WO2021056922A1 - 一种含苄胺结构的芳基硫化物及其合成方法和应用 - Google Patents
一种含苄胺结构的芳基硫化物及其合成方法和应用 Download PDFInfo
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- WO2021056922A1 WO2021056922A1 PCT/CN2020/000198 CN2020000198W WO2021056922A1 WO 2021056922 A1 WO2021056922 A1 WO 2021056922A1 CN 2020000198 W CN2020000198 W CN 2020000198W WO 2021056922 A1 WO2021056922 A1 WO 2021056922A1
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- 0 *c(c(NCc1c(*)c(*)c(*)c(*)c1*)c1)cc(*)c1S(*)=* Chemical compound *c(c(NCc1c(*)c(*)c(*)c(*)c1*)c1)cc(*)c1S(*)=* 0.000 description 11
- HPNYTEYAHBXONK-UHFFFAOYSA-N CC(C1)C(SCC(F)(F)F)=CC(NCC2C=CC(Cl)=CC2)=C1F Chemical compound CC(C1)C(SCC(F)(F)F)=CC(NCC2C=CC(Cl)=CC2)=C1F HPNYTEYAHBXONK-UHFFFAOYSA-N 0.000 description 1
- IZAOHVQYTGCYRO-UHFFFAOYSA-N CC1(C(F)=CC(C)=CC1)[N+]([O-])=O Chemical compound CC1(C(F)=CC(C)=CC1)[N+]([O-])=O IZAOHVQYTGCYRO-UHFFFAOYSA-N 0.000 description 1
- GYBNNPVVTBNURH-UHFFFAOYSA-N CCSc(cc1NCc2c(C)cccc2)c(C)cc1F Chemical compound CCSc(cc1NCc2c(C)cccc2)c(C)cc1F GYBNNPVVTBNURH-UHFFFAOYSA-N 0.000 description 1
- XZMQUSFRMRLAPR-UHFFFAOYSA-N Cc(cc(c(NCc(cc1)ccc1I)c1)F)c1SCC(F)(F)F Chemical compound Cc(cc(c(NCc(cc1)ccc1I)c1)F)c1SCC(F)(F)F XZMQUSFRMRLAPR-UHFFFAOYSA-N 0.000 description 1
- MKHIVUFMQQHJRY-UHFFFAOYSA-N Cc(cc(c(NCc1cccc([N+]([O-])=O)c1)c1)F)c1SCC(F)(F)F Chemical compound Cc(cc(c(NCc1cccc([N+]([O-])=O)c1)c1)F)c1SCC(F)(F)F MKHIVUFMQQHJRY-UHFFFAOYSA-N 0.000 description 1
- MPXPLKCMUDUGGU-UHFFFAOYSA-N Cc(cc(c([N+]([O-])=O)c1)F)c1S(Cl)(=O)=O Chemical compound Cc(cc(c([N+]([O-])=O)c1)F)c1S(Cl)(=O)=O MPXPLKCMUDUGGU-UHFFFAOYSA-N 0.000 description 1
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
- C07C323/23—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
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
- A01N33/10—Amines; Quaternary ammonium compounds containing oxygen or sulfur having at least one oxygen or sulfur atom 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- 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
- A01P7/00—Arthropodicides
- A01P7/02—Acaricides
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- 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
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- 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
Definitions
- the present invention relates to the technical field of pesticides, in particular to an aryl sulfide containing a benzylamine structure and its synthesis method and application.
- Patent documents WO9955668A, CN104995193A, CN105517995A, JP2015036377A, CN103664811B, US2017226107A, WO2018051252A, TW201127291A, CN108290886A, JP2011042611A, JP2011219419A, JP2015036377A and the like describe aryl sulfide oxide derivatives having harmful biological control effects.
- A is oxygen or sulfur
- R 5 is a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted amino group, a nitrogen-containing heterocyclic ring, and the like.
- R 4 represents hydrogen, formyl, C 1-6 alkyl, etc.
- R 5 and R 6 are the same or different and each represents hydrogen, halogen or C 1-6 alkyl, etc.
- R 7 , R 8 , R 9 , R 10 and R 11 are the same or different and each represents hydrogen, halogen, etc.
- X represents oxygen or sulfur.
