WO2021000736A1 - 取代的苯甲酰-吡唑类化合物及其在农业中的应用 - Google Patents
取代的苯甲酰-吡唑类化合物及其在农业中的应用 Download PDFInfo
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- WO2021000736A1 WO2021000736A1 PCT/CN2020/096736 CN2020096736W WO2021000736A1 WO 2021000736 A1 WO2021000736 A1 WO 2021000736A1 CN 2020096736 W CN2020096736 W CN 2020096736W WO 2021000736 A1 WO2021000736 A1 WO 2021000736A1
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- 0 C[n]1nc(*)c(C(c(c(Cl)c2COc3cc(*)n[n]3*)ccc2S(C)(=O)=O)=O)c1O Chemical compound C[n]1nc(*)c(C(c(c(Cl)c2COc3cc(*)n[n]3*)ccc2S(C)(=O)=O)=O)c1O 0.000 description 5
- KLJPFWVJHXRIPL-UHFFFAOYSA-N CC(c(ccc(S(C)(=O)=O)c1C)c1Cl)=O Chemical compound CC(c(ccc(S(C)(=O)=O)c1C)c1Cl)=O KLJPFWVJHXRIPL-UHFFFAOYSA-N 0.000 description 1
- VEOVEVFSFKAKFD-UHFFFAOYSA-N Cc1n[n](C)c(OCc(c(Cl)c(cc2)C(Cl)=O)c2S(C)(=O)=O)c1 Chemical compound Cc1n[n](C)c(OCc(c(Cl)c(cc2)C(Cl)=O)c2S(C)(=O)=O)c1 VEOVEVFSFKAKFD-UHFFFAOYSA-N 0.000 description 1
- RHTZJAVNLMEQAQ-UHFFFAOYSA-N Cc1n[n](C)c(OCc(c(Cl)c(cc2)C(O)=O)c2S(C)(=O)=O)c1 Chemical compound Cc1n[n](C)c(OCc(c(Cl)c(cc2)C(O)=O)c2S(C)(=O)=O)c1 RHTZJAVNLMEQAQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
Definitions
- the present invention provides a new substituted benzoyl-pyrazole compound and a preparation method thereof; a composition containing these compounds and its application in agriculture.
- Substituted benzoyl-pyrazole compounds are a class of compounds with excellent biological activity, and their herbicidal activity reports are described in, for example, WO9910327 and WO9910328. However, the compounds of the present invention described in detail below have not been described in these documents.
- the present invention provides a new substituted benzoyl-pyrazole compound, which has excellent herbicidal effect, broad weed control spectrum and excellent selectivity between crops and weeds.
- the present invention provides compounds represented by formula (I) or stereoisomers, tautomers, nitrogen oxides and salts of compounds represented by formula (I):
- R 1 is hydroxy, cyano, amino, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, halogenated C 1-6 alkyl , Halogenated C 2-6 alkenyl, halogenated C 2-6 alkynyl, halogenated C 1-6 alkoxy or C 3-8 cycloalkyl;
- R 2 is C 1-8 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halogenated C 1-8 alkyl, halogenated C 2-6 alkenyl, halogenated C 2-6 alkynyl Or C 6-10 aryl;
- R 3 is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl or C 3-8 cycloalkyl;
- R 4 is hydrogen or -CH 2 -CO-C 6-10 aryl; wherein the -CH 2 -CO-C 6-10 aryl is optionally selected from halogen or C 1- 6 substituted by the substituent of the alkyl group.
- R 1 is hydroxy, cyano, amino, nitro, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy, halo C 1-4 alkyl, halogenated C 2-4 alkenyl, halogenated C 2-4 alkynyl, halogenated C 1-4 alkoxy or C 3-6 cycloalkyl;
- R 2 is C 1-6 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halogenated C 1-4 alkyl, halogenated C 2-4 alkenyl, halogenated C 2-4 alkynyl Or C 6-10 aryl.
- R 1 is hydroxy, cyano, amino, nitro, methyl, ethyl, n-propyl, isopropyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 , cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
- R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 or benzene base.
- R 3 is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl or C 3-6 cycloalkyl;
- R 4 is hydrogen or -CH 2 -CO-phenyl; wherein the -CH 2 -CO-phenyl is optionally substituted with 1, 2 or 3 substituents selected from halogen or C 1-4 alkyl .
- R 3 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
- R 4 is hydrogen or -CH 2 -CO-phenyl; wherein the -CH 2 -CO-phenyl is optionally substituted with 1, 2 or 3 substituents selected from chlorine or methyl.
- the present invention provides a compound, which is a compound represented by formula (Ia) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ia):
- R 1 and R 2 have the meanings as described in the present invention.
- the present invention provides a compound, which is a compound represented by formula (Ib) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ib):
- R 1 and R 2 have the meanings described in the present invention.
- the present invention provides a compound, which is a compound represented by formula (Ic) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ic):
- R 1 , R 2 and R 3 have the meanings as described in the present invention.
- the present invention provides a compound, which is a compound represented by formula (Id) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Id):
- R 1 , R 2 and R 3 have the meanings as described in the present invention
- R 5 is hydrogen, halogen or C 1-4 alkyl.
- R 1 is C 1-4 alkyl, halo C 1-4 alkyl, or C 3-6 cycloalkyl.
- R 1 is methyl, ethyl, n-propyl, isopropyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 , cyclopropyl, cyclobutyl , Cyclopentyl or cyclohexyl.
- R 2 is C 1-6 alkyl, halo C 1-4 alkyl, or phenyl.
