sulfide of any of claims 1 to 3 directly or indirectly to a medium in need of control of the invertebrate pest and/or its growth.
  10. A method according to claim 9, wherein the method comprises treating a plant grown by an invertebrate pest with a pesticidally effective amount of an aryl sulfide of any of claims 1-3;
    and/or, the invertebrate pest is an acarid pest and/or a nematode;
    and/or the plant is a plant of the phylum gymnosperm and/or phylum angiosperm, preferably at least one of the family rutaceae, the family solanaceae, the family cruciferae, the family leguminosae, and the family rosaceae.
CN202280010782.XA 2021-02-07 2022-01-28 Aryl sulfide and preparation method and application thereof Pending CN117062800A (en)

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