- the present invention provides an aryl sulfide containing a benzylamine structure and a synthesis method and application thereof to solve the above technical problems.
- the inventors synthesized various aryl sulfide derivatives and conducted in-depth studies on their biological activities.
- the aryl sulfide derivatives represented by the following general formula are harmful to various harmful organisms, especially those represented by Tetranychus cinnabarinus, Tetranychus urticae, Tetranychus Kanzawa, Tetranychus citrus, etc.
- Tetranychus mites showed excellent effects, continued research and completed the present invention.
- n 0, 1 or 2;
- X and Y are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy Or (C 1 -C 4 )haloalkoxy;
- R 1 , R 2 , R 3 , R 4 , R 5 are each independently 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, C 1 -C 10 haloalkoxycarbonyl, C 1 -C 10 alkylsulfonyloxy, C 1 -C 10 alkylsulfonyl, 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,N-dimethyl
- 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, C 3 -C 6 ring Oxyalkyl.
- n 0 or 1
- X is fluorine, chlorine or methyl
- Y is chlorine or methyl
- R 1 is hydrogen, fluorine, chlorine, bromine, hydroxyl, nitro, hydroxymethyl, cyano, trifluoromethyl, C 1 -C 3 alkyl, C 1 -C 4 alkoxycarbonyl, acetyl, propyl Acyl, C 1 -C 3 alkoxy, ethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio , Propylthio, 2,2,2-trifluoroethylsulfinyl, vinyloxycarbonyl, 2,2,2-trifluoroethoxycarbonyl or N-methylcarbonyl;
- R 2 is hydrogen, fluorine or chlorine
- R 3 is hydrogen, fluorine, chlorine, bromine or cyano
- R 4 and R 5 are each independently hydrogen
- R 6 is n-propyl or 2,2,2-trifluoroethyl.
- n 0 or 1
- X is fluorine
- Y is chlorine or methyl
- R 1 is methoxycarbonyl, ethoxycarbonyl, ethylthio or 2,2,2-trifluoroethylthio;
- R 2 , R 4 and R 5 are each independently hydrogen
- R 3 is hydrogen, fluorine, chlorine or cyano
- R 6 is 2,2,2-trifluoroethyl.
- the general formula I is selected from the following compounds:
- E-type and Z-type geometric isomers depending on the type of substituent, and the present invention includes these E-type and Z-type geometric isomers.
- optical isomers caused by having one or more asymmetric carbon atoms and asymmetric sulfur atoms.
- the present invention includes all optical isomers and external Racemate or diastereomer.
- nPropyl n-propyl
- nOctyl n-octyl
- nDecyl n-decyl
- the present invention provides a method for synthesizing benzylamine structure-containing aryl sulfide.
- the synthetic route diagram of the specific preparation method is as follows:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y, and n have the meanings described above.
- nitro compound II as starting material, react with chlorosulfonic acid to obtain sulfonyl chloride compound III, further reduce to obtain disulfide compound IV, and then reduce by hydrogen or metal to obtain amino compound V.
- Compound V is further under alkaline conditions.
- the key intermediate VI is obtained by reacting with electrophiles, and then reacted with substituted benzyl bromide or other electrophiles to obtain IA, and IA is oxidized with meta-chloroperoxybenzoic acid or peroxides such as hydrogen peroxide to obtain IB.
- the key intermediate VI can be obtained through the following synthetic route:
- R 6 , X and Y have the meanings described above.
- the amino compound VII is used as the starting material to react with acid chloride or acid anhydride to obtain the amino-protected amide compound VIII, which is further reacted with chlorosulfonic acid under heating to obtain IX, and the sulfonyl chloride is reacted with a reducing agent to obtain a thiophenol compound
- the key intermediate VI is obtained after successively undergoing a hydrolysis reaction under alkaline conditions, and a substitution reaction with an electrophilic reagent.
- the compound XI can be obtained through the following synthetic route:
- the key intermediate III is first subjected to a reduction reaction to obtain the thiophenol compound XII, and then a reduction reaction is performed to obtain XI.
- the present invention provides a method for synthesizing benzylamine structure-containing aryl sulfide.
- the synthetic route diagram of the specific preparation method is as follows:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y, and n have the meanings described above.