- R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 ,- CH 2 CF 3 or phenyl.
- R 3 is hydrogen, C 1-4 alkyl, or C 3-6 cycloalkyl.
- R 3 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
- R 4 is hydrogen or the following sub-structure:
- R 5 is hydrogen, chloro or methyl.
- the present invention provides a composition comprising the compound of the present invention.
- composition of the present invention further optionally includes at least one additional component.
- the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention in agriculture.
- the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention for controlling unwanted plants.
- the present invention provides a method for controlling unwanted plants, which is characterized by applying an effective amount of the compound of the present invention to plants, plant seeds, soil in or on which plants grow, or cultivation areas.
- the present invention provides a method for controlling the growth of weeds in useful plants, which comprises applying an effective amount of the compound of the present invention to the locus of the weeds.
- the compound provided by the present invention is a new type compound that is more effective to weeds, lower in cost, less toxic and safe to the environment.
- the compounds represented by formula (I), formula (Ia), formula (Ib), formula (Ic) or formula (Id) may exist in different stereoisomers or optical isomers or tautomeric forms.
- the present invention encompasses all such isomers and tautomers and mixtures thereof in various ratios, as well as isotopic forms such as deuterium-containing compounds.
- the isotope-enriched compound has the structure described by the general formula given in the present invention, except that one or more atoms are replaced by atoms having the selected atomic weight or mass number.
- Exemplary isotopes that can be incorporated into the compounds of the present invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 17 O , 18 O, 18 F, 31 P, 32 P, 35 S, 36 Cl and 125 I.
- Any asymmetric atom (for example, carbon, etc.) of the compound disclosed in the present invention can exist in a racemic or enantiomerically enriched form, such as (R)-, (S)- or (R,S)-configuration form exist.
- Stereoisomers refer to compounds that have the same chemical structure but differ in the arrangement of the atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans) isomers, atropisomers, etc. .
- Enantiomers refer to two isomers of a compound that cannot be superimposed but are mirror images of each other.
- Diastereoisomers refer to stereoisomers that have two or more chiral neutralities and whose molecules are not mirror images of each other. Diastereoisomers have different physical properties, such as melting point, boiling point, spectral properties and reactivity. Mixtures of diastereomers can be separated by high-resolution analytical operations such as electrophoresis and chromatography, such as HPLC.
- optically active compounds that is, they have the ability to rotate the plane of plane-polarized light.
- the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule with respect to one or more chiral centers.
- the prefixes d and l or (+) and (-) are symbols used to specify the rotation of plane-polarized light caused by the compound, where (-) or l indicates that the compound is levorotatory.
- Compounds prefixed with (+) or d are dextrorotatory.
- a specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture.
- a 50:50 mixture of enantiomers is called a racemic mixture or a racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
- tautomer or "tautomeric form” refers to structural isomers with different energies that can be converted into each other through a low energy barrier. If tautomerism is possible (as in solution), the chemical equilibrium of tautomers can be reached.
- proton tautomers also called prototropic tautomers
- Valence tautomers include interconversion through the recombination of some bond-forming electrons.
- keto-enol tautomerism are those of pentane-2,4-dione, hexane-1,3-dione and 4-hydroxypent-3-en-2-one tautomers Mutual change.
- Another example of tautomerism is phenol-ketone tautomerism.
- a specific example of phenol-ketone tautomerism is the interconversion of pyridine-4-ol and pyridine-4(1H)-one tautomers. Unless otherwise indicated, all tautomeric forms of the compounds of the present invention are within the scope of the present invention.
- keto-enol interconversion there may be keto-enol interconversion:
- the compounds of the present invention can be optionally substituted by one or more substituents, such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
- substituents such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
- substituents such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
- substituents such as the compounds of the general formula above, or the special examples, subclasses, and subclasses contained in the examples.
- a class of compounds can be used interchangeably.
- substituted means that one or more hydrogen atoms in a given structure are replaced by a specific substituent.
- an optional substituent group can be substituted at each substitutable position of the group.
- substituents mentioned herein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxy, alkyl, alkoxy, alkoxyalkyl, alkane Oxyoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl
- C 1 -C 6 alkyl or “C 1-6 alkyl” specifically refers to independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl. base.
- alkyl or “alkyl group” used in the present invention refers to a saturated linear or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally One or more substituents described in this invention are substituted. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-10 carbon atoms; in one embodiment, the alkyl group contains 1-8 In another embodiment, the alkyl group contains 1-6 carbon atoms; in another embodiment, the alkyl group contains 1-4 carbon atoms; in another embodiment, the alkane The radical group contains 1-3 carbon atoms.
- alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), isopropyl (i-Pr, -CH(CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH(CH 3 )CH 2 CH 3 ), tert-butyl (t-Bu, -C(CH 3 ) 3 ), n-pentyl (-CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH(CH 3 )CH 2 CH 2 CH 3 ), 3-pentyl (-CH(CH 2 CH 3 ) 2 ), 2-methyl -2-Butyl (-C(CH 3 ) 2
- alkenyl means a linear or branched monovalent hydrocarbon group containing 2-12 carbon atoms, in which there is at least one unsaturation site, that is, a carbon-carbon sp 2 double bond, wherein the alkenyl group
- the group may be optionally substituted with one or more substituents described in the present invention, which includes the positioning of "cis” and “tans", or the positioning of "E” and "Z”.
- the alkenyl group contains 2-10 carbon atoms; in one embodiment, the alkenyl group contains 2-8 carbon atoms; in another embodiment, the alkenyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2-4 carbon atoms.