- Intermediate VII is first reacted to obtain benzylamine intermediate XIII, and then through sulfonyl chloride formation reaction, reduction reaction, and substitution reaction to obtain I-A, and finally oxidized under the action of m-chloroperoxybenzoic acid or hydrogen peroxide to obtain I-B.
- the so-called agriculturally acceptable salt in the compound of the present invention represented by the general formula I, when a hydroxyl group, a carboxyl group, or an amino group is present in its structure, it means a salt or salt formed with a metal or organic base.
- Salts formed with inorganic or organic acids such as potassium salt, sodium salt, magnesium salt, or calcium salt.
- organic bases include triethylamine or diisopropylamine
- examples of inorganic acids include hydrochloric acid, sulfuric acid, and hydrobromic acid
- examples of organic acids include formic acid, acetic acid, methanesulfonic acid, fumaric acid, and maleic acid.
- the technical scheme of the present invention also includes the use of the compound of general formula I as a medicine for preparing acaricides in agriculture or other fields.
- the compounds of general formula I have high activity against the following species (the objects listed below are only used to illustrate the present invention, but not to limit the present invention): Tetranychidae (Tetranychus cinnabarinus, Panonychus citrus, two-spotted leaf mite) Mites, Apple Panonychus, Kanzawa Tetranychus, Hawthorn Tetranychus), Gallicidae, Acaridae, Pleurotusidae, Myzus persicae, Nematodes, etc.
- Tetranychidae Tetranychus cinnabarinus, Panonychus citrus, two-spotted leaf mite
- Mites Mites, Apple Panonychus, Kanzawa Tetranychus, Hawthorn Tetranychus
- Gallicidae Acaridae
- Pleurotusidae Myzus persicae
- Nematodes etc.
- the amount of the compound varies due to various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, the application method, the application environment, and the application form.
- a compound dose of 8 g to 3 kg per hectare can provide adequate control.
- composition of the present invention can be administered in the form of a formulation.
- the compound of general formula I is used as an active ingredient to be dissolved or dispersed in a carrier or formulated into a preparation so as to be easier to disperse when used as an acaricide.
- these active substances can be made into wettable powders, water dispersible granules, suspensions, water emulsions, liquids or emulsifiable concentrates.
- at least one liquid or solid carrier is added, and a suitable surfactant can be added when necessary.
- the technical scheme of the present invention also includes a method for preventing and controlling harmful mites: applying the acaricidal composition of the present invention to the harmful mites or their growth medium.
- the more suitable effective amount is selected from 8 g to 1000 g per hectare, and the effective amount is preferably 15 g to 300 g per hectare.
- one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers can be added to the acaricidal composition of the present invention. This can produce additional advantages and effects.
- the benzylamine structure-containing aryl sulfide of the present invention is effective against various harmful organisms, especially spider mites represented by spider mites, spider mites Kanzawa, and spider mites. Shows excellent results.
- the compound of the present invention has good characteristics in the application of protecting important crops, livestock and other harmful mites in agriculture and horticulture.
- Step five N-(4-chloro-3-fluorobenzyl)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)aniline (compound 249) preparation
- Step 4 Preparation of 2-fluoro-N-(3-fluorobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl)thio)aniline (compound 229)
- N-(2-fluoro-4-methylphenyl)acetamide (145g, 868mmol) into a 1L round bottom flask, set up an exhaust gas absorption device, and slowly add chlorosulfonic acid (302g, 2.60) under electric stirring. mol), the addition is completed, the heating is turned on until the internal temperature of the reaction solution is 60 degrees Celsius, the stirring is continued for 3 hours and the temperature is lowered to room temperature, and the reaction solution is slowly added dropwise to 2 kg of ice under stirring.
- Step 6 Preparation of 2-fluoro-N-(3-methoxybenzyl)-4-methyl-5-((2,2,2-trifluoroethyl)thio)aniline (Compound 239)
- the compound to be tested is dissolved in acetone and diluted with 0.1% Tween 80 solution to the desired concentration, and the acetone content does not exceed 5%.
- Mortality (number of inoculated insects-number of live insects after medicine) ⁇ number of inoculated insects ⁇ 100%.
- the compounds of the present invention 53, 54, 303, 304, 1165, 1166, 1202, 1203, and bifenazate and butaflufen are selected for parallel tests of killing mites.