- alkynyl means a linear or branched monovalent hydrocarbon group containing 2-12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may optionally be substituted by one or more One of the substituents described in this invention is substituted.
- the alkynyl group contains 2-10 carbon atoms; in one embodiment, the alkynyl group contains 2-8 carbon atoms; in another embodiment, the alkynyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2-4 carbon atoms.
- alkynyl groups include, but are not limited to, -C ⁇ CH, -C ⁇ CCH 3 , -CH 2 -C ⁇ CH, -CH 2 -C ⁇ CCH 3 , -CH 2 CH 2 -C ⁇ CH , -CH 2 -C ⁇ CCH 2 CH 3 , -CH 2 CH 2 -C ⁇ CH 2 CH 3 and so on.
- alkoxy means that the alkyl group is connected to the rest of the molecule through an oxygen atom, where the alkyl group has the meaning as described in the present invention. Unless otherwise specified, the alkoxy group contains 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1-10 carbon atoms; in one embodiment, the alkoxy group contains 1-8 carbon atoms; in one embodiment, the alkoxy group contains 1-6 carbon atoms; in another embodiment, the alkoxy group contains 1-4 carbon atoms; in yet another embodiment, the alkoxy group contains 1-3 carbon atoms.
- the alkoxy group may be optionally substituted with one or more substituents described herein.
- alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3 ), ethoxy (EtO, -OCH 2 CH 3 ), 1-propoxy (n-PrO, n- Propoxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH(CH 3 ) 2 ), 1-butoxy (n-BuO, n- Butoxy, -OCH 2 CH 2 CH 2 CH 3 ), 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH 2 CH(CH 3 ) 2 ), 2-but Oxygen (s-BuO, s-butoxy, -OCH(CH 3 )CH 2 CH 3 ), 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC(CH 3 ) 3 ), 1-pentyloxy (n-pentyloxy, -OCH 2 CH 2 CH 2 CH 2 CH 3 ), 2-(
- halogen refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
- haloalkyl means that an alkyl group is substituted with one or more halogen atoms.
- haloalkyl groups include, but are not limited to, -CH 2 F, -CHF 2 , -CH 2 Cl, -CH 2 Br, -CF 3 , -CH 2 CF 3 , -CH 2 CH 2 F, -CH 2 CH 2 Cl, -CH 2 CH 2 Br, -CH 2 CHF 2 , -CH 2 CH 2 CF 3 , -CH 2 CH 2 CH 2 F, -CH 2 CH 2 CH 2 Cl, -CH 2 CH 2 CH 2 Br, -CHFCH 2 CH 3 , -CHClCH 2 CH 3 , etc.
- haloalkoxy means that the alkoxy group is substituted with one or more halogen atoms.
- halogenated alkoxy groups include, but are not limited to, -OCH 2 F, -OCHF 2 , -OCH 2 Cl, -OCH 2 Br, -OCF 3 , -OCH 2 CF 3 , -OCH 2 CH 2 F, -OCH 2 CH 2 Cl, -OCH 2 CH 2 Br, -OCH 2 CHF 2 , -OCH 2 CH 2 CF 3 , -OCH 2 CH 2 CH 2 F, -OCH 2 CH 2 CH 2 Cl, -OCH 2 CH 2 CH 2 Br, -OCHFCH 2 CH 3 , -OCHClCH 2 CH 3 , etc.
- haloalkenyl means that an alkenyl group is substituted with one or more halogen atoms.
- haloalkynyl means that an alkynyl group is substituted with one or more halogen atoms.
- cycloalkyl refers to a monovalent or multivalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-12 carbon atoms.
- the cycloalkyl group contains 3-12 carbon atoms; in one embodiment, the cycloalkyl group contains 3-10 carbon atoms; in another embodiment, the cycloalkyl group contains 3-8 carbon atoms. Atom; In yet another embodiment, the cycloalkyl group contains 3-6 carbon atoms.
- the cycloalkyl group is optionally substituted with one or more substituents described in this invention.
- Examples of this include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl Alkyl, adamantyl, etc.
- unsaturated means that the group contains one or more degrees of unsaturation.
- heteroatom refers to O, S, N, P, and Si, including any oxidation state of N, S, and P; primary, secondary, and tertiary amines and quaternary ammonium salt forms; or on the nitrogen atom in the heterocycle
- the form in which hydrogen is substituted for example, N (like N in 3,4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like N-substituted pyrrolidinyl) NR).
- aryl means a monocyclic, bicyclic and tricyclic carbocyclic ring system containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic Family, where each ring system contains a ring composed of 3-7 atoms, and has one or more attachment points connected to the rest of the molecule.
- aryl can be used interchangeably with the term “aromatic ring”. Examples of aryl groups may include phenyl, indenyl, naphthyl, and anthracenyl. The aryl group is optionally substituted with one or more substituents described in the present invention.
- the salts of the compound of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines.
- Preferred cations include sodium, potassium, magnesium and ammonium cations having the formula N + (R 19 R 20 R 21 R 22 ), wherein R 19 , R 20 , R 21 and R 22 are independently selected from hydrogen, C 1 -C 6 alkyl and C 1 -C 6 hydroxyalkyl.
- the salt of the compound represented by formula (I), formula (Ia), formula (Ib), formula (Ic) or formula (Id) can be obtained by using metal hydroxides (such as sodium hydroxide) or amines (such as ammonia, Trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine) have formula (I), formula (Ia),
- the compound represented by formula (Ib), formula (Ic) or formula (Id) is prepared by treatment.
- acceptable salts can be formed from organic and inorganic acids, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid. Acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid and similarly known Accepted acid.
- organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid. Acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesul
- the purpose of the present invention is to provide a novel substituted benzoyl compound, a herbicide composition containing the compound and its application.
- the present invention provides compounds represented by formula (I) or stereoisomers, tautomers, nitrogen oxides and salts of compounds represented by formula (I):
- R 1 is hydroxy, cyano, amino, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, halogenated C 1-6 alkyl , Halogenated C 2-6 alkenyl, halogenated C 2-6 alkynyl, halogenated C 1-6 alkoxy or C 3-8 cycloalkyl;
- R 2 is C 1-8 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halogenated C 1-8 alkyl, halogenated C 2-6 alkenyl, halogenated C 2-6 alkynyl Or C 6-10 aryl;
- R 3 is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl or C 3-8 cycloalkyl;
- R 4 is hydrogen or -CH 2 -CO-C 6-10 aryl; wherein the -CH 2 -CO-C 6-10 aryl is optionally selected from halogen or C 1- 6 substituted by the substituent of the alkyl group.
- R 1 is hydroxy, cyano, amino, nitro, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy, halo C 1-4 alkyl, halogenated C 2-4 alkenyl, halogenated C 2-4 alkynyl, halogenated C 1-4 alkoxy or C 3-6 cycloalkyl.
- R 1 is hydroxy, cyano, amino, nitro, methyl, ethyl, n-propyl, isopropyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 , cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
- R 2 is C 1-6 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halogenated C 1-4 alkyl, halogenated C 2-4 alkenyl, halogenated C 2-4 alkynyl or C 6-10 aryl.
- R 2 is C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl or C 6-10 aryl.
- R 2 is C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo Substitute C 2-4 alkynyl or phenyl.
- R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 or phenyl.
- R 3 is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, or C 3-6 cycloalkyl.
- R 3 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
- R 4 is hydrogen or -CH 2 -CO-phenyl; wherein the -CH 2 -CO-phenyl is optionally substituted by 1, 2 or 3 selected from halogen or C 1-4 alkane The substituents of the group are substituted.
- R 4 is hydrogen or -CH 2 -CO-phenyl; wherein said -CH 2 -CO-phenyl is optionally substituted with 1, 2 or 3 substituents selected from chlorine or methyl Replaced.
- the present invention provides a compound, which is a compound represented by formula (Ia) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ia):
- R 1 and R 2 have the meanings described in the present invention.
- the compound represented by formula (Ia) of the present invention may have the following tautomeric structures:
- the present invention provides a compound, which is a compound represented by formula (Ib) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ib):
- R 1 and R 2 have the meanings described in the present invention.
- the compound represented by formula (Ib) of the present invention may have the following tautomeric structures:
- the present invention provides a compound, which is a compound represented by formula (Ic) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Ic):
- R 1 , R 2 and R 3 have the meanings as described in the present invention.
- the present invention provides a compound, which is a compound represented by formula (Id) or a stereoisomer, tautomer, nitrogen oxide or salt of a compound represented by formula (Id):
- R 1 , R 2 and R 3 have the meanings as described in the present invention
- R 5 is hydrogen, halogen or C 1-4 alkyl.
- R 1 is C 1-4 alkyl, halo C 1-4 alkyl, or C 3-6 cycloalkyl.
- R 1 is methyl, ethyl, n-propyl, isopropyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 , cyclopropyl, cyclobutyl , Cyclopentyl or cyclohexyl.
- R 2 is C 1-6 alkyl, halo C 1-4 alkyl, or phenyl.
- R 2 is C 1-4 alkyl, halo C 1-4 alkyl, or phenyl.
- R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, -CHF 2 , -CF 3 , -CH 2 CHF 2 , -CH 2 CF 3 or phenyl.
- R 2 is C 1-4 alkyl.
- R 2 is methyl
- R 3 is hydrogen, C 1-4 alkyl, or C 3-6 cycloalkyl.
- R 3 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
- R 4 is hydrogen or the following sub-structure:
- R 5 is hydrogen, chloro or methyl.
- the present invention provides a compound which is a compound having one of the following structures or a stereoisomer, tautomer, nitrogen oxide or salt thereof of a compound having one of the following structures:
- the present invention provides a composition comprising the compound of the present invention.
- composition of the present invention further optionally includes at least one additional component.
- the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention in agriculture.
- the present invention provides the use of the compound of the present invention or the composition containing the compound of the present invention for controlling unwanted plants.
- the present invention provides the use of the compound of the present invention or a composition containing the compound of the present invention as a herbicide in agriculture.
- the present invention provides a method for controlling unwanted plants, which is characterized by applying an effective amount of the compound of the present invention to plants, plant seeds, soil in or on which plants grow, or cultivation areas.
- the present invention provides a method for controlling the growth of weeds in useful plants, which comprises applying an effective amount of the compound of the present invention to the locus of the weeds.
- application to the locus of weeds includes application to plants, plant seeds, soil in or on which plants grow, or cultivation areas.
- the compound provided by the present invention is a new type compound that is more effective to weeds, lower in cost, less toxic and safe to the environment.
- compositions and formulations of the compounds of the invention are provided.
- the compound of the present invention can generally be used as a herbicide active ingredient in a composition or formulation which has at least one additional component selected from surfactants, solid diluents and liquid diluents
- additional component selected from surfactants, solid diluents and liquid diluents
- the components that meet the requirements of pesticide use, etc. belong to the scope of the present invention.
- the ingredients of the formulation or composition are selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors (such as soil type, humidity, and temperature).
- Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), etc., which may optionally be thickened into gels.
- aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions.
- non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.
- the general types of solid compositions are powders, powders, granules, pellets, pellets, lozenges, tablets, filled films (including seed coatings), etc. They can be water-dispersible ("wettable") Or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are especially useful for seed treatment.
- the active ingredient can be (micro)encapsulated and further formed into a suspension or solid preparation; or the entire active ingredient preparation can be encapsulated (or "coated”). Encapsulation can control or delay the release of active ingredients.
- Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granular formulations. High-concentration compositions are mainly used as intermediates for other formulations.
- Sprayable formulations are usually dispersed in a suitable medium before spraying. Such liquid preparations and solid preparations are formulated into preparations that are easy to dilute in a spray medium (usually water).
- the spray volume can be in the range of about one liter to several thousand liters per hectare, but is more typically in the range of about ten liters to several hundred liters per hectare.
- the sprayable formulation can be mixed with water or another suitable medium in a tank, used to treat leaves by air or ground application, or applied to the growing medium of plants. Liquid and dry formulations can be metered directly into the drip irrigation system, or metered into the furrow during planting.
- the formulation will generally contain effective amounts of active ingredients, diluents and surfactants, the sum of which is 100% by weight.
- Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g. lactose, sucrose), silica, talc, mica, diatoms Soil, urea, calcium carbonate, sodium carbonate and sodium bicarbonate and sodium sulfate.
- Typical solid diluents are described in Watkins et al. Handbook of Insecticide Dust Diluents and Carriers, 2nd edition, Dorland Books, Caldwell, New Jersey.
- Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g. N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g. N-methylpyrrolidone) , Ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffin (e.g.
- Liquid diluents also include glycerides of saturated and unsaturated fatty acids (usually C 6 -C 22 ), such as plant seed and fruit oils (such as olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil) , Sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil and palm kernel oil), fats of animal origin (such as beef tallow, lard, lard, cod liver oil, fish oil), and Their mixture.
- plant seed and fruit oils such as olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil
- fats of animal origin such as beef tallow, lard, lard, cod liver oil, fish oil
- Liquid diluents also include alkylated (eg, methylated, ethylated, butylated) fatty acids, where fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals and can be purified by distillation.
- alkylated (eg, methylated, ethylated, butylated) fatty acids where fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals and can be purified by distillation.
- Typical liquid diluents are described in Marsden's Solvents Guide, 2nd edition, Interscience, New York, 1950.
- the solid and liquid compositions of the present invention generally contain one or more surfactants.
- surfactants also called “surface-active agents”
- surface-active agents usually change, most commonly reducing the surface tension of the liquid.
- the surfactant can be used as a wetting agent, dispersant, emulsifier or defoamer.
- Nonionic surfactants that can be used in the composition of the present invention include, but are not limited to: alcohol alkoxylates, such as based on natural alcohols and synthetic alcohols (which are branched or linear) and are composed of alcohols and ethylene oxide, Alcohol alkoxylates prepared from propylene oxide, butylene oxide or their mixtures; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, Such as ethoxylated soybean, castor and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylation, nonylphenol ethoxylation, dinonylphenol ethoxylate and ten Dialkylphenol ethoxylates (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide or their mixture
- Usable anionic surfactants include, but are not limited to: alkyl aryl sulfonic acids and their salts; carboxylated alcohol or alkyl phenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives Compounds, such as lignosulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and benzene Phosphate esters of vinyl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfates; sulfates and sulfonates of oils and fatty acids; ethoxylated alkylphenols Sulfates and sulfonates of alcohols; Sulfates
- Usable cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkylpropylene diamine, tripropylene triamine and dipropylene tetraamine, and ethoxylated amines, Ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide, or their mixtures); amine salts, such as amine acetate and diamine salts; quaternary Ammonium salts, such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides, such as alkyldimethylamine oxide and di-(2-hydroxyethyl)-alkylamine oxide.
- amines such as N-alkylpropylene diamine, tripropylene triamine and dipropylene tetraamine, and ethoxylated amines,
- Nonionic surfactants and anionic surfactants are also useful in the composition of the present invention.
- Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in multiple published references, including McCutcheon's Emulsifiers and Detergents published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co., North American and International Yearbooks Edition; Sisely and Wood's Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and AS Davidson and B. Milwidsky's Synthetic Detergents, seventh edition, John Wiley and Sons, New York, 1987 .
- composition of the present invention may also contain formulation auxiliaries and additives known to those skilled in the art as auxiliary formulations (some of which may also be considered to function as solid diluents, liquid diluents or surfactants).
- formulation auxiliaries and additives can control: pH (buffering agent), foaming during processing (defoaming agent such as polyorganosiloxane), sedimentation of active ingredients (suspending agent), viscosity (thixotropic thickener) ), microbial growth in the container (antimicrobial agent), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or adhesive), evaporation (anti-evaporation agent), and others Formulation attributes.
- Film forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymer, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alcohol copolymer, and wax.
- formulation auxiliaries and additives include McCutcheon's Volume 2: Functional Materials, North American and International Yearbook Edition published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and those listed in PCT Publication WO03/024222.
- the compound of the present invention and any other active ingredients are usually incorporated into the composition of the present invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid or dry diluent.
- Solutions can be prepared by simply mixing the ingredients, including emulsifiable concentrates. If the solvent of the liquid composition used as emulsifiable concentrate is immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active ingredient when diluted with water.
- a media mill can be used to wet mill active ingredient slurries with a particle size of up to 2,000 ⁇ m to obtain particles with an average diameter of less than 3 ⁇ m.
- the aqueous slurry can be prepared as a finished suspension concentrate (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible particles. Dry formulations generally require a dry milling step, which produces an average particle size in the range of 2 ⁇ m to 10 ⁇ m. Dusts and powders can be prepared by mixing, and usually by grinding (for example, with a hammer mill or a fluid energy mill). Granules and pellets can be prepared by spraying the active substance on a preformed granular carrier or by agglomeration techniques.
- Granules can be prepared as described in US 4,172,714.
- Water-dispersible and water-soluble granules can be prepared as described in US 4,144,050, US 3,920,442 and DE.3,246,493.
- Tablets can be prepared as described in US 5,180,587, US5,232,701 and US5,208,030.
- the film can be prepared as proposed in GB2,095,558 and US3,299,566.
- the herbicide of the present invention can be used by spraying plants, applying to soil, or applying to water surfaces.
- the amount of the active ingredient is appropriately determined to meet the application purpose.
- the content of the active ingredient is appropriately determined according to the purpose.
- the amount of the compound of the present invention depends on the type of compound used, the target weed, the tendency of weed appearance, environmental conditions, and the type of herbicide.
- the amount of the active ingredient is appropriately selected from 1 g to 50 kg, preferably 10 g to 10 kg per hectare.
- the herbicide of the present invention is used in a liquid form, such as an emulsifiable concentrate, a wettable powder, or a flowable formulation, its amount is appropriately selected to be 0.1-50,000 ppm, preferably 10-10,000 ppm.
- the present invention provides a method for controlling weeds in crops of useful plants, the method comprising applying to the weeds or to the locus of the weeds or to the useful plants or the locus of the useful plants.
- the compound or composition of the invention is administered.
- the present invention also provides a method for selectively controlling grasses and/or weeds in crops of useful plants, the method comprising applying to useful plants or their locus or cultivation areas a herbicidal effective amount of plants having the formula (I), Compounds represented by formula (Ia), formula (Ib), formula (Ic) or formula (Id).
- herbicide means a compound that controls or modifies the growth of plants.
- herbicidally effective amount means the amount of such a compound or combination of such compounds capable of producing the effect of controlling or modifying plant growth.
- the effects of control or modification include all deviations from natural development, such as killing, delaying, leaf burn, albinism, stunting, etc.
- plant refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, leaves and fruits.
- location is intended to include soil, seeds, and seedlings, together with established vegetation and includes not only areas where weeds may have grown, but also areas where weeds have not yet appeared, and also includes information about useful plant crops Planting area.
- the "planted area” includes land on which crop plants have grown, as well as land intended to grow such crop plants.
- weed as used herein means any undesirable plant, and therefore includes not only important agronomic weeds as described below, but also volunteer crop plants.
- the useful plant crops that may use the composition according to the present invention include but are not limited to perennial crops, such as citrus fruits, grape vines, nuts, oil palm, olives, pome fruits, stone fruits and rubber, and annual arable crops,
- perennial crops such as citrus fruits, grape vines, nuts, oil palm, olives, pome fruits, stone fruits and rubber
- annual arable crops For example, cereals (such as barley and wheat), cotton, rapeseed, corn, rice, soybeans, sugar beets, sugarcane, sunflowers, ornamental plants, switchgrass, turf and vegetables, especially cereals, corn and soybeans.
- the grasses and weeds to be controlled can be monocot species, such as Bentgrass, Oats, Brachiaria, Brome, Tribulus, Cyperus, Digitaria, Barnyardgrass, Wild millet, Ryegrass, Amuletia, Panicum, Poa, Trichosanthes, Sagittaria, Scirpus, Setaria, Ceratophyllum, and Sorghum, or dicotyledon Species of the genus Amaranthus, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, Laravine, Ipomoea, Kochia, Nasturtium, Polygonum, Lime, White mustard, Solanum Genus, Stellaria, Grannya, Viola and Xanthium.
- the compounds of the present invention can show tolerance to important crops, including but not limited to alfalfa, barley, cotton, wheat, rape, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanut, Vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantain, pineapple, hops, tea and forests such as press trees and conifers (e.g. Loblolly pine), and turf species (such as Kentucky bluegrass, St. Augustine grass, Kentucky cow hair grass and bermudagrass).
- important crops including but not limited to alfalfa, barley, cotton, wheat, rape, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanut, Vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas,
- the compound represented by formula (I), formula (Ia), formula (Ib), formula (Ic) or formula (Id) can also be combined with other active ingredients, such as other herbicides and /Or insecticides and/or acaricides and/or nematicides and/or molluscicides and/or fungicides and/or plant growth regulators are used in combination. These mixtures, and the use of these mixtures to control the growth of weeds and/or undesirable plants form further aspects of the invention.
- the mixture of the present invention also includes two or more different mixtures of compounds represented by formula (I), formula (Ia), formula (Ib), formula (Ic) or formula (Id) .
- the present invention also relates to a composition of the present invention, in addition to the compound represented by formula (I), formula (Ia), formula (Ib), formula (Ic) or formula (Id) At least one additional herbicide is included.
- the compounds of the present invention can be prepared by the methods described in the present invention, unless otherwise specified.
- Proton NMR of the present invention the test conditions: at room temperature, Bruker (Bruker) 400MHz or a 600MHz NMR instrument, to CDC1 3, d 6 -DMSO, CD 3 OD or d 6 - acetone solutions (reported in ppm Unit), using TMS (0ppm) or chloroform (7.26ppm) as the reference standard.