- the test results are shown in Table 2 below:
- the present invention relates to the technical field of pesticides, in particular to an aryl sulfide containing a benzylamine structure and its synthesis method and application.
- Patent documents WO9955668A, CN104995193A, CN105517995A, JP2015036377A, CN103664811B, US2017226107A, WO2018051252A, TW201127291A, CN108290886A, JP2011042611A, JP2011219419A, JP2015036377A and the like describe aryl sulfide oxide derivatives having harmful biological control effects.
- A is oxygen or sulfur
- R 5 is a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted amino group, a nitrogen-containing heterocyclic ring, and the like.
- R 4 represents hydrogen, formyl, C 1-6 alkyl, etc.
- R 5 and R 6 are the same or different and each represents hydrogen, halogen or C 1-6 alkyl, etc.
- R 7 , R 8 , R 9 , R 10 and R 11 are the same or different and each represents hydrogen, halogen, etc.
- X represents oxygen or sulfur.
- the present invention provides an aryl sulfide containing a benzylamine structure and a synthesis method and application thereof to solve the above technical problems.
- the inventors synthesized various aryl sulfide derivatives and conducted in-depth studies on their biological activities.
- the aryl sulfide derivatives represented by the following general formula are harmful to various harmful organisms, especially those represented by Tetranychus cinnabarinus, Tetranychus urticae, Tetranychus Kanzawa, Tetranychus citrus, etc.
- Tetranychus mites showed excellent effects, continued research and completed the present invention.
- n 0, 1 or 2;
- X and Y are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy Or (C 1 -C 4 )haloalkoxy;
- R 1 , R 2 , R 3 , R 4 , R 5 are each independently 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, C 1 -C 10 haloalkoxycarbonyl, C 1 -C 10 alkylsulfonyloxy, C 1 -C 10 alkylsulfonyl, 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,N-dimethyl
- 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, C 3 -C 6 ring Oxyalkyl.
- n 0 or 1
- X is fluorine, chlorine or methyl
- Y is chlorine or methyl
- R 1 is hydrogen, fluorine, chlorine, bromine, hydroxyl, nitro, hydroxymethyl, cyano, trifluoromethyl, C 1 -C 3 alkyl, C 1 -C 4 alkoxycarbonyl, acetyl, propyl Acyl, C 1 -C 3 alkoxy, ethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio , Propylthio, 2,2,2-trifluoroethylsulfinyl, vinyloxycarbonyl, 2,2,2-trifluoroethoxycarbonyl or N-methylcarbonyl;
- R 2 is hydrogen, fluorine or chlorine
- R 3 is hydrogen, fluorine, chlorine, bromine or cyano
- R 4 and R 5 are each independently hydrogen
- R 6 is n-propyl or 2,2,2-trifluoroethyl.
- n 0 or 1
- X is fluorine
- Y is chlorine or methyl
- R 1 is methoxycarbonyl, ethoxycarbonyl, ethylthio or 2,2,2-trifluoroethylthio;
- R 2 , R 4 and R 5 are each independently hydrogen
- R 3 is hydrogen, fluorine, chlorine or cyano
- R 6 is 2,2,2-trifluoroethyl.
- the general formula I is selected from the following compounds:
- E-type and Z-type geometric isomers depending on the type of substituent, and the present invention includes these E-type and Z-type geometric isomers.
- optical isomers caused by having one or more asymmetric carbon atoms and asymmetric sulfur atoms.
- the present invention includes all optical isomers and external Racemate or diastereomer.
- nPropyl n-propyl
- nOctyl n-octyl
- nDecyl n-decyl
- the present invention provides a method for synthesizing benzylamine structure-containing aryl sulfide.
- the synthetic route diagram of the specific preparation method is as follows:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y, and n have the meanings described above.
- nitro compound II as starting material, react with chlorosulfonic acid to obtain sulfonyl chloride compound III, further reduce to obtain disulfide compound IV, and then reduce by hydrogen or metal to obtain amino compound V.
- Compound V is further under alkaline conditions.
- the key intermediate VI is obtained by reacting with electrophiles, and then reacted with substituted benzyl bromide or other electrophiles to obtain IA, and IA is oxidized with meta-chloroperoxybenzoic acid or peroxides such as hydrogen peroxide to obtain IB.
- the key intermediate VI can be obtained through the following synthetic route:
- R 6 , X and Y have the meanings described above.
- the amino compound VII is used as the starting material to react with acid chloride or acid anhydride to obtain the amino-protected amide compound VIII, which is further reacted with chlorosulfonic acid under heating to obtain IX, and the sulfonyl chloride is reacted with a reducing agent to obtain a thiophenol compound
- the key intermediate VI is obtained after successively undergoing a hydrolysis reaction under alkaline conditions, and a substitution reaction with an electrophilic reagent.
- the compound XI can be obtained through the following synthetic route:
- the key intermediate III is first subjected to a reduction reaction to obtain the thiophenol compound XII, and then a reduction reaction is performed to obtain XI.
- the present invention provides a method for synthesizing benzylamine structure-containing aryl sulfide.
- the synthetic route diagram of the specific preparation method is as follows:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y, and n have the meanings described above.
- Intermediate VII is first reacted to obtain benzylamine intermediate XIII, and then through sulfonyl chloride formation reaction, reduction reaction, and substitution reaction to obtain I-A, and finally oxidized under the action of m-chloroperoxybenzoic acid or hydrogen peroxide to obtain I-B.
- the so-called agriculturally acceptable salt in the compound of the present invention represented by the general formula I, when a hydroxyl group, a carboxyl group, or an amino group is present in its structure, it means a salt or salt formed with a metal or organic base.
- Salts formed with inorganic or organic acids such as potassium salt, sodium salt, magnesium salt, or calcium salt.
- organic bases include triethylamine or diisopropylamine
- examples of inorganic acids include hydrochloric acid, sulfuric acid, and hydrobromic acid
- examples of organic acids include formic acid, acetic acid, methanesulfonic acid, fumaric acid, and maleic acid.
- the technical scheme of the present invention also includes the use of the compound of formula I as a medicine for preparing acaricides in agriculture or other fields.
- the compounds of general formula I have high activity against the following species (the objects listed below are only used to illustrate the present invention, but not to limit the present invention): Tetranychidae (Tetranychus cinnabarinus, Panonychus citrus, two-spotted leaf mite) Mites, Apple Panonychus, Kanzawa Tetranychus, Hawthorn Tetranychus), Gallicidae, Acaridae, Pleurotusidae, Myzus persicae, Nematodes, etc.
- Tetranychidae Tetranychus cinnabarinus, Panonychus citrus, two-spotted leaf mite
- Mites Mites, Apple Panonychus, Kanzawa Tetranychus, Hawthorn Tetranychus
- Gallicidae Acaridae
- Pleurotusidae Myzus persicae
- Nematodes etc.
- the amount of the compound varies due to various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, the application method, the application environment, and the application form.
- a compound dose of 8 g to 3 kg per hectare can provide adequate control.
- composition of the present invention can be administered in the form of a formulation.
- the compound of general formula I is used as an active ingredient to be dissolved or dispersed in a carrier or formulated into a preparation so as to be easier to disperse when used as an acaricide.
- these active substances can be made into wettable powders, water dispersible granules, suspensions, water emulsions, liquids or emulsifiable concentrates.
- at least one liquid or solid carrier is added, and a suitable surfactant can be added when necessary.
- the technical scheme of the present invention also includes a method for preventing and controlling harmful mites: applying the acaricidal composition of the present invention to the harmful mites or their growth medium.
- the more suitable effective amount is selected from 8 g to 1000 g per hectare, and the effective amount is preferably 15 g to 300 g per hectare.
- one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers can be added to the acaricidal composition of the present invention. This can produce additional advantages and effects.
- the benzylamine structure-containing aryl sulfide of the present invention is effective against various harmful organisms, especially spider mites represented by spider mites, spider mites Kanzawa, and spider mites. Shows excellent results.
- the compound of the present invention has good characteristics in the application of protecting important crops, livestock and other harmful mites in agriculture and horticulture.
- Step five N-(4-chloro-3-fluorobenzyl)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)aniline (compound 249) preparation
- Step 4 Preparation of 2-fluoro-N-(3-fluorobenzyl)-4-methyl-5-((2,2,2-trifluoroethyl)thio)aniline (compound 229)
- N-(2-fluoro-4-methylphenyl)acetamide (145g, 868mmol) into a 1L round bottom flask, set up an exhaust gas absorption device, and slowly add chlorosulfonic acid (302g, 2.60) under electric stirring. mol), the addition is completed, the heating is turned on until the internal temperature of the reaction solution is 60 degrees Celsius, the stirring is continued for 3 hours and the temperature is lowered to room temperature, and the reaction solution is slowly added dropwise to 2 kg of ice under stirring.