- s singlet
- d doublet, doublet
- t triplet, triplet
- q quartet, quartet
- m multiplet, Multiplet
- br broadened, broad peak
- dd doublet of doublets, doublet of doublets
- dt doublet of triplets, doublet of triplets.
- the coupling constant is expressed in Hertz (Hz).
- the mass spectrometry analysis method used in the present invention is: Agilent 1260 HPLC; Agilent 6120 ESI.
- Phase A Water (containing 0.1% formic acid); Phase B: Acetonitrile (containing 0.1% formic acid).
- MS parameters ESI positive scan, collision induced ionization: 70V.
- AIBN azobisisobutyronitrile
- DCM dichloromethane
- DMF N,N-dimethylformamide, dimethylformamide
- MeOH methanol
- NBS N-bromosuccinimide
- EtOH Ethanol
- EtOAc ethyl acetate
- PE or Petroleum ether petroleum ether
- THF tetrahydrofuran
- TLC thin layer chromatography
- SOCl 2 thionyl chloride
- Na 2 SO 4 sodium sulfate
- K 2 CO 3 potassium carbonate
- DMSO Dimethyl sulfoxide.
- Compound (Ic) can be prepared by synthetic scheme 1, wherein R 1 , R 2 and R 3 have the meanings as described in the present invention.
- alkaline conditions such as sodium carbonate, potassium carbonate
- alkaline conditions such as sodium carbonate, potassium carbonate
- the reaction occurs to obtain compound (A); compound (A) is hydrolyzed under alkaline conditions (such as lithium hydroxide) to obtain compound (B); compound (B) and acid chloride (such as oxalyl chloride) occur at 0°C-100°C
- Halogenation reaction gives compound (C); compound (C) and optionally substituted hydroxypyrazole (D1) undergo esterification reaction at 0°C-35°C to give compound (D); compound (D) and trimethyl Cya
- Compound (Ia) can be prepared by synthetic scheme two, wherein R 1 and R 2 have the meanings as described in the present invention.
- Compound (C) and cyclohexanedione (F1) undergo esterification reaction at 0°C-35°C to obtain compound (F);
- compound (F) and trimethylsilyl cyanide undergo Fries rearrangement reaction at 10°C-40°C ,
- the target compound (Ia) is obtained.
- Compound (Id) can be prepared by synthetic scheme three, wherein R 1 , R 2 , R 3 and R 5 have the meanings as described in the present invention; wherein X is halogen.
- Compound (Ic) and compound (E1) undergo a nucleophilic substitution reaction at 25°C-50°C under alkaline conditions (such as Cs 2 CO 3 , K 2 CO 3, etc.) to obtain the target compound (Id).
- Step 7 Preparation of methyl 2-chloro-3-((1,3-dimethyl-1H-pyrazole-5-oxy)methyl)-4-methanesulfonylbenzoate
- Step 8 Preparation of 2-chloro-3-(1,3-dimethyl-1H-pyrazole-5-oxy)methyl-4-methanesulfonylbenzoic acid
- Step 11 2-(2-Chloro-3-(1,3-dimethyl-1H-pyrazole-5-oxy)methyl-4-methanesulfonylbenzoyl)-3-hydroxycyclohexyl- Preparation of 2-enone
- Step 1 (1,3-Dimethyl-1H-pyrazol-5-yl)-2-chloro-3-(((1,3-dimethyl-1H-pyrazol-5-yl)oxy )Methyl)-4-(methylsulfonyl)benzoic acid ester
- 1,3-Dimethyl-5-hydroxypyrazole (247mg, 2.20mmol) was dissolved in ultra-dry dichloromethane (20mL), then triethylamine (377mg, 3.74mmol) was added to the reaction solution and cooled to 0 °C, add 2-chloro-3-(1,3-dimethyl-1H-pyrazole-5-oxy)methyl-4-methanesulfonylbenzoyl chloride (705mg, 1.87mmol) to the reaction solution In dichloromethane (10 mL) solution, the reaction was carried out at room temperature for 3 hours, and TLC monitored the complete reaction of the raw materials.
- Step 2 5-hydroxy-1,3-dimethyl-4-((2-chloro-3-(1,3-dimethyl-1H-pyrazole-5-oxy)methyl-4-methyl (Sulfonyl) phenyl ketone) -1H-pyrazole preparation
- Table 2 The activity of the compounds of the present invention on weeds at 300g/ha
- Example Abutilon purslane Barnyardgrass Example Abutilon purslane Barnyardgrass Example Abutilon purslane Barnyardgrass Example 1 97 90 98 Example 2 98 98 98 Example 3 97 94 98 Example 4 98 97 92
- Example Abutilon purslane Barnyardgrass Example Abutilon purslane Barnyardgrass
- Example 5 98 98 98
- Example 6 97 100 95
- Example 7 85
- Example 8 90 95 93
- Example 9 90 96 ND
- Example 10 85
- 90 90 Example 11
- Example 12 93
- Example 13 80
- Example 18 95
- Example 19 98 97 98
- Example 20 ND 90 ND
- Example 21 85
- Example 22 90 90 93
- Example 24 100 100 100
- Example 25 100
- Example 26 100 100 100
- Example 27 100 100 100 100 100 To To To To To To To To To To To To To To To To To To To To To To To To To To To To To
- Table 3 The activity of the compounds of the present invention at 75g/ha, 37.5g/ha and 18.75g/ha on Abutilon and Zinnia
- the compounds of the present invention have great effects on broad-leaved weeds (such as velvetleaf, amaranthus, zinnia, snakehead and purslane) and gramineous weeds (such as crabgrass, barnyard grass, ryegrass and setaria). Good control effect. It is safe for crops, has a quick effect on the control of weeds, and has better control effects on weeds than commercially available herbicides and benzoyl-pyrazole compounds with similar structures, and has good application prospects.