- Step 6 Preparation of 2-fluoro-N-(3-methoxybenzyl)-4-methyl-5-((2,2,2-trifluoroethyl)thio)aniline (Compound 239)
- the compound to be tested is dissolved in acetone and diluted with 0.1% Tween 80 solution to the desired concentration, and the acetone content does not exceed 5%.
- Mortality (number of inoculated insects-number of live insects after medicine) ⁇ number of inoculated insects ⁇ 100%.
- the compounds of the present invention 53, 54, 303, 304, 1165, 1166, 1202, 1203, and bifenazate and butaflufen are selected for parallel tests of killing mites.
- the test results are shown in Table 2 below:
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Abstract
Description
化合物编号 | 浓度(ppm) | 死亡率% |
53 | 3.12 | 99 |
54 | 3.12 | 100 |
303 | 3.12 | 99 |
304 | 3.12 | 98 |
1165 | 3.12 | 99 |
1166 | 3.12 | 98 |
1202 | 3.12 | 97 |
1203 | 3.12 | 98 |
联苯肼酯 | 3.12 | 85 |
丁氟螨酯 | 3.12 | 72 |
化合物编号 | 浓度(ppm) | 死亡率% |
53 | 3.12 | 99 |
54 | 3.12 | 100 |
303 | 3.12 | 99 |
304 | 3.12 | 98 |
1165 | 3.12 | 99 |
1166 | 3.12 | 98 |
1202 | 3.12 | 97 |
1203 | 3.12 | 98 |
联苯肼酯 | 3.12 | 85 |
丁氟螨酯 | 3.12 | 72 |
Claims (11)
- 一种含苄胺结构的芳基硫化物,其特征在于,是由通式I表示的:或其农业上可接受的盐;其中:n为0、1或2;X、Y各自独立的为氢、氟、氯、溴、碘、氰基、(C 1-C 4)烷基、(C 1-C 4)卤代烷基、(C 1-C 4)烷氧基或(C 1-C 4)卤代烷氧基;R 1、R 2、R 3、R 4、R 5各自独立的为氢、氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基、C 1-C 10卤代烷氧基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰氧基、C 1-C 10烷基磺酰基、C 1-C 10烷硫基、C 1-C 10卤代烷硫基、C 2-C 10烯氧基羰基、C 1-C 10烷基羰基、氨基羰基、C 1-C 10 N-烷基羰基、N,N-二甲基羰基、N,N-二甲基硫代羰基、C 1-C 10 N-烷基硫代羰基、2-氧代丙氧基羰基、甲氧基甲氧基羰基;R 6为C 1-C 6卤代烷基、C 2-C 6炔基、C 2-C 6烯基、C 1-C 6烷基、C 3-C 6环烷基、C 3-C 6环氧烷基。
- 如权利要求1所述的一种含苄胺结构的芳基硫化物,其特征在于,所述通式I中:n为0或1;X为氟、氯或甲基;Y为氯或甲基;R 1为氢、氟、氯、溴、羟基、硝基、羟甲基、氰基、三氟甲基、C 1-C 3烷基、C 1-C 4烷氧基羰基、乙酰基、丙酰基、C 1-C 3烷氧基、乙硫基、2-氟乙硫基、2-氯乙硫基、2,2-二氟乙硫基、2,2,2-三氟乙硫基、丙硫基、2,2,2-三氟乙基亚硫酰基、乙烯氧基羰基、2,2,2-三氟乙氧基羰基或N-甲基羰基;R 2为氢、氟或氯;R 3为氢、氟、氯、溴或氰基;R 4和R 5各自独立的为氢;R 6为正丙基或2,2,2-三氟乙基。
- 如权利要求1所述的一种含苄胺结构的芳基硫化物,其特征在于,所述通式I中,n为0或1;X为氟;Y为氯或甲基;R 1为甲氧基羰基、乙氧基羰基、乙硫基或2,2,2-三氟乙硫基;R 2、R 4和R 5各自独立的为氢;R 3为氢、氟、氯或氰基;R 6为2,2,2-三氟乙基。
- 一种式I化合物的应用,其特征在于,所述式I化合物及其可用盐在防治螨科中的用途。
- 一种式I化合物的应用,其特征在于,所述式I化合物及其可用盐在防治线虫中的用途。
- 一种农业组合物,其特征在于,所述组合物包含至少一种式I化合物及其可农用盐和至少一种液体或固体载体。
- 一种防治无脊椎动物害虫的方法,其特征在于,所述方法包括用杀虫有效量的式I化合物及其可农用盐处理害虫、其食物链、其栖息地或其繁殖地或害虫生长的植物、土壤。
- 如权利要求10所要求的方法,其特征在于,所述方法包括用杀虫有效量的式I化合物及其可农用盐处理植物。
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AU2020356739A AU2020356739B2 (en) | 2019-09-23 | 2020-08-31 | Aryl sulfide containing benzylamine structure, synthesis method therefor and application thereof |
EP20869958.7A EP4050000A4 (en) | 2019-09-23 | 2020-08-31 | Aryl sulfide containing benzylamine structure, synthesis method therefor and application thereof |
KR1020217028428A KR102644920B1 (ko) | 2019-09-23 | 2020-08-31 | 벤질아민 함유 구조의 아릴기 황화물 및 그 합성방법과 응용 |
JP2021552251A JP7303893B2 (ja) | 2019-09-23 | 2020-08-31 | ベンジルアミン構造を含むアリール硫化物及びその合成方法と応用 |
MX2021010818A MX2021010818A (es) | 2019-09-23 | 2020-08-31 | Estructura de bencilamina que comprende sulfuro de arilo, método para su síntesis y aplicación de la misma. |
DE112020001084.8T DE112020001084T5 (de) | 2019-09-23 | 2020-08-31 | Arylsulfid mit Benzylaminstruktur und dessen Syntheseverfahren und Anwendung |
US17/397,984 US20210360919A1 (en) | 2019-09-23 | 2021-08-09 | Aryl sulfide comprising benzylamine, synthesis method and application thereof |
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EP4045482A1 (de) * | 2019-10-16 | 2022-08-24 | Bayer Aktiengesellschaft | Verfahren zur herstellung von 1,1'-disulfandiylbis(4-fluor-2-methyl-5-nitrobenzol) |
CN114685593B (zh) * | 2020-12-31 | 2024-01-23 | 鲁南制药集团股份有限公司 | 一种氟维司群制备方法及其中间体 |
CN114763331B (zh) * | 2021-01-13 | 2023-07-18 | 沈阳化工大学 | 一种三氟乙基硫醚(亚砜)取代苯类化合物及其用途 |
CN114763330A (zh) * | 2021-01-13 | 2022-07-19 | 沈阳化工大学 | 一种三氟乙基硫醚(亚砜)取代苯类化合物及其应用 |
WO2022166842A1 (zh) * | 2021-02-07 | 2022-08-11 | 山东康乔生物科技有限公司 | 含有苄胺类杀螨剂的组合物及其应用 |
WO2022166837A1 (zh) * | 2021-02-07 | 2022-08-11 | 山东康乔生物科技有限公司 | 芳基硫化物及其制备方法和应用 |
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TW202210456A (zh) | 2022-03-16 |
WO2021056922A9 (zh) | 2021-05-14 |
BR112021019360A2 (pt) | 2022-04-19 |
AU2020356739A1 (en) | 2022-05-12 |
CN111825585B (zh) | 2021-12-14 |
JP7303893B2 (ja) | 2023-07-05 |
CN111825585A (zh) | 2020-10-27 |
CO2022004979A2 (es) | 2022-04-29 |
EP4050000A4 (en) | 2023-06-28 |
KR102644920B1 (ko) | 2024-03-06 |
MX2021010818A (es) | 2021-12-10 |
AU2020356739B2 (en) | 2023-12-07 |
EP4050000A1 (en) | 2022-08-31 |
US20210360919A1 (en) | 2021-11-25 |
JP2022531823A (ja) | 2022-07-12 |
TWI801961B (zh) | 2023-05-11 |
KR20210124389A (ko) | 2021-10-14 |
DE112020001084T5 (de) | 2022-01-27 |
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