- broad-leaved weeds such as velvetleaf, amaranthus, zinnia, snakehead and purslane
- gramineous weeds such as crabgrass, barnyard grass, ryegrass and setaria.
- Good control effect It is safe for crops, has a quick effect on the control of weeds, and has better control effects on weeds than commercially available herbicides and benzoyl-pyrazole compounds with similar structures, and has good application prospects.
Abstract
Description
实施例 | 苘麻 | 马齿苋 | 稗草 | 实施例 | 苘麻 | 马齿苋 | 稗草 |
实施例1 | 97 | 90 | 98 | 实施例2 | 98 | 98 | 98 |
实施例3 | 97 | 94 | 98 | 实施例4 | 98 | 97 | 92 |
实施例 | 苘麻 | 马齿苋 | 稗草 | 实施例 | 苘麻 | 马齿苋 | 稗草 |
实施例5 | 98 | 98 | 98 | 实施例6 | 97 | 100 | 95 |
实施例7 | 85 | 85 | ND | 实施例8 | 90 | 95 | 93 |
实施例9 | 90 | 96 | ND | 实施例10 | 85 | 90 | 90 |
实施例11 | 85 | 97 | 93 | 实施例12 | 93 | 90 | 94 |
实施例13 | ND | 80 | 80 | 实施例18 | 95 | 97 | 95 |
实施例19 | 98 | 97 | 98 | 实施例20 | ND | 90 | ND |
实施例21 | 85 | 90 | 85 | 实施例22 | 90 | 90 | 93 |
实施例23 | 85 | 95 | 85 | 实施例24 | 100 | 100 | 100 |
实施例25 | 100 | 100 | 100 | 实施例26 | 100 | 100 | 100 |
实施例27 | 100 | 100 | 100 |
Claims (10)
- 一种化合物,其为如式(I)所示的化合物或式(I)所示化合物的立体异构体、互变异构体、氮氧化物或盐:其中:R 1为羟基、氰基、氨基、硝基、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 2-6烯基、卤代C 2-6炔基、卤代C 1-6烷氧基或C 3-8环烷基;R 2为C 1-8烷基、C 2-6烯基、C 2-6炔基、卤代C 1-8烷基、卤代C 2-6烯基、卤代C 2-6炔基或C 6-10芳基;Q为以下子结构式:R 3为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基或C 3-8环烷基;R 4为氢或-CH 2-CO-C 6-10芳基;其中所述-CH 2-CO-C 6-10芳基任选地被1、2或3个选自卤素或C 1-6烷基的取代基所取代。
- 根据权利要求1所述的化合物,其中R 1为羟基、氰基、氨基、硝基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基、卤代C 1-4烷氧基或C 3-6环烷基;R 2为C 1-6烷基、C 2-4烯基、C 2-4炔基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基或C 6-10芳基。
- 根据权利要求2所述的化合物,其中R 1为羟基、氰基、氨基、硝基、甲基、乙基、正丙基、异丙基、-CHF 2、-CF 3、-CH 2CHF 2、-CH 2CF 3、环丙基、环丁基、环戊基或环己基;R 2为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、-CHF 2、-CF 3、-CH 2CHF 2、-CH 2CF 3或苯基。
- 根据权利要求1所述的化合物,其中R 3为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基或C 3-6环烷基;R 4为氢或-CH 2-CO-苯基;其中所述-CH 2-CO-苯基任选地被1、2或3个选自卤素或C 1-4烷基的取代基所取代。
- 根据权利要求4所述的化合物,其中R 3为氢、甲基、乙基、正丙基、异丙基、环丙基、环丁基、环戊基或环己基;R 4为氢或-CH 2-CO-苯基;其中所述-CH 2-CO-苯基任选地被1、2或3个选自氯或甲基的取代基所取代。
- 根据权利要求1所述的化合物,其为如式(Ia)所示的化合物或式(Ia)所示化合物的立体异构体、互变异构体、氮氧化物或盐:或者其为如式(Ib)所示的化合物或式(Ib)所示化合物的立体异构体、互变异构体、氮氧化物或盐:或者其为如式(Ic)所示的化合物或式(Ic)所示化合物的立体异构体、互变异构体、氮氧化物或盐:或者其为如式(Id)所示的化合物或式(Id)所示化合物的立体异构体、互变异构体、氮氧化物或盐:其中:各R 1独立地为C 1-4烷基、卤代C 1-4烷基或C 3-6环烷基;各R 2独立地为C 1-6烷基、卤代C 1-4烷基或苯基;各R 3独立地为氢、C 1-4烷基或C 3-6环烷基;R 5为氢、卤素或C 1-4烷基。
- 根据权利要求6所述的化合物,其中各R 1独立地为甲基、乙基、正丙基、异丙基、-CHF 2、-CF 3、-CH 2CHF 2、-CH 2CF 3、环丙基、环丁基、环戊基或环己基;各R 2独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、-CHF 2、-CF 3、-CH 2CHF 2、-CH 2CF 3或苯基;各R 3独立地为氢、甲基、乙基、正丙基、异丙基、环丙基、环丁基、环戊基或环己基;R 5为氢、氯或甲基。
- 一种组合物,包含权利要求1-8任意一项所述的化合物。
- 权利要求1-8任意一项所述的化合物或权利要求9所述的组合物在农业中防治不想要的植物的应用。
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